Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
  • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2201/00—Foams characterised by the foaming process
  • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
  • C08J2201/03—Extrusion of the foamable blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/04—Homopolymers or copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2423/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08J2423/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
  • C08J9/141—Hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/14—Applications used for foams
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

• the present invention relates to butene-based foams and ethylene and more particularly 1-butene-based foams and ethylene.
• copolymer based on ethylene and a ⁇ -olefin were already described, for example in the document EP1373401.
• the LLDPE used is a copolymer which is very rich in ethylene and poor in oolefin.
• the foams obtained thus have the characteristics of foams based on polyethylene. These foams consequently have, for example, relatively good insulating properties, but flexibility or flexibility that is too low for certain applications.
• foams can be richer in oolefin and especially in polybutene-1.
• the present invention also relates to a foaming process for obtaining the butene based foams and ethylene according to the present invention and according to independent claim 12.
• the present invention relates to butene-based foams and ethylene which comprise at least one polymer based on ethylene and ethylene-rich and that at least one polymer based on butene-rich butene-1, the temperature melting thereof being less than 135 ° C. This allows to obtain very flexible foams and having good mechanical properties.
• the use / the addition of a polymer based on butene and rich in butene-1 makes it possible to greatly increase the flexibility / flexible foams obtained. Moreover, this also makes it possible to maintain excellent flexibility / flexibility of the foams obtained over a wide temperature range. In particular, this ensures good flexibility / high-temperature flexibility (eg above 40 ° C) and / or low temperature (eg below 20 ° C).
• the fact to use at least one polymer based on butene-rich polybutene-1, whose melting temperature is lower than 135 ° C, makes it possible, surprisingly, to obtain foams with excellent mechanical properties.
• the polyethylene component achieves good properties in terms of heat insulation.
• the use / the addition of a polymer based on butene-rich butene-1 makes it possible optionally to further improve these properties of thermal insulation.
• a polymer based on ethylene and ethylene-rich may be for example at least one homopolymer or at least one copolymer of ethylene.
• a polymer based on ethylene and ethylene-rich may be for example at least one polymer selected from the following group: polyethylene very low density (PE-TBD / VLDPE), linear low density polyethylene (LLDPE / LLDPE), low density polyethylene (PE-BD / LDPE), polyethylene medium density (PE-MD / MDPE), high density polyethylene (PE-HD / HDPE), very low molecular weight polyethylene (ULMWPE), high molecular weight polyethylene (HMWPE).
• a polymer based on ethylene can be for example at least one copolymer, at least one block copolymer, at least one gradient copolymer, at least one random copolymer, at least one graft copolymer, at least one interpolymer or at least a copolymer which represents a combination of several of these types of copolymers.
• a copolymer is a polymer which comprises at least two different monomers.
• a foam based on butene and ethylene according to the present invention may comprise at least a polymer based on ethylene and ethylene-rich, which may preferably include, for example at least 50%, preferably at least 51%, of preferably at least 55%, preferably at least 60%, preferably at least 70%, preferably at least 75%, preferably at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95%, preferably at least 97%, preferably at least 98% or at least 99% by weight of ethylene.
• Rich in ethylene may therefore mean for example comprising at least 50%, preferably at least 51%, preferably at least 55%, preferably at least 60%, preferably at least 70%, preferably at least 75%, preferably at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95%, preferably at least 97%, preferably at least 98% or at least 99% by mass of ethylene. This allows for example to obtain foams having such good properties of thermal insulation.
• a foam according to the present invention may in one embodiment for example comprise low density polyethylene (PE-BD / LDPE) as an ethylene-rich and ethylene-rich polymer.
• the low density polyethylene may be obtained for example by radical polymerization of ethylene.
• the rate of connection of low density polyethylene is higher than the rate of connection of high density polyethylene (PE-HD / HDPE).
• the low density polyethylene may for example have a density of around 0.91 to 0.935 g / cm 3.
• a foam based on butene and ethylene according to the present invention may comprise at least a polymer based on ethylene and ethylene-rich, the melting temperature determined by DSC can for example be between 30 ° C and 160 ° C, preferably between 40 ° and 155 ° C, preferably between 45 ° C and 150 ° C, preferably between 60 ° C and 147 ° C, preferably between 70 ° C and 146 ° C, preferably between 80 ° C C and 145 ° C, preferably between 85 ° C and 144 ° C, preferably between 90 ° C and 143 ° C, preferably between 95 ° C and 140 ° C ° C, preferably between 100 ° C and 135 ° C, preferably between 102.5 ° C and 132.5 ° C, preferably between 105 ° C and 130 ° C, preferably between 105 ° C and 1 15 ° C or between 120 ° C and 130 ° C.
• the melting temperature of a polymer based on ethylene and ethylene-rich determined by DSC can for example in the case of low density polyethylene (LDPE / LDPE) be between 90 ° C and 120 ° C, preferably between 105 ° C and 1 18 ° C, preferably between 105.5 ° C and 1 17.5 ° C, preferably between 106 ° C and 1 17 ° C, preferably between 107 ° C and 1 15 ° C, preferably between 107.5 ° C and 1 14.5 ° C, preferably between 1 10 ° C and 1 14.25 ° C, preferably between 1 1 1 ° C and 1 14 ° C.
• LDPE / LDPE low density polyethylene
• the melting temperature of a polymer based on ethylene and ethylene-rich, as determined by DSC can for example in the case of high density polyethylene (HDPE / HDPE) be between 1 15 ° C and 135 ° C preferably between 120 ° C and 130 ° C, preferably between 122.5 ° C and 127.5 ° C.
• HDPE / HDPE high density polyethylene
• a foam based on butene and ethylene according to the present invention may comprise at least a polymer based on ethylene and ethylene-rich, which may have a melt index (melt flow index or melt flow rate) for example measured 190 ° C. with a standard mass of 2.16 kg (ISO standard 1,133), which can be for example between 0.1 and 35 g / 10 min, preferably between 0.15 and 30 g / 10 min, of preferably between 0.2 and 25 g / 10 min, preferably between 0.225 and 12 g / 10 min, preferably between 0.25 and 8 g / 10 min, preferably between 0.3 and 5 g / 10 min, of preferably between 0.325 and 4 g / 10 min, preferably between 0.35 and 0.8 g / 10 min, preferably between 0.6 and 0.7 g / 10 min.
• a melt index melt flow index or melt flow rate
• a foam based on butene and ethylene according to the present invention may comprise at least one polymer based on butene and butene-rich, which may preferably include, for example at least 25%, preferably at least 30%, preferably at least 35%, preferably at least 40%, preferably at least 45%, preferably at least 50%, preferably at least 55%, preferably at least 60%, preferably at least 65%, preferably at least 50%; at least 70%, preferably at least 75%, preferably at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95%, preferably at least 97%, preferably at least 98% or at least 99% by weight of butene-1.
• the butene-1 rich can preferably be used, for example, to comprise at least 50%, preferably at least 51%, preferably at least 55%, preferably at least 60%, preferably at least 70%, preferably at least 70%. minus 75%, preferably at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95%, preferably at least 97%, preferably at least 98% or at least 99% by weight of butene-1. This allows for example to obtain foams having flexibility / flexibility.
• a butene-based polymer and / or a butene-based polymer rich in butene-1 may be, for example, a polymer comprising butene-1, 2-butene-2, E-butene-2 and / or or 2-methylpropene.
• a foam based on butene and ethylene according to the present invention may comprise at least one polymer based on butene-rich butene-1, which may preferably include, for example at least 50%, preferably at least 51%, preferably at least 55%, preferably at least 60%, preferably at least 65%, preferably at least 70%, preferably at least 75%, preferably at least 80%, preferably at least 85%, preferably preferably at least 90%, preferably at least 95%, preferably at least 97%, preferably at least 98%, preferably at least 99%, preferably at least 99.5%, preferably at least 99.9%, preferably at least 99%; at least 99.99%, preferably at least 99.999% by weight of butene-1.
• This allows to obtain foams having flexibility / flexibility.
• a polymer based on butene-rich butene-1 optionally also allows to improve tolerance additives (fillers) and / or the properties of thermal insulation.
• a foam based on butene and ethylene according to the present invention may comprise at least one polymer based on butene-rich butene-1, which is preferably for example, have a melt index (melt flow index or melt flow rate ) for example, measured at 190 ° C. with a standard mass of 2.16 kg (ISO standard 1,133), which may for example be between 0.3 and 2 g / 10 min, preferably between 0.325 and 1.5 g. / 10 min, preferably between 0.35 and 1 g / 10 min, preferably between 0.45 and 0.95 g / 10, preferably between 0.4 and 0.6 g / 10 min or between 0.7 and 0.9 g / 10min.
• melt index melt flow index or melt flow rate
• a foam based on butene and ethylene according to the present invention may comprise at least one polymer based on butene-rich butene-1, which may for example be a copolymer, a block copolymer, a gradient copolymer, random copolymer, a graft copolymer, an interpolymer or a copolymer, which represents a combination of several of these types of copolymers.
• a copolymer may be a polymer that comprises at least two different monomers. The addition of a second and / or another monomer and the use of a copolymer used to modify and / or adapt the melting temperature of a polymer based on butene easily.
• the structure / nature of the copolymer can also influence the melting temperature. This allows for example to reduce the melting temperature and / or to obtain a melting temperature e.g. less than 135 ° C while retaining the properties (and particularly the great flexibility / flexibility) of polybutene-1.
• a foam based on butene and ethylene according to the present invention may comprise at least one polymer based on butene, which can be for example a copolymer comprising 1-butene and at least one other oolifine.
• a polymer based on butene may be for example a copolymer comprising 1-butene and ethylene and / or propylene.
• polymer based on butene which is a copolymer comprising 1-butene and at least one other oolifine, reduces the polymer melting temperature based on butene.
• at least one other oolifine such as ethylene and / or propylene
• the incorporation of at least one other oolifine, such as ethylene and / or propylene, in a copolymer comprising 1-butene and at least one other oolifine may optionally allow for example to reduce the temperature of melting of the copolymer for example with respect to polybutene-1.
• the incorporation / I addition of at least one other oolifine, such as ethylene and / or propylene, a polymer based on butene to obtain a copolymer comprising 1-butene and at least one other oolifine may indeed possibly disturb the crystallization of polybutene-1 and the formation of corresponding crystalline domains. This may, for example, lead to a decrease in the melting temperature of the polymer / copolymer, for example.
• the melting temperature of a copolymer rich in butene-1 copolymer comprising butene-1 and at least one other oolifine may preferably e.g. decrease when the content oolifine (e.g., ethylene and / or propylene) increases. This allows for example to reduce the melting temperature and / or to obtain a melting temperature for example below 135 ° C while maintaining the properties (particularly the flexibility / flexibility) of polybutene-1.
• a butene-based polymer rich in butene-1 may, for example, be a copolymer comprising two monomers.
• a polymer based on butene-rich butene-1 can thus for example be a copolymer comprising 1-butene and ethylene or propylene.
• Preferably a polymer based on butene-rich butene-1 may be for example a copolymer comprising 1-butene and ethylene. This eventually prevents alterations in properties due to the presence of one or more types of additional monomers.
• a polymer based on butene-rich butene-1 can preferably for example comprise only a few units of another monomer.
• a butene-based polymer rich in butene-1 may, for example, comprise between 0.001% and 10%, preferably between 0.1% and 9%, preferably between 0.2% and 8%, preferably between 0.3% and 7%, preferably between 0.4% and 6%, preferably between 0.5% and 5.5%, preferably between 0.7% and 5%, preferably between 0.9% and and 4.5%, preferably between 1% and 4% of a other monomer, for example, another ⁇ -olefin such as ethylene or propylene.
• a polymer based on butene-rich butene-1 may preferably comprise for example not mean that approximately 100, 50, 25, 10 or 3 units of another monomer. This also allows for example to reduce the melting temperature and / or to obtain a melting temperature for example below 135 ° C while maintaining the properties (particularly the flexibility / flexibility of the polybutene-1).
• a foam based on butene and ethylene according to the present invention may comprise at least one polymer based on butene and / or a polymer based on butene-rich butene-1, the determined by DSC melting point may be for example less than 135 ° C, preferably less than 134 ° C, preferably less than 133 ° C, preferably less than 132 ° C, preferably less than 131 ° C, preferably less than 130 ° C, preferably less than 129.5 ° C, preferably less than 129 ° C, preferably less than 128.5 ° C, preferably less than 128 ° C, preferably less than 127.5 ° C, preferably less than 127 ° C C, preferably less than 126.5 ° C, preferably less than 126 ° C, preferably less than 125.5 ° C, preferably less than 125 ° C, preferably less than 124.5 ° C, preferably less than 124 ° C, preferably less than 123.5 ° C., preferably less than
• ° C preferably less than 120.5 ° C, preferably less than 120 ° C, preferably less than 1 19.5 ° C, preferably less than 1 19 ° C, preferably less than 1 18.5 ° C, preferably less than 1 18 ° C, preferably less than 1 17.5 ° C, preferably less than 1 17 ° C, preferably less than 1 16.5 ° C, preferably less than 1 16 ° C preferably less than 1 15.5 ° C, preferably less than 1 15 ° C, preferably less than 1 14.5 ° C, preferably less than 1 14 ° C, preferably less than 1 13.5 ° C C, preferably below 13 ° C, preferably below 12.5 ° C, preferably below 12 ° C, preferably less than 1 1 1, 5 ° C, preferably less than 1 1 1 ° C, preferably less than 1 10.5 ° C, preferably less than 1 10 ° C, preferably less than 107.5 ° C or preferably less than 105 ° C.
• the melting temperature is preferably, for example less than 135 ° C to obtain a mixture of a polymer based on ethylene and ethylene-rich on the one hand and a polymer based on butene-rich butene-1 on the other hand, improves so Surprisingly the mechanical properties of foams based on butene and ethylene according to the present invention, obtained with this mixture.
• a foam based on butene and ethylene according to the present invention may comprise at least one polymer based on butene and / or a polymer based on butene-rich butene-1, the determined by DSC melting point may be for example greater than 60 ° C, preferably greater than 70 ° C, preferably greater than 75 ° C, preferably greater than 80 ° C, preferably greater than 85 ° C, preferably greater than 90 ° C, preferably greater than 95 ° C, preferably greater than 100 ° C, preferably greater than 105 ° C, preferably greater than 106 ° C, preferably greater than 106.5 ° C, preferably greater than 107 ° C, preferably greater than 108 ° C, preferably greater than 109 ° C, preferably greater than 1 10 ° C, preferably greater than 1 1 1 ° C, preferably greater than 1 1 1, 5 ° C, preferably greater than 1 12 ° C, preferably above greater than 12.5 ° C, preferably greater than 13 ° C or
• the melting temperature of a polymer or copolymer can be determined for example by differential scanning calorimetry (DSC, differential scanning calorimetry).
• the melting temperature of a polymer or a copolymer may preferably be the melting temperature corresponding to the maximum (top) of a melting peak detected by DSC.
• the melting temperature of a polymer or a copolymer may also be a temperature range corresponding to a melting peak (beginning and end of peak) detected by DSC.
• the melting temperature of a polymer or a copolymer may also be an average of the start value and the end value of a temperature range corresponding to a melting peak detected by DSC (average value start and end value of the peak).
• the melting temperature can for example be measured by DSC by heating a sample in a sealed capsule up to 180 ° C with a temperature ramp of 10 ° C per minute. Alternatively it is for example also possible to carry out a first heating up to 180 ° C with a temperature ramp of 10 ° C per minute, maintaining the temperature at 180 ° C for example for 5 minutes, cooling the sample up to - 20 ° C with a temperature ramp of 10 ° C per minute, maintaining the sample at - 20 ° C for example 5 minutes and then proceed to a second heated up to 180 ° C with a temperature ramp of 10 ° C per minute, to measure the melting temperature during this second heating.
• the melting temperature of a polymer or a copolymer may preferably be the melting temperature of the major form of this polymer or copolymer.
• melting temperature of a polymer or copolymer thus may preferably be the melting temperature corresponding to the detected peak in DSC, of which the area under the peak is the largest.
• the melting temperature of a polymer or a copolymer may preferably be the melting temperature determined for the thermodynamically most stable form of this polymer or copolymer.
• the melting temperature of the polymer may be the melting temperature of the thermodynamically most stable form. of this polymer (for example Form I in the case of polybutene-1) or copolymer.
• a foam based on butene and ethylene according to the present invention may comprise at least a polymer based on ethylene and ethylene-rich on the one hand and at least one polymer based on butene-rich butene-1 of on the other hand, so that the difference between the melting temperatures of a / the polymer based on ethylene and ethylene-rich on the one hand and a / the polymer based on butene-rich butene-1 d on the other hand may be for example less than 40 ° C, preferably less than 35 ° C, preferably less than 30 ° C, preferably less than 25 ° C, preferably less than 20 ° C, preferably less than 15 ° C, preferably less than 10 ° C, preferably less than 6 ° C, preferably less than 3 ° C, preferably less than 2 ° C.
• the difference between the melting temperatures for each pair of polymers used can be for example less than 40 ° C, preferably less than 35 ° C, preferably less than 30 ° C, preferably less than 25 ° C, preferably less than 20 ° C, preferably less than 15 ° C, preferably less than 10 ° C, preferably less than 6 ° C, preferably less than 3 ° C, preferably less than 2 ° C.
• a foam based on butene and ethylene according to the present invention may comprise at least a polymer based on ethylene and ethylene-rich on the one hand and at least one polymer based on butene-rich butene-1 of on the other hand, so that the difference between the melt index (melt flow index or melt flow rate), for example measured at 190 ° C with a standard weight of 2.16 kg (ISO 1133) of a / the polymer based on ethylene and ethylene-rich on the one hand and a / the polymer based on butene-rich butene-1 on the other hand can preferably be for example less than 25 g / 10 min, preferably minus 24 g / 10 min, preferably minus 23.5 g / 10 min, preferably minus 23 g / 10 min, preferably minus 20 g / 10 min, preferably minus 17.5 g / min.
• melt index melt flow index or melt flow rate
• 10 min preferably minus 15 g / 10 min, preferably minus 12.5 g / 10 min, preferably minus 10 g / 10 min, preferably minus 7.5. g / 10 min, preferably minus 5 g / 10 min, preferably minus 2.5 g / 10 min, preferably minus 2 g / 10 min, preferably minus 1, 5 g / 10 min, preferably minus 1.25 g / 10 min, preferably minus 1.2 g / 10 min, preferably minus 1 g / 10 min, preferably minus 0.8 g / 10 min, preferably minus 0 , 5 g / 10 min, preferably minus 0.3 g / 10 min, preferably minus 0.2 g / 10 min.
• the difference between the index (melt flow index flow or melt flow rate) e.g. measured at 190 ° C. with a standard mass of 2.16 kg (ISO standard 1,133) for each pair of polymers used can preferably be, for example, less than 25 g / 10 min, preferably minus 24 g / 10 min, preferably minus 23.5 g / 10 min, preferably minus 23 g / 10 min, preferably minus 20 g / 10 min, preferably minus 17.5 g / 10 min, preferably minus 15 g.
• 10 min preferably minus 12.5 g / 10 min, preferably minus 10 g / 10 min, preferably minus 7.5 g / 10 min, preferably minus 5 g / 10 min, preferably minus 2.5 g / 10 min, preferably minus 2 g / 10 min, preferably minus 1.5 g / 10 min, preferably minus 1.25 g / 10 min, preferably at least 1.2 g / 10 min, preferably at least 1 g / 10 min, preferably at least 0.8 g / 10 min, preferably at least 0.5 g / 10 min, preferably at least 0, 3 g / 10 min, preferably minus 0.2 g / 10 min.
• the foams according to the present invention may also comprise at least one additive (filler).
• additives may for example comprise at least one additive which improves the insulating properties and particularly thermal insulation, such as at least one additive comprising carbon black, carbon nanotubes, fullerenes and / or flakes ( flakes) / metal particles, in particular of flakes of aluminum.
• these additives may also comprise at least one additive which facilitates the implementation and / or foaming, such as for example at least one additive comprising talc, a mixture of talc and polyethylene, a mixture of talc and LDPE, one or more clays, titanium dioxide, silicon dioxide, ⁇ EVA and / or one or more esters of fatty acid and / or glycerol esters, such as one or more stearate (s), as for example barium stearate, sodium stearate, glycerol stearate and / or alpha-glycerol monostearate and / or one or more amides of fatty acid, such as for example stearamide or palmitamide, and / or at least one derivative of at least one of these compounds / additives and / or a mixture of at least two of these compounds / additives.
• at least one additive comprising talc, a mixture of talc and polyethylene, a mixture of talc and LDPE, one
• At least one additive may also comprise for example at least one stabilizer, at least one UV absorber, at least one plasticizer and / or at least one flame retardant and / or at least one derivative of at least one of these compounds / additives and / or a mixture of at least two of these compounds / additives.
• Foams according to the present invention based on ethylene and butene may for example have open cells and / or closed cells. Open cell and / or closed cells can be obtained for example according to the conditions of extrusion and / or foaming. Open cells may for instance also be obtained by mechanical perforation of closed-cell foams or by means of temperature (temperature of implementation when enough / higher foaming) permitting the at least partial opening of the cell walls.
• closed cell foams may for example be rigid and / or less flexible / flexible and / or less compressible.
• polybutene-1 butene-1 homopolymer
• the mixture which contains nodules / core polybutene-1 or high polybutene-1 dispersed in a phase polyethylene or rich polyethylene is weakened because the interface between the nodules of polybutene-1 or rich polybutene-1 and the polyethylene or the polyethylene-rich phase is fragile. Cracks propagate easily between and especially at the interfaces between polybutene-1 or polybutene-1-rich nodules and polyethylene or the polyethylene-rich phase. The incompatibility between polyethylene and polybutene-1 therefore leads accordingly to poor mechanical properties.
• a phase rich in polyethylene may for example be a phase comprising for example at least 50%, preferably at least 51%, preferably at least 55%, preferably at least 60%, preferably at least 65%, preferably at least 55%, preferably at least 70%, preferably at least 75%, preferably at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95%, preferably at least 97%, preferably at least 98%, preferably at least 99%, preferably at least 99.5%, preferably at least 99.9%, preferably at least 99.99%, preferably at least 99.999% by weight, polyethylene and / or ethylene.
• a phase and / or a nodule / nuclei rich in polybutene-1 may mean for example a phase and / or a nodule / nuclei comprising for example at least 50%, preferably at least 51%, preferably at least 55%, preferably at least 60%, preferably at least 65%, preferably at least 70%, preferably at least 75%, preferably at least 80%, preferably at least 85%, preferably at least 90%, preferably preferably at least 95%, preferably at least 97%, preferably at least 98%, preferably at least 99%, preferably at least 99.5%, preferably at least 99.9%, preferably at least 99.99%, preferably at least 99%. at least 99.999% by weight of polybutene-1 and / or butene-1.
• a polymer based on butene-rich butene-1 whose melting temperature is for example less than 135 ° C, and / or especially of a butene-1 copolymer and another oolifine, such as ethylene, rich in butene-1, instead of polybutene-1 (butene-1 homopolymer), does not appear to make it possible to significantly improve the dispersion of the polybutene-1 or rich phase polybutene-1 in the polyethylene phase or rich in polyethylene.
• the rate of oolifine and / or e.g. ethylene a polymer based on butene-rich butene-1, whose melting temperature is for example less than 135 ° C, and / or especially of a copolymer butene-1 and another oolifine, such as ethylene, rich in butene-1, does not seem sufficient to improve the dispersion of the polybutene-1 phase or high polybutene-1 and / or to improve the
• a lower crystallinity of the polybutene-1 or polybutene-1-rich nodules dispersed in the polyethylene or in a polyethylene-rich phase may, for example, lead to a more amorphous and / or predominantly amorphous interface between the two phases. This can potentially allow for example to promote and / or improve the interpenetration of the two phases at the interface therebetween, so that the interface between the two phases can be enhanced.
• the present invention also relates to a foaming process to obtain foams based on ethylene-butene according to the present invention, wherein at least a polymer based on ethylene and ethylene-rich and that at least one base polymer butene-rich butene-1, the melting temperature of the latter being less than 135 ° C, are foamed by means of at least one foaming agent.
• foaming and / or extrusion may / may for example be carried out (s) with temperature implemented during foaming and / or extrusion of less than 150 ° C, preferably less than 145 ° C, preferably less than 140 ° C, preferably less than 135 ° C, preferably less than 132.5 ° C, preferably less than 130 ° C, preferably less than 127.5 ° C C, preferably below 126 ° C, preferably below 125 ° C, preferably below 122.5 ° C, preferably below 120 ° C, preferably below 17.5 ° C, preferably below at 1 16 ° C, preferably below 1 15 ° C, preferably below 1 14.5 ° C, preferably below 1 14 ° C, preferably below 1 13.5 ° C, preferably below 1 13 ° C, preferably less than 12.5 ° C, preferably less than 1 12 ° C, preferably below 1 1 1, 5 ° C, preferably below 1 1 1 ° C, preferably
• the implementation of temperature during foaming and / or extrusion may for example be between 40 ° C and 150 ° C, preferably 50 ° C and 140 ° C, preferably between 90 ° C and 130 ° C, preferably between 100 ° C and 120 ° C, preferably between 102 ° C and 1 17.5 ° C preferably between 105 ° C and 1 16 ° C, preferably between 106 ° C and 1 15.5 ° C, preferably between 107 ° C and 115 ° C, preferably between 107.5 ° C and 1 14.5 ° C, preferably between 108 ° C and 14 ° C.
• Too high a temperature or too low during foaming and / or extrusion may for example cause uncontrolled foaming and / or ineffective and / or inhomogeneous. Under these conditions, it can even be difficult or impossible to obtain such a relatively homogeneous foam and / or foam with a certain dimensional stability and / or foam with well-defined private property. Moreover, it can for example also be very difficult in these conditions to obtain and / or to vary the desired properties. Indeed, the implementation temperature during foaming and / or extrusion is such an important parameter, which can help control foaming.
• a monitoring implementation temperature during foaming and / or extrusion thus allows, if necessary, to obtain homogeneous foams and / or foams having a certain dimensional stability and / or foams with properties specific and well defined.
• the experiments conducted in the context of the present invention have determined that, in the foaming method according to the invention, during the implementation of temperature foaming and / or extrusion (which may preferably correspond, for example to the die bulk temperature) may for example correspond to or be greater than the glass transition temperature or the softening point or the corresponding temperature the top of the melting peak (determined by DSC) or preferably at the polymer melting temperature based on ethylene and / or butene-based polymer and rich in butene-1.
• a temperature can correspond for example to the glass transition temperature or softening point or at a temperature corresponding to the start of the melting peak (determined by DSC) or to the polymer melting temperature based on ethylene and ethylene-rich and / or butene-based polymer rich in butene-1, if it is equal to said temperature plus or minus 50 ° C, preferably plus or minus 40 ° C, preferably plus or minus 30 ° C, preferably plus or minus 25 ° C, preferably plus or minus 22.5 ° C, preferably plus or minus 20 ° C, preferably plus or minus 17.5 ° C, preferably plus or minus 15 ° C, more preferably or at least 14 ° C, preferably plus or minus 13 ° C, preferably plus or minus 12 ° C, preferably plus or minus 11 ° C, preferably plus or minus 10 ° C, preferably plus or minus 9 ° C C, preferably plus or minus 8 ° C, preferably plus or minus 7 °
• the implementation of temperature during foaming and / or extrusion may, for example, be within plus or minus 50 ° C, preferably at plus or minus 40 ° C, preferably at plus or minus 30 ° C, preferably at plus or minus 25 ° C, preferably at plus or minus 22.5 ° C, preferably at plus or minus 20 ° C, preferably at plus or minus 17.5 ° C, preferably at +/- 15 ° C, preferably at plus or minus 14 ° C, preferably at plus or minus 13 ° C, preferably at plus or minus 12 ° C, preferably at plus or minus 1 1 C, preferably to within + 10 ° C, preferably to plus or minus 9 ° C, preferably at plus or minus 8 ° C, preferably at plus or minus 7 ° C, preferably at plus or minus 6
• the agent (s) of foaming (s) used in the foaming process according to the invention may (can), for example comprise at least one chemical foaming agent and / or at least one physical foaming agent.
• a chemical foaming agent may for example comprise at least one compound or a mixture of compounds, which can release at least one gas (such as nitrogen or C0 2).
• a chemical foaming agent may for example comprise azodicarbonamide, of azodiisobutyronitrile, the
• a physical foaming agent used in the foaming process according to the invention may for example comprise at least one gas or at least one liquid, which may preferably be volatile.
• a physical foaming agent may for example include carbon dioxide, nitrogen, argon, water, air, helium, aliphatic hydrocarbons with 1 to 6 carbon atoms, aliphatic alcohols having 1 to 3 carbon atoms, fully or partially halogenated aliphatic hydrocarbons having 1 to 4 carbon atoms, methane, ethane, propane, n-butane, isobutane, n- pentane, isopentane, neopentane, hexane, of isohexane, heptane, the octane, methylpentane, dimethylpentane, butene, pentene, 4-methylpentene, the hexene, 2,2-dimethylbutane, of petroleum ether, methanol, ethanol, n-propano
• foaming may for example take place by means of mechanical means, such as a reactor and / or a mixer and / or extruder.
• the foaming agent may for example be added to the high polymer based on ethylene and the polymer based on butene-rich butene-1 using mechanical means, such as a reactor and / or a mixer and / or extruder, in the foaming method according to the invention and to obtain foams of the invention.
• foaming can therefore preferably be achieved for instance by extrusion. This can allow for example an easy and effective foaming.
• foams based ethylene-butene according to the present having open cells and / or closed cells through a foaming process according to the invention, for example according to the conditions extrusion and / or foaming.
• Conditions for example to obtain closed-cell foams are given in the following examples.
• Open cell foams may still be obtained for example through temperature conditions (work during foaming processing temperature enough / highest) for the at least partial opening of the cell walls.
• the nature of the cells of the foams obtained can, for example, influence their properties.
• closed cell foams can for example be rigid and / or less flexible / flexible and / or less compressible than open cell foams.
• A- mixture of polyethylene and polybutene-1 made for comparison to a mixture of a polymer based on ethylene and ethylene-rich on the one hand and polybutene-1 (homopolymer) of the other part (70% by weight of LDPE / LDPE, 2601 TX17 from SABIC and 30% by weight of polybutene-1, LYONDELLBASELL homopolymer PB 1), there is a phase separation due to incompatibility between the polyethylene or ethylene-rich phase and the phase of polybutene-1 or high polybutene-1 (see Figure 1).
• Figure 1 is an image of a section through the mixing obtained using an electronic microscope. There are small nuclei / nodules of polybutene-1 or polybutene-1-rich dispersed in a polyethylene phase or rich in polyethylene.
• the foams obtained in this case have poor mechanical properties.
• the mixture, which contains nodules of polybutene-1 or high polybutene-1 dispersed in a phase polyethylene or rich polyethylene is weakened because the interface between the nodules of polybutene-1 or high polybutene 1 dispersed in a polyethylene phase or rich in polyethylene is fragile.
• n ' improves accounting and dispersing the polybutene-1 or polybutene-1-rich phase in the polyethylene or polyethylene-rich phase.
• the size of the nodules of the polybutene-1 or polybutene-1-rich phase hardly changes (does not decrease significantly, but remains similar, see Figure 1 and 2).
• the rate of oolifine and / or e.g. ethylene a polymer based on butene-rich butene-1, whose melting temperature is for example less than 135 ° C, and / or especially of a copolymer butene-1 and another oolifine, such as ethylene, rich in butene-1, does not seem sufficient to improve the dispersion of the polybutene-1 phase or high polybutene-1 and / or to improve the
• a lower crystallinity of the polybutene-1 or polybutene-1-rich nodules dispersed in the polyethylene or in a polyethylene-rich phase may, for example, lead to a more amorphous and / or predominantly amorphous interface between the two phases. This may eventually allow for example to promote and / or improve
• Foams according to the present invention were prepared with three different compositions (see entries 1, 2 and 3 of Table 1). In addition, for comparison, a PE-BD / LDPE foam was also prepared under similar conditions (see entry 4, Table 1).
• each mixture (1, 2, 3 and 4) further comprises a mixture of several additives:
• the mixtures 1, 2, 3 and 4 are foamed by extrusion using isobutane through an extruder and using the parameters shown in Table 2.
• Foaming and / or extrusion is / are performed (s) with a temperature of implementation of between 108.8 ° C and one 10.7 ° C. This temperature is in this case the temperature in a die mass. The maximum die mass temperature is therefore in all cases less than 150 ° C.
• the implementation temperature corresponds for example to plus or minus 5 ° C near the melting temperature of the polymer based on ethylene and / or to the polymer melting temperature based on butene-rich butene-1.
• the foaming is effective and the foams thus obtained for each mixture (1, 2 and 3) have good dimensional stability (no collapse of foams during foaming, nor subsequently at room temperature).
• the foams obtained are closed cell foams.
• the foams thus obtained for each mixture (1, 2 and 3) exhibit good mechanical properties despite the incorporation of a polymer based on butene-rich butene-1.
• Foams thus obtained for each mixture (1, 2, 3 and 4) were characterized by measuring their density and the number of cells per square centimeter.
• Foams obtained for each mixture (1, 2, 3 and 4) were also characterized by measuring their density after a heat treatment at 50 ° C allowing degassing (see Table 4).
• the density of the foams according to the invention comprising a polymer based on butene-rich butene-1 (mixture 1, 2 and 3) decreases during the degassing (see Table 4).
• the foams according to the present invention obtained for each mixture (1, 2 and 3) have excellent flexibility / flexibility (see Table 5 and Figure 3).
• the relative stress-strain characteristics in compression are determined by a compression test by measuring the stress (in N / mm 2 ) as a function of the compression ratio (in%).
• thermal conductivity of the foams obtained was also measured (see Table 6).
• the thermal conductivity can give an indication about the properties of thermal insulation foams.
• thermal conductivity of foams according to the present invention comprising a polymer based on butene-rich butene-1 (mixture 1, 2 and 3) is lower than that of a polyethylene foam.
• the properties of thermal insulation foam according to the present invention comprising a polymer based on butene-rich butene-1 (mixture 1, 2 and 3) are therefore accordingly better.
• the thermal conductivity decreases when the butene-based polymer content rich in butene-1 increases.
• the properties of thermal insulation foams according to present invention are therefore improved by the addition of a polymer based on butene-rich butene-1 (mixture 1, 2 and 3).
• Open cell foams may for example be obtained similarly, but using temperature (temperature of implementation when enough / higher foaming) permitting the at least partial opening of the cell walls.
• foams according to the present invention comprising polyethylene as well as a polymer or copolymer based on butene and rich in butene-1, whose melting temperature is for example less than 135 ° C (see entries 1 and 5, 6 and 7 of Table 8).
• the elongation at break increases all the more as the amount of polymer based on butene-rich butene-1, whose melting temperature is for example less than 135 ° C, added to the polyethylene is important.

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