STEAM EXPANDED POLYMERIC COMPOSITION AND METHOD

Abstract: A steam expanded alkenyl aromatic polymer composition (10) is provided. The polymer is mixed with a volatile blowing agent containing, as a primary blowing agent, dichlorodifluoromethane and as a secondary blowing agent, a halogenated hydrocarbon, a hydrocarbon, or an aliphatic alcohol containing from 1 to 4 carbon atoms. The secondary blowing agent has a normal atmospheric boiling point of from 0<o> to 100<o>C. The admixture of polymer and blowing agent may be expanded by steam immediately after extrusion foaming or may be expanded after aging of the composition which has been impregnated with the volatile blowing agent.

Description: I -1- STEAM EXPANDED POLYMERIC COMPOSITION AND METHOD This inv.ention relates to a steam expanded polymeric composition and method of preparation. More particularly it relates to the use_.of a steam expandable alkenyl aromatic polymer composition with specific mixed volatile blowing agent. It also relates to- various methods of expanding the composition in atmospheric steam, particularly those whereby a low density product with high expansion ratio is obtained at high expansion rate. Steam expansion is a widely applied technology in preparing a styreniσ polymer foam. Atmospheric steam (i.e., steam at atmospheric pressure) is often used to expand expandable polystyrene (EPS) resins. Both "on-line" and "off-line" steam expansion techniques have been utilized. "On-line" steam expansion occurs immediately following extrusion of expanded polystyrene foam. For example. Japan Kokai published application No. 42-24071 discloses that steam may be used to expand polystyrene foam at the die of a foam extrusion line. "Off-line" steam expansion utilizes steam to expand polystyrene resin particles which have been impregnated with a volatile blowing agent. For example, both Kajimura, U.S. patent No. 3,994,840. and Yamai, U.S. patent No. 4,065.411. teach impregnation of polystyrene particles with a vola.tile blowing agent such as n-pentane, aging the expandable particles, and then expanding the particles to a cellular foamed structure by exposure to steam. However, most commonly used blowing or expanding agents have a deficiency either in the rate of expansion I j of the polymer, the degree of expansion of the polymer, or the final properties of the expanded polymeric foam. For example, a polystyrene foam expanded with a mixture of dichlorodifluoromethane and methyl chloride expands too slowly and to too low a degree in steam to be practical for commercial activity. A polystyrene foam made with pure trichloromono luoromethane or pentane expands rapidly in steam, but has several deficiencies in expansion characteristics. It results in a softening of the final foam structure, and prevents expansion of the foam to very low densities. Accordingly, a need exists in the art for a steam expandable alkenyl aromatic polymer composition and method for preparation which provides rapid expansion of the composition in steam to very low densities without adversely affecting the final properties or structure of the foam. The present invention meets that need by providing a specific steam expandable polymeric composition and process which expands the composition rapidly to very low densities. According to one aspect of the invention, the expandable composition includes an alkenyl aromatic polymer having a glass transition temperature between 60° to 100°C together with a specific volatile blowing agent mixture. The volatile blowing agent mixture includes a mixture -of from 40 to 90% by weight of a primary blowing agent ' that is- dichlorodi¬ fluoromethane and from 10 to 60% by weight of a secondary blowing agent selected from a halogenated hydrocarbon, ' a hydrocarbon, and an aliphatic alcohol containing from 1 to 4 carbon atoms, or mixtures thereof; the halogenated hydrocarbon, hydrocarbon, and aliphatic alcohol having a normal atmospheric boiling point of from 0° to 100°C. Optionally, small amounts of a silane- crosslinking agent may also be added. it has been found that this specific combination of alkenyl aromatic polymer and mixed blowing agent provides a rapidly expanding composition in atmospheric steam to low densities [i.e., below about 2.0 pcf (32.0 Kg/ )]. In addition to having a glass transition temperature (Tg) of from 60° to 100°C, the polymer preferably has a weight average molecular weight of equal to or less than 250,000. Such molecular weight may be determined by gel permeation chromatography (GPC) , or example. The preferred secondary blowing agent has adequate solubility to plasticize the polymer. This helps lower the glass transition temperature of the polymer, thereby facilitating steam expansion. The secondary blowing agent subsequently diffuses out of the composition without any adverse effect on the final foam properties. This is particularly advantageous since many other plastiσizing agents (such as solid or liquid compounds mixed into the polymer) will permanently remain in the final cellular structure. The specific expandable composition used in the present invention may be used to produce a very low density moldable. material by off-line expansion in steam. It- may also be used " to produce a lower density extruded foam by on-line application of steam. To produce the very low density moldable material, the specific volatile mixed blowing agent is impregnated into a granular alkenyl aromatic polymer having a glass transition temperature between 60° to 100°C. This impregnated polymer may then be heated to activate the blowing agent and expand the composition. Steam may be used to provide the heat for this initial expansion. . or alternatively, the expanded composition may be subjected to further single or multiple expansions in the presence of atmospheric steam. A low density extruded foam may be produced in accordance with the present invention by melt processing under "pressure an alkenyl aromatic polymer having- a glas.s - transition temperature between 60° and 100°C with the specific mixed volatile blowing agent to form a flowable admixture. The admixture is then extruded through a die to a zone of lower pressure where the blowing agent is activated to expand the composition to a cellular structure. This cellular foam is then exposed to atmospheric steam to cause further expansion of the foam to even lower densities. The exposure of the admixture to lower pressure and to atmospheric steam may occur substantially simultaneously. The advantages of the invention will become apparent from the following detailed description, the accompanying drawings and the appended claims. Fig. 1 is a schematic diagram of a steam chamber for the on-line expansion of polymeric foam; Fig. 2 is a graph comparing the expansion ratio versus expansion time for polystyrene foams having different blowing agents and/or levels of silane crosslinking agent based on data set forth in Example I; and Fig. 3 and Fig. 4 are graphs comparing the reduction in foam density versus exposure time for the on-line steam expansion of a polystyrene foam with different blowing agents based on data set forth in Example IV. The expandable polymeric composition used in the present invention includes an alkenyl aromatic polymer resin having a glass transition temperature of between 60° and 100°C and, typically have a weight average molecula -weight equal to or less than 250;000. By the term "alkenyl aromatic polymer" resin, is meant a solid polymer of one or more polymerizable alkenyl aromatic compounds and, optionally, at least one copolymerizable monomer. The polymer or copolyraer includes, in polymerized form, at least 70% by weight of at least one alkenyl aromatic monomer having the general formula: Ar - C = CH. where Ar represents an aromatic hydrocarbon radical, or an aromatic halo-hydrocarbon radical of the benzene series; and R is hydrogen, a methyl group, or an ethyl group. Examples of such alkenyl aromatic polymers are the solid homopolymers of styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-raethylstyrene, ar-ethylstyrene. ar-vinylxylene,. ar-chlorostyrene, and ar-bromostyrene; the solid copolymers of two or more of such alkenyl aromatic compounds with minor amounts of other readily polymerizable olefinic compounds such as acrylonitrile, anhyrides of maleic or itaconic acids; and rubber-reinforced (either synthetic or natural) styrene polymers, and the like. The blowing agent mixture of the present invention includes a mixture of a primary blowing agent and a secondary blowing agent. The primary blowing agent is dichlorodifluoromethane in an amount of from 40 to 90% by weight (preferably 60 to 80% by weight) of total blowing agent. The secondary blowing agent is selected from a halogenated hydrocarbon, a hydrocarbon, and an aliphatic alcohol containing from 1 to 4 carbon ,atoms, or . mixtures thereof wherein the secondary blowing agent has a normal atmospheric boiling point of from 0° to 100°C, in an amount of from 10 to 60% by weight (preferably from 20 to 40% by weight) of total blowing agent. It has been found that this combination of primary and secondary blowing agents in the weight percentages given above provide, in combination with the alkenyl aromatic polymer of the present invention, a composition which is readily and rapidly expandable in atmospheric steam to very low densities below about 0.6 3 pcf (9.6 g/m ). The unique plasticizing effect of the secondary blowing agents aid in lowering the glass transition temperature of the polymer rendering it readily expandable in atmospheric steam. After expansion, the secondary blowing agent diffuses out of the cellular structure. However, the use of too much secondary blowing agent, above the percentage range disclosed above, may cause too much plasticizing effect on the. composition resulting in a permanent softening of the final cellular structure and an inability to expand the composition to ** very low densities. Likewise, the weight percentage of primary blowing agent in the composition is also important. Too much of the primary blowing agent results in a composition which does not rapidly expand in steam. If the level of primary blowing agent is too low, the foam may collapse, may fail to recover its volume after expansion, or may have too low a heat distortion temperature. The preferred 5 concentration of total blowing agent to alkenyl aromatic polymer is from 10 to 30 parts per hundred parts by weight of polymer. It has been found that the optional addition of 0.01 to 2.0 parts per hundred of an azido functional 10 silane as a crosslinking agent to the overall composition further improves the steam expandability of the composition of the present invention. Suitable azido functional silane compounds include the group of azido trialkoxysilanes such as 2-(trimethoxysilyl) ethyl phenyl 15 sulfonyl azide (commercially available from Petrarch Systems, Inc., Bristol, Pennsylvania) and (triethoxysilyl) hexyl sulfonyl azide (commercially available as Azcup D-98 from Hercules, Inc., Wilmington, Delaware). The expandable composition of the present 20 invention may be used to produce very low density material by means of either on-line or off-line expansion techniques. A very low density moldable material may be produced by impregnating the volatile mixed blowing agent of the present invention into a granular alkenyl aromatic 25 polymer composition having a glass transition temperature between about 60° to about 100°C. The polymer impregnated with blowing agent is activated by heating causing the - * composition to expand. Typically, the expansion produces foam beads having a density of about 2-3 pounds per cubic 30 foot (pcf) (32.0-48.1 Kg/m 3 ). After aging, preferably for a period of from about 1 to about 7 days, the foam beads are exposed to steam at substantially atmospheric pressure for a period of from several seconds to two hours, and preferably 5 to 15 minutes. Both single and multiple steam expansions are contemplated. This causes further expansion of the beads to densities as low as 0.2 pcf (3.2 Kg/m 3). The very low density foam beads may then be molded in accordance with known techniques. An alternative method in accordance with the present invention is to produce a low density extruded foam by exposing the foam to steam after the foam leaves the extruder. This exposure to steam may take place after the extruded foam has been aged for a period of time or may take place immediately after the foam has left the die of an extruder. Fig. 1 illustrates, in a schematic diagram, such an on-line steam expansion technique. The mixed volatile blowing agent of the present invention is melt processed under pressure with an alkenyl aromatic polymer having a glass transition temperature between 60° and 100°C to form a flowable admixture or polymer gel 10. Polymer gel 10 then exits extruder 12 through die 14 to a zone of lower pressure. In this instance, the zone of lower pressure is a steam chamber 20 having an inlet 22 for the addition of steam to the chamber at substantially atmospheric pressure. Steam enters the chamber through a porous distributor 23. Steam chamber 20 has walls 24, 25 which may be of any suitable material including metal and a polymer resin. such as a " polycarbonate. Outer wall 25 acts as a shield for inner wall 24. The end of steam chamber 20 is sealed with a flexible rubber seal 28. As the polymer gel 10 exits die 14 it initially expands to a cellular structure having a density typically between 2 to 3 pcf (32.0 to 48.1 Kg/m 3) . Exposure of the foam to atmospheric steam in steam chamber 20 causes further expansion to lower densities. A pair of driven rolls 30, 32 pull the cellular foam out of the steam chamber. Preferably, the steam chamber is designed to provide sufficient residence time for the steam to. act QΏ. . and expand the extruded foam. Typically, such residence " time will be a period of from several seconds to several -- minutes. Accordingly, it can be seen that rapid expansion in steam is quite important in such an on-line technique. The mixed blowing agent of the present invention provides that rapid expansion capability. The very low density foams produced by the above on-line and off-line methods have several benefits. The benefits include low final product cost (because of the very low density product which is produced) and increased flexibility of the foam structure (because of the thinness of the. cell walls). The foams produced may be used as insulation and cushion packaging materials. The specific working examples that follow are intended to illustrate the invention but are not to be taken as limiting the scope thereof. In the examples, parts and percentages are by weight unless otherwise specified or required by the context. Example I The apparatus used in this and other examples was a 1-1/4" screw type extruder having two additional zones for mixing and cooling at the end of usual sequential zones for feeding, melting, and metering. An opening for blowing agent injection was provided on the extruder * barrel between the metering and mixing zones. A small -10- syringe-type pump was connected to the blowing agent stream for optional injection of crosslinking agent. At the end of the cooling zone there was attached a die orifice having an opening of rectangular shape. The height of the opening, called die gap hereinafter, was adjustable while its width was fixed at 0.25 inches (6.35 millimeters) . A granular polystyrene with a weight average molecular weight of about 200,000 and a glass transition temperature greater than 60°C and less than 100°C, was uniformly mixed with a small amount of dibutyl tin dilaurate condensation catalyst (T-12, available from M & T Chemicals, Inc.). barium stearate and talcum powder. The mixture was fed into the extruder at an essentially uniform rate of about 10 pounds per hour. A premixed blowing agent was injected into the extruder at a predetermined rate. Blowing agents used in this example were a 70/30 by weight mixture of dichlorodifluoromethane (sold under the trade name FC-12) and trichloromonofluoromethane (sold under the trade name FC-11) for the other tests. An azido functional silane, 2-(trimethoxysily ethylphenylsulfonyl) azide (C-T2905 distributed by Petrarch Systems, Inc.), was injected into the blowing agent stream at a uniform predetermined rate. The extruder zones were maintained at 170, 190 and 200°C for feeding, melting, metering, and mixing zone, respectively. The temperature of the cooling zone was adjusted so that the gel could be cooled down to a uniform temperature for optimum foam expansion. At a fixed die opening for a given blowing agent system where all formulations provided good quality foams, both pressures at the die and extruder discharge were i I -11- reσorded and samples were taken. The foam samples were aged for about one month at ambient temperature prior to property determination and secondary foaming tests. Secondary foaming was conducted both by atmospheric steam and by hot air (not an example of the present invention). Foam slugs of about 0.25 inch (6.35- millimeters) thickness were sliced out of foam strands and aged-. or about one day at ambient temperature prior to secondary expansions. After exposure to atmospheric steam for varying lengths of time, foam specimens were aged at ambient temperature while their weights and volumes were monitored. Highly expanded foam specimens shrank when taken out of steam but recovered to the final steady state volumes in about two days. Expansion tests in hot air were conducted similarly with the exception that expansion or shrinkage of a foam specimen in the oven was permanent, not needing ambient aging for volume recovery. Tables IA and IB show the good results utilizing of the mixed FC-12/FC-11 blowing agent of the present invention. The tables also show that incorporation of an azido functional silane gradually raises both the die pressure and the extruder discharge pressure. Other noticable effects of silane include enlargement in cell size and cross sectional size which are desirable in foam extrusion. The remarkable effects of the mixed blowing agent of the present invention and silane cfosslinking agent on- steam- expandability of extruded polystyrene foam is seen in Table IB and the graph of Fig. 2, which represents the data reported in Table IB. The optional addition of silane enhances both the rate and extent of foam expansion in steam. At a silane level of 0.2 pph, the foam- expands about twice as much as Test No. 1 to an expansion ratio exceeding 280 in two hours. At this long exposure to steam. Tests No. 1 and 2, one with a low level (0.05 pph) of silane, suffered thermal collapse; the expansion ratios are lower than those at one hour exposure. The type of blowing agent has a significant - • effect on steam expandability of the extruded polystyrene foams.- The FC-12/FC-11 mixerd blowing agent of the present invention showed good expansion ratios. FC-1 , having a high solubility in polystyrene, effectively plasticizes polystyrene for faster and greater expansion. The effect of crosslinking is also seen in hot air expansion tests. As Table IC shows, foams lightly crosslinked with an azido functional silane expand more and withstand hot air longer than the control. For example, a foam crosslinked with 0.15 pph or higher level ' of azido silane keeps expanding during 90 minutes exposure to 100°C air while the control collapses within 60 minutes at the same temperature. Although less pronounced, the σrosslinking effect persists at a lower level of silane as well. Example II The apparatus and its operating procedure used for tests in this example are the same as in Example 1. The polymer feedstock employed for tests in this example was a 50/50 by weight blend of polystyrene with Mw 20.0,000 and polystyrene with Mw 300,000. The mixture of polystyrenes had a glass transition temperature of more than 60°C and less than 100°C. Approximately 0.05 pph T-12, 0.1 pph barium stearate and 0.1 pph talcum powder were mixed in the granular blend of two polystyrenes and fed into the extruder at a uniform rate of 10 pounds per hour. In the TABLE Iλ Azido Foaming Blowing Agent BaSt Talc T-12 Silane Gel Die Die Extruder Foam • Foam Foam Cel l Test Type Ratio Level Level Level Level Level Temp. Gap Press. Press. Thick. Width Density Size ..Ho,. AIL (?) . ( ? ) («) (S) (6) (7) _i-U _-___ (IP) III) (HI (. ** ) ( H I li-il 1 FC-12/FC-11 70/30 IS . . 4 0.05 0.1 0.025 135 0.914 46.4 77.3 17.0. 25.7 34.0 0. 16 z FC-12/FC-11 70/30 IS . . 4 0.0S 0.1 0.025 0.05 134. 0.914 39.7 70.3 16. 5. 27.2 33.0 0.27 3 FC-12/FC-11 70/30 15 . .4 0.0S 0.1 0.025 0.1 134 0.914 45.0 78.0 22.4 30.5 35.2 0.22 4 FC-12/FC-11 70/30 IS . 4 o.os 0.1 0.025 0.15 134 0.914 46.4 80.9 22. 9 32. 5 35.9 0.27 co 5 FC-12/FC-11 70/30 IS . 4 o.os 0.1 0.025 0.2 134 0. 914 48.5 84.4 18.5 32.8 36.0 0.27 6 FC-12/FC-11 70/30 15 . 4 0.05 0.1 0.025 0.25 134 0.914' 51.3 91.4 24.9 36.3 36.5 0.21 (1) - FC-12 - dichlorodifluocoraethane, FC-11 » trichlocomonofluoromethane (2) - mixture ratio by weight of the component blowing agents (3) - parts of blowing agent mixed in pec hundred pacts of polymec (4) - pacts of barium steacate mixed in pec hundred pacts of polymer (5) - parts of talcum powder mixed in per hundred parts of polymer (6) - parts of dibutyl tin dilaurate mixed in per hundred parts of polymer (7) • parts of az do functional silane mixed in per hundred'parts of polymer (8) - temperature of foaming gel in degrees centigrade (9) - the gap of die opening in millimeters . (10)- the pressure in kilograms per square centimeter at the die (11)- the pressure in kilograms per square centimeter at the extruder discharge (12)- thickness of foam -body in millimeters determined af er aging for about a month (13)- width of foam body in millimeters determined after aging foe about a month (14)- density of foam body in kilogcams pec squace meter determined after aging for about a month (IS)- cell size in millimeter in horizontal direction determined per ASTM D-3576 TABLE IB Azido Initial • Blowing Agent Silane Expansion Expansion Ratio after Expand1ng In Steam for Test Type Ratio Level Level Ratio 15 30 1 3 5 7 10 15 20 30 1 2 No. (1) (3) (4) (5) sec. sec. min, min. min. min. min. ■ in,, min. min. Jir. hrβ. J 1 FC-12/FC-11 70/30 15.4 24.6 39.0 57.6 81.2 107 124 129 140 147 140 1S1 145 94 2 FC-12/FC-11 70/30 15.4 0.05 22.5 66.6 76.3 105 136 159 170 170 181 189 185 190 132 3 FC-12/FC-11 70/30 15.4 0.1 24.0 44.2 66.0 98.6 137 150 166 175 193 198 218 237 246 4 FC-12/FC-11 70/30 15.4 0.15 23.7 51.7 69.7 102 138 154 168 175 187 197 218 252 218 5 FC-12/FC-11 70/30 IS.4 0.2 2S.9 57.3 71.0 108 149 179 187 212 217 227 251 266 288 6 FC-12/FC-11 70/30 15.4 0.25 23.4 63.8 82.1 109 136 162 173 155 183 186 186 161 172 (1) - FC-12 - dichlorodifluoromethane. FC-11 > trlchlocomonofluoromethane (2) - mixture ratio by weight of the component blowing agents (3) - parts of blowing agent mixed in per hundred parts of polymer (4) - parts of azido functional silane mixed in per hundred parts of polymer (5) - specific volume of foam body aged for about a month divided by specific volume of the polymer determined prior to steam expansion tests (6) - expansion ratio of foam body determined In about two days after expansion in steam for given period of time TABLE; IC Azido Initial Expan •loη Ratio after Expanding in I ' ' I Blowing Agent Silane Expansion Hot Air at 100*C foe (min .) Teat Type Ratio Level Level Ratio (6) Ho. (1) (2) (3) (4) (51 ** 5 10 IS ?o «s 60 90 1 FC-12/FC-11 70/30 15.4 24.6 29.2 47.8 68.3 59.5 68.8 54.8 12.8 14.0 2 FC-12/FC-11 70/30 15.4 O.OS 22.5 27.6 28.4 68.3 57.2 75.8 79.8 36.2 31.S 3 FC-12/FC-11 70/30 15.4 0.1 24.0 26.7 41.1 56.3 56.3 78.3 87.2 39.9 Sl.S 4 FC-12/FC-11 70/30 15.4 0.15 23.7 26.7 36.3 49.6 66.2 75.6 86.1 50.4 8S.1 5 FC-12/FC-11 70/30 IS.4 0.2 2S.9 26.7 43.0 S3. 64.0 71.8 84.0 97.4 120.3 6 FC-12/FC-11 70/30 15.4 0.2S 23.4 28.6 SO.6 55.7 58.2 74.6 88.2 95.5 106.0 Azido Initial Expansion Ratio ai Eter Expanding in Blowing Agent Silane Expansion Hot Air at U5 « C foe (min. ) Test Type Ratio Level Level Ratio (7) No. (1) (2) (3) (4) (5) 3 5 *<> 15 30 45 60 90 1 FC-12/FC-11 70/30 15.4 24.6 29.2 39.4 57.2 65.6 30.2 9.6 7.9 7.4 2 FC-12/FC-11 70/30 15.4 O.OS 22.5 35.0 38.5 61.8 57.8 48.3 11.6 8.4 6.4 3 FC-12/FC-11 70/30 IS.4 0.1 24.0 27.3 47.7 66.2 51.6 77.7 16.2 11.6 8.4 4 FC-12/FC-11 70/30 15.4 0.1S 23.7 27.3 44.1 58.2 63.0 72.6 13.7 10.1 7.6 5 FC-12/FC-11 70/30 15.4 0.2 25.9 38.2 42.0 61.3 63.0 91.4 25.8 14.3 11.5 6 FC-12/FC-11 70/30 15.4 0.2S 23.4 25.8 40.1 66.2 59.2 83.0 48.3 16.8 11.6 (1) - FC-12 - dichlorodifluoromethane. FC-11 - tcichloromonofluoromethane (2) - mixture catio by weight of the component blowing agents (3) - parts of blowing agent mixed in per hundred parts of polymer (4) - pacts of azido functional silane mixed in per hundred parts of polymer (5) - specific volume of tdaa body aged for about a month divided by specific volume of the polymer determined prior to steam expansion tests (6) - expansion catio of foam body after expanding in hot air of 100*C for specified period (7) > expansion ratio of foam body after expanding in hot air of 115*C for specified period tests a 70/30 mixture of FC-12 and FC-11 was used as the blowing agent. The level of azido silane crosslinking agent was varied up to 0.45 pph. The extruder zo.nes were maintained at about 170, 200 and 200°C for feeding, melting, metering, and mixing zone, respectively. The temperature of the cooling zone was adjusted so that the gel could reach an essentially uniform temperature of about 135°C. When the operating condition reached an essentially steady state, the effects of die opening on foam appearance and line pressure were studied. Foam samples were taken both at the threshold die gap for prefoaming and at a fixed die gap for a given blowing agent system. Property determination and secondary foaming tests were conducted as described in Example I. In general, the use of the mixed blowing agent of the present invention and silane crosslinking have similar effects on this polymer blend. As " shown in Tables IIA, IIB:and IIC, azido functional silane increased die pressure and cel -size permitting achievement of a larger - foam cross section and greater expansion in both steam and hot air. The die may be opened wider at an azido functional silane level 0.25 pph or higher. For this polymer blend also, the type of expanding agent has a pronounced effect on steam expandability. The FC-12/FC-11 mixed blowing agent of the present invention provided good expansion results. This is. ascribed to the low permeability and high solubility of FC-ϊl in polystyrene. TABLE IIA ' - Azido Foaming Threshold for Prefoaming Sampling Blowing Agent Silane Gel Die Die Foam Foam Die Die Extruder Foam Foam Foam Cell Test Type Ratio Level Level Temp. Gap Press. Thick. Hidth Gap Press. Press. Thick. Hidth Density Size No. (1) (2) (3) (*) (5) (6) (7) ( β ) (9) (10) > (12) (13) . («) (15) (16) 1 FC-12/FC-11 7p/30 15.4 135 1.803 43.2 15.7 29.7 1.803 43.2 84.4 15.7 29.7 33.6 0.30 2.032 35.9 78.0 16.5 27.4 36.7 2 FC-12/FC-11 70/30 15.4 0.05 135 2.032 42.5 17.8 30.5 2.032 42.5 91.4 1.7.8 30.5 37.5 0..31 3 FC-12/FC-11 70/30 15.4 0.1 135 2.032 44.3 17.3 32.3 2.032 44.3 94.2 17.3 32.3 38.1 0.35 4 FC-12/FC-11 70/30 15.4 0.15 135 2.032 45.7 20.0 34.0 2.032 45.7 94.9 20.0 34.0 37.6 0.38 5 FC-12/FC-11 70/30 15,.4 0.2 135 2.032 47.1 20.0 33.3 2.032 47.1 96.3 20.0 33.3 37.5 0.43 6 FC-12/FC-11 70/30 15.4 0.25 135 2.261 42.9 20.3 33.0 2.032 49.6 94.9 20.8 34.3 35.2 0.42 7 FC-12/FC-11 70/30 IS.4 0.35 135 2.489 41.5 28.2 38.6 2.032 54.1 101.9 26.2 36.6 35.9 0.56 β FC-12/FC-11 70/30 15.4 0.45 135 2.489 41.5 24.6 33.5 2.032 57.0 103.7 22.4 35.3 33.0 0.42 (1) - FC-12 - dichlorodi luoromethane, FC-11 - trichloro onofluoromethane (2) - mixture ratio by weight of the component blowing agents (3) « pacts of blowing agent mixed in per hundred parts of polymer (4) - parts of azido functional silane mixed in per hundred parts of polymer (5) - temperature of foaming gel in degrees centigrade . i (6) - the gap of die opening in millimeters at the thceshold of pcefoaming (7) - pressure at the die in kilograms per square centimeter at the threshold of prefoaming (8) - thickness of foam body in millimeters at the threshold of prefoaming (9) - width of foam body in millimeters at the threshold of prefoaming (10)- the gap of die opening in millimeters where the foam sample was taken (11)- pressure at the die in kilograms per square centimeter at the sampling die opening (12)- pressure at the extruder discharge in kilograms per square centimeter at the sampling die opening (13)- thickness of foam body in millimeters determined after aging for about a month (14)- width of foam body in millimeters determined after aging for about a month (15)- density of foam body in kilograms per square meter determined after aging for about a month (16)- cell size in millimeter in horizontal direction determined per ASTH D-3576. TABLE IIB Azido Initial ' (6) Blowing J Agent Silane Expansior 1 Expansion Ratio aftec Expanding In Steam for Teat Type Ratio Level. Level Ratio 15 30 1 3 S 7 10 12 IS 20 30 45 1 2 No. (1) (2) (3) (4) (5) sec. sec. min. min. min, min. min. min. min. min. min. min. he hrs. 1 FC-12/FC-11 70/30 15.4 25.7 35,.7 63.2 80.8 99.1 105 10B 114 113 117 126 127 130 116 103 2 FC-12/FC-11 70/30 IS. O.OS 24.6 33.2 60.2 81.4 101 110 109 121 112 129 136 138 157 143 119 3 FC-12/FC-11 70/30 15.4 0.1 24.4 . 34.3 62.0 82.0 105 113 119 119 126 133 130 139 124 131 117 4 FC-12/FC-11 70/30 IS. 0.15 24.6 30.7 63.8 86.2 114 127 131 142 141 145 160 166 159 168 150 5 FC-12/FC-11 70/30 IS.4 0.2 25.4 37.1 71.1 92.9 120 135 134 154 157 169 175 176 160 170 176 6 FC-12/FC-11 70/30 15.4 0.25 26.7 38.9 66.5 95.8 128 143 152 157 167 198 187 190 202 190 169 7 FC-12/FC-11 70/30 S.4 0.35 26.4 41.3 76..4 103 .144 164 178 201 202 202 203 220 185 165 170 8 FC-12/FC-11 70/30 15.4 0.45 27.7 41.3 81.7 99.2 129 143 160 177 179 173 176 187 199 176 167 (1) - FC-12 - dichlorodifluoromethane, FC-ll - trichloromoήofluocomethane (2) - mixture catio by weight of the component blowing agents 1 (3) - pacts of blowing agent mixed in pec hundced pacts of polymec (4) - parts of azido functional silane mixed in per hundred parts of polymer (S> - specific volume of foam body aged foe about a month divided by specific volume of the polymer determined prior to steam expansion tests (6) expansion ratio of foam body determined in'about two days after expansion in steam for given period of time TABLE IIC Azido Initial Expansion Ratio after Expandlng in Blowing Agent Silane Expansion Hot Air at 115'C for (min.) Test Type Ratio Level Level Ratio (6) No. (1) (2) (3) (4) (5) 3 5 to IS 30 45 60 90 1 FC-12/FC-11 70/30 15.4 29.0 56.6 61.9 55.7 38.2 18.1 8.6 7.p 1 6.4 2 FC-12/FC-11 '70/30 15.4 0.05 26.9 54.2 57.1 59.2 56.5 29.0 16.4 10.6 8.4 3 FC-12/FC-11 70/30 15.4 0.1 26.3 53.7 54.1 62.2 57.6 44.0 17.7 15.6 10.0 4 FC-12/FC-11 70/30 15.4 0.15 26.5 54.7 54.4 61.8 58.9 56.8 51.5 17.9 13.2 vO 5 FC-12/FC-11 70/30 15.4 0.2 27.6 58.0 57.5 61.7 65.2 69.2 49.8 14.6 13.8 6 • FC-12/FC-11 70/30 15.4 0.25 28.6 59.2 61.3 59.8 65.0 72.7 70.3 26.3 15.3 7 FC-12/FC-11 70/30 15.4 0.35 28.2 56.1 58.3 57.3 65.3 69.9 72.4 77.1 42.1 8 FC-12/FC-11 0/30 15.4 0.45 29.8 56.2 65.8 60.1 71.2 70.5 66.5 33.7 16.6 (1) - FC-12 - dichlorodifluoromethane. FC-11 - tcichlocomonofluocomethane (2) - mixture catio by weight of the component blowing agents (3) - pacts of blowing agent mixed in pec hundced parts of polymer (4) - parts of azido functional silane mixed in per hundced pacts of polyaee (5) - specific volume of foam body aged for about a month divided by specific volume of the polymer determined prior to steam expansion tests (6) - expansion catio,of foam body after expanding in hot air of 115*C for specified period Example III The apparatus, polymer composition, additives, temperature of extruder zones and operating procedure are the same as in Example II. A 70/30 * by weight mixture of FC-12 and isopropyl alcohol was used as the blowing agent. The process data set forth in Table IIIA manifest the crosslinking-delaying effect of alcohol in the foam extrusion line. The line pressures hardly rise at a silane level as much as 0.20 pph which has resulted in a significant rise in line pressures with FC-12/FC-11 blowing agent (Table IIIA). Only a moderate rise in the line pressures is seen at.a higher silane level. With this blowing agent also, the general effects of azido silane on foam extrusion and secondly expansions may be seen. A close comparison of secondary expansion characteristics between foams expanded with FC-12/FC-11 blowing agent and those expanded with FC-12/i-PrOH blowing agent reveals an interesting tendency. The foams made with FC-12/i-PrOH blowing agent expand faster in steam than those made with FC-12/FC-11 bloving agent but slower than the latter in hot air. It is inferred that isopropyl alcohol not only plasticizes polystyrene but increases the permeation rate of water through the polymer by raising the solubility of water in the polymer/blowing agent phase. For this polymer blend also, the type of expanding agent has a pronounced effect -on the steam expandability. The FC-12/i-PrOH mixed blowing agent of the present invention provided very good expansion results. TABLE Illλ λzldo roaming Threshold Coy Pcefoamlnq . Sampling Blowing Agent Bllanβ Gel Die Die Foam Foam Die Die Extruder Foam Foam Foam Cell Tes t Type Ratio Level Level Temp. Gap Preβa. Thick. width Gap Press. Press. Thick. Width Density Siz _H _. (1) ( 2 ) .11] . -111 15) i-LL 17) 10) m ( 10 ) (ID . 112]... (13) -114). (15) 11* 1 FC- 12/ l-PrOII 70/ 30 15.0 1.803 34.5 16.5 28.2 1.803 34.5 64.0 • 16.5 28.2 34.0 0.37 2 FC-12/ l-PrOII 70/30 15.0 O.OS 1.803 34.1 18.• 27.9 I. B03 34.1 66.8 18.β 27.9 30.0 0.39 3 FC- 12/ l-PrOH 70/30 15.0 0.1 1.803 34.1 19.6 32.3 1.803 34.1 66.8 19.6 32.3 30.4 0.37 4 FC-12/ l-PrOII 70/30 15.0 0.15 1.803 33.0 19.3 28.4 1.803 33.0 66.8 19.3 28.4 29.6 0.49 5 FC- 12/ l-PrOII 70/30 15,.0 0.20 1.803 32.7 20.0 29.7 1.803 32.7 65.4 20.0 29.7 28.2 0.46 6 FC-12/ l-PcOH 70/30 15.1 0.25 1.803 35.9 20.3 29.7 1.803 35.9 73.2 ,' 20.3 33.β 31.9 0.65 7 rC- 12/ i -PrOH 70/ 30 15. 1 0.35 2.03J 29.2 24.4 33.S 1.803 29.2 70.3 22.6 28.7 30.4 0.74 β FC-12/ l-PrOII 70/ 30 15. 1 0.45 2.286 31.3 24.6 36.3 1.803 39.7 73.6 21.6 36.8 31.2 0.52 (1) - FC-12 - dichlorodifluoromethane. 1-PrOH, - isopropyl alcohol ■•- ■ (2) - mixture catio by weight of the component blowing agents (3) - pacts of blowing agent mixed In pee hundred pacts of polymer (4) - pacts of azido functional silane mixed In pec hundced parts of polymec (5) - temperature of foaming gel In degrees centigrade (6) - the gap of die opening In millimeters at the. threshold of prefoaming (7) - pcesβure at the die In kilograms pec square centimeter at the threshold of pcβfoamlng (β) - thickness of foam,body In millimeters at the threshold of prefoaming ι' (9) - width of loam body In millimeters at the threshold of prefoaming (10)- the gap of die opening in millimeters where the foam sample waa taken (11)- pressure at the die In kilograms pee square centimeter a ' the sampling die opening (12)- pressure at the extruder discharge in kilograms pec equate centimeter at the sampling die opening (13)- thickness of foam body In millimeters determined after aging toe about a month (14)- width of foam body in millimeters determined after aging (or about a month (15)- density of foam body In kilograms per square meter determined after aging Cor about a month (16)- cell size in millimeter In horizontal direction determined per ASTM D-3576. • < ' Test Ho_-. 1 2 FC-12/l-PrOII 70/30 15.0 o.os 30.6 51.1 80.8 102 129 137 146 155 153 160 154 156 153 147 131 3 rC-12/l-PrOII 70/30 15.0 0.1 29.0 SO.β 78.8 102 123 133 152 155 157 174 161 166 137 ISO 150 4 FC-12/l-PrOH 70/30 15.0 0.15 31.5 58.2 91.4 106 133 148 156 137 164 160 169 166 162 167 151 5 FC-12/i-PrOII 70/30 15.1 0.2 32.1 51.* 91.7 103 138 150 185 220 171 172 194 163 158 175 148 6 FC-12/l-PrOII 70/30 15.1 0.25 29.7 51.0 92.0 121 154 179 197 209 174 19? 190 201 170 122 134 7 FC-12/l-PtOII 70/30 15.1 0.35 31.1 56.0 96.7 117 166 149 198 207 203 209 207 197 168 178 131 8 FC-12/l-PtOII 70/30 15.1 0.45 31.3 C1.2 99.4 126 174 195 202 198 191 198 202 185 135 158 131 (1) - FC-12 - dichlorodifluoromethane. l-PeOII > isopropyl alcohol (2) - mixture ratio by weight of the component blowing agenta • (3) > pacts of blowing ageiit Mixed In pec hundred partβ of polymer •• (4) - parta of azido functional silane mixed in pec hundred pact* of polymer , (5) - specific volume of loam body aged for about a Month divided by apeclflc volume of the polymer deteralned prior to steam expansion tests (6) - expansion ratio of foam body determined ID about two days after expansion In Bteaa Coc given period of time TABLE MIC λzldo Initial Expanclon Ratio aftet Expanding In Blowing λαent Silane Expansion Hot Air at U5-C for (min .) Test Type Ratio Level. Level Ratio («) Nc ». (1) (2) (?) (1) (5) 1 IP .5 10 45 60 90 1 FC-12/l-Prθll 70/30 15.0 30.1 34.7 44.1 45.8 53.6 56.7 58.8 64.1 15.8 2 FC-12/l-PrOH ( 70/30 15.0 0.05 32.0 • 34.7 34.4 54.'4 51.6 59.2 64.0 67.8 26.7 3" FC-12/l-PrOII 70/30 15.0 0.1 30.9 31.5 46.4 52.5 52.5 56.9 62.1 65.6 60.1 4 FC-12/l-Prθll 70/30 15.0 0.15 33.1 33.1 45.8 54.3 52.2 59.5 64.8 67.4 49.9 5 rc-12/i-pcoιι 70/30 15.0 0.2 34.1 43.8 58.2 54.3 61.1 62.1 64.0 66.5 66.8 6 FC-12/l-PrOII 70/30 15.1 0.25 29.6 35.7 47.9 47.3 51.5 51.2 52.5 57.4 74.2 7 FC-12/i-PrOH 70/30 '15.1 0.35 30.3 30.2 48.2 50.5 50.0 51.9 56.4 59,9 74.1 8 FC-12/l-Proιι 70/30 15.1 0.45 31.0 34.0 39.7 S5.B 64.5 65.8 65.8 65.0 81.9 λzldo Initial Expanision Ratio after Expanding In Blowing Agent Silane Expansion Hot λlr at 120*c for (minr) Test Type Ratio Level Level Ratio (7) No (1) (2) (3) («) (51 1 5 10 15 ?o 45 60 90 1 FC-12/l-PrOII 70/30 15.0 30.1 31.1 33.2 47.7 47.7 11.5 9.6 8.4 7.0 2 FC-12/l-proπ 70/30 15.0 ' 0.05 32.0 32.5 40.1 56.3 56.7 23.1 12.6 8.4 8.1 ' 3 FC-12/l-PrOII 70/30 15.0 0.1 30.9 36.8 30.6 51.C 56.9 24.8 17.2 13.4. 11.4 4 FC-12/l-PrOII 70/30 15.0 0.15 33,1 33.3 40.1 S6.9 58.8 40.1 16.2 14.3 11.S 5 rc-12/l-pcoιι 70/30 15.0 0.2 34.1 47.7 46.8 59.2 57.3 40.1 16.2 13.4 10.5 6 FC-12/l-PrOII • 70/30 15.1 ' 0.25 29.6 33.1 40.4 56.9 61.4 58.6 25.4 18.4 13.1 7 rc-12/i-proιι 'ι70/30 15.1 0.35 30.3 . 38.8 44.4 61.4 59.3 73.5 31.5 20.3 13.7 8 rC-12/i-PeOII .70/30 15.1 0.45 31.0 35.0 S0.1 64.8 66.5 80.5 66.8 31.5 21.0 (1) - FC-12 - dlchlocodlfluocomethane. 1 -Pέoil - lβopropyl alcohol (2) - mixtuce eatloi by welght of the component blowing agenta . 1 (3) - paeta bf blowing agent mixed In per hundred parta of polymer (4) - parts of azido functional ■ ■ailane ■lxed n per hundred parta of polymec (5) - epeclfic volume of foam body aged for about a ■onth divided by specific volume of the polymer determined prior to steam <expansion teata («) * expansion ratio of foam body after expanding In hot air of 115* C for specified period • (7) - expansion catlo of foam body after expanding in hot ale of 120* C for specified period Example IV The apparatus and procedures used in this example were essentially the same as those used in previous examples. A polystyrene with a molecular weight of 200,000 was used. A steam chamber such as that 5 illustrated in Fig. 1 was attached to the outlet die of the extruder to determine the effect of on-line steam application on foam density. Three steam chambers of 0.5, 1.0, and 2.0 feet (15.2, 25.4. and 50.8 cm) in length were used to provide different residence times. The steam 10 chambers consisted of a Lexan© polycarbonate tube having a nominal 2.875 inches (7.3 cm) I.D. and a nominal 3.0 inches (7.6 cm) O.D., an outer shielding tube made of 0.25 inch (0.635 cm) thick, 4 inch (10.16 cm) O.D. Plexiglass©, a steam injection assembly attached at the I 5 die face, and the end piece having a--rubber seal. The steam injection assembly and the end piece were commonly " use_ό for all three tubes. Steam was generated by a. small boiler and was flowed into the chamber through a Tegraglass® porous distributor. The steam impinged on 20 the surface of the expanding foam strand at the die, passed through the chamber, and was permitted to leak out through the clearance between the foam strand and rubber seal. The foam strand was conducted away at a uniform rate by a set of pull rolls. 25 The pull rate was adjusted to give a slight pull to the strand. Control samples were taken p_ιer to steam tests with each chamber. The steam pressure at "he boiler 2 was maintained at about 20 psig (1.41 kg/cm ). After steam was introduced, a few minutes were allowed for the 30 system to equilibrate prior to taking samples. Fig. 3 illustrates how different blowing agent formulations affect the steam expansion rates of foams extruded from a polystyrene having a weight average molecular weight of about 200,000. Since factors ' affecting t'he apparent expansion rate include foam dimensions, foam densities, and foaming temperature, corrections were made for these external factors so that intrinsic expansion rates would be properly compared. Corrections for dimensional variations were made according 0 to the following equation: width x thickness 5 where T* is the corrected exposure time and T is the real exposure time. The normalized corrected exposure time (T*) is approximately equivalent to the exposure time for a cylindrical foam having a one inch diameter. No corrections were made for the variation of foam density o since they were all within a narrow range of 1.9 to 2.3 pcf (30.4 to 36.8 Kg/m 3 ). As can be seen from Fig. 3, the foams made with blowing agents within the scope of the present invention expanded rapidly. The addition of azido silane 5 crosslinking agent further enhances the steam expansion rate. For this foam, density was reduced by 10% in 4 seconds and 20% in about 6 seconds of steam exposure. : " • Fig. 4 shows a similar effect for a mixed FC-12/i-PrOH blowing agent within the scope of the present 0 invention on a 50/50 blend of polystyrenes having weight average molecular weights of approximately 200,000 and 300,000. respectively. Table IV below summarizes all data for on-line steam expansion in terms of steam-exposure time for a 10% reduction in foam density. The data have been normalized for a 1.0 inch diameter, 2.0 pcf polystyrene foam. TABLE IV Time (sec.) for Polymer « • Azido.-Silane 10% Reduction Type Blowinσ Aαent Level (pph) in Densi y A FC-12/EtOH:70/30 ___ 4.6 A FC-12/EtOH:70/30 0.5 3.9 B FC-12/EtOH:70/30 6.9 B FC-12/EtOH:70/30 0.2 4.8 B FC-12/EtOH:70/30 0.5 3.8 B FC-12/i-PrOH:70/30 8.2 A = polystyrene having Mw = 200,000 B = 50/50 blend of polystyrenes having Mw = 200.000 and 300,000. respectively As can be seen, foams made with blowing agents within the scope of the present invention expand rapidly. Having described the invention in detail and by reference to preferred embodiments thereof, it will be apparent that modifications and variations are possible without departing from the scope of the invention defined in the appended claims.

Claims: 1. A process for preparing a foamed product by steam expanding a precursor cellular product that includes a softenable polymer and a mixture of volatile blowing agents characterized in that (1) the polymer is an alkenyl aromatic polymer having a glass transition temperature between 60° and 100 β C; (2) the blowing agent mixture includes dichlorodifluoromethane as a primary blowing agent, in an.amount of from 40% to 90% by weight of * the blowing agent mixture; and from 10 to 50 weight percent of a secondary blowing agent selected from a halogenated hydrocarbon, a hydrocarbon, or an aliphatic alcohol containing from 1 to 4 carbon atoms or mixtures thereof; said halogenated hydrocarbon, hydrocarbon or aliphatic alcohol having a normal atmospheric boiling point of from about 0° to about 100°C; and (3) the precursor cellular product is exposed to steam in substantially atmopsheric pressure to expand further the precursor cellular structure to a foam of lower density. 2. The process according to claim 1 which includes the steps of: (a) melt processing under pressure an alkenyl aromatic polymer having a glass transition temperature of between about 60° to about 100°C together with a volatile blowing agent mixture to form a flowable admixture, said volatile blowing agent mixture including a mixture of from 40 to 90% by^weight of a primary blαwing agent that is dichlorodifluoromethane, and from 10 to 60% by weight of a « • secondary blowing agent selected from a halogenated hydrocarbon, a hydrocarbon, and an aliphatic alcohol containing from 1 to 4 carbon atoms, or mixtures thereof; said halogenated hydrocarbon, hydrocarbon and aliphatic alcohol having a normal atmospheric boiling point of from o β to 100°C; (b) extruding said admixture through a die to a zone of lower pressure and activating said blowing agent, mixture to expand said alkenyl aromatic polymer to a cellular structure;-and - (c) exposing said cellular stxucture to steam at substantially atmospheric pressure to expand fur.th&r said cellular structure to a foam of lower density. 3. The process according to claim 1 which includes the steps of: (a) impregnating a volatile blowing agent mixture into a granular alkenyl aromatic polymer having a glass transition temperature of between about 60° to about 100°C. said volatile blowing agent mixture comprising a mixture of from 40 to 90% by weight of a primary blowing agent_.that is dichlorodifluoromethane and f.rom 10 to 60% by weight of a secondary blowing agent selected from a halogenated hydrocarbon, a hydrocarbon, and an aliphatic alcohol containing from 1 to 4 carbon atoms, and mixtures thereof; said halogenated hydrocarbon, hydrocarbon, and aliphatic alcohol having a normal atmospheric boiling point of from about 0° to about 100°C; (b) heating said granular alkenyl aromatic polymer to activate said volatile blowing agent and expand said granular alkenyl aromatic polymer to a cellular structure; and (c) exposing said cellular structure to steam at substantially atmospheric pressure to expand further said cellula ' r structure to a foam of lower density. 4. The process of claim 3 in which steps (b) and (c) occur substantially simultaneously and said steam supplies the necessary heat to activate said volatile blowing agent mixture. 5. The process of claims 2 or 3 in which said alkenyl aromatic polymer is polystyrene. 6. The process of claims 2 or 3 in which said alkenyl aromatic polymer is a copolymer of styrene and acrylonitrile. 7. The process of claims 2 or 3 in which said volatile blowing agent mixture is present in an amount of from 10-30 parts per hundred of said alkenyl aromatic polymer. 8. The process of claims 2 or 3 in which said volatile blowing agent mixture includes from 60 to 80% by weight dichlorodifluoromethane and from 20 to 40% by weight trichloro onofluoromethane; 9. The process of claims 2 or 3 in which an azido functional silane σrosslinking agent is added to said alkenyl aromatic polymer in step (a). 10. A product prepared according to the process of claim 1. having a density of less than 2.3 pounds per cubic foot (36.8 Kg/m 3). 11. The product of claim 10 having a density of less 3 than 0.6 pounds per cubic foot (9.6 Kg/m ).

Inventors: GARCIA GERALD A, PARK CHUNG POO, GARCIA, GERALD, A., PARK, CHUNG, POO
Applicants: DOW CHEMICAL CO, THE DOW CHEMICAL COMPANY
Application year: 1986
Main classification: C08J9
IPC codes: B29C44, C08J9