• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    In the disclosed process of producing resilient open-celled, cross-linked polyurethane foams, by foaming polyol, polyisocyanate, catalyst and blowing agent, the foaming is effected in the presence of a cross-linker which is a saturated or unsaturated, aliphatic, cycloaliphatic, heteroaliphatic or arylaliphatic crystalline polyhydroxy compound having at least 3 hydroxy groups. The crystalline polyhydroxy compound is insoluble or only slightly soluble in the polyol to be foamed and melts within the temperature range of about 60 DEG -160 DEG C. The amount of crystalline polyhydroxy compound to be used corresponds to about 0.1-5.0 hydroxy equivalent weights per 1 hydroxy equivalent weight of the polyol to be foamed.
    公开号:SU797587A3
    申请号:SU752120690
    申请日:1975-04-07
    公开日:1981-01-15
    发明作者:Кольмейер Ханс-Йоахим；Россми Герд
    申请人:Т. Гольдшмидт Аг (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR OBTAINING ELASTIC POLYURETHANE FOAMS For the polyurethane foam jianijcHT foam from molecular weight, functionality of the component, polyatom of alcohol and isocyanate and, in addition, added c-smyh quantities. For soft foam cells with open cells, mainly polyhydric alcohols and isocyanates with a functionality of -3 are used. Dissolving bridging agents are trifunctional alcohols or amino alcohols, usually used in concentrations of up to 1.5 equivalent weight of hydroxy groups per equivalent of that of hydroxy groups of a polyhydric alcohol. Polyoxyfunctional lithium crystalline bridges can be used in similar quantities, but also in high suicide quantities, since they have an increasing amount of almost or none at all in the foam. It is possible to add 0.1 to 5.0 equivalent of all hydroxy groups of the bridging agent for an equivalent weight of the hydroxy group of the foamable polyhydric alcohol or a mixture of such alcohols; in practice, it is preferable to add 0.2-3.0 equivalent weight of the hydroxy groups of the viecKoro crystal bridging agent per equivalent weight of the hydroxyl groups of a polyhydric alcohol. , The hydroxyl groups of the crystalline polyoxy compounds used can be combined with a primary, secondary or tertiary carbon atom, preferably with a primary or secondary aliphatic saturated carbon atom. They may, however, combine with an aliphatic unsaturated or less commonly with an aromatic carbon atom. Used as bridges include, for example, the following polyoxy compounds: sorbitol, mannitol, erythritol, glucose, sucrose, hexamethylol melamine, trimethylolmelamine, trimethylol ethane, and mixtures of these compounds or lL hydrates. In addition, derivatives of these compounds are suitable, such as, for example, partial esters or ethers of polyoxy compounds, for example, sucrose mono- or di-esters with monocarboxylic acids with 1-20 carbon atoms. Polyoxy functional polymers can also be used, melting or glass transition temperatures of which range from 60-150 ° C. Such substances, for example, include polyvinyl alcohol, polyoxy functional esters of polycondensates of dicarboxylic acids with trifunctional alcohols or higher functional alcohols, or copolymers with hydroxyethyl or hydroxypropyl acrylates with non-functional acrylic or methacrylic acid esters. Lromatic ' s 1 polyoxy compounds are more suitable for the proposed method, since urethanes obtained by reacting isocyanates with aromatic hydroxy compounds are split at elevated temperature into the starting components. Addition of polyoxy-functional, crystalline bridges to polyurethane foam formulations is carried out in a variety of ways. The preparation of polyurethane groups containing foams is produced by reacting polyeocyanates with polyhydric alcohols containing active hydrogen atoms in the presence of water in order to release the active agent as a swelling agent of carbon dioxide and, in appropriate case, an additional swelling agent, such as a low boiling hydrocarbon and adding various activators, as amines and / or metal salts. Conditions of reaction and mixing are necessary in order to achieve a good foaming result. The addition of crystalline polyoxy-functional bridges is carried out in such a way that the bridges are dispersed before use in a polyhydric alcohol containing active hydrogen atoms. However, the crystalline bridge former can be added to the expandable mixture directly in a finely distributed form. As polyols use diols, triols or polyatomic alcohols of higher functionality, as well as polyether monohydric alcohols. Often, direct use of the polyhydric alcohol used for foaming as a dispersion medium is preferred. Depending on the molecular structure and viscosity of the foaming polyhydric alcohol, dispersions can form, whose viscosity is too high for practical purposes, in such cases polyhydric alcohols or polyether monohydric alcohols of lower viscosity can be used as a dispersion medium, the resulting polyurethane foams have a softening effect. Further, other substances can be used as dispersants, such as, for example, alkylene glycols, in particular hexylene glycol. When choosing dispersants, it is necessary that they do not have an undesirable effect on those who have blown during the npct process. reactions and to
    they did not play the role of a mcchitel in the resulting foam.
    Polyester polyhydric alcohols are preferred for use in dispersing bridges in formulations of polyether urethane foam in a kecTBe dispersant. Dispersions added to polyether urethane foam formulations should contain polyether polyols as a dispersant, for example, hydrophobic polyethers can have an anti-foam effect in such formulas.
    The melting points possessed by crystalline polyoxy compounds in the corresponding dispersions, obtained with the help of various dispersants, may differ from the melting points of pure substances. Deviations can be caused by different causes: type of preparation and degree of dispersion, partial dissolution effects caused by the dispersant or the water content of the dispersant. The melting point of the dispersion may vary depending on the method of preparation and later, for example, the re-formation of crystalline particles in dispersions obtained from solutions or melts may in appropriate cases be subject to a longer maturation process. As a result of these phenomena, the melting ranges of the dispersed polyoxy compounds may also include melting points of the compounds melting in a pure, non-dispersed form, outside these specified ranges.
    The preparation of dispersions of crystalline polyoxy compounds, for example, in polymer polyols, can be carried out in various ways. The crystalline polyoxy compounds can be mixed with a polyhydric alcohol, after which the mixture is heated above the melting point of the crystalline polyoxy compound. Both liquid phases are then emulsified, mixing to form an emulsion, in which the polyhydric alcohol is a continuous phase, bridging-dispersed. In addition, an emulsifier may be used.
    Upon cooling of the emulsion, the polyoxy compound recrystallizes to form a fine dispersion. The crystalline polyoxy compound can also be processed together with a polyhydric alcohol with or without the addition of an emulsifier in a ball mill, to obtain a fine dispersion.
    The solution of the crystalline polyoxy compound can then be added to the polyhydric alcohol used as the dispersant. If a solvent is used in this case in which the polyhydric alcohol does not dissolve or dissolves only to a limited extent, when the solution is mixed in the polyhydric alcohol, the polyoxy compound precipitates to form a fine dispersion. The dispersant can remain in the dispersion or it can then be removed in vacuo. If the solvent of a polyoxysilane is also a solvent of a polyhydric alcohol, the solution and the polyhydric alcohol can be mixed, and the solvent, after stirring, can be evaporated. Again, a dispersion of the crystalline bridge former is formed in the polyhydric alcohol serving as a dispersant, and the dispersion can be prepared with or without an emulsifier.
    The dispersion of the crystalline polyoxy compound is added to the polyhydric alcohol used to form the polyurethane foam before mixing the entire expandable reaction mass. Adding a dispersion to a polyhydric alcohol. exist before or after mixing the latter with the used swelling agents, activators and stabilizers.
    The starting materials for the preparation of crosslinked, containing urethane groups of foams are the well-known aliphatic, cycloaliphatic and aromatic polyisocyanates. As examples, 2,4- and 2, b-toluene diisocyanate, trimerized toluene diisocyanate, diphenylmeta, n-4, 4 -diisocyanate or polymeric isocyanates can serve as polyphenyl-polymethylene
    0 -polyisocyanate, as well as the removal of these compounds.
    Starting materials for the preparation of penosystems containing at least two active hydrogen atoms,
    5 polyhydric alcohols mol.ves. 100020000. Gugut polyhydric alcohols are polyether and polyester polyether alcohols. Relevant, Polyester
    0 polyhydric alcohols are obtained, for example, by reacting compounds containing reactive hydrogen atoms, such as di- or polyfunctional alcohols, with oxides
    5 alkylene, for example, ethylene oxide, propylene, butylene, octene-1 or styrene, or epichlorohydrin. Polyfunctional alcohols useful as initiators of diyl include, for example, ethylene glycol,
    0 butanediol-1,4, glycerin, tris-hydroxypropoxypropane, trimethylolpropane, sorbitol. Polyether polyhydric alcohols May consist solely of propylene oxide or of propylene oxide and ethylene oxide. Polyester polyhydric alcohols could be obtained, for example, by polycondensation of dicarboxylic acids with di- and trifunctional alcohols, such as glycol, 1,4-butanediol or trimethyl olpropane. In particular, di- or trioxyfunctional polyether polyhydric alcohols suitable for the process, with an equivalent weight of 700-5000 oxygroup, an equivalent weight of 1500-4000 is preferred. Polyether polyhydric alcohols, differing in the equivalent weight of oxy groups above 1500 and consisting of 80-100% of propylene oxide, cannot be obtained in a certain way by O6X1.1NO alkaline catalysis used, with an increase in the equivalent weight of oxy groups and chain length, reactions leading to the formation of unsaturated end groups, as allyl or propenyl ether groups. This no6o4Hfcj v reaction is accompanied by a reduction in the functionality of polyether polyhydric alcohols, which ultimately leads to the fact that products from polyether polyhydric alcohols can no longer be used to obtain foamed products with spectacular technological properties. However, amorphous polyether polyhydric alcohols with an equivalent weight of 1500-5000 hydroxyl groups and a high content of propylene oxide, in which the functionality caused by the initiator molecule is preserved almost all intact, can be obtained with the help of different organometallic or mixed metal catalysts. Polyether polyhydric alcohols, which can be obtained with the use of -. these catalysts and low-molecular polyoxysilane compounds, such as butane-1,4-diol or tris-hydroxy-propoxypropane, also contain, as molecular initiators, with an equivalent weight of hydroxy groups within the 1500 and 5000, only a small number of terminal unsaturated formed due to rearrangement reactions of molecules, polyether polyhydric alcohols. These polyether polyhydric alcohols, whose functionality and molecular weight are significantly more clearly determined by the type and amount of the starting materials, are particularly preferred for the proposed method. In addition to their initiating modules, the preferred polyester polyhydric alcohols can consist entirely of propylene oxide or 5-20 wt.% Ethylene oxide and 80-95 weight of propylene oxide. In oxide / ethylene containing polyester polyhydric alcohols, 10% or more of the terminal hydroxyl groups may be primary hydroxyl groups. For higher molecular weight polyether polyhydric alcohols containing 5-20% by weight of ethylene oxide, it is preferable that 2050% of their active hydrogen atoms are contained in the form of primary hydroxy groups. By applying higher molecular weight polyether diols and the same triols, the resulting foams are given greater elastomer properties. The crosslinking of relatively long elastomeric segments via polyoxylfunctional bridge formers through e lye provides the ability of foams to withstand high loads at the same time. The polyester polyols used may be foamed in the form of pure components or in the form of mixtures of various polyester polyols. Mixtures may contain polyether polyhydric alcohols of varying functionality, molecular weight and ethylene oxide content. For example, a relatively high molecular weight diol can be foamed mixed with a triol of a lower equivalent weight of hydroxyl groups. Polyester polyhydric alcohols to be foamed may also contain, in a dissolved form, low molecular weight compounds with two active hydrogen atoms or more, having a molecular weight of up to 750. Such compounds, whose task is to stabilize by crosslinking the polymeric foam frame, in the initial stage of its formation, for example, glycerol, trimethylolpropane, and their. adducts to alkylene oxides, such as ethylene oxide and propylene oxide, in addition, triethanolamine and, other adducts of propylene oxide and / or ethylene to aliphatic or aromatic polyamines. The preparation of polyurethane foams can be carried out according to the prepolymerization method or the one-shot method, preferably last. Following the one-shot procedure, foams are obtained at room or elevated temperature by mixing polyether eosyanates with the polyether alcohols described with the addition of water and, in appropriate case, organic swelling agents, and, if necessary, stabilizers or emulsifiers and above this activating auxiliary substances, as crystalline polyoxy compounds according to the proposed method. As stabilizers or emulsifiers, surface-active compounds are used, before. respectfully containing alkylsiloxane groups, with these compounds being modified by polyoxyalkylene segments. Tertiary amines can be used as catalysts, in the appropriate case in combination with organic metal compounds. While tertiary amines preferably catalyze the proceeding, with the release of COg, the interaction of water with isocyanate groups, organic compounds of metals mainly accelerate the interaction of organic hydroxyl groups with isocyanates. Amino-activators include, for example, triethylenediamine, dimethyl ethanol amine, dimethyl benzylamine N-ethyl morpholine. Suitable organic metal compounds which can be used, if necessary, in combination with aminoactivators, are, for example, tin (II) octoate or dibutyl tin dilaurate. The genus, amount, and combination of the activators used are selected so as to be advantageous in terms of the foaming technique of the reaction conditions. The production of polyurethane foams can be made in closed forms or by the open method in the form of block-foam. When foaming in forms, the reaction mixture to be foamed is loaded into a metallic or plastic form. In this case, it is possible to load such an amount of foaming of the reaction mixture that the form will be completely filled. It is possible, however, to use a larger amount of such a mixture. The blocking foaming of the mixture to be foamed is placed in a non-moving open paper form or on a paper-covered belt conveyor moving at a uniform speed. The finished foam blocks or forms thereafter may be subjected to additional processing, for example, by heating with warm air or heat radiation or radiation by microwaves. In polyurethane foams made by the proposed method, when deformed under compression in 25 and 65%, the hardness may increase to the same extent, or the final hardness may increase relatively more than the initial one. In the latter case, the present method, in comparison with identical plastic foam of the same volume weight, but without a bridge former, causes not only an increase in hardness, but also an increase in Sac (load ratio), defined as partial hardness at 65 and 25% deformation under compression. The aforementioned improvement in the properties of polyurethane foams, in particular, is an important factor for foam systems consisting of higher molecular weight {lx, ethylene oxide containing polyether polyatomic alcohols and polyisocyanates of functionality 2 and / or 2. The values and values of hardness and factors obtained in the examples are obtained according to the tests according to ASTM D 1564-64T .: Example 1. A mixture consisting of, by weight parts 10000, polyoxyalkylene, obtained with the help of glycerin as an initiator and consisting of 84% by weight of propylene oxide, 16% by weight ethylene oxide, with ERZHAN 35 OH groups and in which the added weight as a dispersion. hours: sorbitol 1,5; water 3,00; triethylenediamine 0.35; triethanolamine 2.00; polyoxo-modified siloxane (for example, under the trade name TEGOSTAB B 3706) 1.00, trichlorofluoromethane 5.00 and reacted with 51.6 parts by weight. a mixture of 67 weight.h. toluene diisocyanate (T 80} and 33 parts by weight of crude diphenylmethane diisocyanate in an open vessel. A non-shrinking foam with open cells is formed, which has the following mechanical properties: Density, g / l 30.8 Hardness at 25% deformation under compression, gf / cm2-15 , 8 Hardness at 65% deformation under compression, gf / cm 46.5 Factor Sgc2.93 For comparison, the results of foaming without the use of crystalline polyoxysilane are given: a. A) A mixture of the above composition, but without the addition of sorbitol in the form of a dispersion, is subjected to interaction with 47.5 weight parts. the above isocyanate mixture. Formed foam with open cells and the following mechanical properties: Density, g / l 30,2 Hardness at 25% deformation under compression, gc / cm 10.2 Hardness at 65% deformation under compression, gf / cm -30,0 Factor SQIC2, 95, b) The mixture of composition (a) is reacted with 51.5 parts by weight. isocyanate mixture in an open vessel. Thus, the expandable reaction mixture contains an excess of 12 mol% of the isocyanate groups, based on the interactions with the mixture present in the mixture. isocyanate group.
    A closed-cell foam is formed, strongly settling down during storage or storage,
    c) 100.00 parts by weight of polyester polyhydric alcohol added, 4.50 parts by weight, solution of 1.5 parts by weight sorbitol 3.0 parts by weight water, 0.35 weight.h. triethylenediamine, 2.00 weight.h. triethanolamine, 1.00 - weight.h. the above siloxane modified with polyester, 5.00 weight.h. trichlorofluoromethane is mixed with each other and immediately reacted with 51.5 parts by weight. isocyanate mixture in an open vessel.
    Formed foam with closed cells, sitting down during storage or storage. If, after 10 minutes after the foam is obtained, the closed cell structure is broken, the following properties will be achieved:
    Density, g / l31,0
    Hardness at 25% deformation under compression, gf / cm 15.4
    Hardness at 65% deformation under compression, gf / cm 47.5
    SQIC factor, 3.1;
    d) Mixture of composition (a), but containing another 2 parts by weight. added triethanolamine., subjected to interaction with 51.6 parts by weight isocyanate mixture in an open vessel
    Formed foam with closed cells. If it is mechanically pressed before shrinking, the following mechanical properties are found:
    Density, g / l32 / 0
    Hardness at 25% deformation under compression, gf / cm -15.6
    Hardness at 65% deformation under compression, gf / cm 46.6
    Factor SQC.3,0.
    When comparing the resulting foam spreads, it has been shown that an increase in hardness can be achieved both with the help of soluble bridge builders, and with the help of a solution of a crystalline bridge former. Increased open-cell reticulated foam, however, is formed only when a crystalline bridge former is added to the foaming reaction mixture as a dispersed solid phase. However, from the comparison example (b) it can be seen that the advantage achieved is not the result of an increase in the isocyanate content.
    Example 2. A mixture consisting of 60.0 weight.h. polyoxyalkylenetrile of an initiator obtained using glycerol as a cathectTBe and consisting of 84% by weight of propylene oxide and 16% by weight of ethylene oxide in which it is contained. 35 group, 15.0 weight.h. received
    according to example 5 dispersion 1.5 weight.h. sorbitol in the above polyester, 40.0 weight.h. polyoxyalkylene, obtained with glycerol as an initiator and consisting of 92% by weight of propylene oxide and 8% by weight of ethylene oxide, which contains 21.5 OH groups, 3.0 parts by weight. water, 2.0 parts by weight triethanolamine, 0.5 weight.h. triethylenediamine, 1.0 weight.h. polyester-modified polysiloxane under the trade name TEGOSTAB B 3706. 5.0 weight.h. trichlorofluoromethane is subjected to interaction with 50.2 parts by weight. mix 67 weight.h. toluene diisocyanate (a mixture of 80% of the 2.4 - and 20% of 2,6-isomers) and 33 weight.h. crude diphenylmethane diisocyanate.
    A foam is formed with the following mechanical properties: Density, g / l 30.0
    Hardness at 25% deformation under compression, gf / cm 10.0
    Hardness at 65% deformation under compression, gf / cm 30.2
    Factor SQC3,0.
    Example (comparative). A mixture of the above composition, not containing sorbitol, but only 0.35 weight parts. triethylenediamine, in an open vessel, is reacted with 46.1% of the weight of the above isocyanate mixture, obtaining a foam with the following mechanical properties:
    Density, g / l 31,4
    Hardness at 25% deformation under compression, gf / cm 8.0
    Hardness at 65% deformation under compression, gf / cm 23.0
    SQ factor (2.9.
    From a comparison of the mechanical properties of both foams, it is clear that, due to the additional crosslinking with sorbitol, the hardness of the foam increases. If, instead of a crystalline bridge former, the same molar amount of hydroxyl groups are added in the form of a soluble trifunctional bridge former, such as triethanolamine or glycerin, a closed cell foam is formed, settling down on cooling moderately or to a large extent.
    权利要求:
    Claims (1)
    [1]
    Example 3. A mixture consisting of 82.00 pbw of polyoxyalkylenetriol, prepared with glycerol as an initiator and consisting of CG 95 wt.% Of propylene oxide and 5 wt.% Of ethylene oxide, which contains 48 OH groups, 20 , 00 weight.h. obtained according to example 6, the dispersion of 2.0 parts by weight trimethylolmelamine and 18 weight.h. the specified polyhydric alcohol, 4,05 ness.ch. water, 3.00 weight.h trichlorofluoromethia, 0.80 weight.h. modified polyether polysilox on (in trade, for example, under the name TEGOSTAB B 2370), 0,27 weight.h. tin thibate (I), 0.10 fan. dimethylethanolamine, 0.04 weight.h. N-ethyl morpholine is vigorously stirred and reacted with 53.5% by weight of a mixture of 80% by weight of 2.4% and 20% by weight of 2, b-toluene diisocyanate in an open vessel. The foam has the following mechanical properties: Density, g / l 23.6 Hardness at 25% deformation under compression, gf / cm 40.0 Hardness at 40% deformation under compression, gf / cm, 43.5 Hardness at 65% deformation under compression, gs / cm -77,0 Porosity8,5 Factor BOS.2,0. An example (comparative), a) Polypropylene obtained from the above mixture, which, however, does not contain trimethylol melamine and 51.5 parts by weight. specified toluene diisocyanate, shows the following mechanical properties; Density, g / l, 23.5 Hardness at 25% deformation under compression, gf / cm 30.0 Hardness at 40% deformation under compression, gf / cm -32.5 Hardness at 65% deformation at. compression, gf / cm. 61.0 Porosity7.6 Factor Sac.2.05) b, Polyfoam, obtained from the above mixture, in which, however, it contains instead of 2 parts by weight. trimethylolmelamine 1.4 weight.h. triethanolamine and 51.5 weight.h. The above toluene diisocyanate shows a high degree of cell closure, and when cooled, a slight tendency to shrinkage. The porosity is 150 mm. The porosity values given in this example express the velocity of the millimeters of the water column formed when air is forced through the nozzle through the foam 5 directly applied to the foam surface from a height. Thus, higher porosity rates mean lower breathability. From a comparison of the foams obtained, it can be seen that the addition of the proposed bridge former substantially increases the hardness of the foam at a constant density. At the same time, the openness of the cells of foams decreases only slightly, while in case of adding an equimolar amount (n in terms of reactive groups of it) of the solvent and bridging agent, the hardness is greatly reduced. Example 4 A mixture consisting of 87.25 parts by weight nolyoxyalkylene, obtained with glycerol as an initiator and consisting of 83% by weight of propylene oxide and 17% by weight of ethylene oxide and comprising 28 OH groups, 15.00 parts by weight. obtained according to example 7.disperse, containing 10 wt.% sorbitol and 4.5 wt.% water in the same polyhydric alcohol as a dispersant, 2.33 wt.h. water, 2.00 weight.h. triethanolamine, 0.33 weight.h. triethylenediamine, 1.00 weight.h. polyether modified polysiloxane (trade name TEGOSTAB H 3705) 5.00 weight parts. trichlorofluoromethane, intensively stirred and subjected to interaction with 52.5 weight.h. a solution of trimerized toluene diisocyanate in toluyldiieocyanatE, with 39 CNo groups in an open vessel. A non-shrinking, open-cell foam is obtained that has the following mechanical properties: Density, g / l32.0 T1hazardost at 2.5% deformation1 1, and under compression, HS / cm-17.0 Hardness At 65% deformation under compression, gf / cm 58 , 0 Bass factor, - 3,4, Example (comparative), and Mixture of a given composition, but b, without the addition of sorbitol, is subjected to interaction with 48 weight parts. the above polyisocyanate in an open vessel. A foam is formed with the following mechanical properties: Density, g / l32.5 Hardness at 25% deformation under compression, gf / cm -9.9 Hardness at 65% de. formations in compression, gf / cm 28.5 Factor 5ac, b) A mixture of a given composition, but containing 1.5 weight parts instead of sorbitol. glycerol, subjected to interaction with 52.5 weight.h. the above polyisocyanate by the above method. A partially closed foam is obtained, the sides of which shrink during cooling. If the foam obtained in a similar way is mechanically pressed in before starting shrinkage, it shows the following mechanical properties: Density, g / l Hardness at 25% deformation under compression, gf / cm Hardness at 65% deformation under compression, HS / cm Factor Sac .. From comparison The resulting foams of this example show that using the method can greatly increase the hardness. This does not change the openness of the foam cells. The addition of approximately the same molar hydroxyl group of the dissolving bridging group causes a lesser increase in hardness and causes the cells of the foams to be closed. In the following examples, describes the preparation of dispersions of crystalline polyoxy compounds in polyether polyols. Example 5. A mixture consisting of 89.0 parts by weight polyoxyalkylenetriol of the glycerol obtained with the PBM as an initiator and consisting of 84% by weight of propylene oxide and 10% by weight of ethylene oxide and of 35 OH groups, 10.0 parts by weight. sorbitol and 1.0 weight.h. 1,3,5,7-tetramethyl-tetra lauroylpropyl-cyclotetrasiloxane is heated with stirring with a large shearing force up to. Upon rapid cooling of the resulting emulsion, a comparatively stable dispersion of sorbitol is formed in polyether polyhydric alcohol. The melting point of the dispersed phase corresponds. Example b. A mixture consisting of 89 parts by weight polyoxyalkylene, obtained using glycerol as an initiator and consisting of 95% by weight of propylene oxide and 5% by weight of ethylene oxide and it has 48 groups, 10.0 parts by weight. melamine trimethylol and 1.0 weight.h. emulsifier specified in example 5, 24 hours, is processed in a ball mill at room temperature. A dispersion of the melamine derivative is formed in a polyether alcohol, is stable over several weeks. Example 7. B85 weight.h. specified in example 4 of the polyester polyhydric alcohol interfere with the solution of 10 parts by weight sorbitol 4.5 weight.h. water and 0.5 weight.h. specified in example 5 emulsifier. Sorbitol falls out finely dispersed. The dispersion, which is extremely stable during storage, has 4 ~ 24 hours after preparation, according to a differential thermal analysis, with a critical point of 50 BO ° C, increasing over 5 days before. Example 8. A mixture consisting of. 75.0 weight.h. specified in the example of polyoxyalkylene and 25.0 parts by weight sorbitol.24 hours treated at room temperature in a ball mill equipped with steel balls. A stable dispersion is obtained, having a viscosity of 8000 cP at 25 ° C. The melting point of the dispersed phase corresponds to 94 ° C. Example 9. A b-fold amount of a mixture consisting of 94.0 parts by weight. specified in example 1 polyoxyalkylene, 8.0 parts by weight obtained dispersion analogously to Example 8, 3.0 parts by weight water, 2.0 parts by weight triethanolamine, 0.6 weight.h. triethylenediamine, 0.4 weight.h. dimethylethanolamine ,. 1.0 sec.ch. methylphenylsiloxane of the general structural formula CbHs (CHj) $ i-0-ilCHj),. 0 & HCH3) is stirred vigorously with 54.5 parts by weight. specified in example 4 yoliisocyanate and subjected to the interaction in pre-heated to 45c metal form with a capacity of 20 liters An open-cell foam has the following mechanical properties: Density, g / l 46.0 Hardness at 25% deformation under compression, gf / cm-41.0 Hardness at 65% deformation under compression, tf / cm 110.0 Factor Sac., 2 , 7 Pressure drop 75%},% 9.7 Breaking elongation,% 90.0 Tensile strength, kgf / cm .1.7 Elasticity by rebound,% 61.0 Example (control. A) Mixture of reduced composition, but without the addition of the bridge former is reacted with 48.3 parts by weight. described in example 4 of the polyisocyanate as described in metal form. An open-cell foam is obtained with the following mechanical properties: Density, g / l40.6 Hardness at 25% deformation under compression, gf / cm 25.0 Hardness at 65% deformation under compression, HS / cm 67.0 Factor Sat. 2.7 Pressure drop C75%),% 7 Explosive elongation,% 110 Strength of rupture, kgf / cm; 1.5 Elasticity by rebound,% 67 b) A mixture of a given composition, but without the addition of a bridge former, but with the addition of an additional 2.0 weight, h. glycerol, subjected to Wet action with 54.5 parts by weight. the above polyisocyanate in a pre-heated to 45 ° C metal form using the above method. Formed foam with closed cells, bursting at the opening of the form due to the large internal pressure. EXAMPLE 10 7-fold amount of a mixture consisting of 95.2 Ae. specified in example 1 polyhydric alcohol, 8.0 weight.h. obtained analogously to example 8, a dispersion containing, wt%: sucrose 16.7; sorbitol 7.8; water 15.0 in polyoxyalkylene; 60.5; containing 91.0% by weight of propylene oxide and 9.0% by weight,% of ethylene oxide and having 46 OH groups, 1.6 gee.ch. water, 2.0 parts by weight triethanol amine, 0.8 weight.h. triethylenediamine, 0.3 weight.h. dimethylethanolamine, 0.4 weight.h. Methylphenylsiloxane structural formula of Example 9 Sv trade, for example, under the name DD 3043, 10.00 weight parts. trichlorofluoromethane, subjected to interaction with 50.2 weight.h. mixtures.60 wt.% toluene diisocyanate (80% 2.4 and 20% 2, .6.-isomeric mixture and 40 wt.% syrugo diphenylmethandium cyocyanate in a preheated 40 ° C form, a layer of epoxy resin, with a capacity of 24 liters. Foam is obtained with open cells of a bulk weight of 41.2 g / l. Its hardness at 40% deformation under compression is 42% higher than the foam produced, but without adding a bridge former and thus adding only 44.5 ve. isocyanate mixture. If, instead of the bridging agent, add another 2.6 parts by weight of triethanolamine in the above formula, Formed to obtain flexible polyurethane foams by the interaction of polyether polyols containing active hydrogen atoms with an equivalent weight of hydroxyl groups from 700 to 500, polyisocyanates, water, catalysts and cross-linking agents, in order to obtain polyurethane foams with a cellular structure and reduced shrinkage, compounds selected from the group containing sorbitol are used as crosslinking agents , tri- or hexamethylol melamines, glucose and its derivatives or erythritol, which are used as crystalline powder dispersed in polyols, in an amount of from 0.1 to 5.0 equivalent weight of hydroxy groups per equivalent weight of hydroxy groups of expandable polyether-polyol, and the process of interaction wire t at a temperature of 60-160OG. Sources of information taken into account in the examination 1. Patent of England No. 1296981, cl. C 3 R, 1972 (prototype).
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    同族专利:
    公开号 | 公开日
    DE2507161A1|1975-10-16|
    FR2266711A1|1975-10-31|
    NL7504127A|1975-10-10|
    BE827272A|1975-07-16|
    DD116847A5|1975-12-12|
    NL168531B|1981-11-16|
    CH586723A5|1977-04-15|
    JPS5344192B2|1978-11-27|
    NL168531C|1982-04-16|
    FR2266711B1|1979-06-15|
    ATA261075A|1977-03-15|
    SE411762B|1980-02-04|
    AU7907875A|1976-09-16|
    IT1035208B|1979-10-20|
    SE7503834L|1975-10-09|
    US4211849A|1980-07-08|
    DE2507161C3|1981-10-22|
    AT340148B|1977-11-25|
    CA1074048A|1980-03-18|
    DE2507161B2|1980-09-11|
    GB1506771A|1978-04-12|
    JPS50145494A|1975-11-21|
    ZA752233B|1976-03-31|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH489474A|CH586723A5|1974-04-08|1974-04-08|
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