WO2023036801A1

WO2023036801A1 - Ionic monomer- based polyurethane foams and use thereof in trench breakers or pipeline pillows or thermally insulative material

Info

Publication number: WO2023036801A1
Application number: PCT/EP2022/074817
Authority: WO
Inventors: Eranda Wanigasekara; Willie G WESLEY; Sam KHARCHENKO; Michele Natasha ALLEN; Lennart Karl Bernhard GARVE; Johannes David HOECKER
Original assignee: Basf Se
Priority date: 2021-09-07
Filing date: 2022-09-07
Publication date: 2023-03-16

Abstract

The present invention relates to a polyurethane foam (PU foam) and its use in trench breakers or pipeline pillows or as thermally insulative material. Said foam obtained by reacting a mixture comprising: (A) at least one isocyanate component; (B) at least one isocyanate reactive component comprising a first polyether polyol; (C) at least one hydroxy-functionalized ionic monomer of the formula (I),[A]+[Y]-, wherein [A]+ is selected from compounds of the formulae (A.1), (A.2), or (A.3), wherein R is selected from C1-C10 alcohol; R1, R2, R3, R4 and R5 are independently selected from hydrogen, C1-C10 alkyl or C1-C10 alcohol; and [Y]- is a monovalent anion; (D) at least one blowing agent and (E) at least one amine catalyst.

Description

IONIC MONOMER- BASED POLYURETHANE FOAMS AND USE THEREOF IN TRENCH BREAKERS OR PIPELINE PILLOWS OR THERMALLY INSULATIVE MATERIAL

FIELD OF INVENTION

[0001] The present invention relates to an ionic monomer-based polyurethane foam (PU foam) and its use in trench breakers or pipeline pillows or thermally insulative material.

BACKGROUND OF THE INVENTION

[0002] Polyurethanes or PU is a generic term for polymers obtained by reaction of isocyanates with polyols. Types of polyurethanes include rigid, semi-rigid and flexible foams; thermoplastic polyurethane; and other miscellaneous types, employable as coatings, adhesives, and sealants. Flexible foams (e.g. that found in most car cushions) are generally open-celled materials, while rigid foams (e.g. building insulation) usually have a high proportion of closed cells. Semi-rigid foams have properties and applications intermediate to rigid and flexible foams.

[0003] The presence of open spaces in cells of PU foams, where gases can remain entrapped, makes it a useful thermal and electrical insulator. Additionally, the structural rigidity combined with thermo-electrical insulative properties make PU foams attractive choices for use in a wide range of materials including pipeline covers, sheets, wire sheathing materials, building insulation panels, etc. For instance, US8865782 and US9403961 provide PU foams that display flame-resistant and useful thermally-insulative properties.

[0004] Another growing application of PU foams is their use as static dissipative materials for cathodic protection. For instance, in case of pipelines, a cathodic protection system, involves the pipeline acting as the cathode (negatively charged), and sheets of metal buried near the pipeline act as the anode (positively charged). Once the circuit is completed by being attached to a rectifier, the buried metal sheets act as a sacrificial anode which preferentially corrode over the cathode, pipeline, thus protecting the pipeline against corrosion. While coating has been previously used for preventing corrosion, the fact that these coatings have defects as thermal expansion leads to cracking renders them unsuitable for this application.

[0005] PU foams for trench breakers are described in US pat. No. 8,568,061 B2. In particular, floatation resistant foams with sufficient strength and density to provide stability and inhibit erosion at pipeline trench sites are described. The PU foam suitable for use in trench breaker has at least 50% open cell, a density of 1.3 lb/ft3 to 3.50 lb/ft3, a minimum compressive strength of 17 psi parallel to the rise of the foam, and exhibits a buoyancy loss of at least 20% after 24 hours of testing under 10 feet of water.

[0006] However, considering the low inherent conductivity of PU foams, strategies to enhance conductivity is essential for ensuring success in this domain. Thus, electrically conductive PU foams as described in US pat. No. 10,259,923 Bl, employ carbon nanomaterials comprising isocyanate treated nanoplatelets formed by exfoliating graphite oxide nanoplatelets from isocyanate-treated graphite oxide in a dispersing medium.

[0007] Similarly, PCT/EP2021/062800 discloses conductivity improvements in PU foams by introduction of carbon black. While the incorporation of additives such as carbon black leads to an improvement in conductivity, their presence also hinders processability. For instance, the amount of carbon black additive has to be limited in order to avoid unwanted increase in viscosity. Thus, there is an unmet need to obtain PU foams with further improved conductivities that are also thermally stable and reveal suitable flame resistance, while having suitable viscosity (making it easily processable).

SUMMARY OF THE INVENTION

[0008] Surprisingly, it has been found that the above-identified object is met by providing a PU foam which is obtained by reacting a mixture comprising at least one isocyanate component, at least one isocyanate reactive component comprising a first polyether polyol, at least one hydroxy -functionalized ionic monomer of the formula I, [A]⁺[Y]- (I), wherein [A]⁺ is selected from compounds of the formulae (A.1), (A.2), or (A.3),

wherein R is selected from C1-C10 alcohol; Rl, R², R³, R⁴ and R⁵ are independently selected from hydrogen, C1-C10 alkyl or C1-C10 alcohol; and [¥]" is a monovalent anion, at least one blowing agent, and at least one amine catalyst.

[0009] An aspect of the present invention is directed towards a PU foam which is obtained by reacting:

(A) at least one isocyanate component,

(B) at least one isocyanate reactive component comprising a first polyether polyol

(C) at least one hydroxy -functionalized ionic monomer of the formula I,

[A]⁺[Y]- (I), wherein [A]⁺ is selected from compounds of the formulae (A.l), (A.2), or (A.3),

wherein R is selected from Ci-Cio alcohol;

R¹, R², R³, R⁴ and R⁵ are independently selected from hydrogen, Ci-Cio alkyl, or Ci-Cio alcohol; and [¥]" is a monovalent anion,

(D) at least one blowing agent, and

(E) at least one amine catalyst. [0010] In another aspect, the presently claimed invention is directed to a process for preparing the above PU foam.

[0011] In still another aspect, the presently claimed invention is directed to the use of the above PU foam for static dissipative materials.

[0012] In a further aspect, the presently claimed invention is directed to a trench breaker or pipeline pillow comprising the above PU foam.

[0013] In still another aspect, the presently claimed invention is directed to thermally insulative material comprising the above PU foam.

DETAILED DESCRIPTION OF THE INVENTION

[0014] Before the present compositions and formulations of the invention are described, it is to be understood that this invention is not limited to particular compositions and formulations described, since such compositions and formulation may, of course, vary. It is also to be understood that the terminology used herein is not intended to be limiting, since the scope of the present invention will be limited only by the appended claims.

[0015] The terms "comprising", "comprises" and "comprised of' as used herein are synonymous with "including", "includes" or "containing", "contains", and are inclusive or open-ended and do not exclude additional, non-recited members, elements or method steps. It will be appreciated that the terms "comprising", "comprises" and "comprised of' as used herein comprise the terms "consisting of', "consists" and "consists of'.

[0016] Furthermore, the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)" etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein. In case the terms "first", "second", "third" or “(A)”, “(B)” and “(C)” or "(a)", "(b)", "(c)", "(d)", "i", "ii" etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, that is, the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application as set forth herein above or below.

[0017] In the following passages, different aspects of the invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.

[0018] Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment but may. Furthermore, the features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein include some, but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention, and form different embodiments, as would be understood by those in the art. For example, in the appended claims, any of the claimed embodiments can be used in any combination.

[0019] Furthermore, the ranges defined throughout the specification include the end values as well, i.e. a range of 1 to 10 implies that both 1 and 10 are included in the range. For the avoidance of doubt, the applicant shall be entitled to any equivalents according to applicable law.

[0020] PU foam [0021] An aspect of the present invention is directed towards a PU foam which is obtained by reacting:

(A) at least one isocyanate component,

(B) at least one isocyanate reactive component comprising a first polyether polyol,

(C) at least one hydroxy -functionalized ionic monomer of the formula I,

wherein R is selected from Ci-Cio alcohol;

R¹, R², R³, R⁴ and R⁵ are independently selected from hydrogen, Ci-Cio alkyl, or Ci-Cio alcohol; and [Y]’ is a monovalent anion,

(D) at least one blowing agent, and

(E) at least one amine catalyst.

[0022] Preferably, the PU foam is a rigid PU foam characterized with a foam density from to 30 kg/m³ to 150 kg/m³, as determined according to ASTM D1622 and an electrical resistivity in the range from 1.0* 10⁷ Q.m to 1.0* 10¹² Q.m, as determined according to ASTM D257-14. More preferably, the density of the PU foam is from to 30 kg/m³ to 100 kg/m³, or 30 kg/m³ to 80 kg/m³, or 30 kg/m³ to 50 kg/m³.

[0023] Preferably, the PU foam has a self-extinguish time from to 20 sec to 80 sec and bum rate from to 50mm/min to 280 mm/min determined according to UL-94. Preferably, the self-extinguish time is from to 25 sec to 70 sec, or 27 sec to 65 sec, or 27 sec to 60 sec. Preferably, the bum rate from to 80mm/min to 270 mm/min, or 90mm/min to 270 mm/min, or lOOmm/min to 270 mm/min, or 120mm/min to 270 mm/min determined according to UL-94. [0024] Isocyanate component (A)

[0025] In accordance with the invention, the PU foam is obtained by reacting a mixture comprising at least one isocyanate component.

[0026] Preferably the isocyanate component is an aromatic isocyanate, an aliphatic isocyanate or a mixture of aromatic and aliphatic isocyanates.

[0027] Preferably the isocyanate component has an isocyanate functionality of 2.0 or greater. Preferably, the isocyanate component has an isocyanate functionality in the range of from 2. 0 to 4.0. More preferably, the isocyanate component has an isocyanate functionality in the range of from 2. 0 to 3.5. Even more preferably, the isocyanate component has an isocyanate functionality in the range of from 2. 0 to 3.0.

[0028] The isocyanate component can be monomeric, polymeric or be a mixture of monomeric and polymeric isocyanates. Polymeric isocyanates are polymeric of oligomeric isocyanates which are obtainable by self-polymerization of two or more monomeric isocyanates, such that polymeric isocyanates comprise dimers, trimers, higher homologues and/or oligomers.

[0029] Preferable aliphatic isocyanates are tetramethylene 1,4-diisocyanate, pentamethylene 1,5-diisocyanate, hexamethylene 1,6-diisocyanate, decamethylene diisocyanate, 1,12-dodecane diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, 2,4,4- trimethyl-hexamethylene diisocyanate, 2-methyl-l,5-pentamethylene diisocyanate, cyclobutane-l,3-diisocyanate, 1,2-, 1,3- and 1,4-cyclohexane diisocyanates, 2,4- and 2,6- methylcyclohexane diisocyanate, 4,4'- and 2, 4'-di cyclohexyldiisocyanates, 1,3,5-cyclohexane triisocyanates, isocyanatomethylcyclohexane isocyanates, isocyanatoethylcyclohexane isocyanates, bis(isocyanatomethyl)-cyclohexane diisocyanates, 4,4’- diisocyanatodi cyclohexylmethane, pentamethylene 1,5-diisocyanate, isophorone diisocyanate, or mixtures thereof.

[0030] Preferably, the isocyanate component comprises an aromatic isocyanate or an aliphatic isocyanate. [0031] More preferably, the aliphatic isocyanate is selected from tetramethylene 1,4- diisocyanate, pentamethylene 1,5-diisocyanate, hexamethylene 1,6-diisocyanate, decamethylene diisocyanate, 1,12-dodecane diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, 2,4,4-trimethyl-hexamethylene diisocyanate, 2-methyl-l,5-pentamethylene diisocyanate, cyclobutane-l,3-diisocyanate, 1,2-, 1,3- and 1,4-cyclohexane diisocyanates, 2,4- and 2,6-methylcyclohexane diisocyanate, 4,4'- and 2,4'-dicyclohexyldiisocyanates, 1,3,5- cyclohexane triisocyanates, isocyanatomethylcyclohexane isocyanates, isocyanatoethylcyclohexane isocyanates, bis(isocyanatomethyl)-cyclohexane diisocyanates, 4,4’-diisocyanatodicyclohexylmethane, pentamethylene 1,5-diisocyanate, isophorone diisocyanate, or mixtures thereof.

[0032] Even more preferably, the isocyanate component comprises an aromatic isocyanate. More preferably, the isocyanate component consists of no other isocyanate except aromatic isocyanate.

[0033] Still more preferably, the aromatic isocyanate is selected from toluene diisocyanate, polymeric toluene diisocyanate, methylene diphenyl diisocyanate and/or polymeric methylene diphenyl diisocyanate; m-phenylene diisocyanate, 1,5-naphthalene diisocyanate; 4-chloro-l, 3-phenylene diisocyanate; 2,4,6-toluylene triisocyanate, 1,3- diisopropylphenylene-2,4-diisocyanate; l-methyl-3,5-diethylphenylene-2,4-diisocyanate;

1.3.5-triethylphenylene-2,4-diisocyanate; l,3,5-triisoproply-phenylene-2,4-diisocyanate; 3,3'- diethyl-bisphenyl-4,4'-diisocyanate; 3,5,3',5'-tetraethyl-diphenylmethane-4,4'-diisocyanate; 3,5,3',5'-tetraisopropyldiphenylmethane-4,4'-diisocyanate; l-ethyl-4-ethoxy-phenyl-2,5- diisocyanate; 1,3,5-triethyl benzene-2,4,6-triisocyanate; l-ethyl-3,5-diisopropyl ben-zene-

2.4.6-triisocyanate, tolidine diisocyanate, 1,3,5-triisopropyl benzene-2,4,6-triisocyanate, or mixtures thereof.

[0034] More preferably, the aromatic isocyanate is selected from toluene diisocyanate; polymeric toluene diisocyanate, methylene diphenyl diisocyanate and/or polymeric methylene diphenyl diisocyanate, m-phenylene diisocyanate, 1,5-naphthalene diisocyanate; 4-chloro-l, 3- phenylene diisocyanate, 2,4,6-toluylene triisocyanate, l,3-diisopropylphenylene-2,4- diisocyanate, l-methyl-3,5-diethylphenylene-2,4-diisocyanate, or mixtures thereof. Even more preferably, the aromatic isocyanate is selected from toluene diisocyanate; polymeric toluene diisocyanate, methylene diphenyl diisocyanate and/or polymeric methylene diphenyl diisocyanate; m-phenylene diisocyanate, 1,5-naphthalene diisocyanate, 4-chloro-l, 3- phenylene diisocyanate, or mixtures thereof. More preferably, the aromatic isocyanate is selected from toluene diisocyanate; polymeric toluene diisocyanate, methylene diphenyl diisocyanate and/or polymeric methylene diphenyl diisocyanate, m-phenylene diisocyanate, or mixtures thereof. Even more preferably, the aromatic isocyanate is selected from methylene diphenyl diisocyanate, polymeric methylene diphenyl diisocyanate, or mixtures thereof.

[0035] More preferably, the isocyanate component consists of methylene diphenyl diisocyanate and/or polymeric methylene diphenyl diisocyanate.

[0036] Preferably, methylene diphenyl diisocyanate may be in three different isomeric forms, namely 2,2'-methylene diphenyl diisocyanate (2,2'-MDI), 2,4'-methylene diphenyl diisocyanate (2,4'-MDI) and 4,4'-methylene diphenyl diisocyanate (4,4'-MDI).

[0037] More preferably, methylene diphenyl diisocyanate is selected from the mixtures of monomeric diphenylmethane diisocyanates and higher polycyclic homologs of diphenylmethane diisocyanate (polymeric MDI), or mixtures thereof.

[0038] Preferable polymeric methylene diphenyl diisocyanate includes oligomeric species and monomeric methylene diphenyl diisocyanate isomers. Preferably, the polymeric methylene diphenyl diisocyanate may contain a single methylene diphenyl diisocyanate isomer or isomer mixtures of two or three methylene diphenyl diisocyanate isomers, the balance being oligomeric species.

[0039] Preferably, the isomeric ratio as well as the amount of oligomeric species can vary in wide ranges in these products. Preferably, polymeric methylene diphenyl diisocyanate may typically contain 30 wt.-% to 80 wt.-% of monomeric methylene diphenyl diisocyanate isomers, the balance being said oligomeric species. Preferably, the methylene diphenyl diisocyanate isomers are often a mixture of 4,4'-methylene diphenyl diisocyanate, 2.4'- methylene diphenyl diisocyanate and very low levels of 2,2'-methylene di-phenyl diisocyanate. [0040] More preferably the polymeric methylene diphenyl diisocyanate may have isocyanate functionalities greater than 2.0.

[0041] Isocyanate reactive component (B)

[0042] In accordance with the invention, the isocyanate reactive component comprises a first polyether polyol.

[0043] A polyurethane foam comprising only ionic monomer as hydroxyl-functional group (without isocyanate reactive component) leads to brittle and soft foams having large number of bubbles, that are unsuitable for commercial manufacture and production. On the other hand, the incorporation of isocyanate reactive component comprising a first polyether polyol is noted to ensure PU foams that are suitable for manufacturing. Without being bound by theory, it is noted that the presence of said isocyanate reactive component in addition to ionic monomer is noted to be critical for reducing bubble-formation, thereby ensuring enhanced processability of the PU foams.

[0044] Preferably, the nominal functionality of the first poly ether polyol is from to 2.5 to 5.0, or from to 2.5 to 4.7, or from to 2.5 to 4.5, or from to 2.6 to 4.2, or from to 2.6 to 4.1. More preferably, it is from to 2.6 to 4.5, or from to 2.7 to 4.5, or from to 2.8 to 4.5, or from to 2.9 to 4.5, or from to 3.0 to 4.5.

[0045] Preferably, the OH value of the first polyether polyol is from to 250 mg KOH/g to 500 mg KOH/g. More preferably, it is from to 250 mg KOH/g to 480 mg KOH/g, or from to 250 mg KOH/g to 470 mg KOH/g, or from to 260 mg KOH/g to 470 mg KOH/g, or from to 260 mg KOH/g to 460 mg KOH/g, or from to 270 mg KOH/g to 460 mg KOH/g. More preferably, it is from to 270 mg KOH/g to 450 mg KOH/g, or from to 280 mg KOH/g to 450 mg KOH/g, or from to 290 mg KOH/g to 450 mg KOH/g, or from to 300 mg KOH/g to 430 mg KOH/g. Still more preferably, it is from to 310 mg KOH/g to 430mg KOH/g, or from to 330 mg KOH/g to 430 mg KOH/g. In this contest, according to the invention, the OH number is determined according to DIN 53240 and the functionality of the polyols applied is to be understood as theoretical functionality. For poly ether polyols this theoretical functionality for example, can be obtained by calculating the functionality based on the functionality of the starting molecules. Effects of side reactions during the preparation of the polyether polyols, such as disproportionation, are not considered when determining the functionality.

[0046] The first polyether polyols according to the invention are preferably obtainable by known methods, for example by anionic polymerization of one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene moiety with alkali metal hydroxides, e.g., sodium hydroxide or potassium hydroxide, or alkali metal alkoxides, e.g., sodium methoxide, sodium ethoxide, potassium ethoxide or potassium isopropoxide, as catalysts and by adding at least one starter molecule, or by cationic polymerization of one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene moiety with Lewis acids, such as antimony pentachloride boron fluoride etherate, or fuller’s earth, as catalysts.

[0047] The starter molecules are generally selected such that the nominal functionality of the resulting polyether polyol is from to 2.5 to 5.0. Optionally, a mixture of suitable starter molecules is also used.

[0048] Preferably, starter molecules for polyether polyols is selected from amine containing or hydroxyl-containing starter molecules. Amine containing starter molecules include, for example, aliphatic and aromatic diamines, preferably selected from ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, phenylenediamines, toluenediamine, diaminodiphenylmethane, or isomers thereof.

[0049] Preferably, other suitable starter molecules further include alkanolamines, e.g. ethanolamine, N-methylethanolamine and N-ethylethanolamine, dialkanolamines, e.g., diethanolamine, N-methyldiethanolamine and N-ethyldiethanolamine, and trialkanolamines, e.g., triethanolamine, and ammonia.

[0050] Preferably, amine containing starter molecules are selected from ethylenediamine, phenylenediamines, toluenediamine, or isomers thereof.

[0051] Preferably, hydroxyl-containing starter molecules are selected from trimethylolpropane, glycerol, glycols such as ethylene glycol, propylene glycol and their condensation products such as polyethylene glycols and polypropylene glycols, e.g., di ethylene glycol, triethylene glycol, dipropylene glycol, water or a combination thereof.

[0052] Preferably, suitable alkylene oxides preferably have 2 to 4 carbon atoms. More preferably alkylene oxides is selected from ethylene oxide, propylene oxide, tetrahydrofuran, 1,2-butylene oxide, 2,3-butylene oxide, or styrene oxide. Alkylene oxides may be used singly, altematingly in succession, or as mixtures. Preferably, the alkylene oxides are propylene oxide and/or ethylene oxide. More preferably, the alkylene oxides are mixtures of ethylene oxide and propylene oxide that comprise more than 50 wt.-% of propylene oxide.

[0053] Even more preferably, the first polyether polyol is based on ethanolamine and a mixture of ethylene oxide and propylene oxide, with a nominal functionality range of from 2.9 to 3.1 and OH value from to 490 mg KOH/g to 520 mg KOH/g.

[0054] Preferably, the first polyether polyol is present from to 50 wt.% to 100 wt.%, based on the total weight of the isocyanate reactive component. More preferably, it is present from to 50 wt.% to 90 wt.%, or 55 wt.% to 85 wt.%, or 55 wt.% to 80 wt.%. Even more preferably, it is present from to 60 wt.% to 80 wt.%, or 60 wt.% to 75 wt.%. Herein, when the first poly ether polyol is present in an amount less than 100 wt.%, then the rest of the total weight is made up by a second polyol.

[0055] Preferably, the isocyanate reactive component further comprises a second polyol selected from a polyester polyol, a second polyether polyol, a polymer polyol, or a mixture thereof.

[0056] Preferably, the second polyol is a polyester polyol. Preferably, the polyester polyols have a nominal functionality from to 1.9 to 3.5. More preferably, the nominal functionality is from to 1.9 to 3.4, or from to 2.0 to 3.4, or from to 2.0 to 3.3, or from to 2.1 to 3.3. Even more preferably, it is from to 2.1 to 3.2, or from to 2.1 to 3.1, or from to 2.1 to 3.0. More preferably, it is from to 2.2 to 3.0, or from to 2.2 to 2.9, or from to 2.2 to 2.8, or from to 2.3 to 2.8, or from to 2.3 to 2.7. Still more preferably, it is from to 2.3 to 2.6, or from to 2.3 to 2.5, or from to 2.4 to 2.5. [0057] Preferably, the polyester polyols has a OH value is from to 250 mg KOH/g to 400 mg KOH/g. Preferably, it is from to 260 mg KOH/g to 400 mg KOH/g, or from to 260 mg KOH/g to 390 mg KOH/g, or from to 270 mg KOH/g to 390 mg KOH/g, or from to 270 mg KOH/g to 380 mg KOH/g, or from to 280 mg KOH/g to 380 mg KOH/g. More preferably, it is from to 280 mg KOH/g to 370 mg KOH/g, or from to 290 mg KOH/g to 370 mg KOH/g, or from to 290 mg KOH/g to 360 mg KOH/g, or from to 295 mg KOH/g to 350 mg KOH/g, or from to 295 mg KOH/g to 340 mg KOH/g. Still more preferably, is from to 295 mg KOH/g to 340 mg KOH/g, or from to 295 mg KOH/g to 330 mg KOH/g, or from to 295 mg KOH/g to 320 mg KOH/g, or from to 295 mg KOH/g to 310 mg KOH/g.

[0058] Preferably, the polyester polyols include those prepared by reacting a carboxylic acid and/or a derivative thereof or a poly carboxylic anhydride with a polyhydric alcohol. The polycarboxylic acids can be any of the known aliphatic, cycloaliphatic, aromatic, and/or heterocyclic polycarboxylic acids and can be substituted (e.g., with halogen atoms) and/or unsaturated. Preferably, the polycarboxylic acids and anhydrides are selected from oxalic acid, malonic acid, glutaric acid, pimelic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic acid anhydride, pyromellitic dianhydride, phthalic acid anhydride, hexahydrophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride, glutaric acid anhydride acid, maleic acid, maleic acid anhydride, fumaric acid, and dimeric and trimeric fatty acids, such as those of oleic acid which may be in admixture with monomeric fatty acids. Simple esters of polycarboxylic acids can also be used, such as terephthalic acid dimethylester, terephthalic acid bisglycol and extracts thereof. The polyhydric alcohols suitable for the preparation of polyester polyols can be aliphatic, cycloaliphatic, aromatic, and/or heterocyclic. The polyhydric alcohols optionally can include substituents which are inert in the reaction, for example, chlorine and bromine substituents, and/or may be unsaturated. Suitable amino alcohols, such as monoethanolamine, diethanolamine or the like can also be used. Examples of suitable polyhydric alcohols include ethylene glycol, propylene glycol, polyoxyalkylene glycols (such as diethylene glycol, polyethylene glycol, dipropylene glycol and polypropylene glycol), glycerol, and trimethylolpropane. [0059] Preferably, the polyester polyols include aromatic polyester polyols, e.g., those made by trans-esterifying polyethylene terephthalate (PET) scrap with a glycol such as diethylene glycol or made by reacting phthalic anhydride with a glycol. The resulting polyester polyols can be reacted further with ethylene and/or propylene oxide to form an extended polyester polyol containing additional internal alkyleneoxy groups.

[0060] Preferably, the polyester polyol is an aromatic polyester polyol selected from the list above. More preferably, the polyester polyol as second polyol is an aromatic terephthalate polyester polyol with a nominal functionality from to 2.4 to 2.5 and OH value from to 295 mg KOH/g to 310 mg KOH/g.

[0061] Commercially available polyester polyols sold under the tradenames Stepanpol® PS from Stepan Company, Terol® from Huntsman, and Lupraphen® from BASF, may also be used.

[0062] Preferably, the second polyol is a second polyether polyol. The second polyether polyol is different than the first polyether polyol.

[0063] Preferably, the second polyether polyol has a nominal functionality from to 3.5 to 8.0 and OH value from to 100 mg KOH/g to 450 mg KOH/g. Preferably, nominal functionality is from to 3.5 to 7.9, or from to 3.5 to 7.7, or from to 3.5 to 7.5, or from to 3.5 to 7.3, or from to 3.5 to 7.1, or from to 3.5 to 7.0. More preferably, it is from to 3.6 to 7.0, or from to 3.6 to 6.8, or from to 3.6 to 6.6, or from to 3.6 to 6.4, or from to 3.6 to 6.2, or from to 3.6 to 6.0. Still more preferably, it is from to 3.7 to 5.9, or from to 3.7 to 5.7, or from to 3.7 to 5.5, or from to 3.7 to 5.3, or from to 3.7 to 5.1, or from to 3.7 to 5.0. More preferably, it is from to 3.8 to 5.0, or from to 3.8 to 4.9, or from to 3.8 to 4.8, or from to 3.9 to 4.7, or from to 3.9 to 4.5, or from to 3.9 to 4.4, or from to 3.9 to 4.3, or from to 3.9 to 4.2, or from to 3.9 to 4.1.

[0064] Preferably, the OH value is from to 140 mg KOH/g to 450 mg KOH/g, or from to 180 mg KOH/g to 450 mg KOH/g, or from to 220 mg KOH/g to 450 mg KOH/g, or from to 260 mg KOH/g to 450 mg KOH/g, or from to 300 mg KOH/g to 450 mg KOH/g. Preferably, it is from to 340 mg KOH/g to 450 mg KOH/g, or from to 380 mg KOH/g to 440 mg KOH/g, or from to 400 mg KOH/g to 440 mg KOH/g, or from to 410 mg KOH/g to 440 mg KOH/g, or from to 415 mg KOH/g to 435 mg KOH/g.

[0065] Preferably, the second polyether polyol is a Mannich polyol. Mannich polyol is an aromatic polyol obtained as a ring opening addition polymerization product of an alkylene oxide with a nitrogen-containing initiator. Suitable alkylene oxide include ethylene oxide, propylene oxide and mixtures thereof.

[0066] Preferably, the Mannich polyol has an ethylene oxide content from to 10 wt.% to 40 wt.%, or from to 10 wt.% to 30 wt.% based on the total amount of the alkylene oxide and is a ring-opening addition polymerization product of propylene oxide and ethylene oxide with a Mannich compound that is a reaction product of a phenol, an aldehyde, and an alkanolamine. Examples of phenol include phenol, nonylphenol, cresol, bisphenol A, and resorcinol. Examples of aldehyde include formaldehyde, and paraformaldehyde. Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, l-amino-2- propanol, and aminoethyl ethanolamine.

[0067] Preferably, the second polyol is a polymer polyol. Preferably, the polymer polyols has a nominal functionality range of from 2.0 to 8.0 and OH value range of from 20 mg KOH/g to 1000 mg KOH/g.

[0068] Preferably, polymer polyols are stable dispersions of polymer particles in a polyol and thus are not prone to settling or floating. The polymer particles are chemically grafted to the polyol and act as a better reinforcement filler so that the composition of the polymer may be adjusted to give the desired properties. Polymer polyols have a very low moisture content and thus avoid the problems of wet fillers. The polymers in polymer polyols generally have a low density in comparison to inorganic fillers, such as clays or calcium carbonate.

[0069] Preferably, the polymer polyols are selected from styrene-acrylonitrile (SAN) polymer polyols, polyurea suspension (PHD) polymer modified polyols, or polyisocyanate polyaddition (PIPA) polymer modified polyols. [0070] SAN polymer polyols are known in the art and are disclosed in lonescu’s Chemistry and Technology of Polyols and Polyurethanes, 2nd Edition, 2016 by Smithers Rapra Technology Ltd. In the SAN polymer polyols, a carrier polyol is the polyol in which the in-situ polymerization of olefinically unsaturated monomers is carried out, while macromers are polymeric compounds which have at least one olefinically unsaturated group in the molecule and are added to the carrier polyol prior to the polymerization of the olefinically unsaturated monomers. The use and function of these macromers is described, for example, in US 4,454,255, US 4,458,038 and US 4,460,715. The SAN polymer polyols are usually prepared by free-radical polymerization of the olefinically unsaturated monomers, preferably acrylonitrile and styrene, in a poly ether polyol or polyester polyol, usually referred to as carrier polyol, as continuous phase. These polymer polyols are prepared by in-situ polymerization of acrylonitrile, styrene or mixtures of styrene and acrylonitrile, e.g. in a weight ratio of from 90:10 to 10:90 (styrene: acrylonitrile), using methods analogous to those described in DE 1111394, DE 1222669, DE 1152536 and DE 1152537. Moderators, also referred to as chain transfer agents, can also be used for preparing SAN polymer polyols. The use and the function of these moderators is described, for example, in US 4,689,354, EP 0 365 986, EP 0 510 533 and EP 0 640 633, EP 008 444, EP 0731 118.

[0071] PHD polymer modified polyols are usually prepared by in-situ polymerization of an isocyanate mixture with a diamine and/or hydrazine in a polyol, e.g. a polyether polyol. Methods for preparing PHD polymer modified polyols are described in, for example, US 4,089,835 and US 4,260,530.

[0072] PIPA polymer modified polyols are usually prepared by the in-situ polymerization of an isocyanate mixture with a glycol and/or glycol amine in a polyol. Methods for preparing PIPA polymer modified polyols are described in, for example, US 4,293,470 and US 4,374,209.

[0073] Preferably, the second polyol comprises a mixture of the polyester polyol and the second poly ether polyol, as described hereinabove. [0074] Preferably, the second polyol in the isocyanate reactive component consists of a mixture of the polyester polyol and the second poly ether polyol, as described hereinabove.

[0075] Preferably, the ratio of first polyether polyol to the at least one isocyanate component is in the range from 0.2:1 to 1:1. Preferably, the ratio is in the range 0.2:1 to 0.9:1, or 0.2:1 to 0.8:1, or 0.3:1 to 0.9:1, or 0.3:1 to 0.9:1. More preferably, the ratio is in the range 0.4:1 to 0.8:1. Even more preferably, the ratio is in the range 0.5:1 to 0.8:1. Still more preferably, the ratio is in the range 0.5:1 to 0.7:1.

[0076] Ionic monomer of the formula I (C)

[0077] In accordance with the invention, the PU foam is obtained by reacting a mixture comprising a at least one hydroxy -functionalized ionic monomer of the formula I

wherein R is selected from C1-C10 alcohol; R¹, R², R³, R⁴ and R⁵ are independently selected from hydrogen, C1-C10 alkyl or C1-C10 alcohol; and [¥]" is a monovalent anion.

[0078] Preferably, [A]⁺ is selected from compounds of the formulae (A.1) or (A.2),

[0079] Preferably, R is selected from C1-C10 alcohol; and R¹, R², R³, R⁴ and R⁵ are independently selected from hydrogen, C1-C10 alkyl or C1-C10 alcohol, wherein R¹, R², R³, R⁴ and R⁵ are not hydrogen simultaneously.

[0080] Preferably, [Y]’ is a monovalent anion selected from methyl hydrogen phosphite, bistriflimide, dimethyl phosphate, triflate, tosylate, chloride, fluoride, or iodide. Preferably, [Y]’ is selected from hydrogen phosphite, bistriflimide, dimethyl phosphate, triflate, or tosylate. More preferably, [Y]’ is selected from hydrogen phosphite, bistriflimide, dimethyl phosphate, or triflate. More preferably, [Y]’ is selected from hydrogen phosphite, bistriflimide, or dimethyl phosphate. In general, it is noted that organic anions are more suited for the application (electrical dissipation and flame retardancy) in comparison to pure halide anions. Also, organic anions as mentioned above, are highly compatible with the other PU foam ingredients.

[0081] In accordance with the invention, R is selected from Ci-Cio alcohol. Preferably, R is selected from C1-C9 alcohol, or Ci-Cs alcohol, or C1-C7 alcohol, or Ci-Ce alcohol, or C1-C5 alcohol, or C1-C4 alcohol. More preferably, R is selected from C1-C5 alcohol, or C1-C4 alcohol, or C1-C3 alcohol.

[0082] Preferably, R¹ is selected from hydrogen, C1-C10 alkyl, or C1-C10 alcohol. Preferably, R¹ is selected from is selected from C1-C10 alkyl, or C1-C9 alkyl, or Ci-Cs alkyl, or C1-C7 alkyl, or Ci-Ce alkyl, or C1-C5 alkyl. More preferably, R¹ is selected from C1-C4 alkyl, or C1-C3 alkyl, or C1-C2 alkyl. Even more preferably, R¹ is selected from Ci alkyl. [0083] Preferably, R² are selected from hydrogen, Ci-Cio alkyl, or Ci-Cio alcohol. Preferably, R² is selected from is selected from hydrogen, or Ci-Cio alkyl. More preferably, hydrogen, C1-C9 alkyl, or Ci-Cs alkyl, or C1-C7 alkyl, or Ci-Ce alkyl, or C1-C5 alkyl. Even more preferably, R² is selected from hydrogen, C1-C4 alkyl, or C1-C3 alkyl, or C1-C2 alkyl. Even more preferably, R² is selected from hydrogen, or Ci alkyl.

[0084] Preferably, R¹ and R² are independently selected from hydrogen, or Ci alkyl. More preferably, R¹ and R² are Ci alkyl.

[0085] Preferably, R³ are selected from hydrogen, C1-C10 alkyl, or C1-C10 alcohol. Preferably, R³ is selected from is selected from hydrogen, or C1-C10 alkyl. More preferably, hydrogen, C1-C9 alkyl, or Ci-Cs alkyl, or C1-C7 alkyl, or Ci-Ce alkyl, or C1-C5 alkyl. Even more preferably, R³ is selected from hydrogen, C1-C4 alkyl, or C1-C3 alkyl, or C1-C2 alkyl. Even more preferably, R³ is selected from hydrogen, or Ci alkyl.

[0086] Preferably, R⁴ are selected from hydrogen, C1-C10 alkyl, or C1-C10 alcohol. Preferably, R⁴ is selected from is selected from hydrogen, or C1-C10 alkyl. More preferably, hydrogen, C1-C9 alkyl, or Ci-Cs alkyl, or C1-C7 alkyl, or Ci-Ce alkyl, or C1-C5 alkyl. Even more preferably, R⁴ is selected from hydrogen, C1-C4 alkyl, or C1-C3 alkyl, or C1-C2 alkyl. Even more preferably, R⁴ is selected from hydrogen, or Ci alkyl.

[0087] Preferably, R⁵ are selected from hydrogen, C1-C10 alkyl, or C1-C10 alcohol. Preferably, R⁵ is selected from is selected from hydrogen, or C1-C10 alkyl. More preferably, hydrogen, C1-C9 alkyl, or Ci-Cs alkyl, or C1-C7 alkyl, or Ci-Ce alkyl, or C1-C5 alkyl. Even more preferably, R⁵ is selected from hydrogen, C1-C4 alkyl, or C1-C3 alkyl, or C1-C2 alkyl. Even more preferably, R⁵ is selected from hydrogen, or Ci alkyl.

[0088] Preferably, R is selected from Ci-Cs alcohol and R¹, R², R³, R⁴ and R⁵ are independently selected from hydrogen, Ci-Cs alkyl and Ci-Cs alcohol.

[0089] More preferably, R is selected from Ci-Ce alcohol and R¹, R², R³, R⁴ and R⁵ are independently selected from hydrogen, Ci-Ce alkyl and Ci-Ce alcohol. [0090] Even more preferably, R is selected from C1-C5 alcohol and R¹, R², R⁴ and R⁵ are independently selected from hydrogen, C1-C3 alkyl and C1-C5 alcohol.

[0091] More preferably, R is selected from C1-C5 alcohol and R¹ and R² are independently selected from is selected from hydrogen, or C1-C3 alkyl; and R³, R⁴ and R⁵ are independently selected from hydrogen, C1-C5 alkyl and C1-C5 alcohol.

[0092] Even more preferably, R is selected from C1-C5 alcohol and R¹ and R² are independently selected from is selected from hydrogen, or Ci alkyl; and R³, R⁴ and R⁵ are independently selected from hydrogen, C1-C3 alkyl and C1-C5 alcohol.

[0093] Preferably, wherein [A]⁺ is selected from compounds of the formulae (A.1.1) or

(A.2.1),

[0094] Preferably, the amount of hydroxy -functionalized ionic monomer is from to 0.5 wt.% to 10.0 wt.% based on the total weight of the mixture. It is noted herein that hydroxyfunctionalized ionic monomer in the amount from to 0.5 wt.% to 10.0 wt.% based on the total weight of the mixture, ensures a remarkable improvement in electrical conductivity of the PU foam. Preferably, it is from to 1.0 wt.% to 9.0 wt.%, or 1.0 wt.% to 8.0 wt.%, or 1.0 wt.% to 7.0 wt.%, or 1.0 wt.% to 6.0 wt.% based on the total weight of the mixture. More preferably, it is from to 1.0 wt.% to 5.0 wt.% based on the total weight of the mixture. The presence of ionic monomer in a concentration above 10 wt.% is noted to be cost-ineffective.

[0095] Blowing agent (D)

[0096] In accordance with the invention, the PU foam is obtained by reacting a mixture comprising a blowing agent. [0097] Preferably, the blowing agent is selected from water, hydrocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochlorofluorocarbons, hydrochlorofluoroolefins, fluorocarbons, dialkyl ethers, cycloalkylene ethers and ketones, fluorinated ethers, or mixtures thereof. Preferably, the blowing agent is selected from water, hydrofluorocarbons, hydrocarbons, or mixtures thereof. More preferably, the blowing agent is a mixture consisting of water and hydrocarbons. Even more preferably, the blowing agent is water.

[0098] Suitable hydrocarbon blowing agents include lower aliphatic or cyclic, linear or branched hydrocarbons such as alkanes, alkenes and cycloalkanes, preferably having from 4 to 8 carbon atoms. Preferably, hydrocarbon blowing agents is selected from n-butane, iso-butane, 2,3-dimethylbutane, cyclobutane, n-pentane, iso-pentane, technical grade pentane mixtures, cyclopentane, methylcyclopentane, neopentane, n-hexane, iso-hexane, n-heptane, iso-heptane, cyclohexane, methylcyclohexane, 1-pentene, 2-methylbutene, 3 -methylbutene, 1-hexene, or mixtures thereof.

[0099] Preferably, hydrofluorocarbons is selected from 1,1,1,2-tetrafluoroethane (HFC 134a), 1,1,2,2-tetrafluoroethane, trifluoromethane, heptafluoropropane, 1,1,1 -trifluoroethane, 1,1,2-trifluoroethane, 1,1,1,2,2-pentafluoropropane, 1,1,1,3-tetrafhioropropane, 1, 1,1, 3,3- pentafluoropropane (HFC 245fa), 1,1,3,3,3-pentafluoropropane, 1,1,1,3,3-pentafluoro-n- butane (HFC 365mfc), 1,1,1,4,4,4-hexafluoro-n-butane, 1,1,1,2,3,3,3-heptafluoropropane (HFC 227ea), or mixtures thereof. More preferably, the hydrofluorocarbon is 1, 1,1, 3,3- pentafluoropropane (HFC 245fa).

[00100] Preferably, hydrochlorofluorocarbons is selected from l-chloro-1,2- difluoroethane, 1 -chi oro-2, 2-difluoroethane, 1 -chi oro-1,1 -difluoroethane, 1,1-dichloro-l- fluoroethane, monochlorodifluoromethane, or mixtures thereof.

[00101] Hydrofluoroolefins (HFOs), also known as fluorinated alkenes, that are suitable according to the present invention, are propenes, butenes, pentenes and hexenes having 3 to 6 fluorine sub-stituents, while other substituents such as chlorine can be present, examples being tetra-fluoropropenes, fluorochloropropenes, for example trifluoromonochloropropenes, pentafluoro-propenes, fluorochlorobutenes, hexafluorobutenes, or mixtures thereof. Preferably, the HFOs can be selected from cis-l,l,l,3-tetrafluoropropene, trans- 1,1, 1,3- tetrafluoropropene, 1,1,1 -trifluoro-2-chloropropene, 1 -chi oro-3 ,3 ,3 -trifluoropropene,

1,1,1,2,3-pentafluoropropene, in cis or trans form, 1,1,1,4,4,4-hexafluorobutene, 1- bromopentafluoropropene, 2-bromopentafluoropropene, 3 -bromopentafluoropropene,

1,1,2,3,3,4,4-heptafluoro-l-butene, 3,3,4,4,5,5,5-heptafluoro-l-pentene, l-bromo-2,3,3,3- tetrafluoropropene, 2-bromo- 1 , 3 , 3 , 3 -tetrafluoropropene, 3 -bromo- 1 ,1,3,3 -tetrafluoropropene, 2-bromo-3,3,3-trifluoropropene, E-l-bromo-3,3,3-trifluoropropene, 3,3,3-trifluoro-2- (trifluoromethyl)propene, 1 -chi oro-3 ,3 ,3 -trifluoropropene, 2-chl oro-3 ,3 ,3 -trifluoropropene, l,l,l-trifluoro-2 -butene, or mixtures thereof.

[00102] Preferably, the blowing agent is present in an amount from to 1.0 wt.% to 20.0 wt.% based on the total weight of the mixture. Preferably, it is present from to 2.0 wt.% to 20.0 wt.%, or from to 3.0 wt.% to 20.0 wt.%, or from to 4.0 wt.% to 20.0 wt.%. More preferably, it is present from to 5.0 wt.% to 19.0 wt.%, or from to 6.0 wt.% to 19.0 wt.%, or from to 7.0 wt.% to 19.0 wt.%, or from to 8.0 wt.% to 19.0 wt.%. Still more preferably, it is present from to 9.0 wt.% to 18.0 wt.%, or from to 10.0 wt.% to 18.0 wt.%, or from to 11.0 wt.% to 17.0 wt.%, or from to 12.0 wt.% to 17.0 wt.%, or from to 13.0 wt.% to 17.0 wt.%.

[00103] Amine catalyst (E)

[00104] In accordance with the invention, the PU foam is obtained by reacting a mixture comprising amine catalyst.

[00105] Preferably, the amine catalyst is selected from triethylamine, tributylamine, N- methylmorpholine, N-ethylmorpholine, N,N, N', N'-tetramethylethylenediamine, pentamethyldiethylenetriamine and higher homologues, l,4-diazabicyclo(2.2.2)octane, N-methyl-N'- dimethyl-aminoethylpiperazine, bis-(dimethylaminoalkyl)piperazines, tris(dimethylaminopropyl)hexahydro-l ,3,5-triazin, N,N-dimethylbenzylamine, N,N- dimethylcyclohexylamine, N,N-diethyl-benzylamine, bis-(N,N-diethylaminoethyl) adipate, N,N,N',N'-tetramethyl-l,3-butanediamine, N,N-dimethyl-p-phenylethylamine, 1 ,2- dimethylimidazole, 2-methylimidazole, monocyclic and bicyclic amines together with bis- (dialkylamino)alkyl ethers, such as 2,2-bis-(dimethylaminoethyl)ether, or mixtures thereof. [00106] Preferably, the amine catalyst is selected from N-ethylmorpholine, N,N, N', N'- tetramethylethylenediamine, pentamethyl-diethylenetriamine and higher homologues, 1,4- diazabicyclo(2.2.2)octane, N-methyl-N'-dimethyl-aminoethylpiperazine, bis- (dimethylaminoalkyl)piperazines, tris(dimethylaminopropyl)hexahydro-l ,3,5-triazin, N,N- dimethylbenzylamine, N,N-dimethylcyclohexylamine, N,N-diethyl-benzylamine, bis-(N,N- diethylaminoethyl) adipate, N,N,N',N'-tetramethyl-l,3-butanediamine, and N,N-dimethyl-p- phenylethylamine.

[00107] More preferably, the amine catalyst is selected from N-methyl-N'-dimethyl- aminoethylpiperazine, bis-(dimethylaminoalkyl)piperazines, tris(dimethylaminopropyl)hexahydro-l ,3,5-triazin, N,N-dimethylbenzylamine, N,N- dimethylcyclohexylamine, and N,N-diethyl-benzylamine.

[00108] Even more preferably, the amine catalyst is N,N-dimethylcyclohexylamine.

[00109] Preferably, the amine catalyst is present in an amount from to 0.1 wt.% to 5.0 wt.% based on the total weight of the mixture. Preferably, it is present from to 0.5 wt.% to 5.0 wt.%, or from to 1.0 wt.% to 5.0 wt.%, or from to 2.0 wt.% to 5.0 wt.%. More preferably, it is present from to 2.0 wt.% to 4.5 wt.%.

[00110] Additive (F)

[00111] Preferably, the mixture further comprises at least one additive (F) selected from flame retardants, surfactants, dispersing agents, and mixtures thereof.

[00112] Suitable compounds for use as flame retardants include phosphorus compounds, nitrogen compounds and mixtures thereof. Preferably, the phosphorus compounds are selected from tricresyl phosphate (TCP), tris(2-chloroethyl)phosphate (TCEP), tris(2- chloropropyl)phosphate (TCPP), tris(2,3-dibromopropyl)phosphate, tris(l,3- dichloropropyl)phosphate, tris(2-chloroisopropyl)phosphate, tricresylphosphate, tri(2,2- dichloroisopropyl)phosphate, diethylN,N-bis(2-hydryethyl)aminomethylphosphonate, dimethyl methylphosphonate, tri(2,3-dibromopropyl)phosphate, tri(l,3- dichloropropyl)phosphate, tetra-kis-(2-chloroethyl)ethylene diphosphate, triethylphosphate, diammonium phosphate, diethyl ethanephosphonate (DEEP), triethyl phosphate (TEP), dimethyl propanephosphonate (DMPP) and diphenyl cresyl phosphate (DPK), or mixtures thereof. More preferably, the phosphorus compound is selected from TCP, TEP, TCEP, and TCPP. Even more preferably, it is selected from TCPP and TEP.

[00113] Preferably, the nitrogen compounds are selected from benzoguanamine, tris(hydroxyethyl)isocyanurate, isocyanurate, allantoin, glycoluril, melamine, melamine cyanurate, melamine polyphosphate, dimelamine phosphate, melamine pyrophosphate, melamine borate, ammonium polyphosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, condensation product of melamine selected from the group consisting of melem, melam, melon and higher condensed compounds and other reaction products of melamine with phosphoric acid and melamine derivatives, or mixtures thereof.

[00114] Preferably, the flame retardant is present in an amount from to 1.0 wt.% to 15.0 wt.%, based on the total weight of the mixture.

[00115] Suitable surfactants as additives include silicone surfactants. The silicone surfactant is preferably used to emulsify the mixture as well as to control the size of the bubbles of the foam so that a foam of desired cell structure is obtained. Silicone surfactants for use in the preparation of PU foams are available under a variety of tradenames known to those skilled in the art. Such materials have been found to be applicable over a wide range of formulations allowing uniform cell formation and maximum gas entrapment to achieve very low-density foam structure. Preferably, the silicone surfactant comprises a polysiloxane polyoxyalkylene block copolymer. Some representative silicone surfactants include Momentive’s L-5130, L- 5340, L-5440, L-6980, and L-6988; Air Products’ DC-193, DC-197, DC-5582, and DC-5598; and Evonik’s B-8404, B-8407, B-8409, and B-8462.

[00116] Preferably, the surfactant is a non-silicone, non-ionic surfactant. Preferably, surfactants are selected from oxyethylated alkylphenols, oxethylated fatty alcohols, paraffin oils, castor oil esters, ricinoleic acid esters, turkey red oil, groundnut oil, paraffins, fatty alcohols, or mixtures thereof. The preferred non-silicone non-ionic surfactants are Air Products’ Dabco LK-221 and LK-443, and Dow’s Vorasurf™ 504.

[00117] Preferably, the surfactant is present in an amount from to 0.01 wt.% to 3.0 wt.%, based on the total weight of the mixture. Preferably, it is present in an amount from to 0.05 wt.% to 3.0 wt.%, or from to 0.075 wt.% to 2.5 wt.%, or from to 0.1 wt.% to 2.0 wt.%, or from to 0.5 wt.% to 1.5 wt.%.

[00118] Suitable dispersing agent as additives include polymeric dispersants. Preferably, polymeric dispersants are selected from a polyester-based polymer dispersant, acrylic polymer- based dispersant, polyurethane-based polymer dispersant, polyallylamine-based polymer dispersant, carbodiimide-based polymer dispersant, polyamide-based polymer dispersant, or mixtures thereof. More preferably, the dispersing agent is selected from acrylic-based polymer dispersant and polyamide-based polymer dispersant.

[00119] Suitable, polyamide-based polymer dispersant include a polyester chain and side chain having a plurality of comb structure. Preferably, a large number of poly alkyleneimine in its main chain structure having a nitrogen atom, said nitrogen atom via an amide bond to the side chain of the polyester having a plurality of compounds are preferred. Such a polyamide- based polymer dispersant of a comb structure is also available under the tradename of DISPERBYK® from BYK Chemie Co and SOLSPERSE from Lubrizol.

[00120] Preferably, the dispersing agent is present in an amount from to 0.1 wt.% to 15.0 wt.%, based on the total weight of the mixture. Preferably, it is present from to 0.1 wt.% to 12.0 wt.%, or 0.1 wt.% to 10.0 wt.%. More preferably, it is present from to 0.1 wt.% to 9.0 wt.%, or 0.1 wt.% to 8.0 wt.%. Even more preferably, it is present from to 0.1 wt.% to 7.0 wt.%, or 0.1 wt.% to 6.0 wt.%, or 0.1 wt.% to 5.0 wt.%.

[00121] Preferably, the additives may be added to the A-side or B-side component, as long as they do not have a detrimental effect on the properties of the PU foam. More preferably, the additives are added to the B-side component. [00122] Preferably, the mixture may further comprise auxiliaries (G) selected from alkylene carbonates, carbonamides, pyrrolidones, dyes, pigments, IR absorbing materials, UV stabilizers, fungistats, bacterio-stats, hydrolysis controlling agents, curing agents, antioxidants, and cell regulators. Suitable amount of these auxiliaries includes 0.1 wt.% to 20 wt.%, based on the total weight of the mixture. Further details regarding these auxiliaries can be found, for example, in Kunststoffhandbuch, Volume 7, “Polyurethane” Carl-Hanser-Verlag Munich, 1^st edition, 1966, 2^nd edition, 1983 and 3^rd edition, 1993. These ingredients may be added to the A-side or B-side component, as long as they do not have a detrimental effect on the properties of the PU foam.

[00123] Carbon black

[00124] Preferably, the mixture further comprises carbon black.

[00125] Preferably, the carbon black has a BET surface area of from 600 m²/g to 1200 m²/g, as determined according to ASTM D6556-19a. More preferably, the BET surface area is of from 700 m²/g to 1200 m²/g, or of from 700 m²/g to 1100 m²/g, or of from 800 m²/g to 1100 m²/g. Even more preferably, it is of from 800 m²/g to 1050 m²/g, or of from 900 m²/g to 1050 m²/g, or of from 950 m²/g to 1050 m²/g.

[00126] The electrical resistivity of the PU foam is further enhanced by using effective amounts ofthe carbon black in the PU foam, i.e. in the range 1.0*10⁷ .m to 1.0*10¹² .m, as determined according to ASTM D257-14. Preferably, the carbon black is present of from 1.0 wt.% to 10.0 wt.%. More preferably, it is present of from 1.0 wt.% to 8.0 wt.%, or of from 1.0 wt.% to 7.0 wt.%, or of from 2.0 wt.% to 6.0 wt.%.

[00127] In order to obtain the PU foam, carbon black may be added to A-side and/or B-side component. Preferably, the carbon black can be added to both A-side and B-side components, however, the amount of carbon black remains of from 1.0 wt.% to 10 wt.%, based on the total weight of the mixture. Carbon black in the mixture without IM less than 1.0 wt.% results in no change in the electrical resistivity of the PU foam, i.e. the resulting PU foam acts like an insulator. While carbon black in quantities more than 10.0 wt.% results in a highly viscous system, which is very difficult to process using conventional techniques. [00128] Preferably, A-side component includes the isocyanates and optionally the compounds which are non-reactive with the isocyanates, as described herein, for e.g., carbon black. Similarly, the B-side component includes the isocyanate reactive component, at least one hydroxy-functionalized ionic monomer of the formula I, blowing agents, and amine catalyst. Preferably, the B-side component includes at least one hydroxy-functionalized ionic monomer of the formula I, first poly ether polyol, carbon black, blowing agents, amine catalyst, and optionally the second polyol and/or additives, as described herein.

[00129] Commercially available carbon black fulfilling the above requirements can also be obtained under the tradename Printex® from Orion Engineered Carbons.

[00130] Process

[00131] Another aspect of the present invention is directed towards a process for preparing the PU foam. The foam-forming process may be carried out batchwise, semi-continuously or continuously. Preferably, the isocyanate component (A) is reacted with the isocyanate reactive component (B), in the presence of at least one hydroxy-functionalized ionic monomer of the formula I (C), at least one blowing agent (D), and at least one amine catalyst (E). More preferably, the mixture may further optionally comprise at least one additive (F) and/or auxiliaries (G), as described herein.

[00132] Preferably, the isocyanate component (A) and the isocyanate reactive component (B) are mixed at an index from to 0.7 to 1.2. Preferably, the index is from to 0.8 to 1.2, or from to 0.8 to 1.1 , or from to 0.9 to 1.1. In the present context, the index of 1.0 corresponds to one isocyanate group per one isocyanate reactive group.

[00133] Preferably, the at least one hydroxy-functionalized ionic monomer of the formula I (C) is added to the at least one isocyanate component (A) and/or the at least one isocyanate reactive component (B) prior to mixing. More preferably, (C), (D), (E) and optionally (F) and/or (G) are added to (B), prior to mixing. Said otherwise, the ingredients (C), (D), (E), optionally (F) and/or (G) are pre-mixed together with (B), for example in a mixing head, and then mixed with (A).

[00134] Preferably, when the at least one hydroxy-functionalized ionic monomer of the formula I is added to the at least one isocyanate reactive component (B) prior to mixing, the amount is based on the total weight of the respective component. For e.g. if the at least one hydroxy-functionalized ionic monomer of the formula I is added to the B-side, the amount added is from to 0.5 wt.% to 10.0 wt.% based on the total weight of the B-side. Further, the amount added may also vary, as above. Also, the ingredients (C), (D), (E), optionally (F) and/or (G) when pre-mixed to the B-side may be added in their respective amounts.

[00135] Preferably, when the carbon black is added to the at least one isocyanate component (A) and/or the at least one isocyanate reactive component (B) prior to mixing, the amount is based on the total weight of the respective component. For e.g. if the carbon black is added to the A-side, the amount added is from to 1.0 wt.% to 10.0 wt.% based on the total weight of the A-side. Similarly, if the carbon black is added to the B-side, the amount added is from to 1.0 wt.% to 10.0 wt.% based on the total weight of the B-side. Further, the amount added may also vary, as above. Also, the ingredients (C), (D), (E), optionally (F) and/or (G) when pre-mixed to the B-side may be added in their respective amounts.

[00136] Preferably, the ingredients (A), (B), C), (D), (E), and optionally (F) and/or (G) are mixed at temperature from to 10°C to 50°C for the PU foam forming reaction to start. It is usually not necessary to apply heat to the mixture to drive the cure, but this may be done too, if desired.

[00137] The mixture can be employed for pour-in-place applications or spray applications. Preferably, the mixture is useful for pour-in-place applications, wherein it is dispensed into a cavity and foams within the cavity to fill it and provide structural attributes and desired electrical resistivity to an assembly. The term “pour-in-place” refers to the fact that the foam is created at the location, where it is needed, rather than being created in one step and later assembled into place in a separate manufacturing step. Further, the term “cavity” refers to an empty or hollow space of any geometry having at least one open side into which the mixture can be dispensed at conditions such that expansion and curing of the composition occurs to form the PU foam.

[00138] Preferably, the mixture is useful for spray applications. Spraying techniques are used for filling molds and panels and for applying the mixture to plane surfaces. Spraying is particularly useful in applications, where large areas are involved, such as tanks or building walls. Sprayed PU foam coatings provide both physical strength and improved insulation. In spray applications, the mixing is accomplished by atomization. By the term “atomization”, it is referred to the particles or droplets of the mixture obtained from suitable spraying means, such as not limited to, a nozzle or an atomizer.

[00139] Preferably, each of the isocyanate component (A) and the isocyanate reactive component (B), with ingredients (C), (D), (E) and optionally (F) and/or (G) pre-mixed to either A-side and/or B-side, are fed as separate streams, for instance, in a mixing device. Preferably, the presently claimed invention refers to the two-component system (namely A-side and B- side), as described herein. However, it is possible that a multi-component system can also be used. By the term “multicomponent system”, it is referred to any number of streams, at least more than the conventionally existing two streams in the two-component system. For example, three, four, five, six or seven, separate streams can be fed to the mixing device. These additional streams can comprise one or more selected from (A), (B), (C), (D), (E), (F) and (G), as described herein. More preferably, each of the streams in the multicomponent system is different from the A-side and B-side component streams. Hereinafter, the A-side component can be interchangeably also referred as first stream, while the B-side component as second stream.

[00140] Suitable mixing devices for the purpose of the presently claimed invention are well known to the person skilled in the art, for example, a mixing head or a static mixer. While it is preferred that each stream enters separately in the mixing device, it is possible that the components within each stream are well mixed by suitable mixing means, for example, the static mixer. Static mixers are well known to the person skilled in the art for mixing of liquids, for example, as described in EP 0 097 458. Typically, the static mixers are tubular apparatuses with fixed internals which serve for the mixing of individual stream across the cross section of the tube. Static mixers can be used in continuous process for the conduct of various operations, for ex-ample, mixing, substance exchange between two phases, chemical reactions or heat transfer. The homogenization of the streams is brought about via a pressure gradient produced by means of a pump.

[00141] Suitable temperatures for PU foam processing are well known to the person skilled in the art. Preferably, in the mixing device and/or the individual streams, a temperature from to 10°C to 50°C, or from to 15°C to 40°C can be maintained. However, each stream can be maintained at a different temperature and each stream does not necessarily have the same temperature. For instance, the temperature of the first stream can be 20°C, while that of the second stream can be 30°C.

[00142] Preferably, feeding of the streams into the mixing device is conducted preferably by means of pumps, which can operate at low-pressure or high-pressure, preferably at high pressure, in order to dispense the streams into the mixing device. Mixing within the mixing devices can be achieved among others by simple static mixer, low-pressure dynamic mixers, rotary element mixer as well as high-pressure impingement mixer. Mixing can be controlled by suitable means known to the person skilled in the art, for instance by simply switching on and off or even by a process control software equipped with flow meters, so that parameters, such as mixing ratio or temperature can be controlled.

[00143] Preferably, the term “low pressure” refers to pressure from to 0.1 MPa to 5 MPa, while “high pressure” refers to pressure above 5 MPa, preferably from to 5 MPa to 26 MPa.

[00144] Preferably, the ingredients (A), (B), (C), (D), (E), and optionally (F) and/or (G) are mixed in suitable mixing devices in any sequence. For instance, the ingredients can be added to the mixing device all at once or one by one or as pre-mixture of any of these ingredients and in combinations thereof. Preferably, the mixing is carried out at rpm ranging of from 500 rpm to 5000 rpm and for suitable duration known to the person skilled in the art.

[00145] Preferably, the PU foam has the desired electrical resistivity in the static dissipative range, i.e. 1.0* 10⁷ .m to 1.0* 10¹³ .m, as determined according to ASTM D257-14. This renders the PU foam useful for applications including any relevant product requiring efficient electrical dissipation and the electro-magnetic shielding, such as, but not limited to, filled materials and composites for structural and decorative applications. Examples may include, but are not limited to wind turbine blades, airplane wings, and automotive parts. In other instances, such substantially electrically conductive PU-based materials may also target applications where metals have currently been used and where electro-magnetic shielding is required. The PU foam also has acceptable thermal conductivity values (or k-factor), in addition to the mechanical properties, which render it useful for insulation applications as well.

[00146] The acceptable mechanical properties of the PU foam, but not limited to, compressive strength, storage modulus, damping factor and damping capacity, Young’s modulus, hardness, elongation at break, and tensile strength. Some of these have been reported in the example section below.

[00147] Preferably, the PU foam is not used in electronics-manufacturing facility as well as in shipping electronic devices, such as the ones described in US 4,231,901.

[00148] Another aspect of the present invention is directed towards the use of the PU foam for static dissipative materials. Particularly, the static dissipative materials include cathodic protection systems, such as trench breakers or pipeline pillows or electrically conductive pad.

[00149] Yet another aspect of the present invention is directed towards the trench breakers or pipeline pillows comprising the PU foam.

[00150] The PU foam can facilitate the construction and/or placement of new underground pipelines in terms of serving as three-dimensional pads and/or pillows which, as sprayed directly on and around an underground structure in place, may physically support, stabilize and protect the carbon steel structure as placed in an underground trench. The PU foam can further be spray applied to produce trench breakers which as applied in intermittent locations along underground trench may negotiate erosion of the trench created for installing a particular underground hazardous liquid or natural gas pipeline facility. The proficient installation of the PU foam offers several attributes with respect to reduced labour cost, reduced risk of employee injury (and even death) versus use of sandbags and increased productivity resulting from much faster jobsite completion.

[00151] Preferably, the electrically conductive pad, pillow or trench breaker are employable in underground oil and gas pipeline facilities construction and trenches and subsurface construction.

[00152] Another aspect of the present invention is directed towards the use of the PU foam for thermally insulating materials. Preferably, the thermally insulating materials may be shaped into suitable form such as fire-retardant materials, blankets, covers, sheets, clothing, footwear, based on suitability for end-application, such as insulating materials for electrical appliances.

[00153] Another aspect of the present invention is directed towards a trench breaker or pipeline pillow comprising the PU foam.

[00154] Illustrative embodiments of the present invention are listed below, but do not restrict the present invention. In particular, the present invention also encompasses those embodiments that result from the dependency references and hence combinations specified hereinafter. More particularly, in the case of naming of a range of embodiments hereinafter, for example the expression "The polyurethane according to any of embodiments I to IV", should be understood such that any combination of the embodiments within this range is explicitly disclosed to the person skilled in the art, meaning that the expression should be regarded as being synonymous to "The polyurethane according to any of embodiments I, II, III and IV":

I. A polyurethane foam obtained by reacting a mixture comprising:

(A) at least one isocyanate component,

(C) at least one hydroxy-functionalized ionic monomer of the formula I, [A]⁺[Y]- (I), wherein [A]⁺ is selected from compounds of the formulae (A.1), (A.2), or (A.3),

wherein R is selected from C1-C10 alcohol;

R¹, R², R³, R⁴ and R⁵ are independently selected from hydrogen, C1-C10 alkyl or C1-C10 alcohol; and

[¥]" is a monovalent anion,

(D) at least one blowing agent, and

(E) at least one amine catalyst.

II. The polyurethane foam according to embodiment I, wherein the first polyether polyol has a nominal functionality from to 2.5 to 5.0 and OH value from to 250 mg KOH/g to 500 mg KOH/g according to DIN 53240.

III. The polyurethane foam according to embodiments I or II, wherein the first polyether polyol has a nominal functionality from to 2.7 to 4.5 and OH value from to 300 mg KOH/g to 450 mg KOH/g.

IV. The polyurethane foam according to embodiments I to III, wherein the first polyether polyol has a OH value from to 320 mg KOH/g to 420 mg KOH/g.

V. The polyurethane foam according to embodiments I to IV, wherein the isocyanate reactive component comprises a second polyol selected from a polyester polyol, a second polyether polyol, a polymer polyol, and a mixture thereof.

VI. The polyurethane foam according to embodiments I to V, wherein the polyester polyol has a nominal functionality from to 1.9 to 3.5 and OH value from to 250 mg KOH/g to 400 mg KOH/g.

VII. The polyurethane foam according to embodiments I to VI, wherein the second poly ether polyol has a nominal functionality from to 3.5 to 8.0 and OH value from to 100 mg KOH/g to 450 mg KOH/g. VIII. The polyurethane foam according to embodiments I to VII, wherein the second poly ether polyol is a Mannich polyol.

IX. The polyurethane foam according to embodiments I to VIII, wherein the polyurethane foam is a rigid or flexible foam.

X. The polyurethane foam according to embodiments I to IX, wherein [¥]" is a monovalent anion selected from methyl hydrogen phosphite, bistriflimide, dimethyl phosphate, triflate, tosylate, chloride, fluoride and iodide.

XI. The polyurethane foam according to embodiments I to X, wherein [Y] ‘ is a monovalent anion selected from methyl hydrogen phosphite, bistriflimide and dimethyl phosphate.

XII. The polyurethane foam according to embodiments I to XI, wherein R is selected from C1-C5 alcohol and R¹, R², R⁴ and R⁵ are independently selected from hydrogen, C1-C3 alkyl and C1-C5 alcohol.

XIII. The polyurethane foam according to embodiments I to XII, wherein R¹ and R² are Ci alkyl.

XIV. The polyurethane foam according to embodiments I to XIII, wherein [A]⁺ is selected from compounds of the formulae (A.1.1) or (A.2.1),

XV. The polyurethane foam according to embodiments I to XIV, wherein the amount of hydroxy-functionalized ionic monomer is of from 0.5 wt.% to 10.0 wt.% based on the total weight of the mixture.

XVI. The polyurethane foam according to embodiments I to XV, wherein the isocyanate component is selected from methylene diphenyl diisocyanate and polymeric methylene diphenyl diisocyanate.

XVII. The polyurethane foam according to embodiments I to XVI, wherein the mixture further comprises carbon black having a BET surface area from to 600 m²/g to 1200 m²/g, as determined according to ASTM D6556-19a. XVIII. The polyurethane foam according to embodiment XVII, wherein the carbon black has a BET surface area from to 900 m²/g to 1050 m²/g, as determined according to ASTM D6556-19a.

XIX. The polyurethane foam according to embodiments XVII to XVIII, wherein the amount of carbon black is from to 1.0 wt.% to 10.0 wt.% based on the total weight of the mixture.

XX. The polyurethane foam according to embodiments XVII to XIX, wherein the amount of carbon black is from to 1.0 wt.% to 5.0 wt.% based on the total weight of the mixture.

XXI. The polyurethane foam according to embodiments I to XX, wherein the (D) at least one blowing agent selected from water, and hydrocarbons.

XXII. The polyurethane foam according to embodiments I to XXI, wherein the amine catalyst (E) is selected from triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N,N, N', N'-tetramethylethylenediamine, pentamethyl-di- ethylenetriamine and higher homologues, l,4-diazabicyclo(2.2.2)octane, N-me- thyl-N'-dimethyl-aminoethylpiperazine, bis-(dimethylaminoalkyl)piperazines, tris(dimethylaminopropyl)hexahydro-l,3,5-triazin, N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, N,N-diethyl-benzylamine, bis-(N,N-diethyla- minoethyl) adipate, N,N,N',N'-tetramethyl-l,3-butanediamine, N,N-dimethyl- p-phenylethylamine, 1 ,2-dimethylimidazole, 2-methylimidazole, monocyclic and bicyclic amines together with bis-(dialkylamino)alkyl ethers, such as 2,2- bis-(dimethylaminoethyl)ether, and mixtures thereof.

XXIII. The polyurethane foam according to embodiments I to XXII, wherein the mixture further comprises at least one additive (F) selected from flame retardants, surfactants, dispersing agents, and mixtures thereof.

XXIV. The polyurethane foam according to embodiments I to XXIII having a foam density from to 30 kg/m³ to 150 kg/m³ determined according to ASTM D1622 and a bulk resistivity from to 1.0*10⁷ Q/cm² to 1.0*10¹³ Q/cm² determined according to ASTM D257-14.

XXV. The polyurethane foam according to embodiments I to XXIV having a self-ex- tinguish time of from 20 sec to 80 sec and bum rate of from 50mm/min to 280 mm/min determined according to UL-94. XXVI. The polyurethane foam according to embodiments I to XXV having a viscosity of from 50 to 6000 cps.

XXVII. A process for preparing the polyurethane foam according to one or more of embodiments I to XXVI.

XXVIII. The process according to embodiment XXVII, wherein the isocyanate component (A) and the isocyanate reactive component (B) are mixed at an index from to 0.7 to 1.2.

XXIX. Use of the polyurethane foam according to one or more of embodiments I to XXVI or as obtained according to embodiments XXVII or XXVIII for static dissipative materials.

XXX. The use according to embodiment XXIX, wherein the static dissipative material comprises trench breaker or pipeline pillow.

XXXI. A trench breaker or pipeline pillow comprising the polyurethane foam according to one or more of embodiments I to XXVI or as obtained according to embodiments XXVII or XXVIII.

XXXII. Use of the polyurethane foam according to one or more of embodiments I to XXVI or as obtained according to embodiments XXVII or XXVIII for thermally insulating material.

XXXIII. A thermally insulative material comprising the polyurethane foam according to one or more of embodiments I to XXVI or as obtained according to embodiments XXVII or XXVIII.

XXXIV. The use according to embodiment XXXII or material according to embodiment XXXIII, wherein the thermally insulative material comprises cable sheath or fire-proof construction materials.

EXAMPLES

[00155] The presently claimed invention is illustrated by the non-restrictive examples which are as follows:

[00156] Raw materials

Standard method

[00157] Synthesis of hydroxy -functionalized ionic monomer (IM 1)

Dimethylsulfate (258 g, 2.030 mol, 0.99 equiv.) was slowly added to methyldiethanolamine (246 g, 2.050 mol, 1.00 equiv). The reaction temperature was maintained of from 30 - 40 °C, during addition. After the addition, the mixture was stirred for 1 h at room temperature. No further purification was done and the dimethyldiethanolammonium methylsulfate salt was used for the next step as it is.

[00158] The anion exchange was done with a strongly basic (type I) anion exchange resin to obtain the corresponding hydroxide salt. To an aqueous solution (6.00 kg, 12.6%) of the dimethyldiethanolamonium hydroxide salt (756 g, 5.00 mol, 1.00 equiv.), the free acid of bis(trifluoromethylsulfonyl)imide or TFSI (75% in water, 5.00 mol, 1.00 equiv.) was added under pH-control (beginning pH-value at 13.4, end pH-value at 7.05). After the addition, water was removed by reduced pressure. Charcoal (50 g) was added and the mixture was stirred for 10 min at room temperature. The charcoal was filtered off and the colorless product (TFSI-salt) was obtained.

[00159] Synthesis of hydroxy -functionalized ionic monomer (IM 2)

Dimethyldiethanolammonium dimethylphosphate salt was obtained by heating methyldiethanolamine (520 g, 4.364 mol, 1.00 equiv.) to 100 °C, followed by subsequent slow addition (over 180 min) of trimethylphosphate (599 g, 4.277 mol, 0.98 equiv.) at elevated temperature. The reaction temperature was kept of from 100 - 110 °C. After the addition, the mixture was stirred for 3.5 h at 100 °C and the 24 h at 80 °C. No further purification was done. The product was isolated as an orange and viscous oil.

[00160] Synthesis of hydroxy -functionalized ionic monomer (IM 3)

Dimethyldiethanolammonium methylphosphite salt was obtained by heating methyldiethanolamine (600 g, 5.035 mol, 1.00 equiv.) to 100 °C, followed by subsequent slow addition (over 90 min) of dimethylphosphite (543 g, 4.934 mol, 0.98 equiv.). The reaction temperature was kept of from 100 - 110 °C. After the addition, the mixture was stirred for 3.5 h at 100 °C and the 24 h at 80 °C. No further purification was done. The mixture product was isolated as a pale yellow and viscous oil.

[00161] Synthesis of hydroxy -functionalized ionic monomer (IM 4)

1-Methylpyrrolidine (276 g, 3.241 mol, 1.00 equiv.) was dissolved in acetonitrile (1000 mL) and 3-chloro-l,2-propanediol (340.4 g, 3.079 mol, 0.95 equiv.) was added slowly over 60 min. The reaction mixture was heated to 75 °C and stirred for 22 h at 75 °C. The solvent was removed under reduced pressure. The yellow, viscous oil was dissolved in ethanol (300 mL) while heating to reflux. While cooling down the mixture, white crystals are precipitated. The mixture cannot be stirred anymore, and acetonitrile (1200 mL) was added. The mixture was stirred for 30 min and cooled down to 0 °C. The white crystals were filtered off and washed with acetonitrile (lx) to obtain l-(2,3-dihydroxypropyl)pyrrolidinium chloride.

[00162] The anion exchange was done with a strongly basic (type I) anion exchange resin to obtain the corresponding hydroxide salt. To an aqueous solution (5.45 kg, 8.59%) of the pyrrolidinium hydroxide (468 g, 2.640 mol, 1.00 equiv.), the free acid of TFSI (75% in water, 2.640 mol, 1.00 equiv.) was added under pH-control (beginning pH-value at 13.4, end pH- value at 7.05). After the addition, 3 L water was removed by reduced pressure. Charcoal (16 g) was added and the mixture was stirred for 10 min at room temperature. The charcoal was filtered off and the water was fully removed by reduced pressure. The product (TFSI-salt) was isolated in the form of a pale-yellow oil (1110 g, 2.521 mol).

[00163] General synthesis of mixture for producing PU foam

The aforementioned raw materials were added in the amounts mentioned in Table 1 in both the A-side and B-side components (all in wt.%). Both the A-side and B-side components were then added to a mixing device, such as the static mixer of a spray equipment or other mixing approach like a mixing cup, to obtain a desired level of mixing. The temperature of A- and B- sides were controlled as desired, to adjust the viscosity of these components to enable their sprayability. For instance, the mixture was subjected to mixing at rpm of 3000 and the temperature of A-side and B-side components was maintained of from 25°C to 30°C. While replacement of ionic monomer with additional filler/conductive additives such as carbon black lead to high viscosity (> 6000 cps), it was surprisingly identified that the inventive PU foams were readily processable with suitable viscosity.

The PU foams thus obtained, were subsequently processed for testing and the properties determined.

Table 1:

[00164] Thermal stability

[00165] For thermal stability testing, the TGA experiments were run in a platinum pan first under air on a Q500 TA instrument. The samples were heated from ambient temperature to 800 °C at 10 °C/min. There is a small amount of weight loss below 200 °C. In Air, there are mainly two decomposition steps, the decomposition temperatures are listed in Table 2. Table 2. Absolute Decomposition Temperatures at 95% weight loss in air.

[00166] Absolute temperature at 95% wt loss indicates the thermal stability of a material. Results as summarized above in Table 2 clearly indicate the positive influence of ionic monomer on the PU foams. As evidenced by the high absolute temperature, at 10 wt% loading the presence of IM 1 was noted to result in a remarkably high thermal stability versus control foams (without IM).

[00167] Flame resistivity

Flame resistivity experiments were performed according to a procedure similar to UL-94 chimney test. Results are also outlined in Table 4 below, indicates that the PU foams without the presence of an ionic monomer (control), bums -52% faster (refer bum rates) than the inventive examples comprising ionic monomer. For e.g. control vs PU foams with monomer #IM 4. Overall, the presence of the ionic monomer were noted to have at least 15% slower bum rates compared to the control foam.

Table 3. Flame resistivity for rigid foams with 10% ionic monomer.

[00168] Electrical measurement Bulk resistivity was measured in accordance with ASTM D257-14. Various PU foams were obtained as per raw materials in Table 1 and the associated synthesis described hereinabove. Additionally, carbon black (CB 1) was introduced in mentioned amount (the total amount in Table 4 divided equally into A and B side).

Table 4. Electrical properties for foams with ionic monomer.

[00169] As is evident, the IM-based PU foams were found to have surprisingly low electrical resistivity. However, in control PU foams (without IM), carbon black alone is unable to compensate for the absence of IM and as a result poor resistivity was observed. On the other hand, the combination of carbon black with IM-based PU foams, a synergistic reduction in resistivity was noted. Here, PU foams made from mixtures further comprising carbon black were found to significantly reduce electrical resistivity, for e.g. the resistivity was found to reduce from 1.6xlO¹² Q*cmand 3.4X10¹¹ Q*cm for IM 1-based PU foams.

Thus, the present invention PU foam is highly suitable for applications described hereinabove, in particular as trench breakers or pipeline pillows or thermally insulating materials.

Claims

1. A polyurethane foam obtained by reacting a mixture comprising:

(A) at least one isocyanate component,

(C) at least one hydroxy -functionalized ionic monomer of the formula I,

wherein R is selected from Ci-Cio alcohol;

R¹, R², R³, R⁴ and R⁵ are independently selected from hydrogen, Ci-Cio alkyl or Ci-Cio alcohol; and

[¥]" is a monovalent anion,

(D) at least one blowing agent, and

(E) at least one amine catalyst.

2. The polyurethane foam according to claim 1, wherein the first poly ether polyol has a nominal functionality from to 2.5 to 5.0 and OH value from to 250 mg KOH/g to 500 mg KOH/g according to DIN 53240.

3. The polyurethane foam according to any of the claims 1 or 2, wherein [¥]" is a monovalent anion selected from methyl hydrogen phosphite, bistriflimide, dimethyl phosphate, triflate, tosylate, chloride, fluoride, or iodide.

4. The polyurethane foam according to any of the claims 1 to 3, wherein [¥]" is a monovalent anion selected from methyl hydrogen phosphite, bistriflimide, or dimethyl phosphate.

43

5. The polyurethane foam according to any of the claims 1 to 4, wherein R is selected from C1-C5 alcohol and R¹, R², R⁴ and R⁵ are independently selected from hydrogen, C1-C3 alkyl or C1-C5 alcohol.

6. The polyurethane foam according to any of the claims 1 to 5, wherein R¹ and R² are Ci alkyl.

7. The polyurethane foam according to any of the claims 1 to 6, wherein [A]⁺ is selected from compounds of the formulae (A. 1.1), or (A.2.1),

8. The polyurethane foam according to any of the claims 1 to 7, wherein the amount of hydroxy -functionalized ionic monomer from to 0.5 wt.% to 10.0 wt.% based on the total weight of the mixture.

9. The polyurethane foam according to any of the claims 1 to 8, wherein the isocyanate component is selected from methylene diphenyl diisocyanate, or polymeric methylene diphenyl diisocyanate.

10. The polyurethane foam according to any of the claims 1 to 9, wherein the mixture further comprises carbon black having a BET surface area from to 600 m²/g to 1200 m²/g, as determined according to ASTM D6556-19a.

11. The polyurethane foam according to claim 10, wherein the carbon black has a BET surface area from to 900 m²/g to 1050 m²/g, as determined according to ASTM D6556-19a.

12. The polyurethane foam according to any of the claims 10 to 11, wherein the amount of carbon black is from to 1.0 wt.% to 10.0 wt.% based on the total weight of the mixture.

13. The polyurethane foam according to any of the claims 10 to 12, wherein the amount of carbon black is from to 1.0 wt.% to 5.0 wt.% based on the total weight of the mixture.

14. The polyurethane foam according to claims 1 to 13, wherein the (D) at least one blowing agent selected from water, or hydrocarbons.

15. The polyurethane foam according to any of the claims 1 to 14, wherein the amine catalyst (E) is selected from triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N,N, N', N'-tetramethylethylenediamine, pentamethyl-diethylenetriamine or higher homo-

44 logues, l,4-diazabicyclo(2.2.2)octane, N-methyl-N'-dimethyl-aminoethylpiperazine, bis-(di- methylaminoalkyl)piperazines, tris(dimethylaminopropyl)hexahydro-l,3,5-triazin, N,N-dime- thylbenzylamine, N,N-dimethylcyclohexylamine, N,N-diethyl-benzylamine, bis-(N,N-diethyl- aminoethyl) adipate, N,N,N',N'-tetramethyl-l,3-butanediamine, N,N-dimethyl-p-phenylethyl- amine, 1 ,2-dimethylimidazole, 2-methylimidazole, monocyclic and bicyclic amines together with bis-(dialkylamino)alkyl ethers, such as 2,2-bis-(dimethylaminoethyl)ether, or mixtures thereof.

16. The polyurethane foam according to any of the claims 1 to 15, wherein the mixture further comprises at least one additive (F) selected from flame retardants, surfactants, dispersing agents, or mixtures thereof.

17. The polyurethane foam according to any of the claims 1 to 16 having a foam density from to 30 kg/m³ to 150 kg/m³ determined according to ASTM D1622 and a bulk resistivity from to 1.0*10⁷ Q/cm² to 1.0*10¹³ /cm² determined according to ASTM D257-14.

18. The polyurethane foam according to any of the claims 1 to 17 having a self extinguish time from to 20 sec to 80 sec and bum rate from to 50mm/min to 280 mm/min determined according to UL-94.

19. A process for preparing the polyurethane foam according to one or more of claims 1 to 1

20. The process according to claim 19, wherein the isocyanate component (A) and the first poly ether polyol (Bl) are mixed at an index from to 0.7 to 1.2.

21. Use of the polyurethane foam according to one or more of claims 1 to 18 or as obtained according to claims 19 or 20 for static dissipative materials.

22. The use according to claim 21, wherein the static dissipative material comprises trench breaker or pipeline pillow.

23. A trench breaker or pipeline pillow comprising the polyurethane foam according to one or more of claims 1 to 18 or as obtained according to claims 19 or 20.

24. Use of the polyurethane foam according to one or more of claims 1 to 18 or as obtained according to claims 19 or 20 for thermally insulating material.

25. A thermally insulative material comprising the polyurethane foam according to one or more of claims 1 to 18 or as obtained according to claims 19 or 20.

26. The use according to claim 24 or material according to claim 25, wherein the thermally insulative material comprises cable sheath or fire-proof construction materials.

45