Amine-initiated polyols and rigid polyurethane foam made therefrom
SUBSTANCE: amine-initiated polyol, having average functionality higher than 3.0 and less than 4.0, is a product of interaction of at least one C2-C4alkylene oxide with an aminocyclohexane alkylamine initiating compound, wherein said polyol has a hydroxyl equivalent mass from 75 to 560. The initiating compound is represented by any of the structures or , where each of the R groups independently denotes a hydrogen atom or C1-C4alkyl, R1 denotes C1-C4alkyl, and m denotes a number from 1 to 8.
EFFECT: invention enables to obtain foam plastic with a good combination of low k-factor and short demoulding time.
9 cl, 1 tbl, 2 ex
This application has a priority based on provisional application of the United States of America No. 60/898367, filed January 30, 2007
The present invention relates to polyols suitable for the production of rigid polyurethane foams and rigid polyurethane foams obtained from these polyols.
Rigid polyurethane foams for several decades was widely used as insulating foams for appliances and for other purposes, as well as in other diverse applications. These foams are a result of collaboration between polyisocyanate and one or more polyols, polyamines or aminopyrene connections. Polyols, polyamine or connection ansperto can be characterized as having an equivalent mass per isocyanate reactive group in the range of approximately 300 and, on average, more than three hydroxyl and/or amino groups on the molecule. The reaction is carried out in the presence of a blowing agent, which is used in the reaction to form the gas. The gas increases the volume of the reaction mixture and gives it a honeycomb structure.
Initially the preferred foaming agent was "heavy" chlorofluorocarbons (CFCs), such as trichlorethane or DICHLORODIFLUOROMETHANE. Data CFCs very easily processed is camping and form a foam, having very good insulation properties. However, these foaming agents based on Hshow were discontinued due to environmental restrictions.
HFU were replaced by other foaming agents, such as hydrofluorocarbons, low-boiling hydrocarbons, hydrochlorofluorocarbons, connection-based ethers and water (which interacts with the isocyanate to form carbon dioxide). In most cases, these alternative foaming agents are less effective insulator than their predecessor CFCs. The ability of the foam to provide insulation is often expressed by the term "k-factor", which is a measure of the amount of heat conducted through the foam, per unit area per unit time, taking into account the thickness of the foam and the difference of the applied temperature on the thickness of the foam. The foams obtained with the use of alternative blowing agents are characterized by higher values of k-factor than the foams obtained with the use of "heavy" foaming agents based on CFC. This has forced manufacturers of rigid foams to change the formulation of foams in the other direction to compensate for the decrease in the values of thermal insulation as a result of replacement foaming agents. Many of these changes aim is decreasing cell size in the foam. Cells of smaller size provide the best thermal insulation properties.
It is established that changes in the composition of the hard foam that improve k-factor can affect an unwanted manner on the technological characteristics of the composition. The characteristics of the curing composition is especially important when using it for printed thermal insulation, such as foam for different types of household appliances. Refrigerators and freezers, for example, usually isolated partial Assembly of the outer shell and the inner shell and install them in such position, at which between them a cavity. This is usually done using a jigging machine or other apparatus. The composition of the foam is injected into the cavity, where it expands and fills the cavity. The foam provides insulation and adds structural strength of the entire installation. The method of curing the composition of the foam is important at least for two reasons. First, the composition of the foam should quickly be cured with the formation of stable sizes of foam to ready-assembled enclosure can be removed from the jigging machine. This feature is usually called " time "pickup", and it directly affects the rate of production of bodies.
In addition, the curing characteristics of the system affect its the STV, known as the "flow index" just go "fluidity". The composition of the foam will expand up to a certain density (known as the "density at the free foaming"), if she will allow you to expand with minimal restrictions. When the composition must complete the refrigeration or freezer, its expansion may prevent several factors. The composition of the foam should extend mainly in a vertical (rather than horizontal) direction within a narrow cavity. As a result, the composition should expand against considerable pressure of its own weight. The composition of the foam must also flow into the corners and all openings of the cavities of the walls. In addition, the cavity often has a limited number of ventilation holes or not at all, and therefore, the atmosphere inside the cavity exerts additional pressure on the expanding composition of the foam. Because of these limitations requires a greater amount of the composition of the foam to fill the cavity than that which could be calculated based only on the density at the free foaming. The number of compositions of foam required for minimal fill the cavity can be expressed as the minimum density (weight of the composition, divided by the volume of the cavity). The ratio of the minimum density improvement and fill to the density at the free foaming is the flow index. Flow index ideally is 1.0, but used for commercial compositions is about 1.2 to 1.8. Lower flow index is preferred, all other things are equal, because the raw material cost is lower when you need a smaller amount of foam.
Changes in the formulation of foams, which lead to lower k-factor adversely affect the time of removal, the flow index, or both. Therefore, despite the fact that the developed formulations, which are indicators of the k-factor is much closer to traditional recipes based on CFCs, the total cost of the use of compositions on the basis of these formulations are often higher due to poor performance (due to the large time of removal), higher cost of raw materials (due to higher flow index) or because of both factors.
What it needs is a recipe rigid foam, which produces a foam with a low k-factor low-flow index and little time reading.
The present invention in one aspect relates to amine-initiated the polyol having an average hydroxyl functionality greater than a 3.0 up to 4.0, and the polyol is the product of the interaction of at least one2-C4alkalinized with iniciiruem the m connection-based aminocyclohexanone.
The present invention also relates to a method for production of rigid polyurethane foams, including
a) obtaining a reaction mixture containing at least
1) initiated by aminocyclohexanone polyol according to the first aspect of the invention, having a hydroxyl equivalent weight of from 75 to 560, or a mixture of at least one other polyol, provided that the mixture contains at least 5 mass% initiated aminocyclohexanone polyol according to the first aspect of the invention;
2) at least one physical foaming agent-based hydrocarbons, HFC, hydrochlorofluorocarbons, troglita, simple dialkylamide ether or simple fluorinated dialkylamide ether; and
3) at least one polyisocyanate; and
b) bringing the reaction mixture to the point where the reaction mixture expands and cures with the formation of rigid polyurethane foam.
In another aspect, the present invention relates to the rigid foam obtained in accordance with the above method.
It is established that the composition of rigid foams comprising polyol according to the invention, often indicate the desired curing characteristics (as shown by the flow index less than 1.8) and with little time to eat and otverzhdajutsja with the formation of foam, having excellent insulating properties (i.e. low k-factor). These advantages are especially visible when the amine-initiated polyol according to the present invention is used in a mixture that contains one or more polyols having a hydroxyl functionality of from 4 to 8 and a hydroxyl equivalent weight of from 75 to 200.
Initiated by the amine polyol is a simple polyester, which is obtained at least from one aminocyclohexanone initiating the connection. For the purposes of the present invention "aminocyclohexanone" initiating a connection represents that contains a cyclohexane group, substituted on the cyclohexane ring primary amino (-NH2) group and substituted on the cyclohexane group, at least one, and preferably only one, aminoalkyl group. Aminoalkyl group can be represented as -(CR2)m-NH2where each radical R is independently a hydrogen atom or a C1-C4alkyl, and m denotes an integer from 1 to 8. Each radical R preferably represents independently a hydrogen atom or methyl. The primary amino group and aminoalkyl group(s) can be in ortho-, meta - or paraprotex relative to each other and can be in the CIS- (both single side of the ring) or TRANS-(located on opposite sides of the ring) positions relative to each other. Cyclohexane ring may also contain inert substitution. "Inert" substitution is a substitution that (1) is not a reaction to alkalinized under the reaction conditions of alkoxysilane (as described below), (2) is not reactive to isocyanate groups, and (3) does not significantly affect the ability aminocyclohexanone connection to alkoxycarbonyl, and the resulting polyol to interact with the polyisocyanate with the formation of urethane linkages. Inert substitution includes hidrocarburos substitution, such as alkyl, alkenyl, alkylaryl, aryl-substituted alkyl, cycloalkyl and the like, ether groups, tertiary amino groups and the like, it is Preferable that any replacement groups that can be represented With1-C4alkyl, especially methyl. Particularly preferably, cyclohexane ring was methylsiloxane on the carbon atom that is attached to the amino group.
Can be used for initiating a mixture of two compounds, as described above. The initiators of the following patterns may exist in two or more diastereoisomeric forms. In such cases, there may be used any diastereoisomeric forms or a mixture of two or more diastereoisomeric forms.
One class aminocyclohexanone the new compounds includes those which are represented by structure 1:
where R1is1-C4alkyl, and R and m have the meanings specified above. Each R group in structure I is preferably independently a hydrogen atom or methyl and R1preferably represents methyl. In the structure of I -(CH2)m-NH2the group may be ortho-, meta - or paraprotein to the amino group that is connected directly with cyclohexanebis ring. Group-NH2and -(CR2)m-NH2in the structure I can be in CIS - or transpareny relative to each other. In structure I, the carbon atoms cyclohexane ring may contain inert surrogate group in addition to show groups-NH2, -R1and -(CH2)m-NH2. The preferred initiator compound corresponding to structure I, is cyclohexanemethanol, 4-amino-α,α,4-trimethyl-(9Cl), which is also known as p-Menten-1,8-diamine or 1,8-diamino-p-Menten. This compound exists in two following diastereoisomeric forms:
Can be used any of diastereoisomeric forms or a mixture of the two.
The second type aminocyclohexanone initiator corresponds to the structure II:
in which R, R
It also can be used in any of these forms or their mixture.
Commercially available aminocyclohexanone compounds may contain small amounts (usually less than 3% by weight) of impurities, which, as a rule, are other amines or diamines. These commercial materials are eligible the mi for use in the present invention as initiators.
Interact initiating the connection, at least one With2-C4alkalization obtaining amine-initiated polyol according to the invention. Alkalization may be ethylene oxide, propylene oxide, 1,2 - or 2,3-butylenes, tetramethylene or a combination of two or more of the above compounds. If using two or more alkalisation, they can be added to the originating connection at the same time (with the formation of a statistical copolymer), or sequentially (with obtaining the block copolymer). Butylenes or tetramethylene are generally less preferred. Ethylene oxide, propylene oxide and mixtures thereof are more preferred. A mixture of ethylene oxide and propylene oxide may contain oxides in any proportion. For example, a mixture of ethylene oxide and propylene oxide may contain from 10 to 90 weight percent of ethylene oxide, preferably from 30 to 70 weight percent of ethylene oxide, or from 40 to 60 weight percent of ethylene oxide.
The initiator add enough alkalinized(s) with a polyol having an average hydroxyl functionality of from greater than 3,0, so large as to 4.0 hydroxyl groups/molecule. The preferred average hydroxyl functionality of the polyol is from 3.3 to 4.0, the preferred average hydroxyl functionality is from 3.7 to 4.0. The polyol according to the invention used for the production of rigid polyurethane foam, appropriately has a hydroxyl equivalent weight of from 75 to 560. Preferred hydroxyl equivalent weight for the production of rigid foam is from 90 to 175 and more preferred hydroxyl equivalent weight for the production of rigid foam is from 100 to 130.
The reaction alkoxysilane easily spend a mixture of accelerated(s) and initiating the connection and create a mixture of high temperatures and excessive pressure. The temperature of polymerization can be, for example, from 110 to 170°C., and the pressure can be, for example, from 2 to 10 bar (200 to 1000 kPa). Can be used catalyst, especially if you want to add more than one mole of accelerated(s) to the equivalent of amine hydrogen in the originating connection. Suitable catalysts alkoxysilane include strong bases such as hydroxides of alkali metals (e.g. sodium hydroxide, potassium hydroxide, cesium hydroxide and tertiary amines, as well as so-called double metallocyanide catalysts (among which the most notable complexes of zinc-hexacyanocobaltate). The reaction can be carried out in two or more stages, in which the first stage catalyst is not used to the comfort, and add from 0.5 to 1.0 mol of alkalinized to the initiator on the equivalent of amine hydrogen atoms, followed by one or several stages, which add a further allinace in the presence of a catalyst, as described above. After completion of the reaction the catalyst may be deactivated and/or deleted. Catalysts based on hydroxides of alkali metals can be removed, left in the product or neutralized with acid, and the remainder can be left in the product. The remains of the double metallocyanide catalysts can be left in the product, but instead, if desired, can be removed.
Preferred amine-initiated polyols are (a) the product of the interaction of isophorondiamine or 1,8-diamino-p-Mentana with ethylene oxide, (b) the product of the interaction of isophorondiamine or 1,8-diamino-p-Mentana with propylene oxide and (C) the product of the interaction of isophorondiamine or 1,8-diamino-p-Montana with a mixture of from 30 to 70 mole percent of ethylene oxide and from 70 to 30 mole percent of propylene oxide, in each case having a hydroxyl functionality of from 3.3 to 4.0, especially from 3.7 to 4.0 and a hydroxyl equivalent weight of from 90 to 175, especially from 100 130.
Initiated the amine polyols of the present invention can be used for the production of rigid polyurethane foam, the item is when the hydroxyl equivalent weight is from 75 to 560. Rigid polyurethane foam is obtained from forming a polyurethane composition containing at least (1) amine-initiated polyol, optionally in combination with one or more polyols, (2) at least one organic polyisocyanate, and (3)at least one physical blowing agent, as described in more detail below.
Initiated by the amine polyol of the present invention suitably is at least 5 percent by weight of all polyols contained in forming the polyurethane composition. Below this level, the benefits of using a polyol are insignificant. Initiated by the amine polyol according to the invention can be the sole polyol in forming the polyurethane composition. However, it is assumed that in most cases it will be used in mixtures containing at least one other polyol, and that the amine-initiated polyol according to the invention will be from about 5 to about 75% by weight of the mixture of polyols. For example, amine-initiated polyol according to the invention can be from 10 to 60% by weight of a mixture of polyols, or from about 10 to about 50% by weight of the mixture of polyols.
When a mixture of polyols, a mixture of polyols preferably have an average of from 3.5 to about 7 guide is oxolinic groups per molecule and an average hydroxyl equivalent weight of from about 90 to about 175. Any individual polyol in the mixture can have the functionality and/or the equivalent mass outside these intervals, if the mixture meets the given parameters. Water is not considered when determining the functionality or the equivalent mass of the mixture of polyols.
A more preferred average hydroxyl functionality of the mixture of polyols is from about 3.8 to about 6 hydroxyl groups per molecule. And even more preferable average hydroxyl functionality of the mixture of polyols is from about 3.8 to about 5 hydroxyl groups per molecule. A more preferred average hydroxyl equivalent weight of the mixture of polyols is from about 110 to about 130.
Suitable polyols that may be used in combination with amine-initiated polyols according to the invention include simple politically, which are easily obtained by polymerization of accelerated on initiating the connection (initiator or mixture of compounds), which has a number of active hydrogen atoms. The initiator(s) connection(s) may include alkalophile (for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like), ethers, glycols (such as diethylene glycol, triethylene glycol, dipropyleneglycol, Tripropylene the Kohl and the like), glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, glucose, fructose and other sugars, and the like. Part of initiating the connection may be part containing primary and/or secondary amino groups, such as Ethylenediamine, hexamethylenediamine were, diethanolamine, monoethanolamine, N-ethyldiethanolamine, piperazine, AMINOETHYLPIPERAZINE, diisopropanolamine, monoisopropanolamine, ethanolamine, diethanolamine, toluidinen (all isomers) and the like. Initiated the amine polyols data types have a tendency to autocatalyze. Alkilinity used for additional polyol(s)are the same as described above in relation to initiated the amine polyol of the present invention. The preferred alkalization is propylene oxide or a mixture of propylene oxide and ethylene oxide.
In addition, as an additional polyols can be used complex polyether polyols, but they, in General, are less preferred because they have lower functionality. Complex polyether polyols include the reaction products of polyols, preferably diols, with polycarboxylic acids or their anhydrides, preferably dicarboxylic acids or anhydrides of dicarboxylic acids. Polycarboxylic acids or anhydrides can be aliphatic, cycloaliphatic, aromatizes the mi and/or heterocyclic and may be substituted, for example by halogen atoms. Polycarboxylic acids may be unsaturated. The examples of these polycarboxylic acids include succinic acid, adipic acid, terephthalic acid, isophthalic acid, trimellitic anhydride, phthalic anhydride, maleic acid, maleic acid anhydride and fumaric acid. The polyols used to produce complex polyether polyols include ethylene glycol, 1,2 - and 1,3-propylene glycol, 1,4 - and 2,3-butanediol, 1,6-hexanediol, 1,8-octandiol, neopentylglycol, cyclohexanedimethanol, 2-methyl-1,3-propandiol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylacetyl, pentaerythritol, clinical, manitol, sorbitol, methylglucoside, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropyleneglycol, dibutylamino and the like.
In a preferred variant of the invention, the amine-initiated polyol according to the invention is used in a mixture with at least one other simple polyetherpolyols, which has an average functionality of from 4.5 to 7 hydroxyl groups per molecule and a hydroxyl equivalent weight of from 100 to 175. Another simple polyetherpolyols may be, for example, initiated by sorbitol and/or sucrose/glycerine simple polyester. In this case, the amine-initiated polyol of the present invention MoE is et to be from 10 to 70% by weight of the mixture. Examples of suitable initiated sorbitol or sucrose/glycerine polyether that can be used include polyols Voranol® 360, Voranol® RN411, Voranol® RN490, Voranol® 370, Voranol® 446, Voranol® 520, Voranol® 550 and Voranol® 482, all available from Dow Chemical.
In another preferred variant of the invention, the amine-initiated polyol according to the invention is used in a mixture of polyols, which also contains at least one other easy polyetherpolyols having an average functionality of from 4.5 to 7 hydroxyl groups per molecule and a hydroxyl equivalent weight of from 100 to 175, which is not initiated by an amine, and at least one other amine-initiated polyol having an average functionality of from 2.0 to 4.0, preferably from 3.0 to 4.0 and a hydroxyl equivalent weight of from 100 to 225. Other amine-initiated polyol may be initiated, for example, ammonia, Ethylenediamine, hexamethylenediamine were, diethanolamine, monoethanolamine, N-methyldiethanolamine, piperazine, ninetypercent, diisopropanolamine, monoisopropanolamine, ethanolamine, diethanolamine, tolualdehyde (all isomers) and the like. Initiated by Ethylenediamine and tolualdehyde polyols are preferred in this case. The mixture of polyols may contain from 5 to 50% by weight amine-initiated polyalcohols invention; from 20 to 70% by weight is not amine-initiated polyol and from 2 to 20% by weight of another amine-initiated polyol. The mixture of polyols can contain up to 15 weight% of one another, poliyou that is not initiated by the amine and which has a hydroxyl functionality of from 2.0 to 3.0 and a hydroxyl equivalent weight of from 90 to 500, preferably from 200 to 500. Specific examples of mixtures of the polyols described above, include a mixture of from 5 to 50% by weight amine-initiated polyol of the present invention, from 20 to 70% by mass triggered sorbitol and/or sucrose/glycerine simple polyetherpolyols having an average functionality of from 4.5 to 7 hydroxyl groups per molecule and a hydroxyl equivalent weight of from 100 to 225, from 2 to 20% by weight of Ethylenediamine-initiated polyol having an equivalent weight of from 100 to 225, and from 0 to 15% by weight is not amine-initiated polyol having a functionality of from 2.0 to 3.0 and hydroxyl equivalent weight of from 200 to 500.
As described, the mixture of polyols can be prepared by obtaining a polyol components separately, and then mixing them together. In another case, a mixture of polyols can be obtained by forming a mixture of the corresponding initiating connections with the subsequent alkoxycarbonyl initiator mixture with direct formation of a mixture is aiolou. Such "sonalisonania" polyols can be obtained by using aminocyclohexanone and other amine as initiator with the formation of a mixture of amine-initiated polyols. Can also be implemented in a combination of these approaches.
Forming the polyurethane composition contains at least one organic polyisocyanate. The organic polyisocyanate or a mixture predominantly contains an average of at least a 2.5 isocyanate groups per molecule. Preferred isocyanate functionality is from about 2.5 to about 3.6, or from about 2.6 to approximately 3.3 isocyanate groups/molecule. The polyisocyanate or a mixture of predominantly has an isocyanate equivalent weight of from about 130 to 200. It is preferably from 130 to 185 and more preferably from 130 to 170. These values functionality and equivalent weight should not be applied to any one polyisocyanate in the mixture, provided that the mixture as a whole corresponds to the data values.
Suitable polyisocyanates include aromatic, aliphatic and cycloaliphatic polyisocyanates. Aromatic polyisocyanates are, in General, preferred. Examples of polyisocyanates include, for example, m-delete the entry, 2,4 - and/or 2,6-colorvision (the DI), various isomers of diphenylmethanediisocyanate (DHS), hexamethylene-1,6-diisocyanate, tetramethylene 1,4-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotriazine, hydrogenated MDI (N12MDI), naftilan-1,5-diisocyanate, methoxyphenyl-2,4-diisocyanate, 4,4'-biphenylenediisocyanate, 3,3'-dimethoxy-4,4'-biphenyldiol, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 4,4',4”-triphenylethylene, polymethylenepolyphenylisocyanate, hydrogenated polymethylenepolyphenylisocyanate, toluene-2,4,6-triisocyanate and 4,4'-dimethyldiphenylamine-2,2',5,5'-tetrazocine. The preferred polyisocyanates are the so-called polymeric MDI products, which are mixtures of polymethylenepolyphenylisocyanate in Monomeric MDI. Especially suitable MDI products have a content of free MDI from 5 to 50% by weight, more preferably from 10 to 40% by weight. Data polymeric MDI products are available from The Dow Chemical Company under the trademarks PAPI® and Voranate®.
Particularly preferred polyisocyanate is a polymeric MDI product having an average isocyanate functionality of from 2.6 to 3.3 isocyanate groups per molecule and an isocyanate equivalent weight of from 130 to 170. Suitable commercially available products of this type include PAPI™ 27, Voranate™ M229, Voranate™ 220, Voranate™ 290, Voranate™ M595 and Voranate™ M600, all from Dow Chemical.
Also can be the used prepolymers with terminal isocyanate groups and quasilocality (mixture of prepolymers with unreacted polyisocyanate compounds). They are obtained by the reaction of a stoichiometric excess of organic MDI with a polyol, such as polyols discussed above. Suitable methods of obtaining these prepolymers are well known. This prepolymer or quasiparallel preferably has an isocyanate functionality of from 2.5 to 3.6 and isocyanate equivalent weight of from 130 to 200.
The polyisocyanate is used in an amount sufficient to provide an isocyanate index of from 80 to 600. Isocyanate index is calculated as the number of reactive isocyanate groups provided polyisocyanate component, divided by the number of isocyanate reactive groups in forming the polyurethane compositions (including those contained in the reactive isocyanate foaming agents such as water) and multiplied by 100. It is believed that water contains two reactive isocyanate groups on the molecule, so that you can calculate the isocyanate index. Preferred isocyanate index is from 90 to 400, and more preferred isocyanate index is from 100 to 150.
Foaming agent used in forming the polyurethane composition includes at least one physical foaming agent, which is a hydrocarbon, HFC, hydrochlorofluorocarbons, fluorocarbon, simple dialkylamino ether or simple f is artemisinine dialkylamino esters, or a mixture of two or more of them. Foaming agents of these types include propane, isopentane, n-pentane, n-butane, isobutene, cyclopentane, simple, dimethyl ether, 1,1-dichloro-1-foraten (HCFC-141b), Chlorodifluoromethane (HCFC-22), 1-chloro-1,1-differetn (HCFC-142b), 1,1,1,2-Tetrafluoroethane (HFC-134a), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1-differetn (HFC-152a), 1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea) and 1,1,1,3,3-pentafluoropropane (HFC-245fa). Hydrocarbon and gidroftorirovaniya foaming agents are preferred. It is generally preferable to include in addition to the composition of water, in addition to physical blowing agent.
Foaming agent(s) preferably used in an amount sufficient for curing the composition to form a foam having a density after curing from 16 to 160 kg/m3preferably from 16 to 64 kg/m3, particularly preferably from 20 to 48 kg/m3. To achieve these density values simply use hydrocarbon or hydrotherapeutic foaming agent in a quantity in the range of from about 10 to about 40, preferably from about 12 to about 35 parts by weight per 100 parts by weight of polyol(s). Water interacts with isocyanate groups to form carbon dioxide, which acts as an expanding gas. Water is suitably used in which Alceste in the range of 0.5-3.5, preferably from 1.5 to 3.0 parts by weight per 100 parts by weight of polyol(s).
Forming a polyurethane composition will typically include at least one catalyst for the reaction of the polyol(s) and/or water with polyisocyanates. Suitable forming urethane catalysts include those described in U.S. patent No. 4390645 and in WO 02/07934, both introduced in the present document by reference. Typical catalysts include tertiary amines and phosphine compounds, chelates of various metals, acidic metal salts of strong acids; strong bases, alcoholate and the reaction of different metals, organic acid salts of various metals, ORGANOMETALLIC derivatives of tetravalent tin, trivalent and pentavalent As, Sb and Bi, and metal CARBONYLS of iron and cobalt.
Generally preferred are catalysts based on tertiary amines. Among the catalysts based on tertiary amines are dimethylbenzylamine (such as Desmorapid® Rhine Chemie), 1,8-diaza (5,4,0)undecane-7 (such as Polycat® SA-1 from Air Products), pentamethyldiethylenetriamine (such as Polycat® 5 from Air Products), dimethylcyclohexylamine (such as Polycat® 8 from Air Products), triethylenediamine (such as Dabco® 33LV from Air Products), dimethylethylamine, n-ethylmorpholine, the compounds N-alkyldiphenylamine, such as N-ethyl N,N-dimethylamine and N-cetyl N,N-dimethylamine, compound N-alkylphosphine, still is as N-ethylmorpholine and N-commonfolk and the like. Other catalysts based on tertiary amines that may be used include catalysts sold by Air Products under the trade names Dabco® NE1060, Dabco® NE1070, Dabco® NE500, Dabco® TMR-2, Dabco® TMR-30, Polycat® 1058, Polycat® 11, Polycat® 15, Polycat® 33, Polycat® 41 and Dabco® MD45, and catalysts sold by Huntsman under the trade names ZR-50 ZR 70. In addition, some amine-initiated polyols can be used in the present invention as catalytic materials, including those proposed in WO 01/58976 A. can Also be used a mixture of two or more of the above catalysts.
The catalyst is used in catalytically effective amounts. For the preferred catalysts based on tertiary amines suitable amount of catalyst is from about 1 to about 4 parts, especially from about 1.5 to about 3 parts of a catalyst based on tertiary amine per 100 parts by weight of polyol(s).
Forming a polyurethane composition also preferably contains at least one surfactant, which contributes to the stabilization of cells in the composition as the allocation of gas bubbles and foam expansion. Examples of suitable surfactants include the salts of alkali metals and amines of fatty acids such as sodium oleate, stearate is the atrium, ricinoleate sodium, diethanolamine oleate, diethanolamine stearate, ricinoleic diethanolamine and the like: salts of alkali metals and amines, sulfonic acids, such as dodecylbenzenesulfonic acid and dinaftiletilena acid; ricinoleic acid; siloxane-oxacillinase polymers or copolymers and other organopolysiloxanes; ethoxylated ALKYLPHENOLS (such as Tergitol NP9 and Triton X100 from The Dow Chemical Company); ethoxylated fatty alcohols, such as Tergitol 15-S-9 from The Dow Chemical Company; paraffin oil; castor oil; esters of ricinoleic acid; sulfonated castor oil; peanut oil; waxes; fatty alcohols; dimethylpolysiloxane and oligomeric acrylates with polyoxyalkylene and Tarakanova side groups. Data of surface-active substances are usually used in amounts of from 0.01 to 6 parts by weight per 100 parts by weight of polyol.
Typically, the preferred types are silicone surfactants. Commercially available wide selection data organosilicon surfactants, including those sold Goldschmidt under the trade name Tegostab® (such as surfactants Tegostab B-8462, B8427, B8433 and B-8404), those sold OSi Specialities under the trademark Niax® (such as surfactants Niax® L6900 and L6988), as well as various surfactants, commercially available from Air Products and Chemicals, such as surfactant DC-193, DC-198, DC-5000 DC-5043 and DC-5098.
In addition to the above ingredients forming the polyurethane composition may include various auxiliary components, such as fillers, dyes, odor neutralizers, flame retardants, biocides, antioxidants, UV stabilizers, antistatic agents, viscosity modifiers and the like.
Examples of suitable flame retardants include phosphorus compounds, halogenated compounds and melamine.
Examples of fillers and pigments include calcium carbonate, titanium dioxide, iron oxide, chromium oxide, azo/diazo dyes, phthalocyanines, dioxazines, recycled polyurethane foam and carbon black.
Examples of UV stabilizers include hydroxybenzotriazole, dibutyldithiocarbamate zinc, 2,6-distritbution, hydroxybenzophenone, employed amines and phosphites.
Except for the fillers, the above additives are usually used in small amounts, such as from 0.01 percent to 3 percent by weight of the polyurethane composition. Fillers can be used in quantities of up to 50% by weight of the polyurethane composition.
Forming the polyurethane composition is produced by mixing the various components in the conditions under which there is an interaction between what Yalom(s) and isocyanate(s), foaming agent forms a gas, and the composition expands and hardens. All components (or any combination), except for the MDI can be pre-mixed in the finished polyol as one composition, which can, if desired, to mix then with polyisocyanate, when you will need to get the foam. If desired, the components may be pre-heated, but usually this is not necessary, and the components can be mixed at room temperature (~22°C) for the reaction. Usually there is no need of heating the composition to begin curing, but if desired it can also be applied.
The present invention is particularly suitable for implementation in the so-called cases of "fill in place", in which forming the polyurethane composition is injected into the cavity and foams inside the cavity, fills it and gives structural and/or thermal insulating properties of the whole Assembly. The term "fill in place" refers to the fact that the foam is formed at the place of use where it is required, and is not created at one stage and later placed on the application site at a separate stage of production. The filling in place are widely used for manufacturing home appliances such as refrigerators, freezers and coolers, and similar products that have walls, sod is readie insulating foam. The presence of the amine-initiated polyol in forming the polyurethane composition imparts good fluidity and low curing time, at the same time contributing to the formation of foam with a low k-factor.
Wall equipment, such as refrigerators, freezers and coolers, the easiest way to isolate in accordance with the present invention, when first collect the outer casing and inner liner, so that between them a cavity. The cavity defines the space that you want to isolate, and the volume and shape of foam that you want to receive. Usually the casing and inner liner are joined together in a particular way, such as welding, fastening of the melt or the use of various adhesives (or their various combinations) before the introduction of the composition of the foam. The casing and the inner liner may be supported or held in the right vzaimopoleznoe using a clamping device or other device. In the cavity can be arranged in one or more inlets through which may be inserted the composition of the foam. Usually establish one or more vents, to allow air from the cavity could go as filling in the cavity with the composition of the foam and further expansion of the foam composition.
Materials, and which are made case and inner liner, are not particularly important, provided that they can withstand the reaction conditions, the foaming and curing of the composition of the foam. In most cases, the materials of construction are chosen based on specific operational properties required of the final product. Mostly for the manufacture of the body using metals such as steel, especially for large household appliances, such as freezers or refrigerators. For the manufacture of casings for household appliances of smaller size (such as coolers), or equipment, where important light weight, often used plastics, such as polycarbonates, polypropylene, polyethylene, styrene-Acrylonitrile resins, Acrylonitrile-butadiene-styrene resin or high impact polystyrene. The inner liner may be made of metal, but most of it is plastic, as just described.
Then the composition of the foam is injected into the cavity. The various components of the composition of the foam is mixed, and the mixture is then rapidly injected into the cavity in which components interact and expand. A common practice is to pre-mix the polyol(s) with water and foaming agent (and often with a catalyst and/or surface-active agent) to obtain the prepared polyol. Composed of the polyol can be stored until a pen the reservoir, when it is mixed with the polyisocyanate and injected into the cavity. Usually you do not need to heat the components prior to their introduction into the cavity, as well as you do not want to heat the composition in the cavity to harden, but any or both of these stages, if necessary, can be carried out. In some cases, the casing and the inner liner can serve as a means of heat removal and can remove heat from the interactive composition of the foam. If necessary, the shell and/or inner liner can be heated (for example, up to 50°C, but usually up to 35-40°C)to reduce the effect of heat or curing of the foam.
Introduces a sufficient amount of the composition of the foam, so that after expansion of the formed foam fills the part of the cavity where the filling foam. Most typically, when essentially the entire cavity is filled with foam. In General, preferably slightly "to overwhelm the cavity, introducing more of the composition of the foam than the minimum required to fill the cavity, thereby slightly increasing the density of the foam. Overflow provides other benefits, such as better stability of size of the foam, especially at the stage subsequent retrieval. In General, the cavity is overfilled by the value from 4 to 20% by weight. The final density foam for most of the type is in home appliances lies preferably in the range from 28 to 40 kg/m 3.
After the composition of polystyrene foam and enough otverdel to keep the form, the resulting design can be extracted by removing it from the clamping device or other caliper, which is used to support the casing and the inner liner in the correct vzaimopoleznoe. Small time extraction is important for the industry in production of household appliances, as small time extraction can produce more parts per unit of time on this production equipment.
The time of extraction can be estimated as follows: 28-liter form Brett high performance coated antiadhesion, heated to 45°C. In the form of injected 896 g ± 4 g of the composition of the foam to obtain a foam with a density of 32 kg/m3. After 6 minutes the foam is removed from the form and measure its thickness. After 24 hours again measure the thickness of the foam. The difference between the thickness measured after 24 hours and the initial thickness is an indicator of the expansion of the foam after extraction. Retrieval time is large enough, if the expansion of the foam after curing of the foam in this test is not more than 4 mm
As noted, the fluidity is another important property of the composition of the foam. For tasks of this is subramania fluidity was measured using rectangular Brett, having dimensions of 200 cm × 20 cm × 5 cm(~6'6"×8"×2"). Was prepared by forming a polyurethane composition and immediately entered it in the form of Brett, installed vertically (i.e. size 200 cm vertically) and preheated to 45±5°C. the Composition was allowed to expand against its own weight and harden in the form. The amount of the composition forming the polyurethane, selected so that the resulting foam has just filled in the form. Then we measured the density of the resulting foam and compared with the density of the foam at the free foaming obtained from the same composition of the foam (by introducing the composition into a plastic bag or an open cardboard box, where composition could expand freely vertically and horizontally against atmospheric pressure). The ratio of the density of the foam from the mold Brett to the density at the free foaming is the flow index of the composition. In the present invention, the magnitude of the flow index is usually less than 1.8, and preferably from 1.2 to 1.5.
Polyurethane foam mainly shows low k-factor. k factor of the foam may depend on several variables, of which the important one is the density. For many applications a rigid polyurethane foam having a density of from 28.8 to 40 kg/m3(from 1.8 to 2.5, f is now/cubic foot), provides a good combination of physical properties, stability, shape and price. The foam according to the present invention, having a density within this range, preferably gives a k-factor at 10°C not more than 22, preferably not more than 20, and more preferably, not more than 19.5 mW/m·K. the higher density Foam can give some more k-factor.
In addition to foams for appliances and insulation, as described above, the present invention can also be used in the manufacture of transport noise reduction foam, one or more layers of laminated panels, pipe insulation and other products from foam. The present invention is of particular interest when a fast curing, or when foam requires good insulation properties.
If desired, the method according to the invention can be carried out in combination with the methods described, for example, in WO 07/058793, in which the reaction mixture is injected into a closed mold cavity which is at reduced pressure.
The following examples are provided to illustrate the invention and are not intended to limit the scope of its claims. All parts and percentages are given by weight, unless otherwise specified.
A mixture of CIS - and TRANS-isomers of isophorondiamine (from Sigma Aldrich, Gillingham, UK) (5015 g, 29.5 mol)were loaded into a glass reactor, purged with nitrogen and heated to 125°C. In the flask increased the pressure up to ~4500 kPa by propylene oxide, and the pressure maintained until such time as all 5133 g (88,4 mol of propylene oxide was not filled flask. Then the reaction mixture is left for two hours at 125°C, and then added 79,4 g of a 45% solution of potassium hydroxide in water. Water was removed under vacuum at 115°C., and the reactor was again heated to 125°C. Into the reactor was introduced advanced propylene oxide at a rate of 30 g/min until such time as the amount of the propylene oxide was not reached 4356 g (75 mol). Then the reaction mixture was left again for 2 hours, during which time was added 56.7 g of 70% solution of acetic acid in water. The resulting polyol had a hydroxyl number of 440 mg KOH/g (corresponding to a hydroxyl equivalent weight of 127.5) and hydroxyl functionality, close to a 4.0. The polyol had a viscosity 23800 CP at 50°C.
Rigid polyurethane foam obtained from the components described in table 1. The processing composition of the foam was carried out on the machine high pressure Hi Tech CS-50 operating performance 175-225 g/C. the Composition of the foam was injected into the bag (for density measurement at the free foaming) and vertical form Brett, preheated to 45°C. the Temperature of the components before mixing was ~21°C.
|Component||Parts by weight|
|Initiated sorbitol polyol||57,0|
|The polyol of example1||the 15.6|
|Polymeric MDI4(index)||155 (115 index)|
|1Poly(propylene oxide) with a functionality of 6, having a hydroxyl number 482, commercially available as Voranol® RN 482 from Dow Chemical.|
2Poly(propylene oxide)having a hydroxyl number of 500, commercially available as polyol Voranol® RA 500 from Dow Chemical.
3Diol having a molecular weight of about 450, commercial the key is available as a polyol Voranol® R from Dow Chemical.
4Polymeric MDI Voranate™ M 229, available from the Doe Chemical.
The composition has the time of foaming 3.5 sec, the gelation time of 33 seconds and the time to tack-free surface 41 seconds. Density at the free foaming is 22,28 kg/m3and a minimum density at the filling is 32,1 kg/m3. The index of the current is therefore 1,441. The foam has an average compressive strength 145,62 kPa.
k-factor was measured on samples of size 8"×1"×1" (20×2,5×2,5 cm) c using the device for the Laser Comp Fox 200 with the upper temperature of the cold plate 10°C and the temperature of the lower hot plate 38°C, the value of which amounted to 19,15 mW/m·K.
1. Initiated by the amine polyol having an average functionality of greater than 3.0, and up to 4.0, the polyol is the product of the interaction of at least one2-C4alkalinized with aminocyclohexanone initiating a connection with the specified polyol has a hydroxyl equivalent weight of from 75 to 560.
2. Initiated by the amine polyol according to claim 1, where initiating the connection represented by any of structures
where each group R independently represents a hydrogen atom or a C1-C4alkyl, R1is1-C4alkyl, and m denotes a number from 1 to 8.
3. Initiated by the amine polyol according to claim 2, having the functionality of the activity from 3.7 to 4.0 and a hydroxyl equivalent weight of from 100 to 130.
4. Initiated by the amine polyol according to claim 3, where alkalization is ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide.
5. Initiated by the amine polyol according to claim 4, where the originating connection is ISOPHORONEDIAMINE.
6. Initiated by the amine polyol according to claim 4, where the initiating compound is 1,8-diamino-p-Menten.
7. Method of production of rigid polyurethane foam, including
a) obtaining a reaction mixture containing at least
1) amine-initiated polyol according to claims 1 to 6, or its mixture with at least one other polyol, provided that the mixture contains at least 5% by weight amine-initiated polyol according to claims 1-6;
2) at least one hydrocarbon, HFC, hydrochlorofluorocarbons, a fluorocarbon, a blowing agent based on simple dialkylamide ether or fluorinated simple dialkylamide ether; and
3) at least one polyisocyanate; and
b) implementation of the exposure conditions on the reaction mixture, which reaction mixture foams and cures with the formation of rigid polyurethane foam.
8. The method according to claim 7, where the reaction mixture further comprises water.
9. The method of claim 8, where the amine-initiated polyol has a functionality of from 3.7 to 4.0 and a hydroxyl equivalent weight of from 100 to 130.
SUBSTANCE: method involves a step for mixing a carbon additive and a foaming agent with molten polystyrene, homogenisation of the mixture, cooling said mixture to extrusion temperature, extrusion and granulation in conditions which prevent foaming. The ratio of the molar quantity of the foaming agent fed to the specific throughput of the apparatus in the mixing zone (Ks) is kept in the range of 0.08-0.23, while maintaining temperature difference at the input and output of the homogenisation step and cooling step in the range of 30-70°C. The carbon additive used is thermally expanded modified graphite in powder form, which contains separate particles with thickness 0.35-5.0 nm and bunches of particles consisting of 10-30 particles (sheets) with average lateral particle (sheet) size of 5-100 mcm, taken in amount of 0.1-0.6% of the total weight of the load.
EFFECT: use of thermally expanded modified graphite in said amount enables to lower thermal conductivity without deterioration of strength characteristics and simultaneous reduction of water absorption of foamed articles which are made from the foamed polystyrene granulate.
2 cl, 1 tbl, 10 ex
SUBSTANCE: present invention relates to compositions for foaming foam plastic used in insulation materials at low temperatures. The said composition ontains 1,1,1,3,3-pentafluorobutane (HFC - 365mfc) and 1,1,1,3,3-pentafluoropropane (HFC-245fa) with mass ratio HFC-365mfc/HFC-245fa between 65:35 and 73:27.The invention also relates to a premix for producing foamed polyurethane or modified foamed polyurethane which contains such a foaming composition, at least one polyol and a catalyst for reaction of isocyanates and polyols. The invention also describes a method of producing foamed polyurethane or modified foamed polyurethane using the disclosed foaming composition, as well as heat insulation material which contains foamed polyurethane or modified foamed polyurethane made using the said method. When prepared systems are used completely, the foaming composition does not have an ignition point, which provides safe production of (modified) foamed polyurethane.
EFFECT: foam plastics made from such a foaming composition have coefficient of thermal conductivity which varies insignificantly with temperature, and exhibit better insulation properties in a wide temperature range, especially at low temperatures.
9 cl, 3 ex
SUBSTANCE: there is disclosed application of the composition containing at least one fluorohydrocarbon foaming agent and non-halogenated polar organic oxygen-containing compound of boiling temperature at atmospheric pressure within 30°C to 150°C for making polystyrene foam by plastic foam equipment designed so that to be applied with a foaming agent containing at least one chlorfluorohydrocarbon. Besides there is disclosed method for making foam polymers, implying application of said composition. There is also disclosed polystyrene foam composition containing at least one fluorohydrocarbon foaming agent and non-halogenated polar organic oxygen-containing compound of boiling temperature at atmospheric pressure within 30°C to 150°C, where content of non-halogenated polar organic compound is within 10 to 15 wt %.
EFFECT: simplified production process of high-quality product.
13 cl, 3 ex
SUBSTANCE: present invention pertains to the method of obtaining hard polyurethane or polyisocyanurate foams which can be used for making refrigerating machines. The method involves reaction of: (a) organic diisocyanate and/or polyisocyanate with (b) activated aromatic amine polyol, with ratio of equivalents of groups (a) to groups with active hydrogen (b) ranging from 0.9 to 3.0, in the presence of, (c) more carbon dioxide and water, and (d) C3-C5 fluorocarbon. The invention aims at designing a method of producing hard urethane foams, with good physical properties, including a low k-factor, using environmentally acceptable foaming agents. This given task is solved by that, HFC (hydrofluorocarbon) is used as the foaming agent, combined with water and supplementary carbon dioxide.
EFFECT: reduced minimum filling density and filling percentage, required for frost resistant foam plastics at -30°C, as well as the k-factor of the obtained foam plastic.
12 cl, 1 tbl, 6 ex
FIELD: chemical industry; methods of production of the foaming styrene polymeric compounds containing the particles of carbon.
SUBSTANCE: the invention is pertaining to the present in the form of the granules of the foaming styrene polymeric compounds containing the carbon particles and having the low contents of pentane. The invention presents the description of the method of production of the foaming styrene polymeric compound, in which styrene is polymerized in the water suspension at presence from 0.1 up to 25 mass % of the graphite or smut particles and from 2.5 up to 5.5 mass % of pentane, all in terms of the monomers. After the water flushing, the produced mass is subjected to drying during less than 1 second by the air stream with the temperature from 50 up to 100°С. The invention also describes the granules of the styrene foaming polymeric compound with the bulked weight above 600 g/l. The granules contain from 0.1 up to 25 mass % of the particles of the graphite or the smut, and also the volatile foaming agent representing the mixture composed of from 2.2 up to 5.0 mass % of pentane and from 1 up to 10 mass % of the water, all in terms of the granules of the styrene foaming polymeric compound. The technical result of the invention is production of the granules of the styrene foaming polymeric compound with the high contents of the internal water at the low contents of pentane which possess the high capability to the foaming.
EFFECT: the invention ensures production of the styrene foaming polymeric compound granules with the high contents of the internal water and the low contents of pentane, which have the high capability to the foaming.
9 cl, 3 ex, 1 tbl
FIELD: polymer production.
SUBSTANCE: process comprises: polymerization in aqueous suspension of at least one vinylaromatic monomer in presence of suspending agent selected from phosphoric acid salts; discharging foamed granules from reaction vessel; washing thus obtained granules with aqueous solution containing 0.005-2% by weight nonionic surfactant; separating washed granules, whose surface contains no inorganic phosphoric acid salts; and drying these granules in air flow.
EFFECT: achieved lack of foam in effluent after washing of polymer being foamed.
8 cl, 1 tbl, 4 ex
FIELD: polymer production.
SUBSTANCE: invention relates to foaming agent mixture composed of 1,1,1,3,3-pentafluoropropane and 1,1,1,2,3,3,3-heptafluoropropane, and also 1,1,1,2-tetrafluoroethane and/or 1,1,1,3,3-pentafluoropropane; to component containing above mixture, auxiliary substances or additives such as fire retardants or catalysts; and to incombustible mixture precursor containing polyols with ether and/or ester groups, which have molecular weight from below 400 and up to 10000 and more than 8 hydroxyl groups, and foaming agent mixture. Foaming agent mixture, component, and incombustible mixture precursor are destined for preparation of foamed plastics, particularly foamed polyurethanes.
EFFECT: improved inflammation temperature of mixtures intended for preparing high-quality foamed plastics.
6 cl, 2 ex
FIELD: polymer production.
SUBSTANCE: invention relates to production of polyurethane molded products having dense periphery and cellular core using a mixture of foaming agents, particularly containing 50-99% 1,1,1,3,3-pentafluorobutane (HPC 365 mfc) and 1-50% 1,1,1,2,3,3,3-heptafluoropropane (HPC 227 ea). Polyurethane molded products according to invention are characterized by density values varying between 300 and 600 kg/m3 and can be used as wood simulation.
EFFECT: expanded polyurethane foams production possibilities.
3 cl, 2 tbl
FIELD: chemistry of polymers, chemical technology.
SUBSTANCE: invention relates to the foaming agent compositions and to methods for preparing polymeric foams by using such foaming agent compositions, foaming polymeric composition comprising such foaming agents, and to polymeric foams comprising such foaming agents. The suitable combinations of foaming agents involve: (a) composition comprising above 50 wt.-% of carbon dioxide of the composition mass and above 0 wt.-% of at least one fluorinated hydrocarbon with the boiling point above 14°C but below 120°C; (b) composition comprising carbon dioxide and at least one fluorohydrocarbon with the boiling point above 30°C but below 120°C; (c) composition comprising carbon dioxide and at least one fluorohydrocarbon with the boiling point above 14°C and below 120°C and at least one fluorohydrocarbon with the boiling point below 14°C, and at least one additional foaming agent chosen from water, alcohols, ketones and aldehydes. Polymeric foams comprising the foaming agents compositions comprise additionally the infrared radiating blocking agent chosen from the group consisting of carbon black, graphite, gold, aluminum and titanium dioxide dispersed in the indicated polymer. Polymeric foams prepared by using the foaming agents compositions show heat conductivity value less 35 mWt/m x °K later 90 days after their preparing.
EFFECT: improved and valuable properties of composition and polymeric foam.
6 cl, 6 tbl
FIELD: organic chemistry, foaming agents.
SUBSTANCE: invention relates to foaming agent-containing compositions that comprise at least one fluorohydrocarbon with boiling point above 30°C and lower 120°C, at least one fluorohydrocarbon with boiling point lower 30°C and at least one component chosen from low-boiling alcohols and low-boiling carbonyl compounds excepting for CO2. The foaming-agent-containing composition can comprise additional foaming agent chosen from the group consisting of carbon dioxide, nitrogen, argon, water, air, helium, aliphatic or cyclic hydrocarbons. Also, invention relates to methods for preparing polymeric foams by using such foaming agent-containing compositions and to polymeric foams, foaming polymeric compositions comprising such foaming agent-containing compositions. Polymeric foams prepared by using foaming agent-containing composition have closed-porous structure and heat conductivity value less 35 mW/m x °K after 90 days of its preparing.
EFFECT: valuable properties of agent and composition.
4 cl, 4 tbl
SUBSTANCE: method involves binding alkylene oxides to N-functional starting materials in a back-mixing reactor. The starting components are continuously fed into the reactor. One of said N-functional substances is solid at room temperature. Paste is prepared from the solid starting substance and also continuously fed into the back-mixing reactor. The mixture for producing polyether alcohols is in form of a paste and consists of at least one N-functional compound which is solid at room temperature and at least one N-functional compound which is liquid at room temperature.
EFFECT: simple and safe method of producing polyether alcohols, which enables to obtain products with narrow molecular weight distribution and where starting materials can be continuously fed.
22 cl, 4 ex
SUBSTANCE: invention relates to foamed polyurethane used in a wide range of articles, such as inner component parts of cars, structural polyurethane foam, floor covering and sports race tracks, as well as a production method thereof and a continuous method of producing alkoxylated hydroxylate of plant oil. The foamed polyurethane is a product of reaction of at least one polyisocyanate and at least one alkoxylated hydroxylate of plant oil containing from approximately 15 wt % to approximately 90 wt % alkoxylate relative the weight of the alkoxylated hydroxylate of plant oil, wherein alkoxylation is carried out in the presence of a catalyst based on a double metal cyanide (DMC) in amount of 0.0005-1 wt % relative the amount of a polyol derivative, optionally at least one polyol which is not based on plant oil, in the presence of at least one foaming agent and one catalyst different from the catalyst based on DMC, selected from a group comprising organotin and/or amine catalysts, optionally in the presence of at least one surfactant, pigments, fire retardants and filler materials.
EFFECT: foamed polyurethane produced using environmentally acceptable, renewable components, in particular alkoxylated hydroxylate of plant oil, which enables use of the foamed polyurethane in fields where there are high environmental requirements and/or high hydrophobic properties.
30 cl, 3 tbl
SUBSTANCE: invention relates to method of producing short-chain polyester-polyols used in production of hard polyurethane foams. The method includes: (i) contact of amine with first alkylene oxides, which is ethylene oxide block with used ethylene oxide in quantity of about 20-40% relative to total of alkylene oxide, where initial quantity of the first alkylene oxide, contacting with amine is 5-30% from total quantity of alkylene oxide subject to adding to amin, (ii) adding catalyst from alkali metal hydroxide in quantity from about 0.001 to 0.1 wt % relative to mass of the final polyesters-polyols, (iii) contact of amine with the rest quantity of the first alkylene oxide and thereafter with the second alkylene oxide, which is a propylene oxide block, with the quantity of the used alkylene oxide, and (iv) adding hydroxyl carboxylic acid into epoxidized mixture. Simple polyester-polyol prepared by using said method and method of hard foam production including reaction of organic polyisocyanates with said polyester-polyol is also described. Reduction of catalyst quantity used during synthesis of polyester-polyol. Adding such catalyst earlier in reaction of epoxidation after neutralisation of carboxylic acid results in reduction of emitting large quantity of solid wastes, thus providing with transparent simple polyester-polyol originated by amines and which is not required to be filtrating before application.
EFFECT: polyurethane foams prepared by using such polyester-polyols has high flowability, improved time of jellification and foam rise height.
27 cl, 3 tbl, 2 ex
SUBSTANCE: invention concerns mix with activated initiation agent, which can be applied in obtaining polyalkylenepolyenes. Claimed mix with activated initiation agent includes (a) at least one initiation agent activated in advance and comprised by: (i) at least one of first initiation agents with equivalent mass of at least 70; (ii) at least one epoxide; and (iii) at least one DMC-catalyst; and (b) at least 2 mol % per quantity of initiation agent(s) activated in advance of one of second initiation agents with equivalent mass less than equivalent mass of first initiation agent.
EFFECT: elimination of necessity to synthesise expensive initiation agents with high molecular mass with catalysis facilitated by potassium hydroxide in separate assigned reactor.
7 cl, 2 ex
SUBSTANCE: present invention pertains to the method of obtaining polyester alcohols, used for making polyurethanes. The method involves reaction of saturated alkylene oxides with at least, one saturated OH-containing compound or with alkylene oxide, oligo- or polymerised saturated OH-containing compound. The reaction takes place in the presence of a catalyst, based on bimetallic cyanides. An antioxidant is added before the reaction. The quantity of the antioxidant is more than the quantity of the bimetallic cyanide based catalyst, in terms of the mass of the bimetallic cyanide based catalyst.
EFFECT: increased activity of the catalyst, degree of conversion of alkylene oxides and output of the process, as well as reduced the content of impurities in the end product.
6 cl, 1 tbl, 13 ex
FIELD: polymer production.
SUBSTANCE: process comprises interaction of (a) polyol component, containing at least one polyoxyalkylenated polyether-polyol obtained in the form of aluminum phosphonate-based catalyst and having average equivalent weight from about 100 to about 10000, with (b) organic isocyanate in presence of (c) if necessary, one or several lengtheners, (d) if necessary, catalyst, foaming agent and (e) if necessary, crosslinking agents, surfactants, fire retardants, pigments, antioxidants, and stabilizers. Polyurethane foam obtained as described above is also described as well as catalyst based on aluminum phosphonate and having general formula RPO-(AAlR'R")2, wherein P denotes pentavalent phosphorus, O oxygen, Al aluminum, R hydrogen, alkyl or aryl group, and R' and R", independently from each other, halogen, alkyl group, aryl group, aryloxyl group, or derivatives of thus specified aluminum phosphonate, in amount from about 0.001 to about 5.0% based on the total weight.
EFFECT: improved quality, in particular homogeneity of polyurethane foam.
2 cl, 3 tbl, 7 ex
FIELD: polymer production.
SUBSTANCE: invention relates to in situ production of mixture from polyethermonool and polyetherpolyol, which comprises following steps: (A) loading a mixture to reactor, which mixture contains (1) initial initiator (Si) including one or several monofunctional compounds and (2) double metal cyanide catalyst; (B) supplying epoxide including propylene oxide and ethylene oxide to reactor at weight ratio between 100:0 and 10:80; (C) bringing epoxide mixture into interaction with initial initiator (Si) and performing polymerization of epoxides until equivalent weight of multifunctional compound rises by at least 10 wt % and achieves value from about 1500 to about 6000; (D) continuously adding low molecular weight initiator (Sc) having functionality from 2.0 to 8 and equivalent weight from about 28 to about 400 to reactor while continuing addition of epoxides; (E) ending continuous addition of initiator (Sc); and (F) continuing polymerization of the mixture in reactor until resulting monool/polyol mixture achieves average equivalent weight from about 350 to about 750 and average functionality from about 2 to about 4 and includes (1) about 25 to about 75 wt % polyethermonool having equivalent weight from about 1500 to about 6000 and (2) about 25 to about 75 wt % polyetherpolyol having equivalent weight from about 200 to about 500 and average functionality from about 20 to about 8. In situ produced mixtures of polyethermonool and polyetherpolyol as well as viscous-elastic foam production process are also described.
EFFECT: avoided need of preparation, storage, and mixing of separate polyethers and so reduced requirements for multiple tanks, which enhances production efficiency.
3 cl, 6 dwg, 2 tbl
FIELD: chemical industry; methods of production of the polyethers of the aliphatic alcohol.
SUBSTANCE: the invention is pertaining to the method of production of the polyethers of the aliphatic alcohol by alkoxylation of the organic compounds by alkoxylation of the organic compounds with the alkoxylating agent, which is selected from the mono- or multipurpose epoxides having from 2 up to 30 atoms of carbon and the mono- or multipurpose polyesterpolyols having the molecular mass about 600 g/mole, or their mixtures in the presence of the catalytic system, which includes the organometallic framework material containing the pores and, at least, one ion of the metal, and, at least, one bidentate organic compound, which is coupled with the indicated ion of the metal by the coordination bond. At that the ion of the metal is selected from ions of the elements of the groups Ia, IIa, IIIa, IVa up to VIIIa and Ib up to VIb of the Periodic system, and the bidentate organic compound is selected among the substituted or un substituted aromatic polycarboxylic acids which may contain one or several atomic nuclei and the substituted or unsubstituted aromatic polycarboxylic acids, which contain, at least, one heteroatom and which may have one or several kernels. The given method allows to produce the polyethers of the aliphatic alcohols having the small amounts of the impurities, in particular, of the low molecular substances having the intensive odor and which does not include the complex stages of refining of the source materials and-or the intermediate products. The produced polyethers of the aliphatic alcohols are used for production of the polyurethane by interaction of such polyether of the aliphatic alcohol, at least, with one isocyanate.
EFFECT: the invention allows to produce the polyethers of the aliphatic alcohols having the small amounts of the impurities, the low molecular substances with the intensive odor, which does not include the complex stages of refining of the source materials and-or the intermediate products.
2 cl, 4 ex, 2 dwg
FIELD: polymer production.
SUBSTANCE: invention, in particular, relates to improved method for producing polyetherpolyols using double metal cyanide catalysts. Method is accomplished via polyaddition of alkylene oxides to initial compounds having molecular mass between 18 and 2000 and 1 to 8 hydroxyl groups containing active hydrogen atoms, reaction being effected in presence of double metal cyanide catalysts. During the polyaddition reaction, reaction mixture is at least once passed through jet disperser, in which power density is at least 105-106 J/m3 and residence time of reaction mixture per pass is at least 10-5 sec.
EFFECT: enhanced process efficiency and expanded synthetic possibilities.
1 dwg, 3 ex
FIELD: industrial organic synthesis.
SUBSTANCE: production of polyetherpolyols using double metal cyanide catalysts is accomplished via polyaddition of alkylene oxides to starting compounds with molecular mass from 18 to 2000 and 1-8 hydroxyl groups in presence of above catalysts. During polyaddition reaction, reaction mixture is at least once passed through jet disperser, wherein power density is at least 5x105 J/m3 and residence time of reaction mixture in jet disperser is at least 10-6 sec per pass.
EFFECT: expanded assortment of polyetherpolyols allowing production of polyurethane foams characterized by fine cellular structure and lack of pulling-down in the course of formation.
1 dwg, 12 ex
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