URETHANE-MODIFIED POLYISOCYANURATE RIGID FOAM

Abstract: Improved crack-free rigid cellular polyisocyanurate poly­ mers are disclosed that are derived from the reaction of an organic polyisocyanate combination comprising two part­ icular types of polymethylene polyphenyl polyisocyanates (a) and (b), a trimerization catalyst, minor amount of a polyol, a surfactant, and an inert volatile blowing agent having a boil­ ing point from about 30°C to about 90°C. The novel rigid foams are particularly useful in preparing high molded bodies of foam by making multiple pours or lifts on top of each other in a mold. The resultant molded body comprises a multiple of molded parts firmly fused to each other and crack-free. Such high molded bodies and process therefor are particularly useful in the insulation of ships.

Description: This invention relates to a process for preparing cellular polyisocyanurates and is more particularly concerned with improved crack-free polyisocyanurate cellular polymers containing minor amounts of polyurethane linkages and molded bodies produced therefrom. Cellular polymers in which the major recurring polymer unit is isocyanurate, are well known and widely used items of commerce; see for example U. S. Patents 3,745,133, 3,986,991, 3,899,443, 4,011,180, 4,039,487, 4,101,465, 4,237,238, 4,411,949, and 4,417,001. Generally speaking, such foams are characterized by better fire resistance and lower smoke evolution on burning when compared with polyurethane foams of comparable physical properties. While enjoying these beneficial properties, the polyisocyanurate foams have suffered from such problems as brittleness or so-called friability, which, the above prior art teaches, can be overcome by the addition of minor amounts of polyols to form urethane linkages along with the majority isocyanurate linkages. Polyisocyanurate foams having good physical properties and being free of internal cracks can be obtained in the manufacture of rigid slab or bunstock so long as high bun heights are not required. Unfortunately, the prior art polyisocyanurate-polyurethane foams still suffer from the serious drawback of not being moldable to foam heights much over 0.9 to 1.2. Attempts to mold at heights greater than 1.2 result in internal cracks and reactivity problems and poor quality moldings having inferior physical properties. If one attempts to overcome this problem by resorting to multiple pours on top of each other to make high molded foam heights, the results are even worse. Not only do internal cracks occur but also interlaminate cracks form between the molded parts from the different pours. Furthermore, up-lifts occur between pours, that is to say, one molded part separates and curls upward at the edge of the mold away from its lower molded counterpart. Surprisingly, we have now found that through the use of a narrow class of polyisocyanates in combination with a particular class of blowing agents that the problems noted above can be overcome and that relatively high polyisocyanurate-polyurethane moldings can be prepared by employing the multiple pour technique. This invention comprises a process for preparing a moulded body comprising a plurality of fused molded parts of rigid cellular polymer in which the major recurring polymer unit is isocyanurate said molded body having a height of at least 1.5 and being substantially free of internal cracks said process characterized by I. reacting together in a mold of at least equivalent height to said molded body the following ingredients: A. a polyisocyanate combination consisting of 50 to 80% by weight of a first (a) and 50 to 20% by weight of a second (b) polymethylene polyphenyl polyisocyanate mixture wherein (a) has a methylenebis(phenylisocyanate [MDI] content of 25 to 45 percent by weight with the remainder comprising polymethylene polyphenyl polyisocyanates of functionality greater than 2.0 said MDI having a 4,4' isomer content of at least 95 percent; and wherein (b) has an MDI content of 55 to 70 percent by weight with the remainder comprising polymethylene polyphenyl polyisocyanates of functionality greater than 2.0 said MDI having a 2,4'-isomer content from 10 to 15 percent with the balance being substantially the 4,4'-isomer; B. an inert volatile organic blowing agent having a boiling point of from 30 o to 90 o C; C. from 0.05 to 0.5 equivalent, per equivalent of said polyisocyanate combination, of an organic polyol; D. an isocyanate trimerization catalyst; and E. a hydroxyl containing silicone surfactant; II. allowing the cellular polymer from reaction sequence (I) to rise fully to form a molded part; and III. repeating said reaction sequence (I) a plurality of times on top of each preceding fully risen molded part to form said molded body. The invention also comprises the molded foam bodies prepared in accordance with the above process. The improved rigid cellular polyisocyanurates in accordance with the present invention are prepared using any of the procedures and equipment conventional in the foam art. Typical teaching appears in the U. S. patents cited supra and the ingredients to be used in the present invention are described below. The novelty in the present invention resides in the particular choice of polyisocyanate and blowing agent ingredients, both defined above under (A) and (B), which are employed in the preparation of the cellular polymers. In respect of the polyisocyanate combination the first (a) and second (b) polymethylene polyphenyl polyisocyanate mixtures must be employed together. Polymers prepared using either (a) or (b) alone as the polyisocyanate component tend not to be crack-free. More importantly, multiple pours to form high molded bodies cannot be properly made. This aspect of the present invention will be discussed in greater detail hereinbelow. Furthermore, the addition of another polymethylene polyphenyl polyisocyanate mixture not conforming to the limitations of either (a) or (b) will result in foams not in accordance with the present invention. A determination of the exact proportions of (a) or (b) necessary for the optimization of the foam properties is readily determined by one skilled in the art. These proportions can depend on such factors as the respective methylenebis(phenylisocyanate) [MDI] contents of (a) and (b) and their respective isomer contents. Preferably (a) is from 55 to 70 percent by weight and (b) from 45 to 30 percent by weight. Both types of polymethylene polyphenyl polyisocyanate mixtures are very well known and are commercially available. The mixture (a) has an MDI content within the range of 25 to 45 with the remainder comprising the polymethylene polyphenyl polyisocyanates of functionality greater than 2.0. In respect of the isomer content of this mixture the MDI has the predominant 4,4'-isomer content of at least 95 percent with the remainder comprising the 2,4'-isomer. It will be readily understood by one skilled in the art that some mixtures can contain very small proportions, for example from zero to 2 percent of the 2,2'-isomer, and such mixtures can be employed in the present invention. It will also be readily understood that the isomer distributions of the higher functional polymethylene polyphenyl polyisocyanates will be governed according to the isomer proportions of their MDI components. Preferably, the 4,4'-isomer content falls within the range of from 97 to 99.5 percent and the viscosity of the mixture (a) falls within a range of from 500 to 1500 mPas (cps). as determined at 25°C. The mixture (b) can be any of the known polymethylene polyphenyl polyisocyanate mixtures which are rich in MDI content and, further, wherein the MDI isomer content is considerably higher in 2,4'-isomer content than the mixture (a) discussed above. The MDI content is from 55 to 70 percent by weight with the remainder comprising the polymethylene polyphenyl polyisocyanates of functionality greater than 2.0. The 2,4'-isomer content is 10 to 15 percent with the balance being substantially the 4,4'-isomer and any small proportion of 2,2'-isomer which may be present. Similarly to the mixture (a), the isomer distributions of the higher functional polymethylene polyphenyl polyisocyanate members in (b) are governed according to the isomer contents of their MDI components. In respect of the blowing agent (B) any inert organic blowing agent meeting the above limitations can be employed. The term "inert" means any blowing agent that will not react with any of the foam forming ingredients or otherwise interfere with the foam forming process. The term "blowing agent" means a volatile solvent which upon vaporization can cause the blowing action forming the cellular polymer. If the preparation of the present cellular polymers is attempted with a blowing agent having a boiling point outside of the above defined range, the beneficial properties characteristic of the present foams cannot be obtained. For example, the use of monofluorotrichloromethane (b.p. 24°C) results in cracks in the foam, particularly interlaminate cracks between the junction of old and newly formed foam. Blowing agents having boiling points higher than the upper limit set forth above do not provide adequate blowing action. Preferably, the boiling point falls within the range of from 40° to 60°C, and, most preferably, 45° to 50°C. Although any organic blowing agent meeting the above limitations can be employed, the preferred class of blowing agents are the halogenated aliphatic hydrocarbons having a boiling point of from 40° to 60°C. Illustrative but not limiting of the blowing agents are pentane, hexane, cyclohexane, fluorobenzene, methylene chloride, 1,1,2,2-tetrafluoro-1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, chloroform, 1,2-dichloroethane, and trichloroethylene. A preferred group comprises the halogenated aliphatic hydrocarbons set forth above. Most preferred are 1,1,2,2-tetrafluoro-1,2-dibromoethane and 1,1,2-trichloro-1,2,2-trifluoroethane. The blowing agents are employed in an amount sufficient to give the resultant foam the desired bulk density which is generally between 0.06 and 1.3, preferably 0.09 to 0.6, and, most preferably, 0.1 to 0.5 kg/m³. Generally speaking, the blowing agent comprises from 1 to 30, and, preferably from 2 to 15 percent by weight of the total foam forming ingredients. The polyols employed include any of those employed in the art for making polyisocyanurate-polyurethane foams and are well-known materials. For typical polyols see the patents cited supra. Typically, the polyols have a hydroxyl functionality from 2 to 8 or an average value therebetween and a molecular weight falling within the range of 600 to 12,000. Included but not limiting thereof are the polyether polyols, polyester polyols, polyol mixtures derived from the alkoxylation of polymethylene polyphenyl polyamine mixtures, polyols obtained by the Mannich condensation of phenolic compounds with formaldehyde and an alkanolamine, phosphorus containing polyols, the so-called reinforced vinyl polyols (see U. S. 3,304,273 and 3,523,093), and the scrap derived polyester polyols (see U. S. Patents 4,237,238, 4,411,949, and 4,417,001 cited supra); and mixtures of any of the above polyols with diols and/or triols of molecular weight from 60 to 400. A preferred group of polyols for use in the present invention are the scrap derived polyester polyols referred to above. Generally speaking, the scrap polyester polyols are characterized by a hydroxyl number of 30 to 550, a viscosity at 25°C of -1500 to 100,000 mPas (cps) and an acid number from 2 to 10. Included in this preferred group are the Terate® type polyols manufactured and sold by Hercules Incorporated of Wilmington, Delaware. These polyols have been described in detail in U. S. 4,237,238 and they comprise polyol mixtures prepared by the transesterification with a glycol of molecular weight from 60 to 400 of a residue obtained after removal of a portion of dimethyl terephthalate product from its esterified oxidate reaction mixture. The scrap polyester polyols of U. S. 4,411,949 are closely related to those above differing primarily in the higher level of dimethyl terephthalate left in the oxidate residue. The scrap polyester polyols of U. S. 4,417,001 are obtained by the digestion of polyalkylene terephthalate scrap in aromatic or aliphatic polyols having a molecular weight of 500 or less such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol. Particularly preferred are the Terate® type polyols described above. Advantageously, the polyol component falls within the range of from 0.05 to 0.5, preferably from 0.1 to 0.4 equivalent per equivalent of the polyisocyanate combination. The trimerization catalyst employed can be any catalyst known to those skilled in the art which will catalyze the trimerization of an organic isocyanate compound to form the isocyanurate moiety. For typical isocyanate trimerization catalysts see The Journal of Cellular Plastics, November/December 1975, page 329; and the patents cited supra. Typical catalyst classes are the glycine salts and tertiary amine trimerization catalysts and alkali metal carboxylic acid salts disclosed in the above patents and mixtures of the various types of catalysts. Preferred species within the classes are sodium N-(2-hydroxy-5-nonylphenyl)methyl-N-methylglycinate, and N,N-dimethylcyclohexylamine, and mixtures thereof. Also included in the preferred catalyst components are the epoxides disclosed in U. S. 3,745,133. The total quantity of catalyst, including mixtures thereof, in parts by weight per equivalent of polyisocyanate, can be determined easily by trial and error for any formulation in accordance with the present invention. Advantageously, the catalyst is employed within a range of 0.1 parts to 20 parts by weight per equivalent of polyisocyanate, preferably, from 0.5 parts to 10 parts. Any surfactant can be employed according to the invention. The preferred type of surfactants are the silicone surfactants particularly the polydimethylsiloxane-polyoxyalkylene block copolymers which are readily available and well-known to those skilled in the art. Most preferred are those block copolymers having a minor hydroxyl content, that is to say, hydroxyl containing silicone surfactants. Typical of such surfactants are DC-193® supplied by Dow Corning, Midland, Michigan; L-5320® and L-5410® supplied by Union Carbide, Danbury, Connecticut. Advantageously, the surfactant comprises from 0.05 to 10, preferably from 0.1 to 6 weight percent of the total foam forming ingredients. Other optional additives can be employed such as dispersing agents, cell stabilizers, additional surfactants to those called for above, colorants and flame retardants. Illustrative but not limiting of the additional surfactants are the tertiary amine ethoxylates supplied under the trade name M-300® and supplied by Texaco Chemical, Bellaire; Texas. Illustrative but not limiting of the flame retardants which can be employed are tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate, tris(2,3-dibromopropyl)phosphate, and tris(1,3-dichloroisopropyl)phosphate. The cellular polymers can be manufactured as products e.g. in the form of bunstock material, pour-in-place foams or laminate foam sandwich materials. The products can be used in building construction as thermal insulation and also in the field of sound insulation. As noted above, the foams so produced are essentially free of internal cracks, have good uniform cell structure and are further characterized by having the known beneficial properties of polyisocyanurate foams, particularly improved resistance to burning when compared with polyurethane foams. However, the major unexpected benefit inherent in the present cellular polymers makes them particularly useful in the preparation of molded bodies prepared from multiple molded parts or pours (also known as "lifts"). As noted above, the present foams are prepared by a process to form molded bodies of at least 1.5 m in height which consist of a plurality of fused molded parts each consisting of a separately foamed portion of the cellular polymer. Because of the properties of the present foams, the molded parts are firmly fused or bonded to each other without interlaminate separation and without any uplifting near the edges of the molded bodies where the old and the new foam meet. The heights to which such molded bodies can be prepared are limited only by the height of the mold and the amount of foam forming ingredients which can be delivered thereto. Generally speaking, mold heights ranging from 1.5 to 7.6 are readily obtainable with mold lengths and widths of from 0.3 to 7.6 and 0.3 to 3.1 respectively. Preferably, mold heights range from 1.5 to 6.1 with lengths and widths of 1.5 to 4.6 and 0.6 to 2.4 respectively. The height of the individual parts or lifts in any given molded body is not critical but advantageously falls within the range of 0.2 to 0.6 and, preferably, 0.25 to 0.46 It will be obvious to one skilled in the art that each lift does not have to be of equal height but in the interest of smooth operation it is generally preferred to have them all of approximately equal height to facilitate the cycling of the foam forming ingredients to the mold. The novel process for producing the molded bodies in accordance with the present invention is useful for filling deep voids, particularly the bulkheads and inner hulls of ships. Furthermore, the cellular polymers in accordance with the present invention meet all of the specifications required for use in the insulation of ships as set forth in MIL-P-24249 (Ships) published February 10, 1967. The following examples describe the manner and process of making and using the invention and set forth the best mode contemplated by the inventors of carrying out the invention but are not to be construed as limiting. Example 1 This example sets forth the preparation of two polyisocyanurate foam molded bodies (Run 1 and Run 2) in accordance with tne present invention. The molded bodies were prepared by making multiple pours or lifts of polyisocyanurate foam prepared from the following components A and B comprising the ingredients in proportions in parts by weight set forth below. Run 1 employed the components in the proportions exactly as set out below. Run 2 differed only by having an additional 0.2 part of the trichlorotrifluoroethane blowing agent in the B side, by having 0.10 part of the α-methylstyrene also in the A side, and by having 1.50 parts of catalyst instead of 1.6. The foams were prepared using a conventional foam metering and dispensing machine having a mixing head equipped with a pin type impeller. The foam forming mixture was dispensed in the A/B proportions by weight of 63.6 and 36.4 respectively to result in the NCO to OH ratio of 2.89:1. In run 1 a metal mold measuring 1.2 m by 2.4 m in area by 1.5 m in height was employed. Five separate pours or lifts were made wherein in each pour sufficient amounts of the A and B components were discharged to the mold to result in 0.3 meter of fully risen foam of 0.4 kg/m³ density. Thirty min was allowed to elapse between each pour so that fresh foam was formed over fully risen foam. The result was an integrally molded body of polyisocyanurate foam 1.5 m high consisting of five separately molded foam parts. All of the parts were firmly fused to each other with no interlaminate cracking between pours and no internal cracks in the foam itself. The overall density was 0.4 kg/cm³. Run 2 was simply a repetition of run 1 except that the mold was 4.6 m in height rather than 1.5. Fifteen separate pours or lifts were made one on top of the other with 30 min between each pour. The amount of reactants in each pour was sufficient to form a fully risen molded part of 0.286 m in height. Accordingly, the complete molded body was 4.3 m in height with an area of 1.2 by 2.4 m. All fifteen molded parts were firmly fused together with no interlaminate cracks between the molded parts. Also, there were no internal cracks within the molded parts of foams. The molded body was cut into 12 slices each measuring 2.4 m x 1.4 m x 0.3 m. Samples were taken from various locations in each one of the 12 pieces and various tests performed in accordance with the requirements of MIL-P-24249 for ships. The results are set forth below and it will be noted that the foam samples passed all of the required tests. The adhesion tests were carried out not on the samples from the large molded body but on small samples poured in boxes having steel plates in order to facilitate the formation of samples compatible with Instron test equipment. Comparison Example 2 This comparison example sets forth the preparation of a polyisocyanurate foam molded body (Run 3) not in accordance with the present invention. The molded body was made identically to Run 1 above using the same components A and B set forth in Example 1 except that instead of the 6 parts of the 1,1,2-trichloro-1,2,2-trifluoroethane in each of A and B there was employed 8.9 parts of monofluorotrichloromethane in the B side. The five separate pours were made into the five foot high mold to form the molded body. Although there were no internal cracks within any of the four molded parts, there were many interlaminate splits and separations between the parts at the edge of the mold called up-lifts. Comparison Example 3 This comparison example sets forth the preparation of three polyisocyanurate foam molded bodies (Runs 4 to 6) not in accordance with the present invention. The molded bodies were made identically to Run 1 using five separate pours for each run in the five foot high mold. The same components A and B set forth in Example 1 were employed here except as noted in Table I below for the isocyanate and blowing agent ingredients. The results and appearance of each molded body are set forth in Table I under Remarks. It will be noted that using one of the preferred polyisocyanates (PAPI I)® alone, or a non-preferred polyisocyanate (PAPI III)® alone, or admixing PAPI III® with the preferred mixture of PAPI I® and II results in up-lifting between the individual pours of each run. At the same time, internal cracks within each molded part are prevalent in all three runs.

Claims: A process for preparing a molded body comprising a plurality of fused molded parts of rigid cellular polymer in which the major recurring unit is isocyanurate said molded body having a height of at least 1.5 meters and being substantially free of internal cracks said process characterized by I. reacting together in a mold of at least equivalent height to said molded body the following ingredients: A. a polyisocyanate combination consisting of 50 to 80% by weight of a first (a) and 50 to 20% by weight of a second (b) polymethylene polyphenyl polyisocyanate mixture wherein (a) has a methylenebis(phenylisocyanate [MDI] content of 25 to 45 percent by weight with the remainder comprising polymethylene polyphenyl polyisocyanates of functionality greater than 2.0 said MDI having a 4,4' isomer content of at least 95 percent; and wherein (b) has an MDI content of 55 to 70 percent by weight with the remainder comprising polymethylene polyphenyl polyisocyanates of functionality greater than 2.0 said MDI having a 2,4'-isomer content from 10 to 15 percent with the balance being substantially the 4,4'-isomer; B. an inert volatile organic blowing agent having a boiling point of from 30 o to 90 o C; C. from 0.05 to 0.5 equivalent, per equivalent of said polyisocyanate combination, of an organic polyol; D. an isocyanate trimerization catalyst; and E. a hydroxyl containing silicone surfactant; II. allowing the cellular polymer from reaction sequence (I) to rise fully to form a molded part; and III. repeating said reaction sequence (I) a plurality of times on top of each preceding fully risen molded part to form said molded body. A process according to Claim 1 wherein said polyisocyanate combination comprises 55 - 70% percent by weight of said mixtures (a) and 30 - 45 percent by weight of said mixture (b). A process according to Claim 1 or 2 wherein said blowing agent is 1,1,2-trichloro-1,2,2-trifluoroethane. A process according to Claims 1 - 3 wherein said surfactant is a hydroxyl containing silicone surfactant. A cellular polymer obtainable by a process according to one of claims 1 to 4. A molded body comprising a plurality of fused molded parts of a rigid cellular polymer of claim 5. A molded body according to claim 6 having a height of at least 4.3 meters.

Inventors: DEGUISEPPI, DAVID T., GONZALES, GILDA C.
Applicants: THE DOW CHEMICAL COMPANY
Application year: 1986
Main classification: C08G18
IPC codes: C08G18