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WO2014177850A1 - Préparation polymère améliorée - Google Patents

Préparation polymère améliorée Download PDF

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Publication number
WO2014177850A1
WO2014177850A1 PCT/GB2014/051317 GB2014051317W WO2014177850A1 WO 2014177850 A1 WO2014177850 A1 WO 2014177850A1 GB 2014051317 W GB2014051317 W GB 2014051317W WO 2014177850 A1 WO2014177850 A1 WO 2014177850A1
Authority
WO
WIPO (PCT)
Prior art keywords
formulation
phosphate ester
hydroxylamine
polymeric resin
partial phosphate
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/GB2014/051317
Other languages
English (en)
Inventor
Graham Murray
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bac2 Ltd
Original Assignee
Bac2 Ltd
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
Priority claimed from GB201307707A external-priority patent/GB201307707D0/en
Priority claimed from GB201317842A external-priority patent/GB201317842D0/en
Application filed by Bac2 Ltd filed Critical Bac2 Ltd
Publication of WO2014177850A1 publication Critical patent/WO2014177850A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0066—≥ 150kg/m3
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms

Definitions

  • the present invention relates to the use of hydroxylamine as a retarder for a curing reaction of pre-polymeric resin formulations containing pre-polymeric resins and partial phosphate ester curing agents.
  • Thermoset polymers made from acid cured pre-polymer resins including phenol-formaldehyde resoles (PF), furane or furfuryl alcohol resins (FA), melamine-formaldehyde resins (MF), urea-formaldehyde resins (UF), and PF/FA, PF/UF, PF/MF, PF/UF/MF blends of such pre-polymer resins are used in the production of bulk moulding compounds, sheet moulding compounds, abrasives, grinding wheels, disks, friction materials, syntactic foams, foam insulation, mineral insulation and glass fibre insulation, adhesives, inks, coatings, pre-pregs, electronics, laminates, filament winding, pultrusion, glass fibre composites, resin transfer moulding, vacuum bagging, carbon composites, bipolar plates, carbon electrodes, conductive composite electrodes, polymer electrolytes and membranes.
  • PF phenol-formaldehyde resoles
  • FA furan
  • thermoset polymers made from acid cured pre-polymer resins including phenol-formaldehyde resoles (PF), furane or furfuryl alcohol resins (FA), melamine-formaldehyde resins (MF), urea- formaldehyde resins (UF), and PF/FA, PF/UF, PF/MF, PF/UF/MF blends of such pre-polymer resins are used in subterranean rock and coal bed consolidation.
  • PF phenol-formaldehyde resoles
  • FA furane or furfuryl alcohol resins
  • MF melamine-formaldehyde resins
  • UF urea- formaldehyde resins
  • PF/FA PF/UF, PF/MF, PF/UF/MF blends of such pre-polymer resins
  • partial phosphate esters as curing agents is that pot life of the pre-polymeric resin (for example a phenolic resin)/partial phosphate ester mix is only extended for a few hours limiting the use of the partial phosphate ester to processes where long term storage is not required such us hand lay-up and pultrusion. Use of the partial phosphate esters in bulk moulding compounds and sheet moulding compounds, where storage in the order of weeks and months is required, is not possible.
  • a further disadvantage of using partial phosphate esters with pre- polymeric resins is the sharp increase in viscosity on initial mixing of the partial phosphate ester with a pre-polymeric resin (such as a phenolic resole). This increase in viscosity reduces the wetting properties of the resin when added to the glass or other fibrous substrates.
  • pre-polymeric resin such as a phenolic resole
  • This increase in viscosity reduces the wetting properties of the resin when added to the glass or other fibrous substrates.
  • An example of a situation where greater control is desirable is in or after a stimulation operation (known as hydraulic fracturing or "fracking") of subterranean coal bed methane seams.
  • Thermoset polymers can be used to maintain pathways, allowing gases to escape.
  • Latent catalysts can be used to allow the binders to flow into the fractured bed. The elevated temperatures underground can be utilised to activate the latent catalysts and begin the polymerisation reaction. The ability to control this polymerisation until the binder is in place is vital. If the polymerisation occurs on route to the fractured coal bed, the hydraulic fluids may be blocked. If the polymerisation fails to occur or is too slow, the pathways created within the fractured bed can be blocked as loose particles fill up the gaps and pathways preventing the gas escape.
  • a method of retarding a curing reaction of a pre-polymeric resin formulation comprising a pre- polymeric resin and a partial phosphate ester curing agent using hydroxylamine.
  • hydroxylamine as a retarder for the curing reaction of a pre-polymeric resin formulation comprising a pre-polymeric resin and a partial phosphate ester curing agent.
  • a pre-polymeric resin formulation comprising a pre-polymeric resin, a partial phosphate ester and hydroxylamine.
  • the pre-polymeric resin formulation may be used in moulding applications, such as bulk moulding or sheet moulding, abrasives, grinding wheels, disks, friction materials, syntactic foams, foam insulation, mineral insulation and glass fibre insulation, adhesives, inks, coatings, pre-pregs, electronics, laminates, filament winding, pultrusion, glass fibre composites, resin transfer moulding, vacuum bagging, carbon composites, bipolar plates, carbon electrodes, conductive composite electrodes, polymer electrolytes and membranes.
  • the pre-polymeric resin formulation may be used in subterranean rock and coal bed consolidation, for example maintaining pathways created following hydraulic fracturing ("fracking"). Hydraulic fracturing, or “fracking”, uses liquid or gas at high pressure. In one embodiment the pre-polymeric resin formulation may be mixed with the fracking liquid.
  • the formulation is stable without any curing reaction occurring for at least an hour or for at least six hours, or for at least a six days, or for at least five weeks or for at least 12 weeks.
  • the formulation comprises a phenolic resole resin, a partial phosphate ester and hydroxylamine, wherein the particle phosphate ester may be Phencat 382.
  • the amount of hydroxylamine to be added is first calculated by adding to a known amount of partial phosphate ester until a predetermined pH is reached.
  • the pH to be reached may be at least 2, at least 4, at least 6.5, at least 7.
  • the pre-polymeric resin is added with or after the hydroxylamine.
  • the stabilising solvent may be added to the partial phosphate ester before the hydroxylamine.
  • a method of curing a pre-polymeric resin formulation comprising a pre-polymeric resin and partial phosphate ester curing agent and hydroxylamine wherein the method comprises the steps of:
  • an initial pre- polymeric resin formulation for use in the preparation of a pre-polymeric resin formulation according to the invention wherein the initial pre- polymeric formulation comprises a pre-polymeric resin and hydroxylamine.
  • partial phosphate ester formulation for use in the preparation of a pre-polymeric resin formulation according to the invention wherein the partial phosphate ester formulation comprises a partial phosphate ester, hydroxylamine and optionally a stabilising solvent.
  • a retarded pre-polymeric formulation according to the invention has an advantage that it is straight forward to cure the pre- polymeric resin formulation as it is only necessary to heat it to an elevated temperature.
  • Hydroxylamine is a compound used in chemical processes in the electronics industry and pharmaceuticals. It is supplied commercially as a 50% by weight aqueous solution. In its crystalline form, hydroxylamine is highly unstable and can decompose violently at ambient temperature in the presence of metallic impurities.
  • the hydroxylamine is present in an amount sufficient for the pre-polymeric resin formulation to be storage stable.
  • the pH of the partial phosphate ester formulation comprising 50% hydroxylamine solution and a partial phosphate ester may be chosen to optimise storage stability of the pre-polymeric resin formulation whilst still allowing the pre-polymeric resin formulation to be curable.
  • the partial phosphate ester formulation preferentially has a mixture ratio by weight of partial phosphate estenhydroxylamine of from 5 : 1 to 1 : 5, for example 5 : 1 , 5 :2, 5 :3, 5 :4, 1 : 1 , 4: 5, 3 : 5, 2: 5, 1 : 5.
  • the partial phosphate ester formulation preferentially has a mixture ratio by weight of partial phosphate estenhydroxylamine of from 5 : 1 to 1 : 1 , for example 5 :3 to 1 : 1 , such as 5 :4.
  • the mix ratio is 5 :4 of Phencat 382: 50% hydroxylamine. It has been observed that excess hydroxylamine solution may be added where the pre-polymeric resin has high free formaldehyde content to extend the storage life of the pre-polymeric resin formulation. It is advantageous to include hydroxylamine in a quantity sufficient to ensure the pH of the partial phosphate ester formulation is at least 2, for example at least 4, at least 6.5 or least 7.
  • An advantage of at least pH 7 is that the curing of the composition may be delayed for a substantial period of time.
  • partial phosphate ester formulation with a pH of at least 7 can be used to retard curing of a pre-polymeric resin such as a phenolic resole resin for at least 90 days. This is substantially longer than the delay in curing obtained with known retarders. It has been observed through litmus testing, that over time, the pH of the pre-polymeric formulation containing a pre-polymeric resin (such as phenolic resin), a partial phosphate ester (such as Phencat 382) and hydroxlamine may decrease. Yet curing of this reaction mixture does not occur until the mixture experiences elevated temperature.
  • the pre-polymeric resin formulation according to the invention where the pH of the partial phosphate ester formulation is at least 7 is suitable for use in an application where the pre-polymeric resin formulation is prepared at a different location to where it is used.
  • the elevated temperature used in the method of curing according to the present invention is a temperature above the decomposition temperature of hydroxylamine (which is about 1 17°C), for example a temperature at or above 120°C. Above the decomposition temperature of hydroxylamine the rapid decomposition of hydroxylamine quickly lowers the pH and results in a fast cure of a pre- polymeric resin formulation. At lower temperatures for example 50°C or above, or 90°C or above, a slow decomposition of hydroxylamine will lower the pH more slowly and cure rates of pre-polymeric resin formulations will be slow.
  • the pre-polymeric resin may be any resin that when acidified will undergo a polymerisation reaction.
  • resins include:
  • the PF resole resins (a) are generally the reaction products of a phenol and an aldehyde. In some embodiments, from about 1 .1 to 3 mol of an aldehyde per mol of the phenol (optionally from 1 .5 to 2.5 mol of the aldehyde per mol of the phenol) are employed in producing a suitable PF resole resin.
  • the reaction of the phenol and the aldehyde may be conducted in the presence of a basic catalyst such as ammonia, sodium hydroxide, potassium hydroxide or barium hydroxide. In some embodiments, an amount of from 0. 1 to 0.001 mol of catalyst (or optionally from 0.05 to 0.002 mols of catalyst) is used per mol of the phenol.
  • the PF resole resin is generally a liquid.
  • the furane or furfuryl alcohol resins (b) are generally thermosetting resins made by reacting furfuryl alcohol with formaldehyde or by the self-polymerization of furfuryl alcohol, or a combination of reacting furfuryl alcohol with formaldehyde followed by polymerisation.
  • the mole ratio of furfuryl alcohol to formaldehyde may vary from about 3 : 1 to about 0.5 : 1 , respectively, optionally about 2: 1 to about 1 : 1.
  • a water soluble metal salt may be used as the catalyst and may vary from about 0.2 to about 8% by weight of the furfuryl alcohol.
  • the reaction may be carried out at a temperature of about 85 to 105°C at atmospheric pressure or at an elevated temperature under pressure.
  • a melamine-formaldehyde resin (c) may be prepared as follows.
  • a mixture of a resole and a melamine may be heated to effect a melamine formaldehyde reaction to produce a dissolved methylol melamine reaction product (as disclosed in U. S. patent no. 4,960,826, the contents of which are incorporated herein by reference).
  • the term melamine resin is a general term to encompass any melamine- formaldehyde resin with or without other ingredients, e.g., urea groups.
  • a urea-formaldehyde resin (d) may be prepared as follows.
  • a thermosetting urea-formaldehyde (UF) resin may be prepared from urea and formaldehyde monomers or from a UF pre-condensate in a manner well known to a person of skill in the art. Such a person would recognize that the urea and formaldehyde reactants are commercially available in many forms. Any form which can react with the other reactants and which does not introduce extraneous moieties deleterious to the desired reaction and reaction product can be used in the preparation of a urea- formaldehyde resin useful in the invention.
  • Formaldehyde for making a suitable UF resin is available in many forms, for example paraformaldehyde and/or a formalin solution are commonly used forms. Any form of urea or urea in combination with formaldehyde is suitable for use in the practice of the invention. Solid urea, such as prill, and/or a urea solution, for example as aqueous solutions, are commonly available.
  • any of the wide variety of known procedures used for reacting the principal urea and formaldehyde components may be used to form a UF thermosetting resin composition. Suitable examples include staged monomer addition, staged catalyst addition, pH control, and/or amine modification.
  • the urea and formaldehyde may be reacted at a mole ratio of formaldehyde to urea of from about 1. 1 : 1 to about 4: 1 , optionally at a formaldehyde to urea mole ratio of from about 2. 1 : 1 to about 3.2: 1.
  • the UF resin is highly water dilutable, optionally it is water soluble.
  • thermosetting urea-formaldehyde resins are commercially available, such as those sold by Georgia Pacific Resins, Inc. (such as GP-2928 and GP-2980) for glass fiber mat, Momentive and Dynea. These resins are prepared as described above and contain reactive methylol groups that upon curing form methylene or ether linkages.
  • methylol-containing adducts may include N,N'-dimethylol, dihydroxymethylolethylene; N,N'-bis(methoxymethyl), ⁇ , ⁇ '- dimethylolpropylene; 5,5-dimethyl-N,N'dimethylolethylene; and/or ⁇ , ⁇ '- dimethylolethylene.
  • a polymer produced from a partial phosphate ester catalysed resin for use as a pre-polymer includes melamine-formaldehyde, urea- formaldehyde, phenol-formaldehyde, furan polymer and/or a polymer product from a blend of resins e.g. PF/FA, PF/UF, FA/UF, FA/MF, UF/MF, PF/MF, and/or PF/UF/MF.
  • the pre-polymeric resin is a phenol- formaldehyde resole (PF) or a furane or a furfuryl alcohol resin (FA). In one embodiment, the pre-polymeric resin is a phenol-formaldehyde resole (PF).
  • the partial phosphate ester formulation comprising a partial phosphate ester and hydroxylamine also comprises a stabilising solvent to prevent crystallisation of the partial phosphate ester/hydroxylamine mixture. A skilled person would be able to determine a suitable stabilising solvent and a suitable amount of such a solvent to use to prevent such crystallisation.
  • stabilising solvents examples include water, alcohols, glycols (for example ethylene glycol) and ketones. It is noted that the pH of the partial phosphate ester/ hydroxylamine formulation may drop when a stabilising solvent is used. It is appreciated that the skilled man will determine the maximum concentration of stabilising solvent before crystallisation, at a particular storage temperature. The resultant pH may differ depending on the stabilising solvent used. It is noted that in one embodiment, the pH of the partial phosphate ester/hydroxylamine formulation, regardless of what then happens when a stabilising solution is added, is at least 2, for example at least 4, at least 6.5, or at least 7.
  • the partial phosphate ester/hydroxylamine formulation can be in the form of a solid. Solid forms of the partial phosphate ester/hydroxylamine formulation are advantageous as they can be added to liquid and non-liquid pre-polymeric resins.
  • Table 1 displays the mix ratios of 50% hydroxylamine and a partial phosphate ester and the resulting pH.
  • Table 2 shows the compositions of Table 1 where the effect of increasing the mix ratio of hydroxylamine to the partial phosphate ester on the reactivity and gel time of the phenolic resole resin mixture was determined
  • Table 3 shows the altered compositions of Sample 3 where the effect additional hydroxylamine nitrate on the reactivity and gel time of the resin mixture was determined. It was found that increasing levels of 50% hydroxylamine solution increased the pot life of the samples in a similar way to the results displayed on Table 2.
  • a stable one-part syntactic foam mix was prepared using the following formulation.
  • Phencat 382 (partial phosphate ester) 2.0 50% Hydroxylamine 1.23 Spheriglass 45.8
  • the hydroxylamine is added to the resin followed by the partial phosphate ester.
  • the spheriglass glass spheres
  • the one-part foam mix was stored at room temperature for 1 10 days at which time the mix is still soft, mouldable and ready to use. After this storage time, the same mixture was again charged to a plastic mould and cured in an oven at 90°C. After 2 hours the foam product was cooled and a density measured at 752 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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une utilisation d'hydroxylamine en tant que retardateur pour une réaction de durcissement de formulations de résines prépolymères contenant des résines prépolymères et des agents de durcissement à base d'ester phosphorique partiel.
PCT/GB2014/051317 2013-04-29 2014-04-28 Préparation polymère améliorée Ceased WO2014177850A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB201307707A GB201307707D0 (en) 2013-04-29 2013-04-29 Improved polymer preparation
GB1307707.8 2013-04-29
GB201317842A GB201317842D0 (en) 2013-10-09 2013-10-09 Improved polymer preparation
GB1317842.1 2013-10-09

Publications (1)

Publication Number Publication Date
WO2014177850A1 true WO2014177850A1 (fr) 2014-11-06

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PCT/GB2014/051317 Ceased WO2014177850A1 (fr) 2013-04-29 2014-04-28 Préparation polymère améliorée

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WO (1) WO2014177850A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110129074A (zh) * 2019-05-20 2019-08-16 太原理工大学 一种无机盐-自由基淬火剂双重抑制煤自燃的防火材料及其制备方法
CN110564391A (zh) * 2019-08-31 2019-12-13 湖南科技大学 一种用于粉煤原位固结改性的纳米微泡材料及其制备方法
EP4371760A1 (fr) * 2022-11-16 2024-05-22 Advanced Innergy Ltd Structures d'isolation thermique
EP4371759A1 (fr) * 2022-11-16 2024-05-22 Advanced Innergy Ltd Structures passives resistant au feu

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2754069A1 (de) * 1976-12-10 1978-06-15 Azote & Prod Chim Haerter fuer klebstoffe auf basis von aminoplastharzen
US4960826A (en) 1988-02-19 1990-10-02 Borden, Inc. Melamine-containing resole resitol and resite compositions
US5378793A (en) 1991-10-25 1995-01-03 Bp Chemicals Limited Process for hardening phenolic resins
WO2004029119A1 (fr) * 2002-08-26 2004-04-08 Shea Lawrence E Composites thermoplastiques renforces sans formaldehyde
DE102005029479A1 (de) * 2005-06-24 2007-01-04 Saint-Gobain Isover G+H Ag Verfahren zur Herstellung von gebundener Mineralwolle und Bindemittel hierfür
WO2010094979A1 (fr) * 2009-02-20 2010-08-26 Bac2 Limited Préparation polymère améliorée

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2754069A1 (de) * 1976-12-10 1978-06-15 Azote & Prod Chim Haerter fuer klebstoffe auf basis von aminoplastharzen
US4960826A (en) 1988-02-19 1990-10-02 Borden, Inc. Melamine-containing resole resitol and resite compositions
US5378793A (en) 1991-10-25 1995-01-03 Bp Chemicals Limited Process for hardening phenolic resins
WO2004029119A1 (fr) * 2002-08-26 2004-04-08 Shea Lawrence E Composites thermoplastiques renforces sans formaldehyde
DE102005029479A1 (de) * 2005-06-24 2007-01-04 Saint-Gobain Isover G+H Ag Verfahren zur Herstellung von gebundener Mineralwolle und Bindemittel hierfür
WO2010094979A1 (fr) * 2009-02-20 2010-08-26 Bac2 Limited Préparation polymère améliorée

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110129074A (zh) * 2019-05-20 2019-08-16 太原理工大学 一种无机盐-自由基淬火剂双重抑制煤自燃的防火材料及其制备方法
CN110564391A (zh) * 2019-08-31 2019-12-13 湖南科技大学 一种用于粉煤原位固结改性的纳米微泡材料及其制备方法
CN110564391B (zh) * 2019-08-31 2021-06-29 湖南科技大学 一种用于粉煤原位固结改性的纳米微泡材料及其制备方法
EP4371760A1 (fr) * 2022-11-16 2024-05-22 Advanced Innergy Ltd Structures d'isolation thermique
EP4371759A1 (fr) * 2022-11-16 2024-05-22 Advanced Innergy Ltd Structures passives resistant au feu

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