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  • 权利要求
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    • 专利摘要:
    1471091 Polymerisation catalyst: foamed coatings UPJOHN CO 6 Jan 1975 [30 Jan 1974] 419/75 Headings BIE and B2E [Also in Divisions C3 and F4] A catalyst composition for the trimerisation of a polyisocyanate and of use in the formation of cellular isocyanurate polymers comprises (a) 10 to 70 mole % of a tertiary amine isocyanate-trimerisation catalyst; (b) 20 to 80 mole % of an amide salt of formula wherein: M is Li, Na or K; R 1 , R 2 , R 3 are H, C 1 -C 8 alkyl, aryl, aralkyl or cycloalkyl; and R 4 is C 1 -C 8 alkyl or aryl; and (c) 3 to 30 mole % of a dibutyl tin di(alkanoate) wherein the alkanoate residue contains 2 to 12 carbon atoms. Component (a) may be N, N-dimethylethanolamine, -cyclohexylamine, -benzylamine; N, N', N"'-tris(dimethylaminopropyl) hexahydrotriazine; N, N, N', N'-tetramethylpropanediamine or -1, 3-butanediamine; N- methyl-morpholine or N-ethylmorpholine. Component (b) may be potassium N-phenyl- 2-ethylhexamide. Component (c) may be dibutyl tin diacetate, dioctoate, di-2-ethylhexoate or dilaurate. The amide salt may be used as a solution in a diluent, e.g. a mixture of ethylene glycol and dimethylformamide. Cellular isocyanurate polymers produced using the above catalyst composition may be formed in situ as a coating on a substrate by spraying of a mixture of the polyisocyanate, polyol and blowing agent reactants onto the substrate, e.g. building board, gypsum board, asbestos board, wood, sheet metal, paper or cardboard. The Examples disclose the application of foam layers to cardboard, plywood and asbestos board with good adhesion. The resulting materials and thermal insulation uses. Alternatively, a storage vessel may be thermally insulated by coating with the foam polymer, a first layer of optimum insulating composition being applied and then covered with a second protective layer of higher density.
    公开号:SU795491A3
    申请号:SU762355208
    申请日:1976-04-29
    公开日:1981-01-07
    发明作者:Юджин Реймоур(Младший) Гарольд；Карл Зэйн Джон
    申请人:Дзе Апджон Компани (Фирма)；
    IPC主号:
    专利说明:

    (5A) METHOD OF OBTAINING TA FOAMS
    The invention relates to the production of pneumatic materials, in part to the preparation of polyisocyanate foam, which can be used in various industries. A known method for producing foam. polyisocyanurate by trimerization of the isocyanate component in the presence of polyol, blowing agent VII polyol, blowing agent agent and catalyst l. A mixture of epoxide and tertiary amine is used as a catalyst according to a known method. However, when carrying out this method under industrial conditions with a relative difference in the rates of the polymerization reaction and trimerization, the formation of polyurethane often begins before trimerization, which reduces the quality of the foam material. These difficulties are exacerbated if the foaming composition is applied to the surface by sputtering. The foam material results in a fragile non-uniform composition. The purpose of the invention is to obtain penometrial with high fire resistance and at the same time with reduced brittleness. This goal is achieved by using a mixture of 0.005-0.04 eq. on 1 star. isocyanate component of the tertiary amine with 0.001-0.03 equiv. amide salts of the general formula B, lv. -) B, - 1-SvMB4, where M is an alkali metal K B, fi - are the same or different groups, including hydrogen, lower alkyl, aryl, aralkyl, cycloalkyl B / t-lower ashkyl, aryl. c 0.0005-0.005 eq. dibutyltin dialkanoate, in which the alkanoate residue contains 2-12 carbon atoms, and the polyol is taken in an amount of 0.01-0.3 eq. at 1 eq. and isocyanate component. By the term lower alkyl is meant alkyls containing from 1 to 8 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their keomer. By the term aryl is meant phenyl ;, tolyl, xylyl, naphthyl, diphenyl and the like. The term ar-alkyl means benzyl, p-methylbenzyl, p-ethylbenzyl, fb-phenylethyl, naphthyl methyl, etc. The term cycloalkyl refers to cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cyclooctyl, and the like. P. Pyc by the term alkali metal is meant sodium, potassium and lithium. The term alkanoate residue containing 2–12 carbon atoms b. Application of dibutyltin dialkanoate implies acetate, propionate, butyrate, valerate, caproate, anantoate, capriLoat, pelargonate, capriate, gendeyoyat, laurate and their isomers. As already indicated, the need to balance two different reactions, namely those leading to the formation of urethane and isocyanurate when producing polyisodianurates, leads to the importance of the choice of catalyst, especially when preparing systems that are applied by printing. The components of the sonatalyst are brought into mutual contact in the course of the polymerization trimerization reaction or immediately before the reaction. At the optional stage, the tertiary amine and amide salt can be mixed or stored as a mixture, in which case the dibutyl tin dialkanoate is stored separately until used in the trimerization process of the proposed method. The components of the combined catalyst and their concentrations are lower in molecular percentages. Total cyNEvia components 100 mol.%. The concentration of one or more components may vary within certain limits, but their total cyivMa should be 100 mol%. This method of indicating the proportions of the three components of the cocatalyst is suitable for determining the parameters of the cocatalyst itself. However, with particular uses of cocatalyst, for example in the preparation of cellular poly isocyanurate, the amounts of the cocatalyst components are given in absolute values. The tertiary amine component of the combined cocatalyst is advisable to be added to the catalyst in an amount of from about 10 to 95 mol.%, Preferably from 10 to,%. This tertiary amino component can be any tertiary amine known in the art that catalyzes trimerization, including amines, shown on the prototype. Amines are particularly preferred: N, N-dimethyletinolamine, M, M-dimethylcyclohexylamine, N, N-dimethylbenzylamine, N, N, N, N-tetramethyl-1,3-butanediamine, N, N, N, N-tetramethylpropanediamine, N- methylmorpholine, N-ethylmorpholine and N, N, m-tris- (dimethylaminopropyl) hexahydrotriazine. . N, N-dimethylcyclohexylamine is particularly preferred. The amide salt, a component of the combined cocatalyst, is advisable to be added in an amount of about 285 mol% of the cocatalyst, preferably from 20 to 30 mol%. Suitable solvents for this reaction include, for example, low molecular weight polyols, e.g. , P.; cellosolve, butyl cellosolve, carbitol, methylcarbitol, butylcarbitol, etc., ethanolamine, diethanols, triethanolamine} and dipolar aprotic solvents, for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and in the case of the sample, you may be in charge of the sample. The reaction between the salt and the isocyanate proceeds much faster than the reaction between the isocyanate and the hydroxyl-containing solvents; therefore, the retail rate allows the use of the latter as a preferred class of solvents. At an optional stage, the solvent can be distilled off, however, it is advisable to leave the salt as a solution and then use the catalyst in combination with its diluent. By distilling off the solvent, the amide salt can be used in isolated form. Representative salts include, for example, sodium, potassium and lithium acetates, sodium, potassium and lithium propionates, sodium, potassium and lithium capronates, potassium decanoate, 2-methyl potassium capronate, potassium neopentanoate, phenylacetates sodium potassium and lithium potassium | i-phenylphosphate, potassium p-tolylacetate potassium cyclohexylacetate,. Potassium 4-methyl-eiclohexyl acetate, p-cyclohexyl potassium propionate, etc. Typical representatives of the starting organic isocyanate include, for example, butyl eocyanate, octyl isocyanate, phenylazocyanate, tolyl isocyanate, and the like. in combination with a thinner. The diluent may be a solvent, or a mixture of solvents. Particularly preferred class of diluents are ethylene glycol, diethylene glycol, polyethylene glycol 400, mixtures thereof, and mixtures thereof with dimethylformamide. Particularly preferred diluent mixture consists of ethylene glycol and dimethylformamide. The concentration of the amide salt dissolved in diluents is not critical and can vary from 25 to 75 wt.% When using a mixture of diluents, one of them is required in an amount of 10-90 wt. preferably from 25 to 75 wt.%. Tin salt — a component of the combined cocatalyst — is expedient to contribute in an amount of about 145 mol.%, Preferably from 3 to 30 mol.%. This component can be any dialkanoate, dibutyltin, known in the manufacture of foam formations, including dibutylol diacetate, dibutyltin diactate, di (2 ethylhexoate) dibutyltin, dibutyltin dilaurate, preferably dibutyltin diatatate. The polyols used according to the invention for the preparation of polyisocyanurate foams include any polyols indicated by the prototype or any polyols known and useful as a minor component. These polyols can be introduced separately in the process of trimerization of the polyisocyanate component, or they can be preliminarily reacted with polyisocyanate and obtain a prepolymer with terminal isocyanate groups, which is then subjected to trimerization. Polyols, it is advisable to make in the amount of 0.01 to 0.3 eq. on 1 star. isocyanate. Foenivacadium areH-ftj and other optional additives can be used, for example dispersing agents, cell stabilizers, .surfactants, flame retardants, etc. Particularly preferred is the class of additives - flame retardants - phosphorus-containing retardants, for example, tris- (2- chloroethyl) phosphate, tris- (2-chloropropyl) phosphate, tris- (2-dibromopropyl), tris- (1,3th-dichlorisopropyl urophosphate, etc.) Thus, the use of a combined cocatalyst provides the possibility of application by dusting - and heat-resistant polyurethane foam ianurats with a ratio of flCO and OH groups from 1: 1 to 2: 1 and their interval without the need to change the formulation or formulation of the foamed material. To implement the invention, standard foam spraying machines or equipment, such as various types of spray guns, can be used. In accordance with the invention, the foams are well glued to a variety of substrates, including mazonite, building tiles, gypsum tiles, asbestos, wood, plywood, sheet material and paper products, paper Materials such as kraft paper and cardboard. The polyisocyanurate foams obtained according to the inventive method can be applied, in particular, where heat resistance, slow flame spread and slight smoke formation during combustion are required. For example, they can be used as thermal barriers and thermal insulation materials by spraying them onto pipelines exposed to high temperature, furnaces (drying ovens) and tanks for storing liquids at high temperatures. They are also used for the thermal insulation of pipelines and liquid tanks stored at low temperatures. The special form of the spray ratio provides an advantage when spraying a foam material on which an object that needs insulation protection, for example a reservoir for storing a liquid at elevated temperature, sprays the proposed polyisocyanurate foam at a ratio of MCO and He of 1: 1 groups. This gives a cellular foam coating that has an optimal insulating ability. Then, the ratio of pumped components is changed in such a way as to ensure the ratio of MCO and OH groups of 2: 1, and a second more dense layer of cellular foam is applied onto the first layer, which protects the first layer and has more physical strength. The implementation of the invention eliminates the need for recipe changes when it is necessary to change the density of the foam applied by spraying, which is especially convenient when spraying the foam on remote surfaces (areas The resulting thermal and fire resistant foams are particularly suitable because of their ease of application or application in industrial buildings Example: Two foams (applied by spraying), obtained in accordance with the invention, are compared with one of the cocatalyst components missing. t, using a Binsk 4ER spray gun or syringe, equipped with a tip 2640 and a precessor 0.026 inch and two 0.035 Inch mixing nozzles. The A and B components are fed at a pressure of 56.2577, 3 kg / cm at a volume ratio of 1: 1. They are used on cardboard, plywood or panels with good adhesion in all priors. Component A in all experiments (see Table 1) is polymethylene polyenyl isocyanate containing 40% by weight of ethylene bis (phenyl isocyanate), treated with a small amount of monomeric epoxy compound according to the method described by in the prototype. OBTOA (in.%) Loss at
    UG.-
    the resulting polyisocyanate is characterized by an equivalent of isocyanate 135 and an acidity below 0.1%.
    34
    Esterification of 1 mol of chlorendic anhydride with 1.1 mol of diethylene glycol 2.5 mol of propylene oxide.
     Obtained by the esterification of chloroanedic anhydride, 1.1 mol of diethylene glycol and 2.5 mol of propylene oxide.
    5 Measured according to AS TM C421-61.
     Determined by A5 TM p2863-70 (the amount of oxygen required to maintain the sample burning)
    5 Thermogravimetric analysis is carried out using a DuPont model 900 thermal analyzer (model 950 thermogravimetric module used).
    Component B consists of a small amount of a polyol, a surfactant, a blowing agent, and a mixture of catalyst. For foam casings C and D, a combined catalyst of dimethylcyclohexylamine, dibutyltin diacetate, and potassium H-phenyl-2-ethylhexamide with potassium 2-ethylhexoate (a known trimerization catalyst) is used,
    The foam d does not contain hexamide, but a large amount of honest potassium 2-ethylhexoate is added to it to provide time, cream and initiate the same as for B and G. However, a 5-minute cure time of foam D is unacceptable for spraying. . Foams C and D have a high hardening time of fire and heat resistance.
    Component A, g: Polyisocyanate
    Tris- (8-chloroethyl) phosphate Simple polyester i g5340 Simple polyester Z-5310
    Component B, g:
    Polyester
    Polyester (average number 700)
    2
    Getropene -320
    9 Polyol
    Continued table. eleven
    j Example -2. In this example, a Foam E according to the invention and a Foam W are obtained using a catalyst not in accordance with the invention. Both foams are sprayed onto tiles and cardboard at a 2: 1 volume ratio under pressure (components A and B) 73.80 80.9 kg / cm. The E foam exhibits a better compressive stress, and also a better fire resistance — according to the oxygen index and safety test — compared to these 5 foam indicators J. The E and F foams contain the same low acidity polyisocyanate as the polyisocyanate Example 1. E foam obtained from
    0 using the same catalyst as the foams C and D of example 1. The results are shown in Table. 2., ...
    ,Table 2
    134
    15
    30 10
    30 5
    Example 3. Foam 3 and from table. 3 is sprayed at a ratio of components A and B of 1: 1 and 2: 1, using the same formulations as in. previous examples without changing the component, And g: Polnietsianat
    Component B, g: Complex polyester
    Tris- (| b-chloroethyl) phosphate
    Continued table. 2
    nor the concentration of catalyst in component B | but with the adjustment of the ratio of component B, as it follows from the nponoptuif reagents / as shown in Table. 3
    Table 3
    135
    35
    13
    TVA (in wt.% Loss at temperature, C:
    1 See tab. 2 See t abl. one
    With a ratio of 1; 1, the pressure of components A and B, i.e., by which they are supplied) 56:25 kg / cm. At a ratio of 2: 1, the pressure of component A
    权利要求:
    Claims (1)
    [1]
    63.28 kg / cm of component B49, 22kg / cm foam 3 and E have similar properties or lifting characteristics. They have very similar fire and heat resistance, the physical strength of foam 3 is higher than E, which is a consequence of the difference in density between the two materials. Foam formulations use the same epoxy-treated polyisocyanate as in the previous examples. The invention The method of obtaining polyisocyanurate foam by trimerization isocyanate Continuation table. 3
    component in the presence of a polyol, a foaming agent and a catalyst, characterized in that, in order to obtain a foam with high fire resistance and at the same time with reduced brittleness, a mixture of 0.0050, 04 equiv. at 1 eq. isocyanate component of the tertiary amine with 0,0010, 03 EQ. amide salts of general formula
    R v (-).
    RJ-C-CONR4 O- X
     where M is alkali metal
    15 79549116
    EJ ,, B, 8j - the same or different types and polyol is taken in quantity
    groups of water-0.01-0.3 eq. on 1 copy isocyanatrode, lower alkyl, aryl component, aralkyl, cycloalkyl;
    Cd lower alkyl or aryl. Sources of information,
    c, 0005-0.005 eq, dialkanoate. taken into account in the examination
    diolutyl, for which alkanoate 1. US patent 3745133 class. 260bottle contains 2-12 atoms. Coal-2.5, published. 1022.73 (prototype).
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    同族专利:
    公开号 | 公开日
    IT1029393B|1979-03-10|
    JPS50109296A|1975-08-28|
    BE825013A|1975-07-30|
    JPS5242553B2|1977-10-25|
    CA1037648A|1978-08-29|
    US3899443A|1975-08-12|
    DE2502260A1|1975-08-07|
    GB1471091A|1977-04-21|
    DE2502260C3|1982-01-14|
    DD121121A5|1976-07-12|
    AU7692974A|1976-07-01|
    DE2502260B2|1981-05-07|
    DD121118A5|1976-07-12|
    引用文献:
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    NL288184A|1962-03-01|
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    US3732176A|1972-01-12|1973-05-08|Quaker Oats Co|Low resiliency microcellular polyurethane elastomer with integral skin and method for preparation thereof|US4049931A|1975-05-29|1977-09-20|Union Carbide Corporation|Catalyst systems containing dimethylamino ether mono-ols for polyurethane foam formation|
    US4150212A|1976-01-14|1979-04-17|Bayer Aktiengesellschaft|Catalytic process for polyurethane elastomers and foams|
    DE2601082A1|1976-01-14|1977-07-21|Bayer Ag|CATALYSTS FOR ISOCYANATE POLYADDITIONAL REACTIONS|
    DE2830949A1|1978-07-14|1980-01-24|Bayer Ag|NEW PHOSPHONATES AND THEIR USE AS CATALYSTS FOR THE PRODUCTION OF POLYISOCYANURATE PLASTICS|
    US4184022A|1978-09-15|1980-01-15|Owens-Corning Fiberglas Corporation|Polyisocyanurate foam comprising reaction product of a polyisocyanate and a polyol mixture comprising a carboxylic ester polyol and a resole polyether polyol using a catalyst comprising dimethylethanolamine and an alkali metal salt of a carboxylic acid|
    US4189544A|1979-02-21|1980-02-19|The Upjohn Company|Polyisocyanurate polymers prepared using carbamate modifier|
    US4353995A|1979-03-07|1982-10-12|Mobay Chemical Corporation|Novel catalyst system for polyurethane foams|
    US4217247A|1979-03-07|1980-08-12|Mobay Chemical Corporation|Catalyst system for polyurethane foams|
    US4298708A|1979-04-02|1981-11-03|Texaco Development Corp.|Aminated alkoxylated aliphatic alcohol salts as polyisocyanurate catalysts|
    US4243756A|1979-08-27|1981-01-06|Basf Wyandotte Corporation|Stable-liquid isocyanurate-modified polyisocyanate compositions|
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    US4764330A|1983-03-23|1988-08-16|The Dow Chemical Company|Process for the production of organic polyisocyanate-based molded polymers|
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    US20110086217A1|2009-10-12|2011-04-14|Crain Steven P|Spray polyurethane foam for non-covered and non-coated use in structural applications|
    US20130285272A1|2010-09-30|2013-10-31|Dow Global Technologies Llc|Container modifications to minimize defects during reactive polyurethane flow|
    WO2012083038A1|2010-12-16|2012-06-21|Dow Global Technologies Llc|Polyurethane and polyisocyanurate foams|
    CN103764704A|2011-09-02|2014-04-30|陶氏环球技术有限责任公司|Polyurethane rigid foams|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US437781A|US3899443A|1974-01-30|1974-01-30|Novel cocatalyst system for trimerizing polyisocyanates|
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