LOW DENSITY,EXTRUDED ETHYLENIC POLYMER FOAMS

Abstract: Low density ethylenic polymer foam planks having density of from about 0.8 to about 1.9 pounds per cubic foot, dimensional stability, substantially closed-cell structure, a cross-sectional area of at least six square inches and a minimum cross-sectional dimension of at least 0.5 inch. Such foam planks are made from ethylenic polymers by release to lower pressure of flowable, foamable gel under pressure, e.g., by extrusion foaming, wherein the gel comprises at least one ethylenic polymer and at least one volatile blowing agent. The process of making such foam planks is particularly characterized by the improvement wherein the flowable gel is mixed sufficiently to disperse the blowing agent in the gel to an amount from about 13.5 to 35 x 10<s-4>s moles per gram of the ethylenic polymer.

Description: LOW DENSITY, EXTRUDED ETHYLENIC POLYMER FOAMS Background of the Invention • This invention relates to foamed articles 5. of ethyienic polymers. It also pertains to improvement in process whereby are obtained ethyienic polymer foam planks having low density, dimensional stability, and .substantially closed-cell structures. The term "low density ethyienic polymer 10 foam planks" as used herein means cellular struc¬ tures made from ethyienic polymers having densities from about 0.8 to about 1.9 pounds per cubic foot (pcf), a cross-sectional area of at least 6 square inches, and a minimal cross-sectional dimension 15 of at least 0.5 inch. It is well known to make closed-cell ethyienic polymer resin foams by the process of extrusion foaming wherein a normally solid thermo¬ plastic ethyienic polymer resin such as polyethylene is heat-plastified and mixed under pressure with a vαlatile material such as 1,2-dichlorotetrafluoro- ethane to form a flowable gel which is then passed through a shaping orifice or die opening into a zone of lower pressure. Upon the release of pressure, the volatile constituent of the gel vaporizes, forming a gas phase cellular structure in the gel which cools to a corresponding cellular foamed solid resin. Desirably, the resulting gas cells are substantially uniform in size, uniformly dis- tri ut ed through the foam body, and closed, i.e., separated from each other by membrane walls of resin. Although a number of general principles are thought to be understood, much of the extru¬ sion foaming technology is empirical, based on experience, and directed to very specific materials and details to produce saleable products of nar¬ rowly defined specificat on. One of the common requirements of accept¬ able foam resin products is dimensional stability, i.e., it is desired that the linear dimensions and OMPI /,. IPO thus the volume of a piece of foam resin not change appreciably, either to shrink or to expand, under ordinary conditions, from the time its manufacture is complete until the time its ultimate useful life is ended. It is also desired that if any appreci¬ able shrinking of a foam is to occur, which is usually the case with a freshly extruded foam, the foam be able to recover within a reasonable period of time to a substantially constant volume close to that of the foam measured shortly after its extru¬ sion. The difficulties of attaining dimensional stability are particularly acute in foams of rela¬ tively low density (high expansion ratio) when the resin membrane cell walls are relatively thin. It has been explained that the vapors of volatile material originally present in the cell gradually permeate the cell wall and escape from the foam over a period of time, thereby tending to reduce the inner cell pressure and tending to cause the foam to shrink during that time. However, when the foam is exposed to ambient atmosphere, air and its constituent gases also tend to permeate into the foam through the cell wall over a period of time thereby tending to increase the inner cell pressure. The difficulties of attaining dimensional stability are further accentuated in relatively thick foams, i.e., foam planks. It has been observed that with such foams the time to reach substantially constant, commercially acceptable volume is relatively long, ■ i.e., more time is required for rates of diffusion of residual blowing agent out of the foams and air into such foams to balance. Accordingly, the actual change in cell gas pressure and size is the result of complex and often opposite forces, and the resultant effect on resin foam dimensions is difficult to predict. Polyethylene foam planks having thickness greater than about 0.5 inch, dimensional stability, and substantially closed-cell structure are well known items of commerce. Well known end use appli¬ cations of such planks are found in the packaging, automotive, construction, contact and water sports and appliance markets. However, the planks known to date have foam density greater than about 2.0 pounds per cubic foot. In spite of the economic ncentive associated with more efficient use of raw materials, attempts to produce foam planks having density lower than 2.0 pounds per cubic foot using the conventional extrusion technology known in the art have met with repeated failures. As a result, there are no OMPI _ foam planks having thickness greater than about 0.5 inch and having foam density lower than about 2.0 pounds per cubic foot made by the process of, continuous extrusion foaming. Nevertheless, there is a need and desire for foam planks having foam density lower than that of conventional planks for the end use applications discussed hereinabove. Accordingly, an object of this invention is to provide improved ethyienic polymer foam planks. Another object is to provide method and means for making such foam planks. A particular object is to provide such improved method and means for making ethyienic polymer foam planks having dimensional stability, substantially closed-cell structure, and foam density lower than that of the conventional ethyienic polymer foam planks known to date. Other objects and advantages of the present invention are brought out in the description that follows. Summary of the Invention The objects of this invention are obtained in ethyienic polymer resin foam planks having density of from about 0.8 to about 1.9 pounds per cubic foot, dimensional stability, substantially closed-cell structure, a cross-sectional area of at least six square inches, and a minimum cross-sectional dimension of at least 0.5 inch. Also contemplated within the scope of the present invention is a method for making the ethyienic polymer resin foam planks described hereinabove using gel foaming technology, particu¬ larly characterized by improved mixing sufficient to disperse the fluorccarbon blowing agent in the gel to an amount from about 13.5 to 35 x 10 * 4 moles per gram of ethyienic polymer resin. Detailed Description and Embodiments The ethyienic polymer resins used in the present invention include low density polyethylene (LDPE), blend∑rof LDPE with up to about 30% by weight of medium density polyethylene, and blends of LDPE with up to about 30% by weight of ethylene copolymers which comprise ethylene and at least one onoethylenically unsaturated comonomer, especially another olefin or a carboxylic acid or an alkyl ester of a monoethylenically unsaturated carboxylic acid. Examples of such copolymers include ethyl ene- -propylene copolymer, ethylene acrylic acid, ethylene- -methyl methacrylate copolymer, ethylene vinyl acetate copolymer and the like. Methods of making ethyienic polymer resins described hereinabove are readily known in the art. j υREAl OMPI The term "low density polyethylene" as used herein means branched polyethylene having a density from about 0.910 to about 0.930 g/cc and a melt index from about 0.1 to about 10 dg/min, preferably from about 0.2 to about 2.5 dg/min, and most preferably from about 0.2 to about 1.0 dg/min. The medium density polyethylene which is used in accordance with this invention may have a density from about 0.931 to about 0.940. Blends of one or more of low density polyethylene ar-z also included provi ded that the resultant blends have a melt index within the range described hereinabove. In accordance with this invention, blowing agent comprises at least one volatile fluorocarbon. The term fluorocarbon is used herein to mean halo- carbons containing carbon and fluorine atoms, any other atoms being limited to hydrogen or chlorine atoms. The symbol "FC" hereinafter stands for "fluorocarbon" and numbers are chosen for convenience in referring to these fluorocarbon compounds. In one embodiment of this invention, the blowing agent which would provide satisfactory low density ethyienic polymer foam planks comprises at least one fluorocarbon selected from the group I fluorocarbons having two to four carbon atoms in their olecular structure, normal boiling points, i.e., under standard one atmosphere pressure, between -30°C and 30°C and a value for the critical quantity T -0.5V C of between 110 to 145 where T D is the normal boiling point temperature of the fluorocarbon in degrees Kelvin and V c is its critical mole volume in cubic centimeters per gram-mole. [The critical volume of a substance can be experimentally measured, and the values of many are reported in the literature. It can also be computed as the reciprocal of the critical density, converted to gram-mole basis. Approximate values of critical volume can also be calculated from the molecular structure according to the Lydersen equation as described in "Chemical Process Principles" by Olaf A. Hougen, K. M. Watson and R. A. Ragatz, 2nd Edition, published (1954) by John Wiley & Sons, New York, page 88 and Table 6, page 91. The Lydersen equation is V c = 40 + ΣTΔv Where ~ V C is the critical volume in cubic centimeters per gram-mole and ΣΔv is the summation of the contributions for each atom or atomic group that is present, using values set out in Table 6 on page 91 of the publication.] ' Specific examples of such group I fluorocarbons are 1,2-dichlorotetrafluoroethane (FC-114), 1-chloro- -1,2,2,2-tεtrafluorcethane (FC-124A), 1-chloro-l, 1,2,2- tetrafluoroethane (FC-124), and 1,1,1-trifluoropropane (FC-253). Each of these fluorocarbons has a normal boiling point temperature between -30 to 30°C and a value for T -0.5V C between 110-145. There can be up to about 0.35 gram-mole of such blowing agent per 100 grams of resin in the flowable gel. In another embodiment of this invention the blowing agent comprises at least one fluorocarbon selected from the group II fluorocarbons consisting of trichlorofluoromethane (FC-11), dichlorodifluoromethane (FC-12), l,l,2-trichloro-l,2,2-trifluoroethane (FC-113), l-chloro-l,l-difluoroethane (FC-142B), 1,1-difluoroethane (FC-152A) and 2,2-difluoropropane (FC-272), provided, ' however an effective amount of steara ide, for example, from about 0.3 to about 3.0 percent, preferably from about 0.5 to about 1.5 percent, by weight based on the weight of the ethyienic polymer resin, is used in conjunction with the blowing agent to impart the desired dimensional stability to the resultant foam planks. In yet another embodiment of the present invention, up to about 25 parts by weight of the fluorocarbons of group I can be replaced by at least one fluorocarbon selected from group II, .provided that the resultant foam planks are dimensionally stable as defined hereinbelow. OMPI Λ, WIPO Λ>, The blowing agent is compounded nto the starting ethyienic polymer resins in proportions to make the desired degree of expansion in the resulting foamed cellular product, usually up to about 75-fold ' volume expansion to make products having aged foam densities down to about 0.013 g/cc (about 0.8 pound per cubic foot). Depending upon the starting proportion of blowing agent, the resulting foam products, i.e., foam planks, of this invention have densities from about 0.8 to about 1.9 pounds per cubic foot (pcf). The maximum useful proportions of such blowing agent (s) in composition of flowable, foa able gel is in the range of about 0.135 to about 0.35 gram-mole per 100 grams of the starting ethyienic polymer resins. The blowing agent is compounded into the starting ethyienic polymer resin in conventional fashion to make a flowable gel, preferably in con¬ tinuous manner, e.g., in a mixing extruder, using heat to plastify the resin, pressure to maintain the blowing agent in non-gaseous state, and mechanical working to obtain a thorough mixing of the resin and blowing agent. The resulting gel is then cooled if necessary and passed through a suitable die. orifice into a zone ' of low pressure, e.g., normal ambient air temperature, where it expands to a lower density, OMPI cellular mass. As the foamed extrusion forms, it is taken away from the extruder, allowed to cool to harden the ethyienic polymer resin, and collected for further processing, storage or other disposal. The resulting ethyienic polymer resin foam planks have densities from about 0.8 to about 1.9, preferably 1.0 to about 1.8, and most preferably from about 1.2 to about 1.6, pounds per cubic foot, dimen¬ sional stability, substantially closed-cell structure, a cross-sectional area of at least s x square inches, and a minimal cross-sectional dimension of at least 0.5 inch, preferably at least 0.75 inch. The gas. space of the cells of the resulting polyethylene blend foam originally comprises as an essential constituent the particular blowing agent(s) used to make the foams. As time passes, the blowing " agent diffuses out of the foam cells and is gradually ' replaced by air diffusing into such cells. Ultimately, the gas space of the foam cells is essentially occupied by air. It is essential and critical to the present - invention that adequate and thorough dispersion of the blowing agent in the ethyienic polymer resins be obtained. More specifically, it is essential and critical to thoroughly disperse from about 13.5 to ι OMPI .* _.- WIPO Λ , , about 35 x iθ~ 4 moles of the fluorocarbon blowing agent (s) per gram of ethyienic polymer resin. The present invention is not limited by the type of mixer used to carry out adequate and thorough mixing of the blowing agent in the ethyienic polymers. A number of well known static or dynamic mi ers can be used to thoroughly disperse the fluorocarbon blowing agent in the flowable gel to an amount from about 13.5 to 35 x 10 * 4 moles per gram of ethyienic polymer resin. An attempt to incorporate an additional amount of the blowing agent into the gel without thorough mixing would result in an unsatisfactory product. More specifically, the - resulting ethyienic polymer resin foam planks would have blow holes, striations in the cross -sectional area and/or uneven cell size distribution and the like. In one embodiment of this invention, an interfacial surface generator is placed in between the conventional gel extruder and cooler in operative communication therewith. By the term "interfacial surface generator" is meant an in-line motionless mixer, sometimes referred to as a static mixer or static pipe mixer, whose mixing mechanism is generally unrelated to the throughput when the throughput is " flowing in the region of streamline flow. Such mixers may be considered as layering mixers wherein the flowing stream is divided and two component parts reshaped and - joined together in such a way that the interface between the original elements of the stream is substantially increased. Such mixers are well known in the art and some of these mixers and their mode of operations are • described in the following U.S. Patents: 3,206,170; 3,239,197; 3,286,992; 3,328,003; 3,358,749; 3,382,534; 3,394,924; 3,404,869; 3,406,947; 3,506,244; 3,860,217; and 3,918,688. In another embodiment of this invention a rotary mixing device containing inter eshing studs on the rotor and the outer cylinder shell is placed in betv/een the conventional gel extruder and the cooler in operative communication therewith to ensure adequate and thorough dispersion of the blowing agent in the ethyienic polymer resins. Finely divided solid materials such as calcium silicate, zinc stearate, magnesium silicate and the like can advantageously be incorporated with the ethyienic polymer or gel prior to expanding the same. Such finely divided materials aid in controlling the size of the cells, and are usually employed in amounts ' up to one (1) percent by weight of the polymer. Numerous fillers, pigments, lubricants, aπti- oxidants and the like well known in the art can also be OMPI /,. WIPO « incorporated into the ethyienic polymer as desired. For the present purposes, dimensional stability of the foam planks refer to changes which occur in foam plank volume, particularly in later . stages of manufacture and during subsequent storage of the foam product. The dimensional stability of the foam products is measured by observing the changes in volume occurring in a test specimen of the foam plank as a function of time. The test specimen is obtained by quickly cutting, from the foam product soon, e.g., within five minutes, after its formation, a piece and accurately measuring its overall volume, e.g., by cubic displacement of water. The initial volume of this specimen is arbitrarily selected as the bench mark - volume for the subsequent dimensional stability study. The foam plank specimen is exposed to air at atmo¬ spheric pressure and ordinary room temperature; its volume is re-measured from time' to time and related on ' a volume percentage basis to the initial volume. In general manufacturing practice, an ethyienic polymer foam plank is considered to be ' di ensionally stable for practical purposes if the minimum volume to which the foam plank shrinks is not less than about 85, preferably not less than about 90, percent of the initial bench mark volume, and if the volume of the foam plank four weeks, preferably three weeks, after its extrusion is not less than 90 percent of the initial volume and is substantially constant thereafter under ambient atmospheric conditions. The term "dimensionally stable" in reference to the subject ethyienic polymer foam planks is used herein in. the sense of the foregoing definitive description. The specific working examples that, follow are intended to illustrate the invention but are not to be taken as limiting its scope. In the examples, parts and percentages are by weight unless otherwise specified or required by the context. Example 1 Polyethylene having a melt index of 2.3 and a density of 0.921 g/cc is introduced to a plastics extruder having the usual sequential zones denominated by a feed zone, compression zone, metering zone and mixing zone. The normally solid polyethylene is- heat-plastified in the extruder and forwarded under pressure of the screw to which a volatile fluorocarbon 1,2-dichlorotetrafluoroethane is then injected as the blowing agent. The body of mass containing the blowing agent and molten polymer is then mi ed via conventional mixing techniques known in the art of producing cellular polyethylene. The partially mixed gel then passes through an intensive mixer with an average residence time of 4.0 minutes. The intensive mi er used in this example has a rotating stud rotor enclosed within a housing which also has a studded internal surface that intermeshes with the studs on the rotor, the gel flow being in a generally axial di ection. The variable speed rotor creates a wide selection of mixing intensity. The inter eshing studs of the mixer had a relative velocity of 25 feet per minute. The gel leaving the intensive mi er is then cooled to approxi¬ mately 105°C and is thereafter extruded or discharged through an orifice into a zone of. lower pressure, e.g., the atmosphere, wherein the extruded material expands to form a cellular body. Talc was added along with the polymer to aid in controlling the size of the cells. Blowing agent is increased in a stepwise manner while care¬ fully examining the resultant foam product. A plurality of quality stable foams are produced as shown in Tables I and II. The nucleator, talc, is varied inversely with blowing agent level to hold the average cell size of the foam to about 1.2-1.4 mm. Aged densities of these foams ranged from 2.09 pcf o a Tow -Of 1-'2Θ pcf. "BUREA OMPI TABLE I Test FOAM , BLOWING AGENT (2) TALC No. DENSITY^ 1 ) CONCENTRATION^ 3 ) CONCENTRATION ( 3 ) 1.1* 2.09 23 0.35 1.2 1.64 27 0.20 1.3 1.40 33 0.10 1.4 1.20 38 0.06 Notes: * s Not an example of this invention (1) = Density of foam plank aged for a minimum of 90 days in pounds per cubic foot (2) = 1,2-dichlorotetrafluoroethane (3) = Concentrati n in parts per hundred of polymer. TABLE II CROSS- FOAM VERTICAL TENSILE STRENGTH psi (3) COMPRESSIVE Test SECTION OF DENSITY COMPRESSIVE MACHINE CROSS CREEP NO ,; FOAM (INCHES) (PCF) (1) STRENGTH (psi) (2) DIRECTION DIRECTION {%) (4) 2.1* 1.75 x 7 2.09 8.4 61.6 38.6 .6 2.2 1.6 x 7 1.64 7.1 51.0 28.6 1.6 2.3 1.3 x 7 1.40 4.6 62.0 29.2 5.4 en 2.4 1.125 x 71/4 1.20 3.7 56.0 27.0 19.0 I Notes Not an example of this invention. 1 Density of foam plank aged for a minimum of 90 days measured per ASTM D-3575-77-C. 2 Vertical compressive strength at 25% deflection measured per ASTM D-3575-77-B. (3) Tensile strength measured per ASTM D-3575-77-E. (4) Compressive creep at 1.0 psi after 1 week measured per ASTM D-3575-77-BB. Example 2 Polyethylene with a melt index of 0.7 and a density of 0.922 is extruded through the same process as described in Example 1. Residence time within the intensive mi er is reduced to 2.0 minutes. Relative velocity of the inter eshi g studs is varied as set forth in Table III. A plurality of quality, stable foams are produced with various 1,2-dichlorotetrafluoroethane levels as shown in Tables III and IV. TABLE III BLOWING^ MIXER TEST FOAM AGENTS NO. DENSITY (1) LEVELV3) STUD ,Λ X TALC(2) VELOCITY( ) 3.5 1.88 24 .25 15.7 3.6 1.39 31 .06 23.5 3.7 1.28 36 .04 32.0 3.8 1.10 47 — 63.0 Notes: (1), (2) and (3) Same as Table (4) Speed in feet per minute. TABLE IV CROSS- FOAM VERTICAL COMPRESSIVE OPEN-CELL Test SECTION DENSITY COMPRESSIVE CREEP CONTENT No. (INCHES) (PCF) (1) STRENGTH (psi) (2) (%) (3) ( ) (4) 4.5 1.9 x 9.0 1.88 8.4 .8 0 4.6 2.23 x 9.0 1.39 6.3 2.7 9.9 4.7 2.0 x 9.0 1.28 5.8 7.5 1.1 4.8 1.7 x 9.0 1.10 4.9 ND 7.5 Notes ; 1 Density 6f foam plank aged for a minimum of 90 days measured per ASTM D-3575-77-C. 2 Average co pressive strength at 2B% deflection measured per ASTM D-3575-77-B. (3) Compressive creep at 1.0 psi, after 1000 hours measured per ASTM D-3575-77-BB. (4 ) Open-cell content measured per ASTM D-3575-77-DD. Volume changes in percent based on 5 minute initial volume have been measured on Test No. 4.6 and repeated in Table V. The sample which is a typical foam plank of the present invention is dimensionally stable as defined hereinabove. O PI /j, WIPO « Λ_. TABLE V Foam Volume Changes in Percent Based on 5-Minute Initial Volume Test Foam Density Volume Percent After Time in Days No. (pcf) T 18 4.6 1.39 88.4 87.6 87.0 5.2 1.30 96.4 96.6 96.7 Example 3 Polyethylene used in Example 2 is extruded through the same processing equipment as described in Example 1. Average residence time within the intensive mixer is 4.0 minutes with the intermeshing studs having a relative velocity of 31 feet per minute. Stearamide at 0.75 pounds per 100 pounds of polymer is added along with 19.83 x 10"4 moles of dichlorodifluoromethane per gram of polymer. The resulting foam plank has a cross-section of 1.7 in. x 7.9 in. and a density of 1.37 pcf. Volume changes in percent based on 5 minute initial volume have been measured and reported in Table V as Test No. 5.2. As seen from Table V, the sample of Test No. 5.2 is dimensionally stable as defined hereinabove. In place of the particular ethylene poly¬ mer or blowing agent used in the preceding examples, there can be used other ethyienic polymers or blowing agents with substantially similar results in ob¬ taining- low density foam planks having dimensional stability and substantially closed-cell structure. In place of the particular mixing device used in the preceding examples, one or more of the other mixing devices described hereinabove, but not limited thereto, can also be used with substantially similar results. Example 4 The process as described in Example 1 was • duplicated with replacement of the rotary mixing device by five identical elements of in-line motion¬ less mixers. Said static mixers were of the Sulzer Brothers Design licensed by Koch Engineering Co. Inc., each element having 15 corrugated sheets and an L/D ratio of 1.0. Each element also being aligned 90° about the flow axis from the adjacent elements. 1,2-Dichlorotetrafluoroethane at 35.parts per 100 parts of polymer was injected and mixed via con¬ ventional and static mixer techniques. Talc was added at .08 parts per 100 parts of polymer for cell size control. The resulting foam plank had a density of 1.41 pcf and a. cross -sect ion of 1.5 in. x 7.8 in. Example 5 Polyethylene used in Example 2 is extruded through the same processing equipment as described in Example 1. Average residence time within the inten- - sive mixer is 4.0 minutes with the intermeshing studs having a relative velocity of 45.5 feet per minute. Stearamide at 1.5 pounds per 100 pounds I of polymer is added along with .04 parts of talc. A mixed blowing agent was used consisting of 70% by weight of dichlorodifluoromethane and 30% by weight of trichlorofluoromethane. Total blowing agent mass rate being 28 parts per 100 parts of polymer. The resulting foam had a cross-section of 1.79 in. x 8.1 in. and a density of 1.44 pcf after five days of aging time. Volume change based on 5 minute initial volume was 90.6% after 5 days of aging.

Claims: HAT IS CLAIMED IS: 1. A method for making ethyienic polymer resin foam planks having density of from about 0.8 to about 1.9 pounds per cubic foot, dimensional stability, substantially closed-cell structure, a cross-sectional area of at least 6 square inches and a minimal cross-sectional dimension of at least 0.5 inch by forming under heat and pressure a flow¬ able gel composition of an ethyienic polymer resin and at least one fluorocarbon blowing agent selected from fluorocarbons having normal boiling point between -30 and 30°C, from 2 to 4 carbon atoms in its molecular structure, and a value for the critical quantity T5 -0.5V C of between 110 to 145 where T D is the normal boiling point temperature of the fluorocarbons in degrees Kelvin and V c is its critical volume in cubic centimeters per gram-mole, and releasing the resulting flowable gel to ambient - . air atmosphere whereby the blowing agent separates from the gel and forms gas cells in the ethyienic polymer resin, particularly characterized in that the flowable gel is mixed sufficiently to disperse the fluorocarbon blowing agent in the gel to an amount from 13.5 to about 35 x 10"4 moles per gram of the ethyienic polymer resin. OMPI 2. The method of Claim 1 wherein the fluorocarbons are 1,2-dichlorotetrafluoroethane, l-chloro-l,2,2,2-tetrafluoroethane, 1-chloro- -1,1,2,2-tetrafluoroethane and 1,1,1-trifluoropropane. 3. The method of Claim 1 wherein the ethyienic polymer resin is low density polyethylene. 4. The method of Claim 1 wherein the ethyienic polymer resin is a blend of 70 percent by weight of low density polyethylene and 30 per¬ cent by weight of ethylene copolymer which comprise ethylene and at least one monoethylenically unsatu- . rated comonomer. 5. The method of Claim 4 wherein the monoethylenically unsaturated comonomer is another olefin, a carboxylic acid, or an alkyl ester of a monoethylenically unsaturated carboxylic acid. 6. The method of Claim 5 wherein the carboxylic acid is acrylic acid. 7. The method of Claim 1 wherein the flowable gel composition comprises an ethyienic polymer resin, an effective amount of stearamide and at least one fluorocarbon blowing agent selected from the group consisting of trichloro- fluoro ethane, dichlorodifluoromethane, 1,1,2- ,_ , OMPI f,. IPO .. -trichloro-l,2,2-trifluoroethane, l-chloro-1,1- -difluoroethane, 1,1-difluoroethane and 2,2- -d fluoropropane. 8. The method of Claim 7 wherein the effective amount of stearamide is about 0.3 to about 3.0 percent by weight based on the weight of the ethyienic polymer resin. 9. The method of Claim 1 wherein up to 25 parts by weight of the volatile fluorocarbon blowing agent is replaced by at least one fluoro¬ carbon selected from the group consisting of tri- chlorofluoromethane, dichlorodifluoromethane, l,l,2- richloro-l,2,2-trifluoroethane, 1-chloro- -1,1-difluoroethane, 1,1-difluoroethane and 2,2- -difluoropropane. 10. As an article of manufacture, an ethyienic polymer resin foam plank having density of from about 0.8 to 1.9 pounds per cubic foot, dimensional stability, substantially closed- -cell structure, a cross -sectional area of at least 6 square inches, and a minimal cross-sectional dimension of at least 0.5 inch, wherein said ethyienic polymer resin comprises at least one ethylene homopolymer or an ethylene copolymer which consists essentially of ethylene and at least one monoethylenically unsaturated comonomer, further characterized in that the gas space of the foam plank cells originally comprises as an essential constituent a volatile fluorocarbon selected from • fluorocarbons having normal boiling point between -30 and 30°C, from 2 to 4 carbon atoms in its molecular structure, and a value for the critical quantity T5 -0.5V C of between 110 to 145 where T5 is the normal boing point temperature of the fluoro¬ carbons in degrees Kelvin and V c is its critical volume in cubic centimeters per gram-mole, there being up to about 35 x 10~4 moles of such blowing agent per gram of ethyienic polymer resin in the flowable gel. 11. An article of manufacture according to Claim 10 wherein the fluorocarbons are 1,2-dichloro- tetrafluoroethane, l-chloro-l,2,2,2-tetrafluoroethane, l-chloro-l,l,2,2-tetrafluoroethane and 1,1,1-tri- fluoropropane. 12. An article of manufacture according to Claim 10 wherein the ethyienic polymer resin is low density polyethylene. 13. An article of manufacture according to Claim 10 wherein the ethyienic polymer resin is a blend of 70 percent by weight of low density poly- OMPI WIPO - . ethylene and 30 percent by weight of ethylene copolymer which comprises ethylene and at least one monoethylenically unsaturated comonomer. 14. An article of manufacture according to Claim 13 wherein the monoethylenically unsaturated comonomer is another olefin, a carbo>ylic acid, or an alkyl ester of a monoethylenically unsaturated carboxylic acid. 15. An article of manufacture according to Claim 14 wherein the carboxylic acid is acrylic acid. 16. An article of manufacture according to Claim 10 wherein the ethyienic polymer resin foam plank contains an effective amount of stear¬ amide an.d the volatile fluorocarbon is selected from the group consisting of trichlorofluoromethane, dic lorodifluoromethane, l,l,2-trichloro-l,2,2- -t ri f 1 uoroethane , 1-c 1 oro-1 , 1-di f 1 uoroethane , 1,1-difluoroethane and 2,2-difluoropropane. 17. An article of manufacture according to Claim 16 wherein the effective amount of stear¬ amide is from about 0.3 to 3.0 percent by weight based on the weight of the ethyienic polymer resin. 18. An article of manufacture according I to Claim 10 wherein up to 25 parts by weight of the volatile fluorocarbon is replaced by at least one fluorocarbon selected from the group consisting of trichlorofluoro ethane, dichlorodif luoromethane, l,l,2-trichloro-l,2,2-trifluoroethane, 1-chloro- -1,1-difluoroethane, 1,1-difluoroethane and 2,2- -difluoropropane. 19. An article of manufacture according to Claim 10, 16, or 18 wherein the foam plank has a density from about 1.0 to about 1.8 pounds per cubic foot. 20. An article of manufacture according to Claim 10, 16, or 18 wherein the foam plank has a density from about 1.2 to about 1.6 pounds per cubic foot. 21. An article of manufacture according to Claim 10, 16, or 18 wherein the foam plank has a minimal cross-sectional dimension of 0.75 inch. 22. An article of manufacture according to Claim 10, 16, or 18 wherein the gas space of the foam plank cells ultimately comprises as an essential constituent air. O PI /i. WIPO «

Inventors: BUSSEY M, ZABROCKI V
Applicants: DOW CHEMICAL CO, DOW CHEM CO
Application year: 1980
Main classification: B29D27
IPC codes: B29C44, C08J9, C08L7, C08L21, C08L23, C08L33, C08L101