KR910020073A - Moldable Shrinkable Thermoplastic Polymer Beads - Google Patents

Abstract

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Description

Moldable Shrinkable Thermoplastic Polymer Beads

Since this is an open matter, no full text was included.

FIG. 1 is a micrograph of a shrinked polyethylene foam ball made in accordance with the present invention, FIG. 2 is a micrograph of an extrusion-expanded polyethylene foam ball that is not allowed to contract significantly after expansion, and FIG. 3 is granted to Ando. Micrograph of commercially available "Eperan" polyethylene foam beads (density of 1.9 pcf or 30.4 kg / m 3) prepared by Kanegafuchi according to US Pat. No. 4, 483, 809. The beads shown in FIGS. 1, 2 and 3 are all represented at magnifications of approximately 9X.

Claims (56)

Moldable shrunken thermoplastic polymer foam beads. The homopolymer and copolymer alkenyl aromatic, polymer, polyvinyl polymer, polycarbonate, polyamide, polyester, polyphenyl according to claim 1, wherein the thermoplastic polymer described above comprises olefin units having 2 to about 8 carbon atoms. Moldable shrunken foam beads selected from the group consisting of ethers, polyetherimides, pullurocarbon polymers and mixtures thereof. 3. The obtainable foam beads of claim 2 wherein the polymer described above is a polyolefin selected from the group consisting of homopolymers and copolymers comprising olefin units having 2 to about 8 carbon atoms. 4. The moldable shrouded foam ball according to claim 3, wherein said polyolefin is selected from the group consisting of polypropylene, moderate polyethylene, low density polyethylene, linear low density polyethylene, polybutylene and mixtures. 3. The moldable shrinkable foam of claim 2 wherein said alkenyl aromatic polymer is polystyrene, said polyamide is nylon, said polyester is polyterephthalate ethylene and said polyvinyl polymer is polyhalogenated vinyl. marble. 2. The moldable shrunken foam beads according to claim 1, wherein the polymer described above is a thermoplastic elastomer. 2. The moldable shrouded foam ball according to claim 1, having a density, bubble size, and degree of shrinkage effective for obtaining a predetermined molding expansion ratio. 8. The moldable shrouded foam ball according to claim 7, wherein the aforementioned density is in the range of about 0.8 to 20 pcf (12.8 to 320 kg / m 3) and the aforementioned molding expansion ratio is in the range of about 1.1 to 4. 2. The moldable shrunken foam beads according to claim 1, produced by extrusion foaming as blowing agent. 10. The moldable shrinkable foam beads of claim 9 wherein the blowing agent described above is a volatile organic agent selected from the group consisting of hydrocarbons and halogenated hydrocarbons. 10. The moldable shrunken foam ball according to claim 9, wherein the blowing agent described above is a sulfurous gas. 10. The moldable shrouded foam ball according to claim 9, wherein the blowing agent described above is a solid material which decomposes to form a gas. 2. The moldable shrunken foam beads of claim 1, wherein the thermoplastic polymer described above is crosslinked after the beads have shrunk. 14. The moldable shrunken foam beads according to claim 13, wherein the aforementioned crosslinking is effected by electrospinning or chemical means. The method of claim 13, wherein the thermoplastic polymer described above is selected from homopolymers and copolymers composed of olefin units having from 2 to about 8 carbon atoms, and mixtures thereof, wherein the foam is a silane crosslinker and a silane condensation catalyst. And wherein the crosslinking is effected by exposing the contracted foam beads to moisture. 10. The moldable shrunk according to claim 9, wherein the beads described above rapidly shrink after foam due to at least one of the relatively high permeability and the relatively low vapor pressure of the aforementioned blowing agent at room temperature relative to the above blowing agent. Foam beads. 10. The moldable foam beads according to claim 9 having a corrugated foam layer or shell. 10. The moldable shrunken foam beads of claim 9, wherein the shrinkage is substantially completed within about 1 hour after the foam. 10. The moldable foam beads of claim 9, wherein the shrinkage is substantially complete within about 15 minutes after foaming. 10. The moldable foam ball according to claim 9, wherein the polymer foam described above comprises at least one permeability control additive to control the permeability of the aforementioned bubble wall. 21. The moldable foam beads according to claim 20, wherein said permeability control additive is selected from the group consisting of esters of long chain fatty acids and polyhydric alcohols, saturated higher fatty acid amides, saturated higher aliphatic amines and saturated higher fatty acids. 21. The moldable foam beads according to claim 20, wherein the aforementioned permeability control additive comprises a mixture of glycerol mono- and diglycerides. 21. The moldable foam ball according to claim 20, wherein the aforementioned permeability control additive comprises polystyrene. A molded article made by thermoforming the moldable shrinked foam beads of claim 1. (a) mixing the composition comprising the thermoplastic foam forming polymer in an extruder to form a melt; (b) inserting the blowing agent into the melt as described above at a rate effective to form the required foam density in the extrudate; (c) extruding and cutting the melt as described above to form foam beads; And (d) shrinking the above-mentioned beads to a predetermined density. The method of claim 25 further comprising treating the aforementioned beads by chemical means or electromagnetic radiation to crosslink the thermoplastic polymer. 27. The method of claim 25, wherein the type of blowing agent described above and its insertion rate are effective to produce beads having a contractile amount effective to obtain a predetermined expansion ratio in thermal atmosphere molding. The method of claim 27, wherein the predetermined expansion ratio described above is in the range of about 1.1 to 4. 4. The method of claim 27, wherein the aforementioned contraction is substantially completed within about 1 hour. 27. The method of claim 25, wherein the aforementioned composition comprising a thermally crosslinkable foam forming polymer comprises a permeability control additive that has the effect of controlling the relative permeability of the aforementioned blowing agent and the bubble wall of the aforementioned foam to the atmospheric environment. 26. The beads according to claim 25, wherein the beads described above are exposed to subatmospheric pressure and then to atmospheric pressure for a period of time effective after step (c) to remove some of the aforementioned blowing agent from the foam. How to shrink. 27. The method of claim 25, wherein the blowing agent described above is a volatile organic agent selected from the group consisting of hydrocarbon water and halogenated hydrocarbons. The method of claim 25, wherein the blowing agent described above is an inert gas. 27. The method of claim 25, wherein the method is effective for producing foam beads having a density in the range of from about 0.8 to about 20 pcf (12.8 to 320 kg / m 3) after water injection of the aforementioned blowing agent into the melt. 27. The method of claim 25, wherein the beads described above are sufficiently thermally stable to form the aforementioned polymer foams by heat treatment and are sufficient to provide sufficient expansion ratio in thermal atmosphere molding. (a) mixing a composition comprising a thermoplastic foamable polymer in an extruder with a solid foaming agent to form a melt; (b) the aforementioned melt is heated to the activation temperature of the blowing agent described above; (c) maintaining the aforementioned agglomerates at a suitable foam forming temperature in the die of the extruder described above; (d) extruding and cutting the melt as described above to form foam beads; And (e) shrinking the beads described above to a predetermined density. 37. The method of claim 36 further comprising treating the aforementioned beads by chemical means or electromagnetic radiation to crosslink the thermoplastic polymer foam. Moldable foam beads prepared by the method of claim 25. A moldable foam ball prepared by the method of claim 26. A method of molding a solid foam article in a moldable shrunken foam beads made according to the method of claim 25 which applies heat and pressure to the mold and forms the beads into the mold at substantially normal pressure without significant grinding. 41. The method according to claim 40, wherein heated gas is injected into the mold as described above at a temperature and pressure effective to soften the polyolefin foam described above, and the softened beads are expanded to fuse together to form a mold. A molding method for forming a molded article having a density. 42. The method of claim 41, wherein the molded article is removed from the mold, cooled, and subsequently annealed to more closely match the size and shape of the article to the inside of the mold. (a) mixing the silane-modified polyolefin with silane in a extruder to form a composition comprising a condensation catalyst; (b) injecting the blowing agent into the melt as described above at a rate capable of producing a desired foam density in the extrudate; (c) extruding and cutting the melt as described above to form foam beads; (d) shrink the beads described above; And (e) exposing the foam foam described above to moisture to form silane crosslinking of the polyolefin foam. 17. A method of making a moldable shrunken foam beads comprising silane-crosslinked polyolefin foam. 45. The method of claim 43, wherein the aforementioned composition of polyolefin and catalyst further comprises an additive effective to control the relative permeability of the aforementioned foaming agent and the bubble wall of the aforementioned foam to atmospheric pressure. 45. The process of claim 43 wherein the polyolefin foam described above is crosslinked with a silane group by extruding and cleaving the beads described above and then exposing the silanol catalytic catalyst to the aforementioned foam to moisture. 44. The method of claim 43, wherein the insertion rate of the aforementioned blowing agent into the melt is effective in producing foam beads having a density in the range of about 0.8 to about 20 pcf (12.8 to 320 kg / m 3) after shrinkage and exposure to moisture. The way there is. 44. The method of claim 43, wherein said polyolefin is cross-linked to a degree sufficient to be thermally stable to treat the aforementioned beads by heat and pressure and to shrink to a sufficient extent to provide an expansion ratio in thermal atmosphere molding. (a) mixing an silane compound comprising at least one unsaturated group, a free radical initiator and a silanol catalyst in an extruder with an effective amount of a composition comprising at least one polyolefin to make a utility comprising a silane-modified polyolefin; (b) injecting a blowing agent into the melt as described above at a rate effective to produce the required foam density in the extruder; (c) extruding the melt described above to form foam beads; (d) shrink the beads described above; And (e) exposing the foam foam described above to moisture to form silane crosslinking of the polyolefin foam. 17. A method of making a moldable shrunken foam beads comprising silane-crosslinked polyolefin foam. A method of molding a solid foam article from a moldable shrunken foam beads prepared according to the method of claim 43 by applying heat and pressure to the mold and filling the beads into the mold at atmospheric pressure without grinding. 50. The method of claim 49, wherein heating gas is introduced into the aforementioned melt at an effective temperature and pressure to soften the polyolefin foam described above, and the softened beads are fused together to conform to the shape of the mold to form a shaped article. Molding method. 50. The method of claim 49, wherein the molded article is removed from the mold, cooled, and subsequently annealed such that the size and shape of the article is very close to the size and shape of the inside of the mold. The method of claim 51, wherein the article described above is heated at a temperature in a range from about 100 to 200 ° F. (36.8 to 93. ° C.) for about 2 to 48 hours. (a) mixing a composition comprising silane-grafted low density polyethylene in an extruder with a silanol catalyst selected from the group consisting of organotin esters; (b) hydrocarbon or halogenated into said melt at a rate effective to cool said melt to foam temperature and to produce an extruded foam product having a density ranging from about 1.5 to about 2.5 pcf (24.0 to 40.0 kg / m 3). Injecting a hydrocarbon blowing agent; (c) extruding and cutting the melt as described above to form foam beads; (d) shrink the beads described above in an amount such that a predetermined expansion ratio is obtained in thermal atmosphere molding; And (e) exposing the foam beads to a humid atmosphere to produce silane crosslinks of the polyethylene foam. A shrinkable foam ball moldable with silane-crosslinked polyethylene foam prepared according to the method of claim 53. 55. The moldable shrouded foam ball according to claim 54, wherein the foam described above is substantially uniformly crosslinked. 54. The method of claim 53, wherein the polyolefin foam described above is crosslinked to a degree sufficient to be thermally stable to form under heat and pressure and to shrink enough to obtain an expansion ratio in the range of about 1.1 to about 4 in thermal atmosphere molding. ※ Note: The disclosure is based on the initial application.