Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/50—Polyethers having heteroatoms other than oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/50—Polyethers having heteroatoms other than oxygen
  • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
  • C08G18/5054—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
  • C08G18/506—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing two nitrogen atoms in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3271—Hydroxyamines
  • C08G18/3293—Hydroxyamines containing heterocyclic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof

Definitions

• This invention relates to the preparation of rigid polyurethane foams from polyisocyantes.
• U.S. Patent Specification No. 3251787 discloses certain propoxlyated derivatives of N-aminoethylpiperazine (AEP) having a degree of propoxlyation of at least 6 propoxy units per mole. These propoxlyated AEP derivates are described as being useful in the preparation of flexible foam polyurethanes.
• AEP N-aminoethylpiperazine
• U.S. Patent No. 3221016 discloses a propoxylated derivative of aminoethylpiperazine having three propoxy units per molecule. This derivative is described as being useful in preparing a rigid polyurethane foam. (see, specifically, U.S. Patent No. 3251788). However, the described AEP derivative exhibits a significantly high viscosity.
• a method of preparing a rigid polyurethane foam comprises reacting a polyisocyanate with a polyol in the presence of a blowing agent, and preferably a polymerisation catalyst and a surfactant, wherein the polyol has the formula
• R 1 , R 2 , and R 3 are, each independently, hydrogen, a C ⁇ -Cg alkyl group, bearing one or more halogen, hydroxyl, optionally substituted phenyl, optionally substituted cycloalkyl, or optionally substituted phenyl ether substituents, n is 1 or 2, and x + y + z is from 3.5 to 6.
• the polyol (I) When the polyol (I) is included in the polyol content of the starting material for rigid foam production, decreased amounts of polymerisation catalyst are required, and/or reduced foaming (reaction) times are exhibited compared to corresponding systems employing an alk lene amine - initiated polyol in place of the polyol of formula (I). In addition, the resulting product shows a reduced degree of friability.
• polyols of formula (I) exhibit superior processability as compared to the AEP polypols described by U.S.P. No. 3221016, while still maintaining the necessary properties to prepare a rigid polyurethane foam.
• the polyols of Formula I may be prepared easily by the reaction of a compound of the formula
• R is the same as R****, R 2 and R 3 above, with aminoethyl or aminomethylpiperazine.
• the compound of formula (I) may be prepared by initially preparing a pre-polyol in the absence of a catalyst, for example by the techniques set forth in U.S. Patent No. 3221016 until the aminoethylpiperazine is substituted with from 2.5 to 3 alkoxy groups per molecule. Subsequently, the propoxylated aminoethylpiperazine is further reacted with additional amounts of an alkylene oxide of Formula (II) in the presence of a basic catalyst to obtain an AEP derivative having the desired number of alkoxy groups per molecule.
• An alkali metal hydroxide such as potassium hydroxide is preferably employed as the catalyst.
• the initial, uncatalysed reaction between the alkylene oxide and the aminoethylpiperazine is advantageously conducted at a temperature of greater than 50*C, preferably from 80 to 160 * C, more preferably from 80 to 120 * C and the catalytic reaction is preferably conducted at a temperature of from 110 to 150 * C.
• the initial, uncatalyzed reaction continues until the number of alkoxy groups substituted on the AEP reaches about three. Subsequently, in the presence of a basic catalyst, the reaction is substantially stoichiometric and proceeds essentially to completion with the average number of alkoxy units on each AEP molecule being dependent on the proportion of the starting materials.
• the amounts of the AEP and the alkylene oxide added to the reactor are selected accordingly.
• reaction product such as by the addition of acid or treatment with an ion exchange material or absorption by an inert material.
• the group R in Formula II may be a group as defined for R***, R 2 , or R 3 above.
• the compound of Formula II is ethylene oxide or propylene oxide, in which case, Rl, R 2 and R 3 in the said Formula I are each hydrogen or methyl, x + y + z in the said Formula I preferably amount to from 3.5 to 5.5, more preferably from 3.5 to 5, these figures corresponding to the stoichometric ratio of the starting ingredients in the preparation of the compound of Formula I.
• the polyol according to the invention may be formulated with one or more additives, for example an additional polyol component, a blowing agent, a surfactant, a polymerisation catalyst, a fire retardant additive, and/or with a polyisocyanate, to form a novel precursor composition for the production of rigid polyurethane foams.
• additives for example an additional polyol component, a blowing agent, a surfactant, a polymerisation catalyst, a fire retardant additive, and/or with a polyisocyanate
• a precursor composition for use in the preparation of a rigid polyurethane foam which composition comprises a polyol of the Formula I above, together with at least one rigid polyurethane foam ingredient, selected from the group consisting of:-
• the precursor composition When the additional rigid polyurethane foam ingredient of the precursor composition is a polyisocyanate, the precursor composition will generally be short-lived, and will be formed only immediately prior to the production is the desired polyurethane foam. However, when the additional component of the precursor composition is an additional polyol, a blowing agent, a surfactant, a catalyst, or a fire retardant, the precursor composition may be stored and sold, for example as a component of a two component polyurethane system for later mixing with a polyisocyanate.
• any one of a variety of additional polyols may be used in conjunction with the polyol of the Formula I above. Suitable examples are hydroxy-terminated polyesters, polyether-polyols, polyoxethyleneamines, glycerine and mixtures of two or more thereof. All these polyols are conventionally used in the preparation of polyurethane foams.
• the amount of the polyol of Formula I to be employed may be from 1 to 100 parts by weight, per 100 parts by weight of the total polyol content of the reaction mixture. Often, a relatively small amount, for example, as little as 20 parts by weight of the said polyol of Formula I may be required in order to provide the desired extra rigidity.
• the rigid polyurethane foam is generally prepared by reacting the polyisocyanate component with the polyol component in the presence of a blowing agent, polymerization catalyst, and a surfactant.
• a blowing agent, polymerization catalyst and surfactant used herein can be any conventional blowing agent, polymerization catalyst and surfactant useful in the preparation of a rigid polyurethane foam.
• suitable blowing agents are halogen- substituted alphatic hydrocarbons, with a boiling point between -40 and 70 * C, which vapourise at or below the temperature of the foaming mass.
• Examples of such compounds are trichloromonofluormethane, dichlorodifluromethane, dichloromethane, bromotrifluoromethane, trichloromonofluromethane.
• Water may additionally or alternatively be utilised.
• the blowing agent may be used in an amount of from 1 to 50, preferably from 30 to 40 parts by weight, per 100 by weight of the total polyol content of the reaction mixture.
• the surfactant which may be used in the method and composition of the invention may be any surfactant conventionally used in the production of polyurethane foams, and in particular any surfactants conventionally used for the regulation of cell size.
• surfactants are the sodium salt of a castor oil sulphonate, a sodium salt of a fatty acid, a salt of a fatty acid with an amine, an alkali metal or ammonium salt of a sulphonic acid, a water soluble polyether siloxane, or a mixture of two or more thereof.
• the surfactant is preferably used in an amount of from 0.01 to 5 parts by weight, preferably from 0.5 to 1.5 parts by weight, per 100 parts by weight of the total polyol content of the reaction mixture.
• the catalyst which may be used in the method and composition of the invention may be any conventional catalyst for this purpose, for example a tertiary amine, such as triethanolamine, N-methylmorpholine, N,N,N-tetramethylethylenediamine, N-methyl-N-dimethyl- aminoethylpiperazine, 2-methyl imidazole, triethanol ⁇ amine, triisopropanolamine, or diethanolamine, an organometallic compound such as organometallic acetate or octoate, or a trimerisation catalyst, for example an alkali metal salt of a carboxylic acid, or a non basic metal salt of a carboxylic acid.
• the catalyst is preferably used in an amount of from 0 to 15, preferably from 0 to 5 parts by weight, per 100 parts by weight
• the amount of catalysts may vary depending ypon whether or not the other constituents of the polymerisation mixture display catalytic activity themselves.
• the polyol (I) may diaply catalytic activity and in such cirtcumstances, no other catalyst may be required.
• Any conventional fire retardant additive for example styrene oxide, an epihalohydrin, tris(dichloropropyl)phosphate, triethylphosphate, a phosphorous containing polyol, or a mixture of two or more thereof may be utilised.
• the fire retardant additive is preferably used in amount from 0 to 40, more preferably from 5 to 15 parts by weight, per 100 parts by weight of the total polyol.
• the isocyanate used in the invention may be any aromatic or aliphatic polyisocyanate, for example a polymethylene polyphenylisocyanate, 2,4-tolyene diisocyanate, 2,6-tolyenediisocyanate, xylene
• 1,4-diisocyanate or a mixture of two or more thereof.
• the amount of the polyisocyanate is preferably such as to provide a small excess, for example a 5% stoichometric excess, of the isocyanate with respect to the total polyol.
• the method of this invention is particularly useful in the prearation of molded, pour-in-place rigid polyurethane foam.
• foams are commonly used as thermal insulation in refrigerators, freezers, coolers, insulated bottles and similar articles.
• a rigid polyurethane foam-forming composition is poured into an empty space enclosed by the walls of the article.
• the article is held in the desired configuration by the use of a jig. If the jig is released prematurely, the further expansion of the foam formulation causes the article to become distorted. Since the availability of these jigs usually detemines the rate of production of these articles, a shorter cure cycle results directly in incresed production rate.
• the use of an aminoalkylpiperazine-initiated polyol as described herein as the sole or a significant proportion of the polyol(s) used in the rigid polyurethane foam-forming composition provides a particuarly rapid cure.
• the cure rate for molded, rigid polyurethane foams is conveniently measured by injecting the formulation into a mold, permitting it to cure for a predetermined period, and then releasing the pressure on the mold. If curing is incomplete, the molded polyurethane foam will expand somewhat after the pressure is released. Cure rate is then measured in one of two ways. The time required so that no demold expansion of the foam occurs .can be used as a measure of the cure rate, with lesser times indicating a faster cure. More typically, however, industrial processes can tolerate a certain amount of demold expansion. In these processes, it is common practice to employ the shortest demold time at which a tolerable amount of demold expansion occurs.
• cure rate can be determined indirectly by applying pressure to the mold for a predetermined period of time which is less than that required for complete cure, and then measuring the amount of demold expansion which occurs. Smaller demold expansions indicate faster cures.
• the rigid foam formulation exhibits a demold expansion of less than about 0.2", preferably less than avout 0.1", most preferably less than about 0.07" when cured for four minutes at room temperature in a 200 x 20 x 5 cm mold.
• the formulation provides a tolerable demold expansion at a cure time of four minutes or less, preferably about 3.5 minutes or less, more preferably about 3.0 minutes or less.
• molded, rigid polyurethane foam formulations containing the aminoalkylpiperazine-initiated polyol also exhibit good compressive strengths, k-factors, flowability (ability to fill a mold) and non-shrink densities.
• POLYOL PREPARATION I preparation of propoxylated piperazine polyol
• a compound of the Formula I was prepared by the following method. Propylene oxide was slowly added to 2.2 litres of aminoethyl piperazine (AEP) in a 10 litre reactor at 90 ⁇ C. He amount of propylene oxide added was such as to provide a molar ratio of 2.9 propylene oxide units, per mole of piperazine, and the temperature of the reaction mixture was maintained at approximately 120 ⁇ C during the addition of the propylene oxide and for two hours after the addition was complete.
• AEP aminoethyl piperazine
• Viscosity (at 25 * C) 14,000 centistokes (0.0140 m 2 /s) Water Content 500 ppm
• COMPARATIVE POLYOL PREPARATION An AEP initiated polyol was prepared by slowly adding propylene oxide to 2.2 litres of aminoethyl piperazine in a 10 litre reactor at 90 # C. The amount of propylene oxide added was such as to provide a molar ratio of 3.0 propylene oxide units per mole of piperazine. The temperature of the reaction mixture was maintained at approximately 120 * C during the addition of the propylene oxide and for two hours after the addition was complete.
• the resulting product is the polyol described in USP No. 3221016.
• the properties of the polyol were examined as in Preparation 1 and found to be as follows:
• Viscosity at 25'C 22 500 centistokes (0.0225 m 2 /s)
• the cream time, gel time, tack free time, friability, and free-rise density of the resulting foams were measured.
• the components of the foam mixtures are shown in Table 1, and the properties of the resulting foams in Table 2.
• Tables 1 and 2 also show as Comparative Example 1 a similar composition in which no polyol of Formula I was used.
• the cream time, gel time, and tack free time of the compositions in which the polyol I was used were substantially shorter than those of Comparative Example 1, and the performance of the resulting product in the abrasion test (indicative of the friability of the product) was also significantly improved.
• Preparation 1 was repeated, except that the amount of propylene oxide added in the second stage was such as to provide a propyleneoxy content of 5.7 units per mole in the resulting polyol.
• the properties of the polyol were examined as in Preparation 1, and found to be as follows:- Per cent Hydroxyl 11.1
• Viscosity at 25'C
• centistokes 0.0055m 2 /s
• Water Content 550 ppm
• Rigid polyurethane foams were prepared from the thus- prepared polyol by. the method of Examples 1 to 4, using the ingredients as shown in Table 1. The properties of the foams are shown in Table 2. TABLE 1

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Polyurethanes Or Polyureas (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

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• 1985
  • 1985-07-03 GB GB858516826A patent/GB8516826D0/en active Pending
• 1986
  • 1986-06-30 US US06/880,382 patent/US4704411A/en not_active Expired - Fee Related
  • 1986-07-02 BR BR8606753A patent/BR8606753A/pt unknown
  • 1986-07-02 WO PCT/EP1986/000391 patent/WO1987000186A1/en unknown
  • 1986-07-02 AU AU61366/86A patent/AU574581B2/en not_active Ceased
  • 1986-07-02 KR KR1019870700186A patent/KR900003467B1/ko not_active Expired
  • 1986-07-02 JP JP61503915A patent/JPS62502267A/ja active Granted
  • 1986-07-02 CA CA000512870A patent/CA1271594A/en not_active Expired - Fee Related
  • 1986-07-02 PT PT82904A patent/PT82904B/pt not_active IP Right Cessation
  • 1986-07-03 EP EP86305161A patent/EP0208512A1/en not_active Ceased
  • 1986-07-03 ES ES8600102A patent/ES2000915A6/es not_active Expired
  • 1986-07-03 AR AR86304434A patent/AR247225A1/es active
• 1987
  • 1987-03-02 NO NO870857A patent/NO169446C/no unknown
  • 1987-03-03 DK DK110287A patent/DK110287D0/da not_active Application Discontinuation

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