Classifications

• • 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
  • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
• • 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
  • B29C44/3415—Heating or cooling
• • 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
  • B29C44/35—Component parts; Details or accessories
  • B29C44/355—Characteristics of the foam, e.g. having particular surface properties or structure
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0014—Use of organic additives
  • C08J9/0023—Use of organic additives containing oxygen
• • 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
  • C08J9/0014—Use of organic additives
  • C08J9/0028—Use of organic additives 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
  • C08J9/0014—Use of organic additives
  • C08J9/0033—Use of organic additives containing sulfur
• • 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
  • C08J9/0014—Use of organic additives
  • C08J9/0038—Use of organic additives containing phosphorus
• • 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
  • C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
• • 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
  • C08J9/06—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 chemical blowing agent
• • 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
  • C08J9/06—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 chemical blowing agent
  • C08J9/08—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 chemical blowing agent developing carbon dioxide
• • 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
  • C08J9/22—After-treatment of expandable particles; Forming foamed products
  • C08J9/228—Forming foamed products
• • 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
• • 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
  • B29K2105/0002—Condition, form or state of moulded material or of the material to be shaped monomers or prepolymers
• • 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
  • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
  • B29K2105/0014—Catalysts
• • 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
  • B29K2105/046—Condition, form or state of moulded material or of the material to be shaped cellular or porous with closed cells
• • 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
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
• • 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
  • C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
• • 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
  • C08J2205/00—Foams characterised by their properties
  • C08J2205/04—Foams characterised by their properties characterised by the foam pores
• • 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
  • C08J2205/00—Foams characterised by their properties
  • C08J2205/04—Foams characterised by their properties characterised by the foam pores
  • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
• • 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
  • C08J2300/00—Characterised by the use of unspecified polymers
  • C08J2300/24—Thermosetting 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
• • 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

Definitions

• the present invention relates to thermoset solid foams obtained by reaction and chemical foaming of an expandable composition containing a polyol component, a polyacid component, a surfactant and an esterification catalyst.
• thermoset polyester foams by reaction of a polyol and a polyacid.
• a highly crosslinked polyester is obtained in two steps: the first step consists in forming a non-crosslinked prepolymer by reacting a polyol and a polyacid at a first relatively low temperature and the second step in crosslinking the prepolymer either at a second temperature higher than the first, or at a moderate temperature in the presence of a crosslinking agent or a polymerization catalyst (esterification).
• the absence of the catalyst in the first step seems to be essential to be able to implement this process in two stages.
• Some cured polymers are described as foams. Their density is however relatively high (Example 12: 350 kg / m 3 , Example 16: 190 kg / m 3 ). The use of physical or chemical foaming agents is envisaged (see [0040]).
• the international application WO2012 / 052385 describes an expanded polymer obtained by reaction of glycerol and citric acid at a temperature between 80 and 130 ° C until the degree of conversion is at least equal to 90%, possibly in the presence an esterification catalyst. When a conversion of at least 90%, preferably 98%, is reached, the reaction mixture is heated to a higher temperature, close to 150 ° C.
• the first step at low temperature is intended to avoid as far as possible the decarboxylation of citric acid.
• the process described in this document requires very long reaction times, ranging from several hours to several tens of hours.
• the polymerization is preferably carried out in non-stick molds, for example in Teflon.
• the foams thus obtained have a density of between 200 and 850 g / liter.
• the international application WO2013 / 121033 describes an improvement of this process where the polymerization of glycerol and citric acid is carried out in contact with a substrate with an outer layer comprising at least one metal, a metal oxide or a metal halide. .
• This process provides foams having a more regular pore size than those prepared by the method described in WO 2012/052385.
• the densities claimed are between 50 and 850 g / liter.
• the foams prepared in the examples according to the invention have densities of between 282 g / liter and 482 g / liter.
• the present invention is based on the discovery that the use of an esterification catalyst and a surfactant in the initial reaction mixture containing glycerol and citric acid made it possible to obtain, in a single polymerization step, at high temperature and in a limited time, foams of excellent quality, having a lower density than known foams and having a fine and uniform porosity.
• the Applicant does not seek to avoid the decomposition of citric acid into aconitic acid and CO 2 . On the contrary, it heats the reaction mixture rapidly at an elevated temperature in order to use citric acid as a chemical blowing agent (chemical expansion agent, chemical foaming agent) which makes the addition of a blowing agent superfluous. physical.
• a chemical blowing agent chemical expansion agent, chemical foaming agent
• thermoset polyester foam comprising the following successive stages:
• a polyacidic component comprising citric acid
• thermoset polyester foam (c) heating the expansible and thermosetting composition at a temperature of at least 135 ° C., preferably at least 150 ° C., even more preferably at least 175 ° C., so as to react the polyol component with the polyacid component and form a block of thermoset polyester foam.
• a polyol component comprising at least one element chosen from glycerol, diglycerol and glycerol oligomers,
• a polyacidic component comprising citric acid
• thermosetting expandable composition thus comprises four essential components: the polyol component, the polyacid component, the surfactant and the esterification catalyst.
• the polyacid component may comprise polyacids other than citric acid and the polyol component may include polyols, i.e., polyhydroxy compounds, other than glycerol, diglycerol and glycerol oligomers. Examples of other polyacids and polyols will be given below.
• polyol or polyacid components are always understood for all the polyols or for all the polyacids present in the composition.
• This definition of the polyol and polyacid components does not exclude the possibility that certain surfactants are considered to be part of the polyol or polyacid components.
• alkylpolyglycosides APG which are part of the preferred surfactants.
• the alkylpolyglycosides comprise one or more sugar units (polyhydroxylated units) and play both the role of surfactant by modulating and controlling the porosity of the foams obtained, and the role of polyols capable of participating in the formation of a three-dimensional network. hardened by reaction with the acid groups of the polyacid component.
• a compound, present in the expandable and thermosetting composition when a compound, present in the expandable and thermosetting composition, can be considered both as a first of the four essential components and as a second of the four essential components of the composition (polyol component, polyacid component, surfactant , esterification catalyst) it will be considered both as one and the other. This implies that it will be taken into account in the quantities of each of these two components.
• alkylphosphonic acids R-PO H 2 where R is a fatty chain
• R-PO H 2 alkylphosphonic acids
• the first essential component of the expandable composition is the polyol component.
• This component comprises at least one element selected from the group consisting of glycerol, diglycerol and oligoglycerols. Oligoglycerols of compounds of formula
• n is an integer of 3 to 6
• the aliphatic mono- or polyethers of the compounds of formula (1) in which up to 30% of the -OH functions may be etherified with aliphatic alcohols.
• the polyol component preferably comprises, based on the total dry weight of the polyol component, at least 15% by weight, preferably at least 20% by weight, in particular at least 25% by weight of glycerol.
• the Applicant has indeed found that a significant amount of glycerol monomer makes it possible to obtain foams of low density and uniform porosity.
• the polyol component preferably contains at most 30% by weight, in particular at most 20% by weight and ideally at most 10% by weight, based on the total dry weight of the polyol component, of polyols which are neither glycerol nor diglycerol or oligomers of glycerol.
• polyols are preferably biosourced polyols, in particular sugars and sugar alcohols (hydrogenated sugars).
• the sugars usable as part of the polyol component may be reducing sugars or non-reducing sugars.
• Reducing sugars are carbohydrates of formula C n (H 2 O) p having at least one aldehyde or ketone group (reducing group).
• Reducing sugars for use in the present invention include monosaccharides (monosaccharides) and osides (disaccharides, oligosaccharides, and polysaccharides).
• monosaccharides mention may be made of those comprising from 3 to 8 carbon atoms, preferably the aldoses and advantageously the aldoses containing 5 to 7 carbon atoms.
• the particularly preferred aldoses are natural aldoses (belonging to the D series), in particular hexoses such as glucose, mannose and galactose. Lactose or maltose are examples of disaccharides which can be used as reducing sugars.
• starch hydrolysates obtained by enzymatic hydrolysis or acid hydrolysis of starch It is also possible advantageously to use starch hydrolysates obtained by enzymatic hydrolysis or acid hydrolysis of starch.
• the non-reducing sugars that can be used are sucrose and trehalose.
• hydrogenated sugars mention may be made of erythritol, arabitol, xylitol, sorbitol, mannitol, iditol, maltitol, isomaltitol, lactitol, cellobitol, palatinitol, maltotritol and hydrogenation products of starch hydrolysates.
• the second essential component of the expandable composition is the polyacid component.
• the polyacid component preferably comprises at least 50% by weight, in particular at least 65% by weight and most preferably at least 80% by weight of citric acid, based on the total weight of the polyacid component.
• polyacids that may react with the polyol component to form a polyester network may be present.
• These other polyacids are preferably monomeric polyacids, that is to say polyacids which are not formed by polymerization of monomeric units carrying acid groups such as poly (acrylic acid).
• the other polyacids are preferably polycarboxylic acids, for example dicarboxylic, tricarboxylic or tetracarboxylic acids.
• the dicarboxylic acids include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malic acid, tartaric acid, tartronic acid, aspartic acid, glutamic acid, fumaric acid, itaconic acid, maleic acid, traumatic acid, camphoric acid, phthalic acid and its derivatives, in particular containing at least one boron or chlorine atom, tetrahydrophthalic acid and its derivatives, in particular containing at least one atom chlorine such as chlorendic acid, isophthalic acid, terephthalic acid, mesaconic acid and citraconic acid;
• Tricarboxylic acids include, for example, tricarballylic acid, 1,2,4-butanetricarboxylic acid, aconitic acid, hemimellitic acid, trimellitic acid and trimesic acid;
• Tetracarboxylic acid for example 1,2,3,4-butane-tetracarboxylic acid and pyromellitic acid, may be mentioned.
• the polyol and polyacid components as defined above together represent at least 60%, preferably at least 70% and in particular at least 80% of the dry weight of the expansible and thermosetting composition.
• the polyol component is preferably from 15 to 60% by weight, in particular from 20 to 50% by weight and most preferably from 25 to 45% by weight of the total weight of the polyol and polyacid components. It follows logically that the polyacid component preferably represents 40 to 85% by weight, in particular 50 to 80% by weight, and ideally 55 to 75% by weight of the total weight of the polyol and polyacid components.
• the respective amounts of the polyol and polyacid components will be adjusted so that the -OH functions and the -COOH functions are present in a molar ratio of between 0.65 and 1.5, preferably between 0.8. and 1, 4, in particular between 1.0 and 1.3.
• the third essential component of the expandable and thermosetting composition is a surfactant.
• this term also encompasses mixtures of several surfactants.
• This ingredient is to improve the quality of the foam, i.e. to reduce the pore size, to tighten the pore size distribution and to reduce the density of the cured foams obtained.
• the surfactant preferably has a hydrophilic / lipophilic balance (HLB) between 3 and 13, preferably between 5 and 8.
• HLB hydrophilic / lipophilic balance
• the surfactant is a mixture of an anionic surfactant and a cationic surfactant.
• a combination of two types of surfactants with opposite charges makes it possible to stabilize the film of surfactants at the water / air interface by reducing the repulsion between molecules of the same charge.
• the Applicant has obtained excellent results with a mixture of sodium dodecyl sulphate (SDS) and tetradecyltrimethylammonium bromide (TTAB) and the use of a combination of these two agents.
• SDS sodium dodecyl sulphate
• TTAB tetradecyltrimethylammonium bromide
• surfactants is therefore a preferred embodiment.
• the ratio by weight TTAB / SDS is preferably between 1, 5 and 2.5, in particular between 1, 8 and 2.2 and ideally close to 2.
• Nonionic surfactants are an interesting alternative to the combination of anionic surfactant and a cationic surfactant. Indeed, for nonionic surfactants, there are no repulsive forces between hydrophilic heads of the same filler and some nonionic surfactants are therefore particularly suitable for the formation of good quality foams.
• the nonionic surfactants used in the present invention preferably have an HLB of between 3 and 13.
• alkylpolyglycosides which are molecules comprising a hydrophilic head formed of one or more sugar units, grafted alkyl fatty chain.
• the alkylpolyglycosides preferably have 1 to 2 glucoside units and the alkyl chains preferably have 8 to 14 carbon atoms and are preferably linear alkyl chains.
• alkylpolyglycosides mention may be made of Glucopon branded products, in particular Glucopon 600 CSUP (lauryl glucoside) and Glucopon 650 EC (coco glucoside).
• the amount of the surfactant is preferably from 0.1 to 10%, preferably from 1 to 8% and in particular from 2 to 6% of the total dry weight of the foamable composition.
• the fourth essential ingredient of the expandable and thermosetting composition used in the process of the present invention is an esterification catalyst.
• This catalyst is preferably, but not necessarily, a phosphorus-containing compound.
• preferred phosphorus catalysts are those selected from the group consisting of alkali metal hypophosphite (H 2 PO 2 M), alkali metal phosphite (HPO 3 M 2 ), alkali metal polyphosphate (M 3 PO).
• alkali metal hydrogenphosphate M 2 HPO
• phosphoric acid H 3 PO
• alkylphosphonic acid RPO 3 H 2
• Alkaline metal hypophosphite is particularly preferred.
• the concentration of the esterification catalyst is typically from 0.1 to 10% by weight, preferably from 1 to 8% by weight, and in particular from 2 to 6% by weight, based on the dry weight of the foamable composition.
• the mixture of the four essential components described above is advantageously a solution.
• the water may also serve to fluidify the composition to facilitate its flow or spreading during step (b) of the process of the invention.
• it will generally be sought to limit the amount of water in the expandable composition because the esterification reaction will begin after complete evaporation of water and the evaporation of water has an undesirable energy cost.
• the expandable composition used in the present invention may further contain up to 30% by weight, preferably up to 20% by weight, in particular up to 10% by weight, based on the dry weight of the total expandable composition of one or more mineral or organic fillers.
• the expandable composition may contain one or more other additives conventionally used in the industry for the processing and processing of polymers such as dyes, pigments, antibacterial or antifungal agents, flame retardants, UV absorbers, hydrophobic agents. These additives represent in total preferably at most 10% of the dry weight of the composition.
• the expandable composition may contain, in principle, an organic blowing agent such as pentane, it is important to note that it is not necessary to add it.
• citric acid present in the polyacid component, acts as an expansion agent.
• the expandable composition is heated, in step (c), to a temperature close to 175 ° C.
• the citric acid decomposes, in a known manner, into aconitic acid and CO 2 (MM Barbooti et al., Thermal Decomposition of Citric Acid, Thermochimica Acta, 98 (1986), 19-126, D. Wyrzykowski et al., "Thermal Behavior of Citric Acid and Isomeric Aconitic Acids", J. Therm Anal Calorim (2001), 104: 731-735).
• step (c) is carried out at a temperature above 170 ° C, the addition of an organic blowing agent is superfluous.
• the expandable composition is therefore substantially free of organic physical blowing agent.
• the thickness of the film, before heating, that is to say before expansion and hardening is advantageously at least equal to 1 mm, preferably less than 2 mm, in particular at least 5 mm, and more preferably at least 10 mm.
• the volume of the foam block formed can vary between very wide limits. When the expandable composition is used in a process continuous forming for example strips or profiles of insulating materials, it is potentially infinite. When the expandable composition is used to form discrete blocks, for example sheets or sheets of foams, the amount thereof is preferably such that the volume of each solid thermoset foam block is at least 500 cm 3 , preferably at least equal to 0.001 m 3 , in particular at least 0.01 m 3 .
• the foam block is preferably in the form of a plate.
• any conventional means known in the field of processing and processing of polymers such as hot air, thermal radiation, microparticles, can be used in principle. -ondes or the contact with a hot support (mold).
• the temperature of the heating means may be greater than the reaction temperature mentioned above, for example between 160 and 210 ° C.
• the duration of the heating step (step (c)) depends not only on the temperature, but also the heating means and the volume / area ratio of the foam block formed. It is generally between 10 minutes and 5 hours, preferably between 20 minutes and 4 hours and in particular between 30 minutes and 3 hours.
• the present invention also relates to a solid polyester foam obtainable by the method of the present invention.
• the solid foams prepared by the process of the invention are generally light in color, typically ivory, yellow or beige in color. Their density is between 20 and 80 kg / m 3 , preferably between 25 and 50 kg / m 3 , in particular between 27 and 48 kg / m 3 .
• thermosetting expansible compositions are prepared by adding powdered citric acid to an aqueous solution containing glycerol, diglycerol, oligoglycerol or a mixture thereof.
• the esterification catalyst sodium hypophosphite monohydrate
• the mixture is stirred at room temperature until the citric acid powder is dissolved.
• Table 1 indicates the respective amounts of the ingredients used, expressed as solids, as well as the total solids content of the compositions obtained.
• the reactive solution is then poured into rectangular molds whose bottom is covered with aluminum foil.
• the thickness of the liquid film is about 1 mm.
• the molds are heated for 3 hours in a ventilated oven thermostated at 180 ° C.
• the thickness of the foam formed is evaluated using the following rating scale:
• TTAB tetradecyltrimethylammonium bromide
• SDS sodium dodecyl sulphate
• polyglycerol-4 (CAS No. 25618-55-7) contains about 2% diglycerol, 43% triglycerol, 34% tetraglycerol, 14% pentaglycerol, 6% hexaglycerol
• the foams obtained all have a fine and regular porous structure. They are ivory or beige.
• Figures 1 and 2 show by way of example respectively a plate and a block of foam obtained.
• Alkylpolyglycosides (neutral surfactants) give results comparable to the TTAB / SDS combination.
• the Applicant has carried out tests with an anionic surfactant (Disponil® SUS 87 Spez, disodium salt of an ethoxylated decyl alcohol ester), but this surfactant used in the absence of a cationic surfactant does not allow obtaining a foam.
• an anionic surfactant Disodium salt of an ethoxylated decyl alcohol ester
• non-ionic surfactant having an HLB of 14 (Disponil® PGE 110, polyglycolic diether of an aliphatic diol) also does not result in a foam.
• Table 2 shows the results obtained by tests carried out under the same conditions as those in Table 1. About one-third of the glycerol / diglycerol / oligoglycerol has been replaced by a different polyol (hydrophobic starch, trimethylolpropane, pentaerythritol).
• TTAB tetradecyltrimethylammonium bromide
• SDS sodium dodecyl sulphate
• Table 3 shows the results obtained by tests carried out under the same conditions as those in Table 1, except that all the glycerol / diglycerol / oligoglycerol has been replaced by a different polyol (hydrophobic starch, maltitol, isosorbide ).
• TTAB tetradecyltrimethylammonium bromide
• SDS sodium dodecyl sulphate
• Table 4 below shows the results obtained by tests carried out under the same conditions as those in Table 1, except that some or all of the citric acid has been replaced by another polyacid.
• TTAB tetradecyltrimethylammonium bromide
• SDS sodium dodecyl sulphate
• TTAB tetradecyltrimethylammonium bromide
• SDS sodium dodecyl sulphate
• TGA Thermogravimetric analysis

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