Internal anti-adhesion lubricant for moulding polyurethane products, polyol composition for moulding
专利摘要:
Internal mold release compositions suitable for use in preparing polyurethane and polyurea moldings comprise a tertiary amine compound, a metal salt of a carboxylic acid, amidocarboxylic acid, phosphorus-containing acid or boron-containing acid. The metal is from Group IA, IB, IIA, or IIB metal or aluminum, chromium, molybdenum, iron, cobalt, nickel, tin, lead, antimony or bismuth. 公开号:SU1741605A3 申请号:SU864027321 申请日:1986-04-16 公开日:1992-06-15 发明作者:Л.Нэльсон Дональд;Дж.Матиджега Рони;П.Миллер Деннис 申请人:Дзе Дау Кемикал Компани (Фирма); IPC主号:
专利说明:
obtained by coating the surface of these forms with a special agent that facilitates the separation of the product from the walls of the form. However, anti-adhesive lubricants intended for external use tend to adhere to the surface of the molded (molded) product when removing the finished product from the mold, thereby necessitating re-coating the inner surface of the mold for molding or pouring the specified agent after each use of the mold. When using external anti-adhesive lubricant it is very important to ensure uniform coverage of the entire surface of the mold in order to prevent the molded ( th) of the article some part to the mold surface. All this leads to a significant cost increase and to the cost of time during the processes of molding (pouring) products from polyurethanes. In addition, accumulation of an external anti-gelling lubricant occurs, since the mold for molding (pouring) is reused. These accumulations cover the parts on the surface of the mold that are in contact with the moldable (molded) product. If these accumulations are significant, they can lead to a change in the size of the molded (molded) product. Therefore, periodically it is necessary to clean the surface of the mold, which leads to waste of time. The use of too large amounts of external anti-adhesive lubricants can lead to undesirable effects on the polymers, since solvents are contained in compositions intended for use as external anti-adhesive lubricants. The use of spraying technology on the surface of the form of external anti-adhesive lubricants, especially those that contain a solvent, poses a risk of environmental pollution and / or problems of hygienic nature. It is known to use external, liquid anti-adhesive lubricants in the process of molding articles from polyurethane .- five 0 five When using such external anti-adhesive lubricants, there are numerous seeps or deformations of the surface of the molded (molded) product, thereby deteriorating the ability of the product to be painted. Other external anti-adhesive lubricants are incompatible with polyols used in the molding (casting) of polyurethane products. Many of these external release agents lubricants reduce the activity of the catalysts used in the reaction mixture. In many cases, the physicomechanical properties of polyurethane products obtained by molding (casting) are reduced. An external anti-adhesion lubricant, containing the primary or secondary amine and the metal salt of certain acids, is also known. However, this lubricant is often too reactive due to the presence of primary and secondary amines o ; The purpose of the invention is to simplify the molding process. The internal anti-adhesion lubricant (BAC) provides an effective reduction in the adhesion of the molded (molded) polyurethane to the walls of the mold cavity in which the product is molded. The proposed BAC contains a metal salt of an organic acid, as well as a tertiary amine compound, which is a substance that provides compatibility for the metal salt, which is in a mixture containing active hydrogen, but which does not cause significant compatibility with the metal salt in the reaction mixture containing the active hydrogen-containing composition and polyisocyanate, and contains a sufficient amount of tertiary amine in order to combine the metal salt in the active hydrogen-containing position. Compatibility is achieved when the mixture is dissolved or suspended in an active hydrogen-containing composition for a period of time long enough to ensure its reaction with polyiso 0 five 0 five cyanate. The inability of the tertiary amine to ensure the compatibility of the metal salt in the reactive hydrogen-containing mixture is confirmed by a reduction in the time and effort required to remove the product from the mold. In order to speed up and facilitate the process of mixing the internal anti-adhesive lubricant with the polyol and /., / Or the polyisocyanato to form polyurethanes of other similar polymers, a concentrate is prepared in which the internal anti-adhesive lubricant undergoes dissolution or dispersion in a certain portion of the polyol at a concentration value, which is higher than the above. Such a concentrate preferably contains S- tO wt.% (Preferably), 10 to 25 wt.% Of the metal salt and the tertiary amine compound in an amount that ensures compatibility, which are dissolved or dispersed in a suitable polyol for these purposes. The concentrate thus obtained is diluted using an additional amount of polyol to obtain a resultant active hydrogen-containing composition suitable for carrying out a reaction with a polyisocyanate. The concentrate may contain a frothing agent (trichlorofluoroamide en, water). Preferably, the polyol and additional additives do not contain primary or secondary amines or contain them in amounts less than necessary to ensure the compatibility of metal salts and polyol o The polyol composition containing the proposed internal anti-adhesive lubricant is produced by mixing a tertiary amine compound, a metal salt and other components. The mixing is performed at the melting point temperature of one of these components. For many metal salts, this process needs to be carried out at a higher temperature, i.e., about 0 — it is necessary for mixing the tertiary amine and the metal salt because of the high melting point of the metal salt. In addition, internal anti-adhesive lubricant can be produced by mixing the tertiary amine, a metal salt in the presence of a polyol, a polyisocyanate or 0 five 0 in the presence of a reaction mixture consisting of a polyol and isocyanate. In addition to the tertiary amine compound and metal salt, the internal anti-adhesion lubricant may contain carboxylic, amidocarboxylic, phosphorus-containing or boron-containing acid in an amount of 0.1-1.0% by weight of the metal salt. The use of such acids often has a positive effect. Polyols used include polyether polyols, polyester polyols, phosphorus compounds containing polyhydroxyl, hydroxyl-terminated ester resins, hydroxyl-terminated amines, hydroxyl-terminated polyamides, as well as the corresponding amine-terminated polyether and / or polyester polyols, as well as so-called polymeric and copolymer polyols, which contain S dispersion of the added polymers as a copolymer in the continuous full-phase phase. The proposed polyol composition can be obtained by adding the proposed internal anti-helium lubricant to an active hydrogen-containing compound suitable for this purpose. The components of the polyol composition can be pre-treated. Extra mixing or added separately to the polyol to form a polyol composition. The concentrate can also be used in the preparation of such a composition. The polyol composition is reacted with a polyisocyanate in a mold for molding or casting, resulting in a molded or molded product from a polymer, As polyisocyanates can be applied organic aromatic polyeiocyanate, aliphatic polyisocyanates or mixtures of these compounds, As an aromatic polyisocyanate, a polyisocyanate containing two or more NCO groups per molecule can be used, such as, for example, 2, -toluene diisocyanate, 2,6-toluene diisocyanate-, para, para, para - diphenylmethane diisodioate, naphthalene diisocyanate, para0 five 0 five 0 five Lenine diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl isocyanates, and mixtures of these compounds. Suitable organic aromatic and / or aliphatic polyesocyanates are isocyanate-containing prepolymers derived from polyisocyanates and compounds containing two or more active hydrogen atoms, as well as such polyisocyanates and / or prepolymers that have been modified in such a way that contain uretonimine or carbodiimide bonds Organic poly aliphatic isocyanate include, in addition to the hydrogenated derivatives of the above organic aromatic polyisocyanates, such compounds as 1,6-hexamethylene diizotsmanat, isophorone diisocyanate, 1, d sildiizotsianat cyclohexane, 1, -bis-isocyanomethyl cyclohexane, and also mixtures consisting of the indicated compounds Suitable polyisothiocyanates are also suitable. Polyurethanes can be obtained with or without the use of a catalyst. As catalysts, for example, organometallic compounds, tertiary amine compounds, alkali metal alkylates, or mixtures of these compounds can be used. Suitable organometallic catalysts include, for example, organometallic compounds containing tin, zinc, lead, cadmium, bismuth, antimony, iron, manganese, cobalt, copper, vanadium, as well as metal salts of carboxylic acids containing 2-20 carbon atoms, inclusive, for example, tin tetravalent octoate, dimethyl / tin dilaurate, dibutyl tin dilaurate, dibutyl tin diacetate, tin divalent acetyl acetonate, lead octoate, phenyl mercuric propionate, lead naphthenate, manganese naphthenate, sodium naphthene, sodium acetate, naphthenyl naphthenate, lead naphthenate, manganese oil, naphthene naphthenate, sodium naphthene, naphthene naphthenate, naphthenate propylene, mercury naphtha a, cobalt octoate, cobalt acetate, copper oleate, vanadium pentoxide, or mixtures thereof ,, Suitable amine catalysts include, for example, triethylenediamine, triethylamine, tetramethyl butane diamine, M, M-dimethyl ethanol amine, N-ethyl morpholine, bis- (2-dimethylamino 0 five 0 five 0 five O five otyl) ether, M-methylmorpholine, N-ethylpiperidine, 1,3-bis- (dimethyl-amino) -2-propanol, N, N, N, N, -tetramethylethylenediamine or mixtures indicated / compounds, Suitable alkali metal alcohols include such compounds that can be used as catalysts for urethane formation reactions and which are, for example, sodium ethoxide, potassium ethoxide, sodium propyl, potassium propyl, sodium butylate, potassium butylate, lithium tilate, lithium propyl, lithium butilate, alkali metal salts of polyols 0 Preferably, these urethane catalysts are in liquid form, but if they are solid products at a temperature corresponding to the application temperature, they can be dissolved in a suitable liquid, for example, dipropylene glycol, or they can be dissolved or dispersed in one of the components. The catalysts can be used in amounts of 0.001-2.0, preferably 0.01-1.0 wt., H0 based on the total weight of the polyol used, the amount of catalyst depends on its activity. Very weak catalysts can be used in amounts exceeding 5.0 Maeo per 100 mayoch. polyol. The density of the proposed polymers can be reduced by introducing a gas-forming agent (pore-forming agent) into the composition, for example, water, as well as the so-called azo-forming gas-forming agents and low boiling halogenated hydrocarbons, such as methylene chloride and trichloromethyl fluoride. Density can be reduced by foaming by injecting inert gas into a mixture consisting of urethane and other components forming a polymer. These suitable inert gases include, for example, nitrogen, oxygen, air, carbon dioxide, xenon, helium, and mixtures consisting of the specified gases. Agents that regulate cell size in the structure of a polymer product can be used, such agents are used to make foamed microporous or reduced density products. Polyurethanes and other polymeric products may additionally contain coloring agents, flame retardants, fillers, and modifiers. Components that react to form polymer products can be molded or cast into desired products that have a given shape, by loading the reaction mixture into molding or casting molds that are able to withstand the heating resulting from an exothermic reaction, and which are not they react and are not exposed to solvents when the molds for casting or molding are in contact with the liquid reaction mixture. Particularly suitable are molds made from aluminum, copper, bronze or steel. In some cases, molds for casting or molding, made from non-metallic materials such as polyethylene, polypropylene, polyethylene terephthalate, or silicone elastomers, or epoxy can be used. compositions. Although in accordance with the invention, molds for casting or molding from uncoated metal can be used, it is often desirable when preparing a series of parts produced by casting or molding, to mold the mold with an external release agent such as wax or soap. Such an external anti-hedge lubricant is usually used before the manufacture of the very first product in such form, and sometimes also in the manufacture of the subsequent one or two products. After casting or molding the first two products, an external anti-adhesive agent can be applied periodically, i.e. after every 10 to 100 products. However, in many cases it is possible to remove the articles from the injection mold even when an external anti-adhesive lubricant is not used. The present invention is particularly suitable for processes of the so-called injection reaction mold 7416051 ° vanilla, injection molding, injection molding (RIH). In cases where relatively , the rapidly hardening mixture is introduced into massive metal molds, to ensure good characteristics of the outer surface of the molded or molded products, to produce preheated molds at appropriate temperatures so that the mold does not take the heat of polymerization from the reaction mass and thus does not occur 15 would delay the curing of the reaction mixture in the injection mold. On the other hand, in the event that the mold for casting or molding will have thin walls (when the mold is made of metal), this will lead to a minimal effect of thermal settling on the relatively large cross-section of the body and thus thin metal-shaped walls can Do not require preheating. After the polyurethane has sufficiently cured, which ensures the stability of the specified dimensions of the product, this product is removed from the mold. The force and / or time required for extraction is less than in cases where no internal anti-adhesive lubricant is used. The form does not require processing before manufacturing the following products. In some cases, when the production of a series of products begins, it may be necessary to process the mold with an external anti-adhesive lubricant composition to obtain the first product or several first products. Example t. Polyol compositions 1 and 2 were obtained by mixing together the components indicated in the table. one thirty 35 40 45 Polyol A is a triol resulting from the reaction 50 between the glycerol initiator and the mixture consisting of propylene oxide (PO) and ethylene oxide (EO) in a ratio of 92: 8, resulting in a polymer having a mass of 55 3000, I VL-2 is a catalyst - mrccaptool represented by Wicco chemical Corp .. 1117 VL-28 is a catalyst — dimethyl tin dilaurate manufactured by Witco chemical Copr, Tertiary amine A4 is an aminoethyl ethanolamine initiated poly (propylene oxide), with a molar mass of 278 ° The tertiary amine B is a polyol obtained by condensation of ethylene diamine with 5f5 mol of propylene oxide to obtain a polymer with an equivalent weight of 89. In both compositions 1 and 2, zinc stearate is dissolved in the presence of a tertiary amine, Each of compositions 1 and 2 is subjected to reaction with a polymeric polyisocyanate at index 103 using the reaction casting facility under pressure of the Accuratio VRNI-6G type, which allows the manufacture of molded (molded) sheets of the size mm , are obtained using the substrate on the oh-juve of wax deposited on the surface of the mold. The number of successively made products that were separated from the walls of the form is shown in Table 2. Table 2 also presents the characteristics of the products obtained by molding (casting). As can be seen from the data in Table 2, the inclusion of the proposed internal anti-adhesion lubricant in a polyol composition (composition containing active hydrogen) provides excellent characteristics of extractability of articles from injection molds and good physical properties of polyurethane polymers obtained as a result. EXAMPLE 2 Polyol compositions 3 through 5 are prepared by mixing the components indicated in Table 3. Polyol A- is a triol obtained in the reaction between the glycerol initiator and the mixture consisting of propylene oxide (PO) and ethylene oxide (EO) in a ratio of 92: 8, to obtain a polyurethane with a molar mass of 3000 ° Ethoxylated glycerin - triol having a mass five 12 Polyol B is a glycerinated propylene oxide with mol. weighing 255 " The flame retardant is a chlorinated phosphate ester, is a mercapto-tin. VL-28 is dimethyl tin dilaurate. Each of compositions 3-5 is subjected to reaction with a polymeric polyisocyanate and molded (cast) according to the procedure specified in example 1 „The number of successively produced extracts of products from the mold and the physical properties of the polymeric products thus obtained are presented in the table. Primer3 In accordance with this example, various compositions containing polyols, analogous compositions 1 in example 1, are obtained. thirty 35 45 SO 55 except that in a composition containing lithium stearate, 1 a stable dispersion of salt in a polyolve is obtained. To study the effect of the internal anti-adhesion lubricant on the reactivity of the polyethylene composition, each of these compositions is mixed with the polymer polyisocyanate described in Example 1, at index 103, the casting is done manually in an aluminum form. As a result, a product of the size mmo is obtained. The time required for the gelation of the mixture is given in Table 5 All polymeric products manufactured in this way to separated from the surface of the mold is provided with re easy separation of these products from the mold surface. The results presented in Table 5 show that the use of an internal anti-adhesive lubricant composition avoids undesirably rapid reactions in the form. EXAMPLE 4 A polyol composition 10 is prepared using the following components, wt. Polyol C9 Ethylene glycol 5 Diethylene glycol 1 Triisopropanolamine 10 Zinc laurate 2 In this composition, polyol C is glycerolinated primary hydroxyl - capped poly () propylene oxide / triol The polyol composition is obtained by mixing an amine and zinc laurate at 80-110 ° C and mixing the mixture thus obtained with the other components at room temperature. The result is a homogeneous mixture. Example 5. By 93 May. including polyol L, representing glycerinization propylene oxide with mol. by weight , 900 add 7 mph. tertiary amine on A: The mixture thus obtained is heated to 80-100 ° C with stirring and then 3 mAh of zinc dilaurate is added. The mixture is stirred until it becomes homogeneous, and then it is cooled. Next, 5 may be added to this mixture, h, 15% carbon dispersion in its pure form, in polyol D, May, h, ethylene glycol, 2 wt. . polyethylene glycol with a molar mass of 2000, 0.65 wt. "Cho" of a 33% aqueous solution of a triethylenediamine catalyst in a glycol carrier, and on May 15 "h of Freon-11", Next, to 100 ppm, the mixture thus obtained was added 35.2 May. including polyisocyanate. The mixture thus obtained is vigorously stirred and introduced into a mold made of uncoated aluminum, of a size of mm, which is preheated to 3. The reaction mixture is heated to 3 ° C in the form, and then removed from the mold. The product has a microporous structure with a total film thickness of 4.8 mm, I For example, K 95, polyol E, which is a glycerol-i-initiating-uroxy primary polypropylene oxide with a mole weight of 850, is added 6 ppm of a tertiary amine C, ten 15 20 25 ether, 2.5 May, h, water and 0.5 May, h, of a solution of a triethylene diamine amine catalyst. Various molded (molded) mm-sized products are obtained by a reaction between portions of the composition thus obtained, containing active hydrogen, using polymethylene polyphenylene. isocyanate with indices 98, The reaction is carried out in a mold made of uncoated aluminum metal for k min at 5 ° C. All parts are easily removed from the mold and have good physical properties. EXAMPLE 7 A polyol composition was prepared consisting of the following components, by weight, Polyol D100 Tertiary Amine C8 Laurat zinc Ethylene glycol4 Freon 11 (trichlorofluoromethane) 15 Triethylenediamine 0.15 Polyol D and tertiary amine C are mixed, heated and stirred. Overhead, zinc is ingested to form a homogeneous dispersion. The remaining components are then mixed. The polyol composition is subjected to reaction with a polyisocyanate with an index of 100 in a form made from uncoated aluminum, for k min at 3 ° С Made from such a composition, the products are easily removed from the mold Example 3 A polyol composition is prepared by mixing 30 wt. H of the tertiary amine A, 35 wt.h about dibromoneopentyl glycol and 2 wt.h. zinc dilaurate at 95 ° C in a nitrogen atmosphere. The solution thus obtained is cooled to 65 ° C, added on 5 May, h. polyol E, May 10, h diethylene glycol and 20 wt0h neutral phosphorous (containing three 45 propylene oxide. The mixture thus obtained is heated to 80 ° C. which is the reaction product of the "valence phosphorus) polyol, a stable mixture is obtained as a result of aminoethyl piperazine and 6 mol tate. May 1, h, surfactant, wt, h, polyol with amine end groups with a mol, weighing about 00 are added in order to impart cohesive strength to the molded (cast) product m. The resulting Polyol composition then 3 wt. h of zinc laurate is admixed to it. After obtaining a homogeneous dispersion, this mixture is cooled and added to it on 20 May, h. dispersion consisting of styrene / acrylonitrile polymer in a polySS simple polyol subjected to molding (casting) on 0 five 0 five ether, 2.5 May, h, water and 0.5 May, h, solution of triethylenediamine catalyst. Various molded (molded) mm-sized products are obtained by reacting between portions of the thus-obtained composition containing active hydrogen using polymethylene polyphenylene isocyanate with indices of 98. The reaction is carried out in an injection mold made of uncoated metallic aluminum for k min at 5 ° C. All parts are easily removed from the mold and have good physical properties. EXAMPLE 7 A polyol composition was prepared consisting of the following components, by weight, Polyol D100 Tertiary Amine C8 Laurat zinc Ethylene glycol4 Freon 11 (trichlorofluoromethane) 15 Triethylenediamine 0.15 Polyol D and tertiary amine C are mixed, heated and stirred. Zinc is concentrated in order to form a homogeneous dispersion. Then the remaining components are mixed. The polyol composition is subjected to reaction with a polyisocyanate with an index of 100 in a form made from uncoated aluminum, for k min at 3 ° С Made from such a composition, the products are easily removed from the mold Example 3 A polyol composition is prepared by mixing 30 wt. H of the tertiary amine A, 35 wt.h about dibromoneopentyl glycol and 2 wt.h. zinc dilaurate at 95 ° C in a nitrogen atmosphere. The solution thus obtained is cooled to 65 ° C, added on 5 May, h. polyol E, May 10, h diethylene glycol and 20 wt0h neutral phosphorous (containing three five SS The resulting polyol composition subjected to molding (casting) on 15, Accuracio VRHT-60 injection molding machine at an index of 1.03 using polyisocyanate. Mold temperature 57 - 66 ° C. Molding time (pour) 2 min. A casting mold of mm size was applied. After 13 consecutive light extracts that were easy, the All ceases experience. molded (molded) products have good physical properties.
权利要求:
Claims (1) [1] 1. Internal anti-adhesion lubricant for forming polyurethane products, including metal salts and a modifying agent, about 30 and 30 forgiveness of the molding process, as a metal salt, it contains a compound selected from the group including zinc stearate, zinc laurate, zinc ilaurate, calcium stearate, 25 cadmium stearate and lithium stearate, and as a modifying agent a compound selected from the group including Aminoethyl-tanblamin-initiated polypropylene oxide with ol.m. 27, the reaction product of ethylenediamine with propylene oxide at the rate of 5.5 mol of propylene oxide per 1 mol of hydrogen with an equivalent weight of 89 is the reaction product of 1 mol of aminoethylpyperazine with 6 mol of propylenoxoxide or 35 triisopropanolamine in the following ratio of lubricant components, gcho & o f% Metal salt 6, 40 Modifying additive50, 2, A polyol composition for molding a polyurethane product, including a polyol or a mixture of polyols 45 and a catalyst, which, in order to simplify the process of molding products, it additionally contains an internal anti-adhesive lubricant of the composition: metal salt 50 is selected from the group consisting of zinc stearate, zinc laurate, zinc dilaurate, calcium stearate, cadmium stearate and lithium stearate, and a modifying additive — a compound selected from the group comprising aminoethyl ethanolamine-initiated polypropylene oxide mol. . 278; product sixteen 0 S 0 of ethylene diamine and propylene oxide condensation at the rate of 5.5 mol of propylene oxide per 1 mol of hydrogen with an equivalent weight of 89, the reaction product of 1 mol of aminoethylpiperazine with 6 mol of propylene oxide and triisopropanolamine with a ratio of lubricant components | ME with Metal salt. 6.2-50.0 Modifying add 50,0-93,8 in the following ratio of components of the polyol composition, ma.ch .: Polyol or mixture polyols Catalyst Internal release agent specified composition 90-YO 0.06-0.50 9-32 0 5 5 0 5 0 5 3 ° The method of molding articles from polyurethane by mixing the isocyanate component and the polyol component with subsequent loading into the mold and heat treatment, characterized in that, in order to simplify the molding process, the composition of the composition is used as a polyol component, wt .: Polyol or mixture of polyols. . Catalyst 0.06-0.50 Internal anti-lubricant lubricant composition: metal salt selected from the group including zinc stearate, zinc laurate, zinc dilaurate, calcium stearate, cadmium stearate and lithium stearate, and a modifying additive — a compound selected from the group that includes aminoethylethanolamine-initiated polypropylene oxide with mol.m., the condensation product - ethylene diamine with propylene oxide based on the mole of propylene oxide per 1. mole of hydrogen with an equivalent weight of 89, the reaction product 17 1 mol of aminoethylpiprazine with 6 mol of propylene oxide and triisopropanolamine, taken at a ratio of components ,18 grease, masd: metal salt 6.2 - 50; modifying additive 50.0 - 93.8 9-32 Thermal deformation temperature, ° С at 455 kPa Table 1 Table 2 t55 Id 4 nineteen four at 1.82 MPa The number of consecutive extraction form In accordance with ASTM D-790 methodology “In accordance with ASTM D-638. 50 trials stopped after 15 consecutive extraction from the mold Spreadsheets Polyol Ethoxylated glycerin 50 Polyol B50 Trimethylolpropane Diethylene glycol 10 10 Dibromoneopentyl glycol 35 35 Moderator burning 10 10 Zinc Stearate 55 Tertiary $ min A 5 5 VL-240.03 0.03 VL-280.03 0.03 20 Continuation of table 2 I 90 71 Over 15 Over 15 Indicators Density, g / cm 1.20 Strength on bending, MPa Not determined - 84.1 120.7 lena Flexural modulus, MPa Strength at stretching g, MPa Heat distortion temperature, ° С, at 1.82 IPa Impact strength according to Gardne-RU (impact viscosity — impact strength), m / kg 0.35 0.29 0.46 The number of consecutively extracted products from the form4 Over 10 Over 10 Over 50 In accordance with ASTM D-790. In accordance with ASTM D-638, in accordance with ASTM D-648. 0pyt was terminated after performing the specified number of product extraction from the mold without any damage to the product during the extraction. .one: Table Composition - I Composition - I Composition 3 qi I q 5 M5 M5 1,379 1,965 2, sic Undefined Undefined 64.1 linen is divided 93 Not determined 10 23 .1741605Ј Table Composition No. Metal salt (Processing time (vani gel, s 1 Zinc Stearate, 5 6Dilaurate zinc13.0 7Cal-15.0 qi stearate 8Cadmium Stearate 15.0 9 Lithium stearate 26.0
类似技术:
公开号 | 公开日 | 专利标题 SU1741605A3|1992-06-15|Internal anti-adhesion lubricant for moulding polyurethane products, polyol composition for moulding polyurethane products, and method of moulding polyurethane products EP0033498B1|1985-05-08|A process for preparing reaction injection molded polyurethane compositions employing aliphatic amine chain extenders SE447658B|1986-12-01|AMIN-MODIFIED POLYURETHANELASTOMER US4895879A|1990-01-23|Internal mold release compositions KR950009757B1|1995-08-28|Elastomer and process for production thereof US4518521A|1985-05-21|Homogeneous, storage-stable polyol compositions of high ethylene glycol content and their use for the production of polyurethanes JPH05239170A|1993-09-17|Reaction system for preparing polyurethane/polyurea EP0007484B1|1983-01-12|Process for the preparation of a polyurethane from an organic polyisocyanate or polyisothiocyanate and three different active hydrogen atom containing compounds EP0027498A2|1981-04-29|Rigid, non-cellular urethane polymer composition modified with reaction product of an isocyanate and an alcohol and a process for producing it US3492251A|1970-01-27|Polyurethane foams prepared from a mixture of toluene diisocyanate and polyphenylmethylene polyisocyanate EP0305678B1|1997-08-20|Polyurea foams made from N-|-N-|amines US4086214A|1978-04-25|Process for preparing poly| polyurethanes JP4352850B2|2009-10-28|Polyurethane resin production catalyst composition and polyurethane resin production method US3277027A|1966-10-04|Polyurethane plastics prepared from a nitrogen containing polyol US3936483A|1976-02-03|Organic polyisocyanates EP0445614A2|1991-09-11|Process for the production of molded products using internal mold release agents JPH06256450A|1994-09-13|Catalyst system useful for srim method US10767009B2|2020-09-08|Process for preparing polyether polyol using DMC catalyst and continuous addition of starter KR900001329B1|1990-03-08|Internal mold release composition EP0500214B1|1996-02-28|Process for preparing foams AU615783B2|1991-10-10|Polyurethane/urea foams from isocyanate prepolymers and isocyanate reactive imino/enamino functional reactants US11225550B2|2022-01-18|Polyurethane product with sulfur-containing polyester polyol EP3919537A1|2021-12-08|Method for preparing a rigid polyurethane foam US3156658A|1964-11-10|Preparation of urethanes using polycyclic polyamine catalysts CN111630080A|2020-09-04|Polyisocyanurate comprising foams with long cream time and fast curing behaviour
同族专利:
公开号 | 公开日 DE3580352D1|1990-12-06| JP2703180B2|1998-01-26| BR8506890A|1986-12-09| JPH0770429A|1995-03-14| JPH0798853B2|1995-10-25| ES8703904A1|1987-03-01| AU4726685A|1986-03-07| JPH054406B2|1993-01-20| ES546211A0|1987-03-01| EP0190317B1|1990-10-31| ZA856202B|1987-03-25| CA1269775A|1990-05-29| WO1986001215A1|1986-02-27| CS269971B2|1990-05-14| JPS61501575A|1986-07-31| EP0190317A4|1987-01-10| AU565357B2|1987-09-10| AR240332A1|1990-03-30| US4585803A|1986-04-29| JPH0388845A|1991-04-15| CS592085A2|1989-09-12| EP0190317A1|1986-08-13|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题 CA739028A|1966-07-19|R. Dempsey Jay|Rotational casting compositions and process| US3262889A|1962-02-27|1966-07-26|M & T Chemicals Inc|Liquid anhydrous stannous soap compositions| US3767743A|1972-01-12|1973-10-23|Quaker Oats Co|Method for preparing microcellular polyurethane elastomers with integral skins using a combination of tertiary amine organomercury compound and organolead as catalyst| US4038088A|1975-03-10|1977-07-26|The Goodyear Tire & Rubber Company|Mold release agent| JPS5650917A|1979-09-28|1981-05-08|Mooney Chemicals|Polyurethane composition and tis manufacture| US4263411A|1978-10-30|1981-04-21|Mooney Chemicals, Inc.|Polyurethane compositions and process for preparing polyurethane emitting reduced amounts of toxic fumes on burning using a cobalt, copper, nickel or manganese salt| DE3147736A1|1981-12-02|1983-06-09|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING ELASTIC MOLDED BODIES| JPS6352056B2|1983-02-16|1988-10-17|Dow Chemical Co| US4431753A|1983-05-13|1984-02-14|Abbott Laboratories|Catalyst blend containing 1,2-dimethylimidazole| US4519965A|1984-08-23|1985-05-28|Mobay Chemical Corporation|Internal mold release agent for use in reaction injection molding|US5051466A|1983-02-16|1991-09-24|The Dow Chemical Company|Internal mold release compositions| US4876019A|1983-02-16|1989-10-24|The Dow Chemical Company|Internal mold release compositions| US5011647A|1983-02-16|1991-04-30|The Dow Chemical Company|Internal mold release compositions| US5008033A|1983-02-16|1991-04-16|The Dow Chemical Company|Internal mold release compositions| US4895879A|1984-08-17|1990-01-23|The Dow Chemical Company|Internal mold release compositions| US4519965A|1984-08-23|1985-05-28|Mobay Chemical Corporation|Internal mold release agent for use in reaction injection molding| DE3535711A1|1985-10-05|1987-04-09|Basf Ag|METHOD FOR THE PRODUCTION OF CELLED OR COMPACT POLYURETHANE-POLYHURENE MOLDED BODIES WITH IMPROVED DEFLECTING PROPERTIES, AND INNER MOLD RELEASE AGENTS AND THE USE THEREOF FOR THE POLYISOCYANATE POLYAD ADDITION PROCESS| JPS62295916A|1986-06-16|1987-12-23|Mitsui Toatsu Chem Inc|Exceedingly flexible polyurethane elastomer of improved heat resistance| DE3626673A1|1986-08-07|1988-02-11|Bayer Ag|RELEASE COMPOSITION, MIXTURES CONTAINING THIS RELEASE COMPOSITION, A METHOD FOR THE PRODUCTION OF ELASTIC MOLDED BODIES AND THE MOLDED BODIES OBTAINED BY THIS METHOD| DE3627078A1|1986-08-09|1988-02-18|Bayer Ag|METHOD FOR THE PRODUCTION OF MOLDED BODIES BASED ON POLYURETHANE AND / OR POLYURANE AND THE MOLDED BODIES OBTAINED BY THIS METHOD| DE3629630A1|1986-08-30|1988-03-03|Basf Ag|METHOD FOR THE PRODUCTION OF ELASTIC, SUBSTANTIALLY COMPACT, POLYURETHANE MOLDED BODIES WITH IMPROVED DEFORMING PROPERTIES| JPH0338305B2|1986-09-16|1991-06-10|Sumitomo Bayer Urethane Co| DE3631842A1|1986-09-19|1988-03-24|Basf Ag|INNER MOLD RELEASE AGENTS, THE USE THEREOF FOR THE PRODUCTION OF MOLDED BODIES BY THE POLYISOCYANATE POLYADDITIONAL PROCESS AND METHOD FOR THE PRODUCTION OF THE MOLDED BODIES| DE3639502A1|1986-11-20|1988-06-01|Bayer Ag|RELEASE COMPOSITION, MIXTURES CONTAINING THIS RELEASE COMPOSITION, A METHOD FOR THE PRODUCTION OF ELASTIC MOLDED BODIES AND THE MOLDED BODIES CONTAINED BY THIS PROCESS| EP0268906A3|1986-11-26|1988-12-07|The Dow Chemical Company|Compatibilized blends of alpha, omega-alkylene glycols and polyether polyols and process for preparing the same| US4734455A|1986-12-05|1988-03-29|The Dow Chemical Company|Stabilizers for filled polyol compositions| AU602525B2|1986-12-05|1990-10-18|Dow Chemical Company, The|Process for preparing static dissipative linear segmented polyurethanes| JPH0777733B2|1986-12-15|1995-08-23|三井東圧化学株式会社|Cast polymerization method for lenses made of sulfur-containing urethane resin| US4758604A|1987-04-07|1988-07-19|The Dow Chemical Company|Polyurea rim systems having improved processibility| US4758603A|1987-08-28|1988-07-19|The Dow Chemical Company|Dithiocarbamate internal mold release agents| DE3734340A1|1987-10-10|1989-04-27|Bayer Ag|HEAT-CURABLE ADHESIVE SYSTEM AND A METHOD FOR GLUING MATERIALS| GB8807684D0|1988-03-31|1988-05-05|Ici Plc|Internal mould release composition| US4897428A|1988-08-31|1990-01-30|Mobay Corporation|Internal mold release agent for use in molding polyurethanes and/or polyureas| US4886838A|1988-08-31|1989-12-12|Mobay Corporation|Internal mold release agent for use in reaction injection molding| US5019600A|1988-08-31|1991-05-28|Mobay Corporation|Internal mold release agent for use in reaction injection molding| US5002999A|1988-09-07|1991-03-26|Mobay Corporation|Internal mold release agent for use in reaction injection molding| US5211749A|1988-09-12|1993-05-18|Miles Inc.|Internal mold release agent for use in reaction injection molding| US5076989A|1988-09-12|1991-12-31|Mobay Corporation|Internal mold release agent for use in reaction injection molding| US4868224A|1988-10-21|1989-09-19|Mobay Corporation|Process for the production of molded products using internal mold release agents| JPH02302464A|1989-05-16|1990-12-14|Sumitomo Bayer Urethane Kk|Low-viscosity polyol composition containing potassium titanate needle crystal| US5019317A|1989-05-24|1991-05-28|Mobay Corporation|Process for the production of molded products using internal mold release agents| DE3920218A1|1989-06-21|1991-01-03|Gerd Thoene|METHOD FOR PRODUCING A CHIPBOARD AND CHIPBOARD PRODUCED BY THIS METHOD| GB8916573D0|1989-07-20|1989-09-06|Atlas Europol Spa|Internal mould release compositions| US4981877A|1989-08-25|1991-01-01|The Dow Chemical Company|Blends of alkylene glycols and relatively high equivalent weight active hydrogen compounds containing multipurpose additives| US5057543A|1989-08-25|1991-10-15|The Dow Chemical Company|Blends of alkylene glycols and relatively high equivalent weight active hydrogen compounds containing additives| US5070110A|1989-08-25|1991-12-03|The Dow Chemical Company|Blends of alkylene glycols and relatively high equivalent weight active hydrogen compounds containing multipurpose additives| US5135962A|1990-04-06|1992-08-04|Miles Inc.|Internal mold release agent for use in polyurea rim systems| GB9021524D0|1990-10-03|1990-11-14|Ici Plc|Isocyanate reactive blends and internal mould release compositions| BR9105449A|1990-12-11|1992-08-25|Dow Chemical Co|COMPOSITION TO PREPARE A MOLDED FRAMED POLYMERIC ARTICLE AND PROCESS FOR COMPATIBILIZATION OF A RELATIVELY HIGH MOLECULAR WEIGHT| US5160538A|1991-04-22|1992-11-03|Miles Inc.|Internal release agents, active hydrogen containing mixtures which contain such agents and the use thereof in a process for the production of molded products| US5125974A|1991-04-22|1992-06-30|Miles Inc.|Internal mold release agents and the use thereof in the production of molded products| US5125973A|1991-04-22|1992-06-30|Miles Inc.|Internal mold release agents and use thereof in the production of molded products| US5158607A|1991-05-08|1992-10-27|Miles Inc.|Internal release agents, active hydrogen containing mixtures which contain such agents and the use thereof in a process for the production of molded products| DE4122872A1|1991-07-11|1993-01-14|Bayer Ag|MOLDED FOAMS| US5255483A|1991-08-30|1993-10-26|Donnelly Corporation|Squeak resistant panel/window assembly for vehicles| US5212209A|1991-11-18|1993-05-18|The Dow Chemical Company|Compatibilized internal mold release composition for preparations of foamed and fiber-reinforced polymeric articles| GB9125918D0|1991-12-05|1992-02-05|Ici Plc|Reaction system for preparing polyurethane/polyurea| US5453455A|1993-01-25|1995-09-26|Basf Corporation|Rigid polyurethane foams containing lithium salts for energy absorbing applications| US5248703A|1992-03-13|1993-09-28|Basf Corporation|Rigid polyurethane foams containing lithium salts for energy absorbing applications| CA2107950C|1992-10-22|2001-08-14|Bayer Corporation|Stabilization of rim systems containing acidic additives| US5312845A|1992-12-16|1994-05-17|Air Products And Chemicals, Inc.|Rim polyol blends containing acidic siloxane internal mold release agents and tin catalysts| US5358985A|1992-12-16|1994-10-25|Air Products And Chemicals, Inc.|Ionic siloxane as internal mold release agent for polyurethane, polyurethaneurea and polyurea elastomers| US5283311A|1992-12-30|1994-02-01|Basf Corporation|Fatty prepolymers and fatty-modified polyisocyanates as internal mold release agents| US5324759A|1993-01-26|1994-06-28|Air Products And Chemicals, Inc.|RIM polyol blends containing acidic siloxane internal mold release agents and quaternary ammonium phenoxides| US5420186A|1993-01-26|1995-05-30|Air Products And Chemicals, Inc.|Internal mold release agents comprising metallic soaps compatibilized with liquid quaternary ammonium salts| CA2120648C|1993-04-22|2004-06-22|Neil H. Nodelman|Novel catalyst package for use in rim systems containing acidic additives| US5308880A|1993-05-20|1994-05-03|Air Products And Chemicals, Inc.|Tin catalysts for use in rim polyol blends containing acidic internal mold release agents and diethyltoluenediamine chain extender| US5389696A|1993-09-17|1995-02-14|Miles Inc.|Process for the production of molded products using internal mold release agents| US5500176A|1993-09-17|1996-03-19|Bayer Corporation|Process for the production of molded products using internal mold release agents| JPH07233235A|1994-02-24|1995-09-05|Sanyo Chem Ind Ltd|Production of rigid polyurethane foam| US5710231A|1994-04-08|1998-01-20|Imperial Chemical Industries Plc|Isocyanate-reactive compositions containing internal mold release agents| US5529739A|1994-11-15|1996-06-25|Bayer Corporation|Process for the production of molded products using internal mold release agents| US5665288A|1994-12-29|1997-09-09|Basf Corporation|Method of making water-blown polyurethane sealing devices| US5741865A|1995-07-18|1998-04-21|Witco Corporation|Fatty alkly diethanolamines to stabilize the optical clarity of polyols containing zinc fatty acid salts| JP3715014B2|1995-12-25|2005-11-09|日本合成化学工業株式会社|Two-component solventless urethane resin coating agent| US6448364B1|2001-03-16|2002-09-10|Bayer Corporation|IMR having synergistic effect with stabilizing system additives and catalyst package| US6981303B2|2001-07-23|2006-01-03|Honda Giken Kogyo Kabushiki Kaisha|Blank feeding method| US20050131136A1|2003-12-16|2005-06-16|Rosthauser James W.|Soft polyurethaneurea spray elastomers with improved abrasion resistance| US7901762B2|2005-11-23|2011-03-08|Milgard Manufacturing Incorporated|Pultruded component| US8101107B2|2005-11-23|2012-01-24|Milgard Manufacturing Incorporated|Method for producing pultruded components| US7875675B2|2005-11-23|2011-01-25|Milgard Manufacturing Incorporated|Resin for composite structures| US8597016B2|2005-11-23|2013-12-03|Milgard Manufacturing Incorporated|System for producing pultruded components| JP4530987B2|2005-12-28|2010-08-25|三洋化成工業株式会社|Active energy ray-curable urethaneacrylate composition| JP5155018B2|2007-05-31|2013-02-27|三洋化成工業株式会社|Active energy ray-curable resin composition| WO2014172411A1|2013-04-19|2014-10-23|Bayer Materialscience Llc|In mold electronic printed circuit board encapsulation and assembly| JP2016088997A|2014-10-31|2016-05-23|Nok株式会社|Manufacturing method of polyurethane elastomer, polyurethane elastomer, hdd stopper, use of internal mold release agent and polyurethane elastomer raw material| EP3268200A4|2015-03-10|2019-02-20|Peterson Chemical Technology LLC|Low delamination mold release| US20210385937A1|2018-10-09|2021-12-09|Covestro Llc|Insert-molded electronic modules using thermally conductive polycarbonate and molded interlocking features|
法律状态:
优先权:
[返回顶部]
申请号 | 申请日 | 专利标题 US06/641,883|US4585803A|1984-08-17|1984-08-17|Internal mold release compositions| 相关专利
Sulfonates, polymers, resist compositions and patterning process
Washing machine
Washing machine
Device for fixture finishing and tension adjusting of membrane
Structure for Equipping Band in a Plane Cathode Ray Tube
Process for preparation of 7 alpha-carboxyl 9, 11-epoxy steroids and intermediates useful therein an
国家/地区
|