Permanent elastomeric polyurethane molded product and method thereof
The invention relates to a light-resistant, elastomeric, polyurethane molded products. Describes microporous or non-porous, light-resistant, elastomeric, flexible or semi-flexible polyurethane molded articles having a density of at least 900 kg/m3and the modulus of elasticity in bending according to ASTM D790, from 5 to 300 MPa, obtained from the reaction mixture by reaction injection molding, in which a) the isocyanate component containing a mixture of isophorondiisocyanate trimer/monomer having an NCO content of from 24.5% to 34% by weight, interacts with) the isocyanate-reactive components containing1) polyetherpolyols having a terminal OH group, the average nominal functionality of from 2 to 4 and an average equivalent weight of from 800 to 4000;2) at least one chain extension having as functional groups only aliphatic or alicyclic Oh-group;3) at least one amine initiator; in the presence of C) at least one catalyst component selected from the group consisting of svyazivayuschego (II), vismutorganicheskikh (III) and ORGANOTIN (IV) the catalyst is Obtained polyurethanes reduce the collection time of the product from the mold, as well as to improve the mechanical properties of products manufactured on the basis of the inventive polyurethanes. 3 S. and 44 C.p. f-crystals, 9 PL. The invention relates to microporous or non-porous, light-resistant, elastomeric, flexible or semi-flexible polyurethane molded products having a density of at least 900 kg/m3and the modulus of elasticity in bending according to ASTM D790, between 5 and 300 MPa, in particular between 10 and 120 MPa, obtained from the reaction mixture by way of reaction injection molding, and the way they are received.It is known that to obtain permanent polyurethanes used aliphatic or alicyclic isocyanates, instead of aromatic isocyanates. However, compared to aromatic isocyanates aliphatic or alicyclic isocyanates have a much lower reactivity, which creates problems associated with achieving a relatively short period of time for extraction of the product from the mold. From a commercial point of view, the collection time of the form should preferably be less than 60 seconds.Reduction of time demoulded through the use of specific catalytic systems is discussed, for example, in US-A-4150206 and US-A-4292411 bole is, from the combination of amine initiator with a low molecular weight and svyazivayuschego or vismutorganicheskikh catalyst. The proposed system catalysts described with reference to a wide range of different foams with monolithic membrane or elastomer and presents various examples, in which time demoulded is 1-6 minutes.The present invention is directed, however, to receive lightfast polyurethane elastomers which are particularly suitable for the so-called sealing of Windows, which on the periphery of the window, including car Windows, form the gasket, designed for installation of a window in the vehicle frame. A gasket or other molded device must meet the requirements for light fastness and heat resistance, and mechanical strength, softness of the material and the strength of adhesion to the window and the frame. It is clear that the applied method of molding must also provide a sufficiently short time extraction of the product from the mold, preferably less than 60 seconds, so that this method could be profitable for its implementation in practice.As a component, the method according to the present invention, promariner, HDI (hexamethylenediisocyanate), which removes the first fraction of the monomer, as described, for example, in application EP-A-0 690085, due to its high volatility and strong effects, irritating the user's eyes. However, a big disadvantage of isophorondiisocyanate is its reactivity, which is even less than the HDI (hexamethylenediisocyanate). With this purpose in the application EP-A-0690085 and in U.S. patent 5502147 offer to apply HDI instead of isophorondiisocyanate as isocyanate, as the use of IPDI in the above-mentioned U.S. patent 4772639 usually requires the time demoulded was approximately 3-10 minutes, and in particular examples, even 5-10 minutes, despite the fact that the ORGANOMETALLIC catalyst is used in combination with amine initiator of polymerization and with specific products trimerization based on HDI and possibly IPDI.According to the present invention has developed a new way, a new set of polyol as one of the mixture and isocyanate mixture, and new polyurethane elastomer, which allow to obtain, within economically acceptable cycle time, permanent elastomeric polyurethane molded product based on isocyanate component based on IPDI, which is suitable, in particular, the personal components of the polyurethane reaction mixture, as well as the conditions under which the method of the reaction injection molding, as defined in paragraph 1 of the claims.In General, the method according to the present invention is aimed at obtaining permanent elastomeric polyurethane moulded products by way of reaction injection molding, which is suitable for use in sealing of Windows, but which can be used for other applications, for example for parts of interior decoration of automobiles or other vehicles, such as door panels, bedspreads, etc. or even for furniture parts. The obtained polyurethane molded product is non-porous or microporous, and it has a density of at least 900 kg/m3. It is flexible or semi-flexible and has, in particular, the modulus of elasticity in bending according to ASTM D790, between 5 and 300 MPa, usually between 10 and 120 MPa, and most typically between 10 and 70 MPa.In the method according to the present invention, the reaction mixture is injected under high pressure into a closed shape, which is placed usually in advance of the insert, such as a peripheral device window. This reaction mixture contains, as a component, isocyanate-based IPDI, the components of the in antioxidant and scavenger of ultraviolet rays.Isocyanate component And contains a mixture of trimer/monomer IPDI, where IPDI the trimer is preferably isophorondiisocyanate trimer, and which has an NCO content of from 24.5 to 34, preferably from 26 to 32% by weight, and, consequently, the calculated average functionality of from 2.2 to 2.7 and the calculated content of the trimer from 20 to 70% by weight. These calculated values are based on the assumption that the pure Monomeric IPDI has a theoretical NCO content = 37.8% functionality = 2, while net IPDI trimers has a theoretical NCO content% to 18.9% and theoretical functionality - 3, thus the possible oligomers that may be present in the IPDI trimer, are not included in the above calculated values. It is established that in combination with a particular selection described later other components you can get a reasonably short time demoulded and good lightfastness and heat resistance for values greater than the specified lower limits, although these values should remain below the specified upper limits, since otherwise the mechanical strength will be lower (that is, the polyurethane material is more brittle), the material is more rigid, and the viscosity isocyanatobenzene preferred IPDI trimer, which is derived IPDI.In addition to the monomers and trimers IPDI isocyanato component may also optionally contain up to 10% by weight of the prepolymers IPDI with compounds reactive with isocyanate, which contain from 2 to 4 groups reactive towards isocyanate containing hydrogen, preferably hydroxyl groups. The addition of such prepolymers can improve adhesion properties to glass.As for the isocyanate component, it should be noted that this component may contain, in addition to the mixture of monomer/trimer of IPDI, a small number of other isocyanate monomers or polymers, in particular HDI trimers (hexamethylenediisocyanate) in an amount of less than 5% by weight based on the weight of isocyanate component.Components In reactive with isocyanate contain politically component (1), the chain extension as a component (2) only with HE-groups, in particular glycols and amine initiator (3), which forms Socialisticheskaya system with a basic catalyst (catalysts) (C), and which contains cross-linking agents and/or chain extenders.Politically componentHowever, in a preferred variant of the method according to the present invention is used as polyetherpolyols component1, the product of the merger of propylene oxide (PO) and possibly of ethylene oxide (EO) on the initiator polisportiva type with a low molecular weight, and the amount of ethylene oxide, if present, is less than 30% of the total number of ethylene oxide and propylene oxide.Nominal functionality of such polyetherpolyols corresponds to the functionality of the initiator used or nominal average functionality initiators used in the case of using the mixture of polyols. In practice, the actual functionality of conventional polyetherpolyols significantly somersalo during the polymerization reaction, thus formed also unsaturated mono-Ola (having functionality = 1). In the case of ordinary katalizowania alkaline (KOH) of polymerization equivalent to the content of the mono-ol may be, for example, up to 20%, but usually it is between 5 and 20%, thus, the nominal functionality equal to, for example, 2 and 3 will correspond to a typical real functionality equal to about 1.7, and respectively about 2.5. Currently, however, there is a new generation of DMS (double metal cyanide) catalyzed polyether polyols having significantly less equivalent to the content of the mono-ol (below 5%, and typically between 0.5 and 3%), so their real functionality significantly approaching their nominal functionality. Such polyether polyols may be available, for example, the firm ARCO series (ACCLAIM), as well as the firm OLIN, and they are disclosed e.g. in US-A-5426081; 470813 and US-A-5498583 listed here for reference.According to the present invention can be applied polyether polyols having a low initial content of IT, for example, even zero, however, achieved a sufficient curing rate. Due to the further reduction of the time overiden occhialino apply polyetherpolyols, with the primary content of IT, at least 70%, preferably at least 80%, and/or apply basic polyetherpolyols, which is subjected to the preliminary polymerization with a part of the isocyanate component, preferably with IPDI monomer with the aim of obtaining quasi-polyesterpolyol (QPP) having terminal Oh group. In the case of quasi-polyesterpolyol, the preferred primary content HE is at least 40%, and more preferably at least 70%. The reaction of the preliminary polymerization to obtain a quasi-polyesterpolyol (QPP) is carried out in the presence of an appropriate catalyst, for example Svencioneliai, ORGANOTIN or vismutorganicheskikh carboxylates and/or at a higher temperature, for example at a temperature in the range of 20-100oWith depending on the level of the catalyst. The optimum final viscosity of the quasi-polyesterpolyol 1.5-10 times higher than the viscosity of the base polyol, whereas the viscosity of the final polyol QPP at a temperature of 25oWith must be, in any case, below 10000 MPawith and preferably less than 6000 MPa(mns/m2); (mPas) for the applications of quasi-polyesterpolyol is primarily he increases the reactivity, that is, the speed of curing of the reaction mixture (because of its higher initial molecular weight, leading to a more rapid increase in molecular weight of the reaction mixture) compared with the isocyanate prepolymers with terminal PSO-groups (where the decrease in the NCO content leads to a decrease in the number of exothermic reactions), and secondly, that increases the viscosity of the mixture of polyol and thus improves, in particular, its physical stability; in other words, when the mixture is not stirred, the mixture is less sedimentation or decantation and separation of the components. Due to these advantages makes specific reference to the use of quasi-polyesterpolyol end HE-groups (QPP) in the method according to the present invention.In the case of conventional polyether polyols are preferred nominal average functionality of from 2.5 to 4 and an average equivalent weight of from 1000 to 1500 due to the decrease of the time required for curing or demoulded, especially if polyetherpolyols has a primary content IT is less than 70%, or if polyetherpolyols modified quasi-polyesterpolyol, has the primary content of the Deposit or collection of forms can be reduced by applying polyetherpolyols, having a low content of mono-ol, in particular equivalent to the content of mono-Ola less than 5%. As described, such polyether polyols are available, for example, by ARCO. These polyether polyols catalyzed by DSM, have not only a low content of mono-ol, but in most cases almost zero content of the primary HE and SW. Such polyether polyols with low equivalent content of mono-Ola preferred in the method according to the present invention not only because of their higher reactivity, but also because of the additional mechanical strength and resistance to weathering, which can be obtained with them, compared with conventional polyether polyols with the same nominal functionality and, consequently, with lower real functionality.In the case of polyether polyols having a low content of mono-ol, are preferred in view of reducing the curing time or demoulded, the average nominal functionality of from 2 to 4, preferably from 2 to 3, for the minimum stiffness of the elastomer, and an average equivalent weight of from 1000 to 2000, especially if polyetherpolyols has the content HE primary less than 40%. Polak, as a conventional polyether polyols to obtain quasi-polyesterpolyol (QPP) with integral IT groups.The advantage of the above-described preferred options, in which it is possible to achieve a further reduction in the curing time or time demoulded, is that they allow you to apply a small amount of catalysts for this time of extraction from the mold, thereby improving the properties of the elastomer. Further, it may be important to the use of polyether polyols or mixtures thereof having a low average primary content, for example between 0 and 40%, and, therefore, the low average content of EO, in particular less than 20% and preferably less than or equal to 10%, especially due to the absorption of water and related characteristics wrinkling of the elastomer, as a certain number of primary Oh-groups in polyetherpolyols end formed by the group of ethylene oxide (EO), and therefore for the formation of a certain number of primary Oh-groups requires a minimum amount of ethylene oxide. In the case of the use of polyether polyols with low content of primary HE in the way, according to the present invention, it is preferable to use polyols containing quasi-polyesterpolyol and/or small is oseney to the sum of ethylene oxide and the polyol can easily be less than 10% and may contain 0% to achieve maximum reduction of water absorption and the associated effects of wrinkling sealed polyurethane elastomer.Indeed, due to the decrease of water absorption amount of the hydrophilic groups of ethylene oxide in polyetherpolyols preferably less than 20% of the total number of EO and RO, i.e. from the sum of the number of EO groups and RO, and more preferably less than or equal to 10%.As noted, used the polyether polyols have a nominal functionality of from 2 to 4. In the case of conventional polyether polyols and a nominal functionality of preferably equal to about 3, whereas for types of polyether polyols with low content of mono-Ola nominal functionality is preferably in the range from 2 to 3. In combination with the above features polycomponent can thus receive the desired softness, mechanical strength, light resistance and heat resistance (WOM properties), and this combined with the relatively short time demoulded. To reduce water absorption elastomer or, in other words, for the exception described later risk of so-called "wrinkling", to improve resistance to weathering and to reduce the time demoulded preferred real average functionality equal to at least 2.Finally, chr/963.gif">1, since in many cases it was found inexplicable effect of migration/incompatibility, leading to the formation of sebaceous surface of the polyurethane after aging.The chain extension as a component of2 contains the extension only with HE-groups as functional groups, in particular aliphatic or alicyclic Oh-group, and it is used in an amount of about 3-20% by weight, preferably about 5-15% by weight, based on the weight of components1,2 and3. Due to the necessary a short time for demoulded, in combination with the required properties of the elastomer, i.e. softness, mechanical strength and so on, these chain extenders are, according to the present invention, a functionality equal to 2 equivalent weight, at most 80, and the content of the primary HE at least 50%.Typical examples of extension chains2 with only the HE-groups as functional groups are: ethylene glycol, propandiol (various isomers), butanediol (various isomers), pentanediol (various isomers), hexanediol (various isomers), diethylene glycol, 2-IU is initiator amine polymerization is used, as a component of3, in an amount of about 2-10% by weight, and preferably about 2.5 to 6% by weight based on the weight of components1,2 and3. Taking into account the required short time demoulded and the necessary mechanical properties and light fastness and heat resistance of the polyurethane elastomer amine initiators are, according to the present invention, two to three functional aliphatic NH, NH2or Oh group, at least one of which is a secondary or primary amino group, and an equivalent weight of at most up to 150, preferably up to 100 at best. Thus these compounds are aliphatic or alicyclic polyamines or alkane-laminae.Amine initiators chosen preferably from the following various compounds: I. cross-Linking agents alkanolamines type with one secondary NH group and two HE-groups, preferably primary HE-groups. Typical examples are, for example, diethanolamine (DEQA) and Diisopropylamine, and preferred diethanolamin.II. Extension chain with one primary NH2group and one is here primary NH2group related decreases WITH HE band due to spatial difficulties and/or activity of the oxygen atom in the adjacent Oh group, as removing an electron.This essential part of this type of amine initiators can be represented as follows:Typical examples are monoethanolamine (deed are the measurement) and 2-amino-2-methyl (or ethyl) - 1-propanol, and the preferred monoethanolamine.III. Extension chain with one secondary NH group and one primary HE-group. Typical examples are N-methyl (or ethyl) ethanolamine (= monomethyl (or ethyl) ethanolamine).IV. Extension chain with two primary NH2groups, at least one of which is located on the alicyclic ring. A preferred example is isophorondiamine (ACCESSORIES>).V. Extension of circuits with two secondary NH groups having a branched alkyl or cycloalkyl group with at least four adjacent atoms With or suturing with three secondary NH groups, at least two of which have a branched alkyl or cycloalkyl group attached thereto, at least four atoms C. Branched alkyl or cycloalkyl are- R-group in the examples (1)-(3) is isohexyl
-R1group in example (4) is
- R"group in example (5) is tert.butyl.Especially preferred amine initiators classes I, II and V.Due to the optimum time demoulded, amine initiator preferably contains at least 1% by weight of diethanolamine (DEOA) as a crosslinking agent, calculated on the weight of components1,2 and3, and to improve the characteristics of mechanical strength, it contains DEOA, preferably in combination with aminoven initiator type of chain extension, in particular monoethanolamine (deed are the measurement), the resulting average amine functionality of the initiator is between 2 and 3. In General, higher functionality leads to more short time demoulded, but also a low mechanical strength for elastomers soft types, and, conversely, low functionality provides increased mechanical strength, but increases BP is e soft types of polyurethane elastomer, having a modulus of elasticity in bending below 120 MPa, particularly less than 70 MPa, and in particular less than 30 MPa, good mechanical properties can be reconciled with the relatively short time demoulded for an average amine functionality of the initiator (s), located between 2 and 3, unless you apply catalyzed polyols with low content of mono-tins, in this case, the amine functionality of the initiator may be equal to 3, allowing you to achieve good mechanical strength for elastomers soft types.In relation to the number of amine initiators also found that if the amine initiator contains 2 primary aliphatic NH2group, its content should preferably be less than 1.5% by weight based on the weight of components1,2 and3, and preferably less than 3 mass%, if at least one NH2group attached to the alicyclic ring, to exclude the poor flow of the reaction mixture in the form as well as a longer time demoulded.The catalytic system in the method according to the present invention contains, in addition benzofuranes (II), vismutorganicheskikh (III) and ORGANOTIN catalysts, the latter catalyst in combination with sincopirovannam and/or victorhanson.com, and/or in combination with diazabicyclo-alkanoyl catalyst.Suitable twintowercasino and vismutorganicheskikh catalysts are described respectively in U.S. patents-And-4150206 and 4292411 listed here for reference. Set Svencioneliai and vimalaramsi catalysts are, in particular, salts of lead (II) or bismuth (III) carboxylic acids.According to the present invention, the maximum concentration twintowercasino catalyst is 1.5% by weight, preferably 1% by mass, and more preferably 0.5% by weight based on the weight of components1,2 and3 in order to reduce the risk of unwanted metallic luster on the surface of the polyurethane elastomer after aging or storage in the case of dark colors. In that case, if the time demoulded still long, you can apply other socializaton in addition to aminoven initiators, and preference is given, among others, diazobicyclo the x this last socialization. Diisobutylaluminum catalyst, in combination with sincopirovannam catalyst is used preferably in an amount of from 0.1 to 1% by weight, and ORGANOTIN catalyst is used in amount of 0.2-1% by weight based on the weight of components1,2 and3. To compensate for small amount of twintowercasino catalyst can also reduce the time demoulded by applying the above-described quasi-polyesterpolyol, polyols containing a small amount of mono-ol or by adding vismutorganicheskikh catalyst.According to the present invention, the maximum concentration vismutorganicheskikh catalyst is 1.5%, and preferably at most 1% by weight based on the weight of components1,2 and3. Indeed, a higher number may create problems in regard to chemical resistance of the mixture of polyols, as vimalaramsi the catalyst contains some amount of free acid, which can be an obstacle for potential alkali catalyst or components of amine initiator polyol as one in the but less than 25%, better less than 10%.When used Svencioneliai catalyst, the collection time of the forms can also be reduced through the use of quasi-polyesterpolyol, polyols containing a small amount of mono-ol, or additional diisobutylaluminum or ORGANOTIN catalysts in the above quantities, and in this case, preference is given to combinations vismutorganicheskikh catalyst with ORGANOTIN catalyst. Next, you can apply vimalaramsi catalyst in combination with sincopirovannam catalyst.In that case, if the ORGANOTIN catalyst is used without twintowercasino catalyst or vismutorganicheskikh catalyst, its maximum concentration is 3% by weight based on the weight of components1,2 and3. In this case, the ORGANOTIN catalyst is used in combination with diisobutylaluminum catalyst, more preferably in combination with 0.3-1% by weight, based on the weight of components1,2 and3, this latter catalyst.ORGANOTIN katalizatoriai
where R1= (C1-C4) alkyl radical, a R'-(C1-C12) branched or unbranched alkyl radical; or Sn(IV) carboxylates or dialkylaminoalkyl corresponding to the General formula
where R1= (C1-C4) alkyl radical, a R2forms (C1-C12) alkyl radical or a radical of naphthenic acids, alkyl radicals, linear or branched, preferred compounds in which R1is a methyl group, a R2- (C1-C11) alkyl radical or a radical of naphthenic acid or where R1- butyl group, a R2- (C1-C4) alkyl group; or dialkylaminoalkyl, in which the alkyl group is C1-C4alkyl group.The most preferred Sn(IV) carboxylates, where R1is a methyl group, a R2- C1-C11alkyl group.Diisobutylamine catalysts are either diisobutylamine, as such, or their salts with weak acids, including phenol, having the value of the PKamore than 4. They correspond to the General formula
the well-7, and octotoma or feoletovo salt of this compound, with the most preferred Fedosova salt.In the method according to the present invention, used as inorganic or organic pigments, which are insoluble in the reaction mixture and which are usually dispersed in the isocyanate reactive compound. They are, essentially, enough light and heat resistant and used at a concentration of 0.15 to 10% by weight solids based on the weight of the reaction mixture and preferably the minimum concentration of at least 0.3 percent by weight solids.Typical examples are gas carbon black, titanium oxide, etc. are Used pigments provide the "opacity" of polyurethane material, in other words, it becomes more opaque, which is especially important for the intended application for sealing boxes or interior of the car.In these latter applications, polyurethane elastomeric materials should be resistant to harsh weather conditions, including the combination of ultraviolet rays, oxygen and heat, and in these conditions they may not discolour. Therefore, in the method according to the present invention, used policy oxidant, namely, preferably:
0.1 to 1% by weight, preferably 0.2 to 0.6% by weight, based on the weight of the entire reaction mixture, the primary antioxidant of the type of the substituted phenol; and
0.1 to 1% by weight, preferably 0.2 to 0.6% by weight, based on the weight of the entire reaction mixture, HALS (Employed Aliphatic light stabilizers) is a type of substituted alicyclic amines; and possibly secondary antioxidant, namely:
0-5% by weight, preferably less than 3% by weight, based on the weight of the entire reaction mixture, peroxide decomposers, preferably aliphatic or aromatic type organophosphate.Applied absorbers of ultraviolet rays are preferably benzotriazole type and their use, in particular in an amount of 0.1-1% by weight, preferably 0.2 to 0.6% by weight based on the weight of the reaction mixture.In the method according to the present invention can also be applied to other components, namely:
topolitical, which added to the reaction mixture of the isocyanate with the aim of reducing the risk of formation of pin holes, for example zeolites, dry calcium oxide, etc.;
emulsifiers/modifiers fluidity (viscosity), among other things, to improve mixing and compatibility of the e;
internal releasing agent to be added to the polyol or perhaps in the isocyanate mixture, for example a polydimethylsiloxane-polyether copolymers with free HE-groups, metal salts of fatty acids (e.g., zinc stearate), and various derivatives of fatty acids (esters, amides.... fatty acids), which allow to reduce the concentration and frequency of application of external lubricants on the form;
inner glass primer type silanes (including, in particular, also reactive silanes, i.e. silanes with active groups, relative to the polyurethane elastomer), which allows to eliminate or reduce the number of external primers for glass during sealing of the window; as well as other additional components, which are known essentially intended for methods of forming polyurethane.In the method according to the present invention, the above-described polyurethane reaction mixture is treated in accordance with the technology of the reaction injection molding (RIM), in particular according to the technology of two-component injection moulding under pressure from the mixture in countercurrent, in which the mixture of isocyanate and polyol serves under high pressure in the mixing chamber, the isocyanate index (NCO index) 90-120, more preferably 95-110, and even better from 100 to 110. This form usually contains already located it hard or flexible insert, especially the periphery of the window, which is intended for sealing flexible or palpably polyurethane gasket. In some applications, the entire surface of the insert may be coated with polyurethane elastomer, for example, in the case if, for example, in the front panel, you must install the small details or even large items, for example, in the entire door panel. The thickness of the polyurethane elastomer is typically between 0.5 and 5 mm, and typically between 1 and 4 mm,Both components as a whole or a mixture of the reaction mixture, i.e. the isocyanate mixture and Palilula mixture containing the above-described various components. Isocyanate mixture contains, in particular, the isocyanate component And ORGANOTIN catalyst and possibly antioxidant, absorbers of ultraviolet rays, an internal lubricant for shape and glass primer. On the other hand, Palilula mixture contains isocyanate reactive components1,2 and3, the catalysts (except ORGANOTIN catalyst), the pigments may, antio the La shape and glass primer.An important aspect paleologou mixture is its chemical and physical resistance. Chemical resistance is achieved by reducing the number of "acid" vismutorganicheskikh catalyst, lack of ORGANOTIN catalyst and a limited amount of water, which is especially important in the presence of twintowercasino catalyst. Physical stability is achieved through the use of mixtures of components1,2,3, dispersion colour pigment and, possibly, emulsifiers, especially if the component is2 contains branched glycols, such as 2-methyl-1, 3-propandiol and 3-methyl-1,5-pentanediol, and also due to viscosity paleologou mixture, which is quite high when the temperature of the source material during storage or manufacture. Viscosity paleologou mixture at a temperature of 25oWith exceed, for example, 400 MPawith, preferably 700 MPasecond, whereas the viscosity at 45oWith the above, for example, 100 MPawith, preferably above 200 MPaC. As stated, this viscosity can, for example, be increased by the way, the according to the present invention, is heated to a temperature from 60 to 130oC, preferably from 80 to 120oWith special preference is given to temperatures form, at least 90oOr more, particularly preferably a temperature of from 95o110oC, and the reaction mixture is injected at a temperature of between 30 and 80oC, preferably between 40 and 60oC. At these temperatures Palilula and isocyanate mixture have a viscosity of preferably 150-2500 MPas, more preferably 200-2000 MPaC.Before injectionem the reaction mixture, in particular, before closing the form to the surface form is applied as a surface lubricant. Especially in the case of applications for sealing the window in which the elastomeric material will be glued to the frame of the vehicle separate PU polyurethane adhesive, preferably applied, in accordance with the present invention, the wax having a melting point or range of the melting temperature at least equal, but preferably higher than the temperature of the shape, usually 0-30oWith the temperature of the mold. The mold temperature is at least preferably 80oWith, and for the form is usually between 110 and 130oC. the Wax is dispersed in particular in water or in an organic solvent.Unexpectedly it was found according to the present invention, that the use of high temperatures to form (more than 60oWith, preferably more than 80oWith, and even better between 95 and 110o(C) in combination with the lubricant to form, having a melting point that is equal to at least the temperature of the shape, the number of pin holes (craters) on the surface of the polyurethane elastomer can be reduced to a minimum. This is important not only for optimal visual aspect, for example, that required according to the specifications of the cars, but also for optimal adhesion on polyurethane elastomer insert or polyurethane glue used to secure the window in the frame of the car.The minimum number of pin holes can also be achieved by not using physical pore and reduce the water content in the isocyanate reaction mixture to a value of less than 0.2% by weight, preferably less than 0.1% by weight, the quantity of water in the entire reaction mixture is smaller than 0.15% by weight, preferably less than 0.1% by mass.PU is e to the value approaching even to a zero value. In this case, the risk of formation of pin holes is also reduced even at a lower temperature range of forms, for example, when 60-80oC.According to the present invention have found that when the above choice of process conditions and components of the reaction mixture have a way of reaction injection molding (RIM), which is surprisingly suitable for use in sealing of Windows, despite the harsh conditions, which must withstand the resulting elastomers, and specific characteristics that must be elastomers, in particular the softness, adhesion, mechanical strength, etc. Some of these aspects are summarized below.The adhesion of the polyurethane elastomer to a glass slide or polyurethane glue
In case of application for sealing of Windows must achieve good adhesion between the polyurethane elastomer and, on the one hand, between the local surface of a glass paste, which inject the polyurethane elastomer in the form; and on the other hand, in the last phase, between a polyurethane adhesive used for bonding polyurethane elastomer to the frame of the car.In the described method, with the boron various components of the polyurethane reaction mixture;
2) the use of external lubrication for the form, having a melting point greater than or equal to the temperature of the shape, thus on the surface of the elastomer does not form a film of melted grease which is difficult to remove and which forms a physical and chemical barrier to interactions between the surface of the polyurethane elastomer and glass or primer polyurethane adhesive;
3) education minimum number of pin holes, as explained above;
4) use appropriate cleaners, primers (adhesion promoters). A typical example of such cleaners, primers, applied to the surface of the glass is a mixture of reactive silane, solvent, well-known, essentially, for example, ethyl acetate, and perhaps polyurethane prepolymers with excess CO-groups; and a typical example of cleaners, primers, applied to the polyurethane elastomer is a mixture of polyurethane prepolymer with excess JI-groups, and solvents; and
5) a sufficiently high mechanical strength of the polyurethane elastomer, namely the limit of the tensile strength and tear resistance, high enough for the efforts of exfoliation during tests on the adhesion Fastness and heat resistance
The method according to the present invention allows to obtain a polyurethane elastomer, which can be used for external sealing of Windows, in which you must follow strict requirements. During the following tests weather should not be a significant destruction of the surface (surface cracks, dusting chalk), discoloration or changes in the gloss:
accelerated testing (WOM) within 1000-2000 hours using as light source a xenon lamp or carbon arc lamp and temperature completely black panel 45-90o;
continuous or alternating light/rain, for example, according to the test standard ASTMG26-83, standard test GM GME 00-002/SAE J1960, etc.;
long practical field trials for more than one year, for example, in Florida and Arizona.This property can be obtained, for example, by a combination of the following elements in the compositions of the polyurethane elastomer:
1. special choice of the isocyanate component containing, in particular at least 20% of the trimer of isophorondiisocyanate (IPDI) in a mixture isophorondiisocyanate trimer/monomer and having an average functionality, hence the amine initiators, have a functionality of at least 2; and
4.) the type and concentration of colour pigments.The combination of the desired softness and mechanical strength
Polyurethane elastomers obtained by the process according to the present invention, must have, in most cases, the modulus of elasticity in bending according to ASTM D790 in the range of 5 are 300 MPa, and most typically in the range of 10-70 MPa.However, the characteristics of mechanical strength such as tensile strength tensile and tear resistance, decrease, on the other hand, if: the material is softer, that is, in the case of low concentration of chain extenders and/or low NCO; increased percentage of trimer in a mixture of isophorondiisocyanate (IPDI).According to the present invention found that, on the one hand, sufficient softness of the polyurethane material, and on the other hand, a sufficient mechanical strength, sufficient light resistance and heat resistance and a short time demoulded (fast curing) can surprisingly be combined with each other, even when applied isophorondiisocyanate due to the particular compositions in accordance with the present invention, namely:
2.) the mixture isophorondiisocyanate trimer/monomer containing 20-70% by weight of trimer (average functionality = 2,2-2,7) and having an NCO index between 90 and 120, preferably between 95 and 110;
3. ) the type and concentration of HE-extension circuit containing two Oh-group; and
4.) the type and concentration of amine initiators.The water absorption and the formation of wrinkles
In case of high water absorption, for example, when sealed in a polyurethane window, immersed in water (especially cold water), polyurethane elastomer can occur dimensional local deformation ("shrinkage") after a specified time, especially if you use a polyurethane elastomer and/or some m the but the present invention is installed, what phenomenon can be reduced by:
1) the minimum number of pin holes (micropores) on the surface of a polyurethane elastomer; and
2) sufficient physical-chemical and chemical crosslinking of the polyurethane elastomer by especially selected compositions, for example: type, functionality (f) and the concentration of polyetherpolyols (1) (the actual functionality2 and % SW <30%, preferably <20%, and more preferably <10% relative to the amount of polyol (PO) and (EO), extension cords, chains (2), amine initiators (3) (f2) and the use of isophorondiisocyanate trimer, so the functionality isocyanate component, at least over 2.2; index NCO, preferably greater than 95, and more preferably greater than or equal to 100 in the case of major conventional underground with a relatively high content of Mineola and SW.According to the present invention, the water absorption can be reduced to values less than 10 mass%, and if the content of EO is10%, even less than 3% by weight of water absorption after immersion of the sample polyurethanefoam the invention, illustrated hereinafter with reference to some specific examples.EXAMPLES 1
1. Conditions of preparation of the test plates obtained by reaction injection molding (RIM)
The mixture of polyol (side a) and a mixture of isocyanate (side B) are mixed in a mixing head FPL1O (CANNON) high pressure intended for mixing two components, which is attached to the form, and then injected through the radial sprue in the test form of die-cast aluminum size 10002003 mm with a total production of 200 grams/second.The temperature of the source material on the sides and At 45oC.Mold temperature: varies (standard 105oC).Prior to injection on the surface of the mold sprayed outer grease (ERA) type of wax dispersed in water.For testing of samples obtained by reaction injection molding, adhesion to glass (sealed box) in a special test form is placed a glass insert. These glass panels are then sealed in place through a system of injected polyurethane reaction injection molding.The various components in the compositions of the RIM are separated (mixed) as follows:
atory, the type of catalyst 1, catalyst 2 or the catalyst 4
some antioxidants/absorbers of ultraviolet rays as components (AO/UV), dispersion colour pigment,
possibly other additives, such as internal lubrication for the form, emulsifiers, defoamers, topolitical (e.g., zeolites).The b-side (isocyanate compound):
isocyanate (mixture isophorondiisocyanate monomer/ isophorondiisocyanate of isocyanurate,
The type of catalyst, catalyst 3 (a tin catalyst).Some of the components as antioxidants/absorbers of ultraviolet rays.Typical viscosity of the parties a and b at a temperature of 45o(MPaC) (see tab. A).II. The source materials used in the Examples: abbreviation
Poliferation obtained by polyaddition of oxides of alkylene (propylene oxide and ethylene oxide) in glycerol starting material with the use of CON-catalyst.Molecular weight (MW): 4800/ON-number=35/nominal functionality: 3/85% of primary Oh-groups/15% of ethylene oxide
(SW)/viscosity at a temperature of 25oWith 800 MPawith
Polyetherdiol obtained by polyaddition prop is a metallic cyanide (LCA), while receiving less mono-ol/unsaturated by-products compared with normal CON-catalysts.Brand: ACCLAIM 2200 (ARCO CHEMICAL Co)
Molecular weight =2000/number ON =56/functionality:2
Zero content of primary Oh-groups (100% secondary Oh-groups)
Zero content ethylenoxide (100%-the content of the propylene oxide)
The viscosity at 20oWith 460 MPa(160 MPawith the 40oC)
Unsaturated (mono-Ola): 0.005 milliequivalent/g
Poliferation obtained by polyaddition of propylene oxide (PO) to the glycerol source material with the use of a catalyst based on double metal cyanide (LCA)
Brand: ACCLAIM 6300 (Firm BRIGHTLY CHEMICAL TOo)
Molecular weight =6000/number ON =28/functionality:3
Zero content of primary Oh-groups (100% secondary Oh-groups)
Zero content of ethylene oxide (EO) (100% propylene oxide)
The viscosity at 20oFrom 1900 MPa(600 MPawith the 40oC)
Unsaturated (mono-Ola): 0.015 milliequivalent/gram.The polyols In the quasi-prepolymer and a C-quasi-prepolymer
Quasi-forprimary polyols with conc the Ola In and polyol With a number isophorondiisocyanate (IPDI) monomer, resulting in polyol with high molecular weight, having increased viscosity and reduced the number ON.Synthesis of polyols In the quasi-prepolymer and a C-quasi-prepolymer
The base polymer or pre-mixed with lead octoate (catalyst 1) at room temperature. Then add isophorondiisocyanate with stirring. A maximum of 24 hours to get the final equilibrium viscosity and the number ON (see tab.B).Polyol D
Polyetherdiol obtained by polyaddition of propylene oxide and ethylene oxide to glycol source material using a special catalyst based on double metal cyanide CDOP) the result is less manual/unsaturated by-products compared with normal CON-catalysts.Molecular weight (MW):2000 /number ON =56/functionality =2/EW:1000
55% of the content of primary Oh-groups/9% ethylene oxide (EO)
The viscosity at 25oWith 430 MPawith
Unsaturated (mono-Ola): 0.005 milliequivalent/gram.Polyol E
Poliferation obtained by polyaddition to glycerin source material with conventional KOHN-catalyst.Molecular weight (MW):4000/number Oulevay % content of ethylene oxide (100% content of propylene oxide)
The viscosity at 25oWith 700 MPawith
OUT AND OUT, IN and OUT WITH (ISO)
Serve in place of the mixture of monomer isophorondiisocyanate (IPDI) and the trimer of IPDI isocyanurate obtained by the trimerization in the place of the monomer isophorondiisocyanate at high temperature in the presence of a trimerization catalyst, and then the reaction mixture is diluted with a monomer isophorondiisocyanate until then, until you get the desired final CO content (see table.C).FROM D (ISO)
clean IPDI (isophoronediisocyanate)
functionality: 2/ NCO content of 37.8% / viscosity at 20oWith 15 MPawith
the monoethylene glycol (chain extension)
functionality: 2/ equivalent weight 31
2-methyl-1,3-propandiol (chain extension)
functionality: 2/ equivalent weight 45
diethanolamin (stapler / "amine initiator)
functionality: 3/ equivalent weight 35
Deed are the measurement
monoethanolamine (chain extension / "amine initiator)
functionality: 2/ equivalent weight 30
ethylhexoic lead (2) (swinecast") = Pb (II) carboxylate containing 33% by weight of the metal lead.Note: This level of Catalyst 1 in the examples, the composition includes what limera in examples 9-12.Catalyst 2
ethylhexoic bismuth (2) (vismuttia") = Bi (III) carboxylate containing 24% by weight of the metal bismuth and less than 5% free acid.Catalyst 3
salt of the phenol 1.8 diazabicyclo [5.4.0] undecene-7.A mixture of antioxidant/absorber of ultraviolet rays (AO/UV), consisting of:
0.5 parts of triethylene glycol-bis-3(3-tert.butyl-4-hydroxy-3-were) propionate, which is added to the a-side (polyol mixture),
0.5 parts of 2(2-hydroxy-3,5-di-tert.amyl-phenyl)-2H-benzotriazol that add to the side And,
0.5 parts of bis(1,2,2,6,6-pentamethyl-4-piperidyl) salt sabatinovka acid, which add to the party (a mixture of isocyanate).4.5 parts of Tris(nonylphenyl)FOSFA that add to the side Century.Colored pigments
black = carbon black
white = the titanium oxide (rutile type)
Balit L (Baylith L) (Beyer):
Zeolite water-absorbing paste containing 50% digidratirovannogo potassium-sodium aluminosilicate.Note the weight ratio of the various components in the examples
All compositions are expressed in parts by weight related to 100 parts of N-active, that is reactive with isocyanate components is respectively 20% solids for black and 50% solids for white.Of these dispersions in the composition was added 5 parts suitable for:
black: 1 part solids + 4 parts polyol And
white: 2.5 parts of solid particles + 2.5 parts of polyol A.Polyol And present in these color dispersions include in the General level of polyol, for example, presented in the songs.ERA 1 and ERA 2 (external lubrication for the form)
Wax, pre-dispersed in organic solvents (hydrocarbons/propanol)
typical melting point of the wax in the outer grease 1 approximately 120oC; outdoor grease 2 approximately 90oC.typical solids content of the wax dispersions of external lubricants to form 1-2%.Ill. Data reactivity and physical properties are presented in the examples: abbreviation.1) reactivity Data
2) FT: the formation of fibers (in seconds): indicates the beginning of gelation (gel formation), i.e. the time during which it is possible to pull the fiber from the reaction mixture with a glass rod.DT: time demoulded (in seconds), i.e. the duration of curing in a form that allows to obtain a sufficient cohesive strength during the excavation of the shape of the product obtained R is of the form.2) Properties (samples 3 mm thick)
D: density molded polyurethane elastomer in g/litre (= kg/m )
Emod: the modulus of elasticity in bending (MPa) according to test method ASTM D790.IB
Shore A: surface hardness shore (in units) according to the method of testing in accordance with DIN 53505.ER: elongation at break (in %) according to test method ASTM D412A
RR: tensile strength (MPa) according to test method ASTM D412A
TR: tear resistance (N/cm) according to test method ASTM D624C
WA: water absorption, expressed in % by weight absorbed water after immersion of the sample material obtained by reaction injection molding, in water at a temperature of 2oWith in 72 hours
WOM: the test weatherometer (accelerated test of light fastness, heat/humidity) under the following conditions tested according to ASTM G 26/1
the device ASTM C134 continuous lighting xenon arc lamp
the intensity of the incident radiation 0/55 watts/m at 340 nm
the temperature of the black panel 63oWith
cycle: 102 minutes dry/ 18 minutes of water spray
filters: exterior: quartz / inner: borosilicate
test time is 1500 hours.what Imatra)
the gloss retention (%) when the initial gloss of the sample was approximately 75% in the form of testing large glitter
% save the original Dan Shine after polishing the surface of the test sample subjected to aging.destruction: the visual code:
About: the absence of any surface degradation, even under a microscope (magnification: 50x)
1.: the tendency to the formation of surface cracks under a microscope
2.: minor surface cracks under a microscope
3. : moderate surface cracks under a microscope (but invisible without a microscope)
4/5: trend or minor to moderate surface cracks visible without a microscope.Adhesion to glass (in case of application for sealing Windows)
a) preparing the sample:
typical automotive glass elements (inserts) purified heptane, and then sequentially process:
the cleaner BETAWI VP04604-GURIT ESSEX: by wiping/drying (solution reactive silane in isopropanol)
primer: BETHAPRIM 5001 - GURIT ESSEX: by wiping (solution isocyanato of prepolymers and non-chemical active silanes in methyl ethyl ketone).Drying glass and primer for amemait in a special test form then carry out the injection under high pressure into the system reaction injection molding.Sealed through a system of reaction injection molding (RIM) plate glass store then for 7 days at ambient conditions (23oC/ 50% relative humidity) before testing adhesion of glass to the surface of the RIM by measuring the peeling.b) test for exfoliation (= "the adhesion of glass") measurement of the adhesion strength (N/cm) between the glass (primer) and the RIM surface by peeling at an angle of 90oaccording to the method DIN EN 1464.If the glass/paint primer and the interface RIM there is a gap, it means that there is no coupling between them. (AF).If a break occurs in the core of the sample RIM, it means that there is no cohesion (CF).Tests are conducted on samples sealed glass:
at the initial stage, i.e. without additional aging;
after the test under cyclic effects cataplasme aging:
immersion in water at a temperature of +23oC for 7 days, the aging of the wet samples (Packed in aluminum foil in the dryer at a temperature of 70oC for 7 days (at 100% relative the establishment in ambient conditions for 16 hours (23oC/50% relative humidity) before testing will occur.Adhesion to polyurethane glue
(in the case of specified applications for sealing window, where a sealed box glued to the vehicle frame polyurethane adhesive applied on the surface of the material obtained by the process of reaction injection molding, sealed box).a) Preparation of sample:
the surface of the sample material obtained by reaction injection molding, purified heptane, the surface is treated with a cleaner/activator type BETA VIP 4000 (GURIT ESSEX) by cleaning (solution polyisocyanates in ethyl acetate);
after 5 minutes, the treated surface of the RIM is applied BETA-FORCES HV3 (GURIT ESSEX). HV3 is a high viscosity, single component polyurethane adhesive based on aromatic polyisocyanates from 0.7% content of free NCO,
integrated RIM/HV3 adhesive stored in ambient conditions for 7 days, allowing the glue HV3(PU) fully Tvarditsa.C) Tests on peeling (adhesion of polyurethane glue)
- evaluation of adhesion (visual) glue between HV3 and the surface of the RIM by manually testing the peeling angle 180o:
initial samples RIM/HV3,
- the 7 days, and their recovery in ambient conditions (23oC/50% relative humidity)
assessment criteria OK = lack of cohesion (CF) in the very core of HV3, evaluation criteria no OK = no adhesion (AF) between the boundary of the material of the RIM and glue HV3.Visual appearance --> metallic luster (code)
After storage for 2 months in the dark products obtained by reaction injection molding, they may appear in some cases "bright metal" Shine, which can be seen especially in cases, if:
they are dark colored,
too high content twintowercasino catalyst (katalysator 1).Visual code after 2 months of storage at the production site or in the atmosphere of their processing in a typical flexible polyurethane foam.Code 0: no metallic luster.Code 1: minor trend: almost invisible.Code 2: minor to moderate trends (visible).IV. Comments (interpretation of the results in examples a Number of Examples 1A to I1 (Fig. 1-3).According to the present invention has been soft permanent elastomers RIM by way of reaction injection molding, having exceptional characteristics the temperature of the form <60 o(C): the set of micropores on the surface of the material of the RIM and the limit in respect of the adhesion of the polyurethane adhesive and acceptable time demoulded:
Example 1F: poor adhesion of polyurethane adhesive owing to the low melting point external lubrication (ERA) for the form in relation to the temperature of the form;
Example 1G: the surface of the RIM (1 part catalyst 1) has the appearance of moderate metallic luster;
Example 1C: the higher the water absorption due to the lower index NCO 90 in combination with the polyol A.The group of examples 2-8
By way of reaction injection molding (RIM) were obtained elastomers with outstanding characteristics reactivity and properties except for comparative examples 7 and 8.Example 7 (clean isophorondiisocyanate monomer/trimer)
--> too long demoulded / low reactivity
--> different point hole on the surface of the elastomer RIM
--> low hardness and ultimate tensile strength despite the use of higher level chain extension and the NCO index
--> moderate metallic luster (with the aim of increasing reactivity of the used 1 part catalyst 1)
- /> Example 8 (too high content of trimer in a mixture of isophorondiisocyanate)
--> too reactive/ too viscous isocyanate mixture, resulting in poor mixing and poor flow in the form, on the surface there are defects such as, for example, point hole, etc.,--> more fragile elastomer compared to other typical examples of such rigidity.Note: by replacing in example 3 monoetilenglikolju chain extension on MRI diology extension chain (2-methyl-2,3-propanediylbis the chain extension) is sufficient to improve physical resistance paleologou mixture: after storage for 7 days at room temperature visual deposition (decantation) was absent.The group of examples 9-17
Received permanent RIM elastomers with different softness, which had exceptionally good characteristics reactivity and properties.Good results have been achieved, even if the polyether polyols used without modification quasi-polyesterpolyol and/or with conventional KOH catalyst (examples 13-17). In these examples, increased the level of amine initiator or catalyst level to compensate for some losses in the reaction sposobnostey DHC (double metal cyanide) with low content of mono-ol.In examples 15 and 16, based on the use of diol-based DMC-catalyst (without modification quasi-polyesterpolyol) containing 55% of primary Oh-groups and limited content (9%) of ethylene oxide (EO), receive exclusive characteristics of reactivity. In this case, the values of water absorption from good to exceptional (even when the NCO index = 95), although they are somewhat higher compared to the use of the main polyols with zero content of ethylene oxide. For example, water absorption in Example 10 is still very low, despite the use of low NCO equal to 90. This is the result of applying a hydrophobic polyol based essentially of propylene oxide.These samples also showed exceptional results during the practical test for shrinkage: after placing the glass samples, sealed RIM, in cold water at a temperature of 20oWith over 72 hours was not deform the surface of a material, obtained by reaction injection molding.
1. The method of producing microporous or non-porous, light-resistant, elastomeric, flexible or semi-flexible polyurethane fourmeau the Darth ASTM D790, between 5 and 300 MPa by injection moulding under pressure from the reaction mixture, whereby a) the isocyanate component consisting of a mixture of isophorondiisocyanate trimer/monomer having an NCO content of from 24.5% to 34% by mass, possibly including up to 10% by weight of the prepolymer on the basis of isophorondiisocyanate with terminal isocyanate groups with compounds reactive towards isocyanate containing from 2 to 4 reactive towards isocyanate groups containing hydrogen, and/or may also consist of less than 5% a slew of other isocyanate monomers or polymers, is subjected to reaction with In) components, reactive towards isocyanate, which contain1) polyol as one component, consisting of simple polyetherpolyols having terminal Oh-group, the average nominal functionality of from 2 to 4 and an average equivalent weight of from 800 to 4000;2) from about 3 to 20% by weight, based on the weight of components1,2 and3, at least one chain extension, having, as functional groups, only aliphatic or alicyclic Oh-group, f is src="https://img.russianpatents.com/chr/963.gif">3) about 2-10% by weight, based on the weight of components1,2 and3, at least one amine initiator forming system of socialization component C as catalyst and having from 2 to 3 functional aliphatic NH, NH2or Oh-groups, at least one of which is the secondary or primary amine groups and an equivalent weight of up to 150, in the presence of C) at least one catalyst selected from the group consisting of twintowercasino (II), vismutorganicheskikh (III) and ORGANOTIN (IV) catalysts, the maximum content of each of these catalysts, respectively - for twintowercasino catalyst of 1.5% by weight, for vismutorganicheskikh catalyst of 1.5% by weight, and for ORGANOTIN catalyst 3% by weight, in calculating the masses of the components1,2 and3, with the ORGANOTIN catalyst is used in combination with sincopirovannam and/or victorhanson.com catalyst, or in combination with diisobutylaluminum catalyst and/or a salt of this last catalysate is re, one antioxidant/absorber of ultraviolet rays; however, these components are processed by reaction injection molding two-component polyurethane mixture, free from solvent, when the indicator of the content of the isocyanate from 90 to 120, reaction injection molding is carried out in the form of pre-heated to a temperature in the range of 60-130oWith that inject the reaction mixture at a temperature between 30 and 80oS, and the polyurethane reaction mixture is essentially free of gas developing agents, and it contains up to 0.15% by weight of the largest, based on the weight of the reaction mixture, of water.2. The method according to p. 1, characterized in that the modulus of elasticity in bending of the molded products is equal to between 10 and 120 MPa.3. The method according to PP. 1 and 2, characterized in that the NCO content of the mixture of trimer/monomer is 26-32% by mass.4. The method according to PP.1-3, characterized in that the polyol as one component has an average equivalent weight of from 1000 to 2000.5. The method according to PP.1-4, characterized in that the chain extension is contained in an amount of from about 5 to about 15% by weight based on the weight of components1,2 and3.6. The method according to PP.1-5, is onenew1,2 and3.7. The method according to p. 6, characterized in that the amine initiator has an equivalent weight of up to 100.8. The method according to PP.1-7, characterized in that the maximum content twintowercasino catalyst is 1% by weight, based on the weight of components1,2 and3.9. The method according to PP.1-8, characterized in that the content of isocyanate in the processing components by reaction injection molding is from 95 to 110.10. The method according to p. 9, characterized in that the temperature of the reaction mixture is equal to between 40 and 60oC.11. The method according to PP.9-10, characterized in that the polyurethane reaction mixture contains up to 0.10% by weight, based on the weight of the reaction mixture, of water.12. The method according to p. 1, characterized in that as a simple polyetherpolyols component1 apply the product accession of propylene oxide and possibly of ethylene oxide with an initiator with a low molecular weight, and the amount of ethylene oxide, if present, is less than 30% of the total number of ethylene oxide and propylene oxide.13. The method according to p. 12, characterized in that under item 12 or 13, characterized in that a simple polyetherpolyols has a primary substance, IT is at least 70%.15. The method according to any one of paragraphs.12-14, characterized in that a simple polyetherpolyols subjected to preliminary polymerization with a part of the isocyanate component to form quasiperiodically end IT groups.16. The method according to p. 14 or 15, characterized in that a simple polyetherpolyols has an average nominal functionality of from 2.5 to 4 and an average equivalent weight of from 1000 to 1500.17. The method according to any of paragraphs.12-16, characterized in that use simple polyetherpolyols having low contents Mineola, in particular, is equivalent to the content of Mineola less than 5%.18. The method according to p. 17, characterized in that a simple polyetherpolyols has a nominal average functionality of from 2 to 3 and an average equivalent weight of from 1000 to 2000.19. The method according to any of paragraphs.15-18, characterized in that a simple polyetherpolyols has a primary substance, IT is at least 40%.20. The method according to p. 1, characterized in that as a simple polyetherpolyols component1 apply polytetramethylene.21. The method according to any of paragraphs.1-20, characterized in that isophorondiisocyanate the trimer is according to any of paragraphs.1-21, characterized in that the pre-form is heated to a temperature of from 80 to 120oC.23. The method according to PP.1-22, characterized in that the pre-form is heated to at least 90oC.24. The method according to any of paragraphs.1-23, characterized in that the outer lubricant, which use wax, applied to the form before the injection of the reaction mixture, and grease form has a melting point equal to at least, but preferably above the temperature of the mold, in particular, 0-30oWith higher temperature form.25. The method according to p. 24, characterized in that the wax is dispersed in water or in an organic solvent.26. The method according to any of paragraphs.1-25, characterized in that is used Svencioneliai and/or vimalaramsi catalyst, in particular, in combination with 0.2 to 1% by weight, based on the weight of components1,2 and3, ORGANOTIN and/or in combination with 0.1 to 1% by weight, based on the weight of components1,2 and3, diisobutylaluminum catalyst.27. The method according to p. 26, characterized in that Svencioneliai catalyst iresult vimalaramsi catalyst in combination with an ORGANOTIN catalyst.28. The method according to any of paragraphs.1-27, wherein the amine initiator is selected from the following different types: I. cross-linking agents alkanolamines type with one secondary NH group and two HE-groups, preferably primary HE-groups; II. extension chain with one primary NH2and one of the primary IT is a group that is located on the carbon atoms in the adjacent position; III. extension chain with one secondary NH group and one primary HE-group; IV. extension chain with two primary NH2groups, at least one of which is attached to the alicyclic ring; and V. extension chain with two secondary NH groups having a branched alkyl or cycloalkyl group with at least four adjacent atoms, or cross-linking agents with three secondary NH groups, at least two of which have a branched alkyl or cycloalkyl group with at least four attached atoms With.29. The method according to p. 28, characterized in that the amine initiator contains at least 1% by weight, based on the weight of components1,2 and3, diethanolamine.30. The method according to p. 29, otlichayusta type of chain extension, in particular, monoethanolamine, to achieve the average functionality of between 2 and 3.31. The method according to any one of paragraphs.1-29, characterized in that the antioxidant/absorber UV rays contains 0.1 to 1% by weight, preferably 0.2 to 0.6% by weight, based on the weight of the reaction mixture, the primary antioxidant of the type of the substituted phenol; 0.1 to 1% by weight, preferably 0.2 to 0.6% by weight, based on the weight of the reaction mixture, difficult aliphatic type light stabilizers substituted alicyclic amines; 0-5% by weight, preferably less than 3% by weight, based on the weight of the reaction mixture, peroxide decomposers, preferably aliphatic or aromatic organophosphites type; and 0.1-1% by weight, preferably 0.2 to 0.6% by weight, based on the weight of the reaction mixture, of an absorber of ultraviolet rays, which is preferably of the type benzotriazole.32. The method according to any of paragraphs.1-31, wherein the molded polyurethane material is applied in the form of a flexible or palpably strip on the periphery of the window by placing a window with its periphery in the form, the form is closed and injection of the polyurethane reaction mixture in a closed form.33. Microporous or non-porous SV is greater least 900 kg/m3and the modulus of elasticity in bending according to ASTM D790, between 5 and 300 MPa, which can be obtained by reacting according to the method of reaction injection molding (A) isocyanate component consisting of a mixture of isophorondiisocyanate trimer/monomer having an NCO content of from 24.5% to 34% by weight, may also consisting of up to 10% by weight of the prepolymer with terminal isocyanate groups, from isophorondiisocyanate with reactive isocyanate compounds containing 2-4 reactive towards isocyanate groups containing hydrogen, and/or may also also consisting of less than 5% by weight more isocyanate monomers or polymers In) components reacting with isocyanate, which contain1) polyol as one component containing a simple polyetherpolyols having terminal Oh-group, the average nominal functionality of from 2 to 4 and an average equivalent weight of from 800 to 4000;2) from about 3 to about 20% by weight, based on the weight of components1,2 and3, at least one chain extension having as functional groups only Alie content HE at least 50%;3) from about 2 to about 10% by weight, based on the weight of components1,2 and3, at least one amine initiator, forming a catalytic system component and having from 2 to 3 functional aliphatic NH, NH2or Oh-groups, at least one of which is a secondary or primary amino group and an equivalent weight of 150 at the most, in the presence of C) at least one catalyst component selected from the group consisting of twintowercasino (II), vismutorganicheskikh (III) and ORGANOTIN (IV) catalysts, and the maximum number of each of these catalysts, respectively for twintowercasino catalyst to 1.5% by weight, for vismutorganicheskikh catalyst of 1.5% by weight, and for ORGANOTIN catalyst - 3% by weight, in calculating the masses of the components1,2 and3; and the ORGANOTIN catalyst is used in combination with sincopirovannam and/or victorhanson.com catalyst, and/or in combination with diisobutylaluminum catalyst and/or a salt of this latter one antioxidant/absorber of ultraviolet rays; with named components processed by way of the reaction injection molding of polyurethane two-component mixture: free from solvent, the isocyanate index 90-120, in the form of pre-heated to a temperature of from 60 to 130oWith in which the reaction mixture is injected at a temperature of between 30 and 80oS, and the polyurethane reaction mixture is essentially free from physical gas developing agents and it contains up to 0.15% by weight, based on the total weight of the reaction mixture, of water.34. The article on p. 33, characterized in that it has a modulus of elasticity in bending between 10 and 120 MPa and has a gasket to seal the window.35. Article on PP 33 and 34, characterized in that the NCO content of the mixture of trimer/monomer is 26-32% by mass.36. Article on PP.33-35, wherein the polyol as one component has an average equivalent weight of from 1000 to 2000.37. Article on PP.33-36, wherein the chain extension is contained in an amount of from about 5 to about 15% by weight based on the weight of components1,2,3.38. Article on PP.33 to 37, characterized in that the amine initiator is contained in an amount of from Prim and3.39. The article on p. 38, characterized in that it has an equivalent weight of 100 greatest.40. Article on PP.33-39, wherein the maximum content twintowercasino catalyst is 1% by weight based on the weight of components1,2 and3.41. Article on PP.33-40, characterized in that the content of isocyanate in the processing components by reaction injection molding is from 95 to 110.42. The article on p. 41, characterized in that the temperature of the reaction mixture is equal to between 40 and 60oC.43. Article on PP.41 and 42, characterized in that the polyurethane reaction mixture contains up to 0.10% by weight, based on the total weight of the reaction mixture, of water.44. Article on PP.41-43, wherein the mold temperature is from 80 to 120oC.45. Article on PP.41-44, wherein the mold temperature is equal to at least 90oC.46. The article on p. 33, characterized in that it has a water absorption of less than 10, preferably less than 3% by weight of water absorption after immersion polyurethane sample having a thickness of about 3 mm in water at a temperature of 2oWith during 72 hours47. Souvenier according to any one of paragraphs.1-32.
FIELD: resin industry and organometallic synthesis.
SUBSTANCE: organometallic composition for solidifying polyisocyanate materials, which may be used for binding lignocellulose, contains complex of at least one metal ortho-ether having formula M(ROAcAc)x(OR')y, where M represents titanium, zirconium, or hafnium; ROAcAc represents moiety of acetoacetic acid ester with alcohol ROH wherein R is optionally cyclic, branched, or linear alkyl, alkenyl, aryl, or alkylaryl group having 1 to 30 carbon atoms or mixture thereof; OR' represents alcohol R'OH residue wherein R' is optionally cyclic, branched, or linear alkyl, alkenyl, aryl, or alkylaryl group having 7 to 30 carbon atoms or mixture thereof; each of x and y ranges between 1 and 3 and x+y=4. Mixture to be solidified contains organic isocyanate compound or mixture of organic isocyanate compounds and above-indicated organometallic composition. Lignocellulose product, containing lignocellulose material and polyisocyanate composition including above-indicated organometallic composition, is prepared by bringing lignocellulose material into contact with above polyisocyanate composition to allow lignocellulose material to be bound.
EFFECT: improved process characteristics of organometallic composition.
12 cl, 1 tbl, 7 ex
FIELD: polymer materials.
SUBSTANCE: invention relates to ionomer thermoplastic polyurethane, method for preparation thereof, use of indicated ionomer thermoplastic polyurethane to prepare aqueous dispersions thereof, as well as to a method for preparing aqueous dispersions of ionomer thermoplastic polyurethanes. Ionomer thermoplastic polyurethane is prepared via continuous reaction of (i) 4-50% if diisocyanate; (ii) 35-95% of bifunctional polyatomic alcohol selected from group comprising (a) polycaprolactone with mean molecular mass between 500 and 15000 and general formula I: (I), (b) polyesterdiol with mean molecular mass between 500 and 15000 and general formula II: (II), (c) polyesterdiol selected from polypropylene glycol, polytetramethylene glycol, and polyethylene glycol, (d) polycarbonatediol with mean molecular mass between 500 and 15000 and general formula III: (III), and (e) copolymers obtained from two bifunctional polyatomic alcohol from groups (a), (b), (c), or (d); (iii) 0.2-16% of chain-elongation glycol of general formula IV: (IV); and (iv) 0.2-3% of chain-elongation anionic-type ionomer glycol of general formula V: (V).
EFFECT: enabled preparation of ionomer polyurethane suitable for being stored in solid form for subsequent preparation of aqueous dispersions of thermoplastic polyurethanes appropriate as industrial adhesives and coating materials for flexible and rigid substrates.
34 cl, 2 tbl, 10 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for synthesis of rigid urethane-modified foam polyisocyanurates. Method involves reaction of organic polyisocyanate with polyfunctional component possessing reaction capacity with respect to isocyanate groups at isocyanate index in the range from 150 to 450%. Reaction is carried out in the presence of carboxylic acid, water foam forming agent and/or hydrocarbon, and/or fluorohydrocarbon and metal salt as a trimerization catalyst taken in the amount in the range from 0.5 to 5 wt.-% as measured for the composition possessing reaction capacity with respect to isocyanate groups. Invention provides design of system providing good conversion degree to isocyanurate and obtaining good refractoriness.
EFFECT: improved method of synthesis.
12 cl, 3 tbl, 10 ex
FIELD: polymer materials.
SUBSTANCE: invention, in particular, relates to preparing microcellular and noncellular polyurethane material with density above 500 kg/m3, wherein reaction mixture of polyurethane precursors is brought into reaction resulting in polyurethane material, reaction mixture consisting of (i) isocyanate component containing at least one isocyanate compound with at least two NCO groups, which are not directly linked to aromatic group, (ii) components reacting with isocyanates, and (iii) lead-free catalysts containing at least one organobismuth(III) compound containing C13-C19-alkyl or alkenyl group or organotin(IV) compound containing C13-C19-alkyl or alkenyl group, or linear or branched C1-C19-alkyl or alkenyl group substituted by one or more OH groups. Catalyst may further contain organozinc carboxylate compound. Polyurethane obtained using above catalyst is also described. Material according to invention contains below 250 ppm, preferably below 100 ppm, volatile organic compounds.
EFFECT: reduced content of volatile organics in polyurethane material.
2 cl, 1 tbl
SUBSTANCE: composition includes catalyst- dimethylethanolamine, stabiliser - surface - active substance based on oxyalkylene methylsiloxane block copolymers, and additionally contains foaming agent - water.
EFFECT: ecological safety, preserving catalyst ability during long storage and ensuring obtaining rigid foam-polyurethane, optimal for formation of even product structure start time, density and improved strength characteristics.
FIELD: medicine, pharmaceutics.
SUBSTANCE: invention relates to coating composition, applied, for instance, as transparent coatings, base coatings, pigmented coating layers, used, prime coatings, etc. Composition contains polyisocyanate, polyol, metal-based catalyst for carrying out reaction of addition reaction between isocyanate groups and hydroxyl groups, thiol-functioning compound and carboxylic acid, carbonyl group of carboxylic acid being in connection with π-electronic system.
EFFECT: creation of novel coating composition, demonstrating presence of favourable property balance, namely, low level of volatile organic solvent content with operation viscosity, high rate of hardening and long viability, which results in obtaining coatings, which demonstrate good outlook characteristics, in particular, low liability to formation of pinholes, and good hardness.
14 cl, 2 tbl
SUBSTANCE: invention relates to an actinic radiation cured coating composition containing a compound which contains at least two isocyanate groups, a compound which contains at least two hydroxyl groups, a sensitising agent and a photolatent catalyst for an isocyanate-hydroxl coupling reaction, where the photolatent catalyst is an organometallic compound, containing tin as a catalytically active metal, and where the atom of the catalytically active metal in the organometallic compound is not bonded to atoms of other metals. The invention also describes a method of coating a substrate, involving a step for applying said composition onto the substrate, as well as a set of parts for preparing said actinic radiation cured coating composition.
EFFECT: obtaining an actinic radiation cured coating composition having a good balance of long life and fast curing after application and irradiation, and leads to formation of cured coatings, the colour of which is not affected by coloured residues or photolatent catalyst fragments.
13 cl, 6 ex, 4 tbl
FIELD: industrial chemistry.
SUBSTANCE: present invention refers to a pulverizable system based on polyurethane that is applicable for production of the bottom layer for polyurethane formed parts that contains a polyol component (A) and an isocyanate component (B) and does not contain amine catalysts. The polyol component (A) contains: (a1) at least one compound that goes into reaction with isocyanate, (a2) at least one agent that is able to prolong the reactive chain with at least two groups that are able to go into reaction with isocyanate; at least one group that is able to go into reaction with isocyanate is represented by a free primary group NH2-, and (a3) at least one metallic catalyst and (a4) if necessary, other additives. The invention also refers to the way of production of the polyurethane bottom layer for formed parts, to the bottom layer that is manufactured in such a way and to application of this bottom layer in production of seats, control panel, remote controls, pockets and boxes or parts of the internal or external automobile siding.
EFFECT: production of the bottom layer for formed parts from the polyurethane-based pulverizable system that is characterized by low emanation of low-boiling components and condensing components, improved mechanical properties, in particular by breaking strength rupture limit, extensibility and breaking strength tearing limit as well as a small amount of time necessary for extraction from the mould if compared with the residency in an opened position.
20 cl, 4 tbl
SUBSTANCE: invention relates to a method of producing a polymer-modified polyol, where olamine reacts with organic polyisocyanate in the presence of a polyol and at least one catalyst which is a metal salt of an organic acid, where the olamine reacts, at least preferably polyfunctionally, with isocyanate, where said catalyst or at least one said catalyst is a metal salt of an organic acid which does not have a metal-carbon bond, and where viscosity of the polymer-modified polyol is at least 2250 mP when measured at 25°C using a Brookfield viscosimeter or is compatible with a Brookfield viscosimeter system. The invention also describes versions of the method of producing a polymer-modified polyol, where the catalyst has the formula M(O.CO.R.CH3)2, where M is a metal, R is a carbon chain with 6-20 carbon atoms, wherein the chain is straight or branched with side functional OH groups, and/or with or without double bonds, and where the catalyst is a metal salt of a fat monohydroxy acid, respectively. Described also is a polymer-modified polyol produced using the disclosed methods, a method of producing polyurethane foam plastic (foamed polyurethane) using such a polyol and elastic polyurethane foam plastic (elastic foamed polyurethane) produced using said method.
EFFECT: use of metal-carboxylate catalysts when producing polymer-modified polyols, which results in stability of the obtained polyols, stability of foamed products from such polyols, as well as solving the environmental problem.
27 cl, 16 ex, 8 tbl, 3 dwg
SUBSTANCE: invention relates to aqueous compositions for gluing substrates, a method of obtaining such compositions, as well as a method of making latent-reactive coatings, films and powders from said compositions. The aqueous compositions for gluing substrates contain: polymers dispersed in water, having groups capable of reacting with isocyanate, such as urethane groups and urea groups; at least one dispersed solid aliphatic polyisocyanate which is not surface-active, with softening temperature higher than or equal to 40°C; one or more compounds of group (subgroup) 5 and 6 elements, in which the oxidation state of said element is at least +4; and optionally other additives and auxiliary materials.
EFFECT: obtaining novel compositions for gluing substrates and latent-reactive coatings, films and powders based thereon, which are stable during storage and stable with respect to colour.
18 cl, 1 dwg, 6 ex
FIELD: chemical industry; methods of production of a thermosetting elastomers.
SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the methods of production of a thermosetting polyurethane elastomer and also to the elastomer produced according to the given method. The invention presents the method of production of the polyurethane elastomer having a total apparent density exceeding 150 kg/m3 and providing for an interaction of polyisocyanate and a reactive to isocyanate composition not necessarily at presence of water, according to which the reaction conduct at an isocyanate index of 85-120. At that the polyisocyanate component is composed of: al) 80-100 mass % of diphenylmethanediisocyanate containing at least 40 mass % of 4.4'- diphenylmethanediisocyanate and-or a derivative of the indicated diphenylmethanediisocyanate, which (the derivative) is a may be a liquid at the temperature of 25°C and has NCO value of no less than 20 mass % and a2) 20 mass % of the other polyisocyanate; the reactive to isocyanate composition b) consists of b1) 80-100 mass % of a simple polyol polyester having an average nominal functionality - 2-8, average reactive equivalent weight of 750-5000, an average molecular mass of 2000-12000, the share of oxyethylene - 60-90 mass % and the share of the primary hydroxyl groups of 70-100 mass % calculated for the total number of the primary and the secondary hydroxyl groups in polyol; b2) a reactive to isocyanate extender of the chain in such a quantity, that the ratio of the rigid block makes less than 0.45; and b3) - 20-0 mass % of one or more of other reactive to isocyanate composition excluding water. At that the amount of the polyol of 61) and the reactive to isocyanate composition 63) is calculated from the total amount of the indicated polyol 61) and the composition 63). The invention presents also description of the thermosetting elastomer produced according to the indicated method.
EFFECT: the invention ensures production of a thermosetting polyurethane elastomer.
10 cl, 2 ex
FIELD: chemistry of polymers, chemical technology.
SUBSTANCE: invention relates to a method for preparing polyurethane material, and to material made of in relation with the indicated method. Invention describes a method for preparing polyurethane material showing the vitrification point 25°C, not below. Polymer is prepared by interaction of polyisocyanate component consisting of the following components: a) 80-100 wt.-% of diphenylmethane diisocyanate comprising 4,4'-diphenylmethane diisocyanate and/or variant of indicated diphenylmethane diisocyanate, 40 wt.-%, not less, and 0-20 wt.-% of another polyisocyanate with the isocyanate-reaction composition consisting of the following components: a) 80-100 wt.-% of simple polyetherpolyol with the average nominal polyfunctionality 3-8, average equivalent mass 200-2000 Da, average molecular mass 600-8000 Da, the oxyethylene content 50-100% and the content of primary hydroxyl groups 70-100%; b) reaction elongating agent and/or cross-linking agent taken in the amount wherein the ratio of hardness blocks = 0.60; and c) 0-20 wt.-% of one or some other isocyanate-reaction compounds but excluding water, and material made of the indicated method. Polyurethanes made of the proposed method show density value 957 kg/m3, the Shore hardness value 77 and the virtification temperature 87°C that can be used in making show footings, arm rests, door panels an car sun glass baffle plates.
EFFECT: improved preparing method.
5 cl, 1 tbl, 2 ex