WO2013113465A1 - Process for the production of pet foams and pet foams obtained with said process - Google Patents

Process for the production of pet foams and pet foams obtained with said process Download PDF

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Publication number
WO2013113465A1
WO2013113465A1 PCT/EP2013/000079 EP2013000079W WO2013113465A1 WO 2013113465 A1 WO2013113465 A1 WO 2013113465A1 EP 2013000079 W EP2013000079 W EP 2013000079W WO 2013113465 A1 WO2013113465 A1 WO 2013113465A1
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WO
WIPO (PCT)
Prior art keywords
pet
process according
blowing agent
imidazole
catalyst
Prior art date
Application number
PCT/EP2013/000079
Other languages
French (fr)
Inventor
Leone Lauri
Raffaela Bressan
Luigi ALIPERTA
Eva-Lotta Magdalena Petersson
Original Assignee
Diab International Ab
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Diab International Ab filed Critical Diab International Ab
Priority to MX2014008973A priority Critical patent/MX351792B/en
Priority to US14/371,146 priority patent/US9394417B2/en
Priority to KR1020147021754A priority patent/KR101958513B1/en
Priority to ES13703317.1T priority patent/ES2567322T3/en
Priority to BR112014017887A priority patent/BR112014017887A8/en
Priority to CN201380007688.XA priority patent/CN104204090B/en
Priority to AU2013214578A priority patent/AU2013214578B2/en
Priority to EA201491192A priority patent/EA201491192A1/en
Priority to CA2861004A priority patent/CA2861004C/en
Priority to DK13703317.1T priority patent/DK2809724T3/en
Priority to EP13703317.1A priority patent/EP2809724B1/en
Priority to JP2014555114A priority patent/JP6088547B2/en
Publication of WO2013113465A1 publication Critical patent/WO2013113465A1/en

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3442—Mixing, kneading or conveying the foamable material
    • B29C44/3446—Feeding the blowing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/36—Feeding the material to be shaped
    • B29C44/46—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length
    • B29C44/50—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length using pressure difference, e.g. by extrusion or by spraying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/003—PET, i.e. poylethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
    • B29K2995/0015—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0063—Density
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the invention relates to an enhanced process for the production of PET foams.
  • the invention is also extended to PET foams obtained with this process and to the bodies of expanded material obtained from these foams.
  • the field of the invention is the production of PET (polyethylene terephthalate) foams, normally used in the production of panels with numerous types of processing to make them suitable as a "core material” for various types of sandwich structures and also with a thermal insulation function.
  • PET polyethylene terephthalate
  • Extending PET chains with pyromellitic anhydride and other crosslinking agents is known, for giving PET the necessary consistency for receiving the blowing agent, thus obtaining an expanded and stable foam.
  • pyromellitic anhydride and other crosslinking agents are known, for giving PET the necessary consistency for receiving the blowing agent, thus obtaining an expanded and stable foam.
  • more or less significant phenomena of polymer degradation may arise, which in any case represent problems with respect to the quality of the final product .
  • thermoplastic polymer foam in the presence of epoxides, crosslinked by means of photosensitive catalysts
  • photosensitive catalysts are also known (US 6,323,251), wherein the crosslinking reaction of the epoxide is effected downstream of the injection of the blowing agent, in particular outside the extrusion.
  • the known process is consequently not suitable for providing a foam having the necessary consistency for the formation of the final product.
  • photosensitive catalysts only act on the surface layer of the foam, which does not allow the crosslinking reaction to also take place inside the foamy mass.
  • the main objective of the present invention is to provide a method suitable for obtaining a PET foam which, unlike the known methods, has characteristics of stability at the outlet of the extruder, without altering, however, the structure of the PET chains.
  • the invention offers the advantage of providing a stable PET foam, in which the structure of the polymer chains is kept unchanged.
  • the system also has viscoelasticity characteristics which allow the mixture of PET/epoxy homopolymer to receive the expanding action of the blowing agent, as far as the innermost and deepest layers of foam also having a significant thickness.
  • figure 1 illustrates a scheme of the extruder used for effecting the process of the invention
  • figures 2 and 3 illustrate the exothermic homopolymerization reaction of the epoxy resin, when activated in the presence of imidazole and its derivatives, compared to those in which different catalysts or no catalyst is used;
  • figure 4 illustrates the graph of a DSC (Differential Scanning Calorimetry) analysis for evaluating the crosslinking of the epoxy resin, of the samples processed as in figure 2;
  • figure 5 represents an image obtained with an Atomic Force Microscope (AFM) of the nanodispersion of an epoxy homopolymer in the PET thermoplastic matrix.
  • AFM Atomic Force Microscope
  • the extruder as schematically represented in figure 1 and used for effecting the process of the invention, is substantially divided into a step 1 for melting and mixing the PET mass 10, catalyst and other possible additives fed through the hopper 2, a reactive extrusion step 3 (homopolymerization of the epoxy phase) an injection step 6 of the blowing agent and a cooling step 7.
  • the PET used is in particular a PET suitable for being processed by extrusion, having the following chemical formula (I) :
  • the catalyst is then added to the PET, which, according to the invention, consists of imidazole, derivatives of imidazole and mixtures thereof, represented by the following formula (II) :
  • Rl, R2 , R3 are inorganic or organic groups the aromatic or aliphatic type
  • Some non- limiting examples of catalysts used in the process of the invention 2-methylimidazole, 2- ethyl -4 -methylimidazole, 1 -Benzyl -2 -methylimidazole, 1- Methylimidazole , 1 , 2 -Dimethylimidazole and mixtures thereof .
  • additives suitable for improving the processability, appearance, and properties of the PET foam, the following can be mentioned, alone or combined with each other:
  • the catalyst used in the invention is in liquid phase and, in step 1 of the extruder, it is closely mixed inside the PET mass.
  • the mixture thus obtained is then sent, from the screw of the extruder (not represented) , towards a subsequent step 3 for putting the PET mass in contact with the catalyst and mixing them with an injection 4 of epoxy resin, also in liquid state .
  • Preferred epoxy resins for the invention are those having the following formula (III)
  • n are integers (0, 1, 2, 3, ..)
  • Rl, R2 and R3 represent an aliphatic or aromatic group, or an inorganic chain.
  • polyhedral glycidyl oligomer based on silicon- silicone (example: CAS: 445379-56-6; CAS: 307496-38-4) .
  • the epoxy resin undergoes a homopolymerization process, which develops inside the extruder itself (so-called reactive extrusion) . Furthermore, due to the use of epoxy resins in the liquid state (or previously not crosslinked) , a nanodispersion of homopolymer particles can be obtained inside the continuous PET mass (see figure 5) .
  • the latter is provided with the viscoelasticity necessary for the introduction of the blowing agent, to allow the subsequent foaming phase to take place.
  • the high catalytic activity of imidazole and its derivatives towards the homopolymerization reaction of the epoxy resin also allows this homopolymerization reaction to be completed within the above-mentioned step 3, therefore without involving the PET chains present in the reaction environment, thus leaving their chemical structure unaltered.
  • the catalyst according to the invention has an exothermic section (a) whose peak, compared with the flat trend of the corresponding sections (b) of the curves relating to the catalysts used according to the known art, or with the trend of the curve in the absence of catalyst, indicates the completion of the homopolymerization reaction of the epoxy phase, without involving the PET molecules, thus leaving them unaltered.
  • Figure 4 shows the DSC analysis of the samples tested as in figure 2, after simulation of the extrusion process. From the graph, it can be observed that the only sample that has undergone the homopolymerization reaction is that corresponding to the catalyst 2-ethyl-4-methylimidazole (curve c) of figure 4), which in fact has a glass transition temperature value (Tg) of 99.3°C.
  • Tg glass transition temperature value
  • step 3 of the extruder within the PET mass, the latter is provided with a viscoelasticity sufficient for introducing 5 the blowing agent in step 6 of the extrusion, thus making it suitable for the subsequent foaming phase at the outlet 8 of the extruder.
  • Said foaming phase is preceded by a cooling step 7 of the extruded product 9, the latter consisting of a continuous flow of expanded material, whose cooling process is completed at room temperature. End-products consisting of bodies of expanded material are subsequently obtained from this extruded product 9.
  • formulations of the PET foam used in the process of the invention are provided hereunder, wherein the percentages refer to the weight of the mixture .
  • the pressure value (indication of the viscoelasticity of the mixture) inside the extruder is not such as to keep the blowing agent in a homogeneously dispersed supercritical fluid phase. Attempts at foaming the PET therefore failed as the polymeric mass at the outlet of the extruder does not have a sufficient viscoelasticity for keeping the gas phase enclosed in cells.
  • the blowing agent was added through the injection point (5) :
  • the pressure value (indication of the viscoelasticity of the mixture) inside the extruder is not such as to keep the blowing agent in a homogeneously dispersed supercritical fluid phase. Attempts at foaming the PET therefore failed as the polymeric mass with a low viscoelasticity at the outlet of the extruder is not capable of keeping the gas phase enclosed in cells.
  • the blowing agent was added through the injection point (5) :
  • the pressure value (indication of the viscoelasticity of the mixture) inside the extruder is not such as to keep the blowing agent in a homogeneously dispersed supercritical fluid phase. Attempts at foaming the PET therefore failed as the polymeric mass with a low viscoelasticity at the outlet of the extruder is not capable of keeping the gas phase enclosed in cells.
  • EXAMPLE 4 Presence of epoxy resin and catalyst - 2 -ethylpiperidine
  • the pressure value (indication of the viscoelasticity of the mixture) inside the extruder is not such as to keep the blowing agent in a homogeneously dispersed supercritical fluid phase. Attempts at foaming the PET therefore failed as the polymeric mass with a low viscoelasticity at the outlet of the extruder is not capable of keeping the gas phase enclosed in cells.
  • the blowing agent was added through the injection point (5) :
  • the pressure value (indication of the viscoelasticity of the mixture) inside the extruder is such as to keep the blowing agent in a homogeneously dispersed supercritical fluid phase.
  • attempts at foaming the PET were therefore successful, as the polymeric mass at the outlet of the extruder was sufficiently viscoelastic to keep the gas phase inside closed cells having a reduced dimension (less than 0.7 mm), producing a stable foam having a density ranging from 60-140 Kg/m 3 .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Epoxy Resins (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

A process for the production of PET foams which comprises the extrusion of a mixture of PET, epoxy resin, catalyst consisting of imidazole, derivatives of imidazole or mixtures thereof plus a blowing agent, wherein the homopolymerization reaction of the epoxy phase is effected in the extruder, upstream of the introduction of the blowing agent. Compared to the methods of the known art, the process of the invention offers the advantage of providing a stable PET foam, in which the structure of the polymer chains is kept unaltered. The system therefore has viscoelasticity characteristics which allow the PET/epoxy homopolymer to receive the expanding action of the blowing agent, as far as the innermost and deepest layers of foam also having a significant thickness.

Description

PROCESS FOR THE PRODUCTION OF PET FOAMS AND PET FOAMS OBTAINED WITH SAID PROCESS
The invention relates to an enhanced process for the production of PET foams.
The invention is also extended to PET foams obtained with this process and to the bodies of expanded material obtained from these foams.
The field of the invention is the production of PET (polyethylene terephthalate) foams, normally used in the production of panels with numerous types of processing to make them suitable as a "core material" for various types of sandwich structures and also with a thermal insulation function.
Extending PET chains with pyromellitic anhydride and other crosslinking agents is known, for giving PET the necessary consistency for receiving the blowing agent, thus obtaining an expanded and stable foam. As a result, during the following extrusion phases of the foam, more or less significant phenomena of polymer degradation may arise, which in any case represent problems with respect to the quality of the final product .
Preparing a thermoplastic polymer foam in the presence of epoxides, crosslinked by means of photosensitive catalysts is also known (US 6,323,251), wherein the crosslinking reaction of the epoxide is effected downstream of the injection of the blowing agent, in particular outside the extrusion. The known process is consequently not suitable for providing a foam having the necessary consistency for the formation of the final product. In addition, photosensitive catalysts only act on the surface layer of the foam, which does not allow the crosslinking reaction to also take place inside the foamy mass.
The main objective of the present invention is to provide a method suitable for obtaining a PET foam which, unlike the known methods, has characteristics of stability at the outlet of the extruder, without altering, however, the structure of the PET chains.
These and other objectives are achieved by the present process, the PET foam and expanded material according to the respective claims 1, 10 and 11. Preferred embodiments of the invention are indicated in the remaining claims.
Compared to the methods of the known art, the invention offers the advantage of providing a stable PET foam, in which the structure of the polymer chains is kept unchanged. The system also has viscoelasticity characteristics which allow the mixture of PET/epoxy homopolymer to receive the expanding action of the blowing agent, as far as the innermost and deepest layers of foam also having a significant thickness.
These and other objectives, advantages and characteristics appear evident from the following description of a preferred embodiment of the invention illustrated, as a non-limiting example, in the figures of the enclosed drawings .
In these :
figure 1 illustrates a scheme of the extruder used for effecting the process of the invention; figures 2 and 3 illustrate the exothermic homopolymerization reaction of the epoxy resin, when activated in the presence of imidazole and its derivatives, compared to those in which different catalysts or no catalyst is used;
figure 4 illustrates the graph of a DSC (Differential Scanning Calorimetry) analysis for evaluating the crosslinking of the epoxy resin, of the samples processed as in figure 2; and
figure 5 represents an image obtained with an Atomic Force Microscope (AFM) of the nanodispersion of an epoxy homopolymer in the PET thermoplastic matrix.
The extruder, as schematically represented in figure 1 and used for effecting the process of the invention, is substantially divided into a step 1 for melting and mixing the PET mass 10, catalyst and other possible additives fed through the hopper 2, a reactive extrusion step 3 (homopolymerization of the epoxy phase) an injection step 6 of the blowing agent and a cooling step 7.
The PET used is in particular a PET suitable for being processed by extrusion, having the following chemical formula (I) :
Figure imgf000005_0001
(I)
The catalyst is then added to the PET, which, according to the invention, consists of imidazole, derivatives of imidazole and mixtures thereof, represented by the following formula (II) :
Figure imgf000005_0002
R2
wherein Rl, R2 , R3 are inorganic or organic groups the aromatic or aliphatic type
Some non- limiting examples of catalysts used in the process of the invention 2-methylimidazole, 2- ethyl -4 -methylimidazole, 1 -Benzyl -2 -methylimidazole, 1- Methylimidazole , 1 , 2 -Dimethylimidazole and mixtures thereof .
Among the additives that can be used in the process of the invention, suitable for improving the processability, appearance, and properties of the PET foam, the following can be mentioned, alone or combined with each other:
• plasticizers
· pigments
• flame-retardants
• fillers
• stabilizers
• surfactants
· nucleating agents
• nano-additives
The catalyst used in the invention is in liquid phase and, in step 1 of the extruder, it is closely mixed inside the PET mass. The mixture thus obtained is then sent, from the screw of the extruder (not represented) , towards a subsequent step 3 for putting the PET mass in contact with the catalyst and mixing them with an injection 4 of epoxy resin, also in liquid state .
Preferred epoxy resins for the invention are those having the following formula (III)
Figure imgf000007_0001
wherein :
m and n are integers (0, 1, 2, 3, ..)
Rl, R2 and R3 represent an aliphatic or aromatic group, or an inorganic chain.
Among the epoxy resins that can be used in the process of the invention, the following can be cited:
• epoxidized novolacquers from phenol or cresol (polyphenyl-glycidyl ether - co - formaldehyde, poly-o-cresyl-glycidyl ether - co - formaldehyde) ;
• mono- or poly- glycidyl ether or ester, aliphatic or aromatic (polibisphenol A-co-epichlorohydrin- glycidyl terminated; 2-ethylhexyl glycidyl ether; 1- 4-butanediol of glycidyl ether; tertaglycidyl - methylbisbenzeneamine ; butylphenyl- glycidyl ether) ,
• organic or inorganic epoxidized chains
(glycidoxypropyltrimethoxysilane ;
glycidoxypropyltriethoxysilane ; butyldimethylsilane- glycidyl ether; bis-glycidyloxypropyltetra- methyldisiloxane) ;
polyhedral glycidyl oligomer based on silicon- silicone (POSS) (example: CAS: 445379-56-6; CAS: 307496-38-4) .
In this step of the process of the invention, the epoxy resin undergoes a homopolymerization process, which develops inside the extruder itself (so-called reactive extrusion) . Furthermore, due to the use of epoxy resins in the liquid state (or previously not crosslinked) , a nanodispersion of homopolymer particles can be obtained inside the continuous PET mass (see figure 5) .
As a result of the presence of nanodispersed epoxy homopolymer in the PET mass, the latter is provided with the viscoelasticity necessary for the introduction of the blowing agent, to allow the subsequent foaming phase to take place.
The high catalytic activity of imidazole and its derivatives towards the homopolymerization reaction of the epoxy resin also allows this homopolymerization reaction to be completed within the above-mentioned step 3, therefore without involving the PET chains present in the reaction environment, thus leaving their chemical structure unaltered.
The elective behaviour towards the epoxy resin of the catalyst used in the process of the invention, without involving the molecules of the PET polymer, is shown by the graphs in figures 2 to 4. In particular, figure 2 compares the elective action of 1,2- dimethylimidazole having formula
Figure imgf000009_0001
wherein R1=H; R2= CH3; R3=CH3
with that offered by the catalysts of the known art, in particular triphenyl sulfonium hexafluoroantimonate , dimethylbenzylamine, 2 -heptylpiperazine , or in the absence of catalyst .
From the graph of figure 2, which simulates upon
DSC analysis, the operative conditions of the extrusion process of a mixture of epoxy resin alone (100 parts) with catalyst (2 parts) , it can be observed that the catalyst according to the invention has an exothermic section (a) whose peak, compared with the flat trend of the corresponding sections (b) of the curves relating to the catalysts used according to the known art, or with the trend of the curve in the absence of catalyst, indicates the completion of the homopolymerization reaction of the epoxy phase, without involving the PET molecules, thus leaving them unaltered.
The same conclusions can be drawn from examining the exothermic sections represented in figure 3, this time relating to the family of imidazoles that can be used in the process of the invention.
Figure 4 shows the DSC analysis of the samples tested as in figure 2, after simulation of the extrusion process. From the graph, it can be observed that the only sample that has undergone the homopolymerization reaction is that corresponding to the catalyst 2-ethyl-4-methylimidazole (curve c) of figure 4), which in fact has a glass transition temperature value (Tg) of 99.3°C. The flat trend of the remaining curves, relating to the samples of epoxy resin treated with catalysts different from that according to the process of the invention or samples without catalyst, indicates that the homopolymerization reaction has not taken place.
As a result of the formation of nanodispersed epoxy homopolymer, in step 3 of the extruder, within the PET mass, the latter is provided with a viscoelasticity sufficient for introducing 5 the blowing agent in step 6 of the extrusion, thus making it suitable for the subsequent foaming phase at the outlet 8 of the extruder. Said foaming phase is preceded by a cooling step 7 of the extruded product 9, the latter consisting of a continuous flow of expanded material, whose cooling process is completed at room temperature. End-products consisting of bodies of expanded material are subsequently obtained from this extruded product 9.
Some examples of formulations of the PET foam used in the process of the invention are provided hereunder, wherein the percentages refer to the weight of the mixture .
EXTRUDER
Foaming process by extrusion obtained using a
Leistritz ZSE40MAXX-44D extruder, as schematized in figure 1 and with the following temperature profile:
Figure imgf000011_0001
EXAMPLE 1 - Absence of catalyst and epoxy resin The following reagents were charged into the extruder through the hopper 2 :
• PET: Polyclear 1011 of Invista (IV=0.83)
• Talc dispersed in PET (1.3-3% with respect to PET) The blowing agent was added through the injection point (5) :
• Cyclohexane in liquid phase
The pressure value (indication of the viscoelasticity of the mixture) inside the extruder is not such as to keep the blowing agent in a homogeneously dispersed supercritical fluid phase. Attempts at foaming the PET therefore failed as the polymeric mass at the outlet of the extruder does not have a sufficient viscoelasticity for keeping the gas phase enclosed in cells.
EXAMPLE 2 - Absence of catalyst and presence of epoxy resin
The following reagents were charged into the extruder through the hopper 2 :
• PET: Polyclear 1011 of Invista (IV=0.83)
• Talc dispersed in PET (1.3-3% with respect to PET) The following epoxy resin in liquid phase was added through the injection point (4) :
• Poly-epoxy: Lindoxy 290 (in liquid phase)
The blowing agent was added through the injection point (5) :
• Cyclohexane in liquid phase
Also in this case, the pressure value (indication of the viscoelasticity of the mixture) inside the extruder is not such as to keep the blowing agent in a homogeneously dispersed supercritical fluid phase. Attempts at foaming the PET therefore failed as the polymeric mass with a low viscoelasticity at the outlet of the extruder is not capable of keeping the gas phase enclosed in cells.
EXAMPLE 3 - Presence of epoxy resin and catalyst - dimethylbenzylamine
The following reagents were charged into the extruder through the hopper 2 :
• PET: Polyclear 1011 of Invista (IV=0.83)
• Talc dispersed in PET (1.3-3% with respect to PET)
• dimethylbenzylamine (in a percentage of up to 2.3% with respect to the epoxy resin)
The following epoxy resin in liquid phase was added through the injection point (4) :
• Poly-epoxy: Lindoxy 290 (in liquid phase) from 1.3 to 5%
The blowing agent was added through the injection point (5) :
• Cyclohexane in liquid phase
Also in this case, the pressure value (indication of the viscoelasticity of the mixture) inside the extruder is not such as to keep the blowing agent in a homogeneously dispersed supercritical fluid phase. Attempts at foaming the PET therefore failed as the polymeric mass with a low viscoelasticity at the outlet of the extruder is not capable of keeping the gas phase enclosed in cells. EXAMPLE 4 - Presence of epoxy resin and catalyst - 2 -ethylpiperidine
The following reagents were charged into the extruder through the hopper 2 : · PET: Polyclear 1011 of Invista (IV=0.83)
• Talc dispersed in PET (1.3-3% with respect to PET)
• 2 -ethylpiperidine (in a percentage of up to 2% with respect to the epoxy resin) .
The following epoxy resin in liquid phase was added through the injection point (4) :
• Poly-epoxy: Lindoxy 290 (in liquid phase) from 1.3 to 5%.
The blowing agent was added through the injection point (5) : · Cyclohexane in liquid phase
Also in this case, the pressure value (indication of the viscoelasticity of the mixture) inside the extruder is not such as to keep the blowing agent in a homogeneously dispersed supercritical fluid phase. Attempts at foaming the PET therefore failed as the polymeric mass with a low viscoelasticity at the outlet of the extruder is not capable of keeping the gas phase enclosed in cells.
EXAMPLE 5 - Presence of epoxy resin and catalyst based on imidazole The following reagents were charged into the extruder through the hopper 2 :
• PET: Polyclear 1011 of Invista (IV=0.83) or CLEARTUF P76 by M&G (IV=0.74)
• Talc dispersed in PET (1.3-3% with respect to PET)
• Catalyst based on imidazole (tests respectively effected with 2 -methylimidazole , 2 -ethyl -4- methylimidazole and 1 , 2 -dimethylimidazole , in percentages of up to 2% with respect to the epoxy resin) .
The following epoxy resins in liquid phase were added through the injection point (4) :
• Poly-epoxy: Lindoxy 290 (in liquid phase, from 1.3 to 5% with respect to PET)
• Mono- or di -epoxy: 2-Ethylhexyl glycidyl ether or 1 , 6-hexanediol diglycidyl ether (from 0 to 0.5% with respect to PET)
The blowing agent was added through the injection point (5) :
• Cyclohexane in liquid phase
The pressure value (indication of the viscoelasticity of the mixture) inside the extruder is such as to keep the blowing agent in a homogeneously dispersed supercritical fluid phase. For the various percentages of epoxy resin and catalyst, suitably dosed, attempts at foaming the PET were therefore successful, as the polymeric mass at the outlet of the extruder was sufficiently viscoelastic to keep the gas phase inside closed cells having a reduced dimension (less than 0.7 mm), producing a stable foam having a density ranging from 60-140 Kg/m3.

Claims

1) A process for the production of PET foams, characterized in that it includes the extrusion of a mixture of PET, epoxy resin, a catalyst consisting of imidazole, derivatives of imidazole or mixtures thereof and a blowing agent, wherein the homopolymerization reaction of the epoxy phase is effected in the extruder, upstream of the introduction of the blowing agent .
2) The process according to claim 1, characterized in that said PET is of the type which can be processed by extrusion, having the chemical formula:
Figure imgf000017_0001
3) The process according to claim 1, characterized in that said catalyst consists of imidazole, derivatives of imidazole or mixtures thereof, having the formula :
Figure imgf000017_0002
wherein Rl, R2 and R3 are inorganic or organic groups of the aromatic or aliphatic type.
4) The process according to claims 1 and 3, characterized in that said catalyst is mixed with PET in a melting and mixing step (1) , with the catalyst in the liquid state.
5) The process according to claim 1, characterized in that said epoxy resin is in the liquid state and has the followin formula:
Figure imgf000018_0001
wherein :
m and n are integers (0, 1, 2, 3, ..)
Rl, R2 and R3 are organic, aliphatic or aromatic groups, or an inorganic chain.
6) The process according to claim 1, characterized in that it comprises a step (3) in which the epoxy resin undergoes a homopolymerization process which takes place inside the extruder (reactive extrusion) .
7) The process according to claim 6, characterized in that in said step (3) the nanodispersion takes place of epoxy homopolymer particles inside the continuous PET mass, the chemical structure of the PET chains in the reaction environment being kept unaltered.
8) The process according to one or more of the previous claims, characterized in that it also comprises a step (6) for the introduction of the blowing agent (5) into said dispersion, a cooling step (7) and a foaming step (8) .
9) The process according to one or more of the previous claims from 1 to 7, characterized in that said mixture also includes, alone or combined with each other :
* plasticizers * pigments
* flame-retardants
* fillers
* stabilizers
* surfactants
* nucleating agents
* nano-additives .
10) A PET foam, characterized in that it is obtained by means of the process in accordance with one or more of the previous claims.
11) A body of expanded material, characterized in that it consists of the foam according to claim 10.
PCT/EP2013/000079 2012-02-02 2013-01-14 Process for the production of pet foams and pet foams obtained with said process WO2013113465A1 (en)

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MX2014008973A MX351792B (en) 2012-02-02 2013-01-14 Process for the production of pet foams and pet foams obtained with said process.
US14/371,146 US9394417B2 (en) 2012-02-02 2013-01-14 Process for the production of PET foams and PET foams obtained with said process
KR1020147021754A KR101958513B1 (en) 2012-02-02 2013-01-14 Process for the production of pet foams and pet foams obtained with said process
ES13703317.1T ES2567322T3 (en) 2012-02-02 2013-01-14 Procedure for the production of PET foams and PET foams obtained with said procedure
BR112014017887A BR112014017887A8 (en) 2012-02-02 2013-01-14 PROCESS FOR THE PRODUCTION OF PET FOAM, PET FOAM, AND EXPANDED MATERIAL BODY
CN201380007688.XA CN104204090B (en) 2012-02-02 2013-01-14 The method producing PET foams and the PET foams using described method to obtain
AU2013214578A AU2013214578B2 (en) 2012-02-02 2013-01-14 Process for the production of PET foams and PET foams obtained with said process
EA201491192A EA201491192A1 (en) 2012-02-02 2013-01-14 METHOD FOR OBTAINING POLYETHYLENEREPHTALATE FOAMS AND POLYETHYLLENEREPHTHALATE FOAMS OBTAINED BY INDICATED METHOD
CA2861004A CA2861004C (en) 2012-02-02 2013-01-14 Process for the production of pet foams and pet foams obtained with said process
DK13703317.1T DK2809724T3 (en) 2012-02-02 2013-01-14 A process for producing foam PET and PET foam obtained with this method
EP13703317.1A EP2809724B1 (en) 2012-02-02 2013-01-14 Process for the production of pet foams and pet foams obtained with said process
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