Methods for improving flame, smoke and / or toxicity resistance in materials containing polyisocyanurate / polyurethane (PIR / PUR)

Abstract

The present application discloses a material containing polyisocyanurate and / or polyurethane (PIR / PUR) with improved flame retardant, smoke and / or poison retardant properties and a method for forming the material containing PIR / PUR. Based on the total weight of the material containing PIR / PUR, the PIR / PUR material contains at least 0.2 wt% of a compound with a number average equivalent weight <160 g / mol and at least one unpolymerized ethylenically unsaturated portion, and optionally 0.01 wt% up to 1 wt% of one or more free radical initiator compounds, based on the total weight of the material containing PIR / PUR.

Description

Technical Field

[0001] The present invention relates to a method for improving the flame, smoke and / or toxicity (FST) retardancy of a material containing polyisocyanurate and / or polyurethane (PIR / PUR).

[0002] The present invention also relates to polyisocyanurate and / or polyurethane (PIR / PUR) containing materials comprising a significant amount of compounds having at least one unpolymerized ethylenically unsaturated moiety.

[0003] More specifically, the present invention relates to polyisocyanurate and / or polyurethane (PIR / PUR) containing materials containing significant amounts of acrylates, methacrylates, acrylic acid, methacrylic acid, allyl alcohol and / or maleic acid and derivatives thereof having at least one un-polymerized ethylenically unsaturated moiety. Background Art

[0004] Traditionally, halogen-containing additives have been used as flame retardants for organic resins. That is, the additive compound contains fluorine, chlorine, or bromine. The most common brominated resins are strong oxidizers. When exposed to heat, the weak bonds between the bromine and the rest of the resin's atomic structure break and form bromine radicals, which interfere with the extremely exothermic oxidation reaction and thereby suppress the flame. While it is this reaction that gives the brominated resin its flame retardant properties, the bromine removed by this reaction subsequently reacts with hydrogen to form hydrogen bromide (HBr). If the brominated resin is exposed to more and / or hotter flames, the HBr density increases. The resulting fumes are much more toxic than those produced by non-halogenated resins.

[0005] In rigid polyurethane (PU) foams, TCPP (trichloropropyl phosphate) is widely used. In many PU applications, countries such as Canada have recently proposed restrictions for furniture and bedding applications. Likewise, the US Environmental Protection Agency (EPA) is also working on it. The US Consumer Product Safety Commission (CPSC) is evaluating potential regulations or even considering banning the use of organic chlorinated substances as flame retardants. In view of the restrictions of TCEP, TCPP and TDCP in PU flexible foams for children's products and residential furniture, the European Chemicals Agency (ECHA) has started a public consultation, which may be extended to other applications. In addition, there is increasing pressure on flame retardants through the promotion of "flame retardant-free articles". In California, for example, there is a push for flame retardant-free insulation boards.

[0006] In view of recent developments, there is a need to develop new solutions that can not only improve the flame retardance and flame resistance of materials containing polyisocyanurates (PIRs) and / or polyurethanes (PURs), but also reduce smoke and toxicity. These alternative solutions and / or compounds should not rely on TCPP or organohalogen substances and should be suitable for use as additives in reactive formulations for the manufacture of materials containing polyisocyanurates (PIRs) and / or polyurethanes (PURs) without negatively affecting the properties of the finally obtained materials containing PIRs and / or PURs. The compounds are referred to herein as flame, smoke and toxicity reducing (FST) compounds.

[0007] Purpose of the Invention

[0008] It is an object of the present invention to provide materials comprising polyisocyanurates and / or polyurethanes (PIR / PUR) which have effective and improved flame retardant, smoke and / or toxicant properties (FST) when exposed to fire.

[0009] This objective is achieved by the presence of flame, smoke and / or toxicity (FST) reducing compounds in the PIR / PUR containing material.

[0010] Surprisingly, we have found that certain ethylenically unsaturated compounds, optionally in the presence of a free radical initiator, can be used as additives in PIR / PUR containing materials to reduce the flame, smoke and toxicity generated by the PIR / PUR containing materials when exposed to fire.

[0011] Definitions and terminology

[0012] In the context of the present invention, the following terms have the following meanings:

[0013] 1) The expression "isocyanate index" or "NCO index" or "index" refers to the ratio of NCO groups to isocyanate-reactive hydrogen atoms present in the formulation, given as a percentage:

[0014]

[0015] In other words, the NCO index expresses the percentage of isocyanate actually used in the formulation relative to the amount of isocyanate theoretically required to react with the amount of isocyanate-reactive hydrogen used in the formulation.

[0016] It should be observed that the isocyanate index used herein is considered from the perspective of the actual polymerization process for preparing the material involving isocyanate components and isocyanate-reactive components. In calculating the isocyanate index, any isocyanate groups consumed in the preliminary steps of preparing the modified polyisocyanates (including isocyanate derivatives known in the art as prepolymers) or any active hydrogen consumed in the preliminary steps (e.g., reaction with isocyanates to form modified polyols or polyamines) are not taken into account. Only free isocyanate groups and free isocyanate-reactive hydrogens (including water, if used) present at the actual polymerization stage are taken into account.

[0017] 2) The expressions "isocyanate-reactive compound" and "isocyanate-reactive hydrogen atoms" used in this document for calculating the isocyanate index refer to the sum of the active hydrogen atoms in the hydroxyl and amine groups present in the isocyanate-reactive compound; this means that for the purpose of calculating the isocyanate index in the actual polymerization process, one hydroxyl group is considered to contain one active hydrogen, one primary amine group is considered to contain one active hydrogen, and one water molecule is considered to contain two active hydrogens.

[0018] 3) The term "OH value" or "hydroxyl number" is a measure of the free hydroxyl content of a chemical substance, usually expressed in milligrams of potassium hydroxide (KOH), equivalent to the hydroxyl content of one gram of chemical substance (mg KOH / g). The analytical method used to determine the hydroxyl value traditionally involves acetylation of the free hydroxyl groups of the substance with acetic anhydride in pyridine solvent. After the reaction is complete, water is added and the remaining unreacted acetic anhydride is converted to acetic acid and determined by titration with potassium hydroxide.

[0019] 4) The term "average nominal hydroxyl functionality" (or simply "functionality") is used herein to mean the number average of the hydroxyl groups per molecule of a polyol or polyol composition, assuming that this is the number average functionality (number of active hydrogens per molecule) of the initiator or initiators used in its preparation, although in practice it will usually be somewhat less due to some terminal unsaturation.

[0020] 5) Unless otherwise stated, the term “average” refers to the numerical mean.

[0021] 6) As used herein, "trimerization catalyst" or "PIR catalyst" refers to a catalyst that can catalyze (promote) the formation of isocyanurate groups from polyisocyanates. This means that isocyanates can react with each other to form macromolecules with an isocyanurate structure (polyisocyanurate = PIR).

[0022] 7) As used herein, "polyurethane catalyst" or "PU catalyst" refers to a catalyst capable of catalyzing (promoting) the reaction of isocyanate groups with isocyanate-reactive groups, such as but not limited to the formation of polyurethane groups from polyisocyanates.

[0023] 8) As used herein, "polyisocyanurate-containing material" and "PIR-containing material" refer to materials containing more than 50 wt%, preferably more than 70 wt%, and most preferably more than 85 wt% of polyisocyanurate. PIR-containing materials are typically obtained using an isocyanate index above 180, preferably above 250.

[0024] 9) As used herein, "polyurethane-containing material" and "PUR-containing material" refer to materials containing more than 50 wt%, preferably more than 70 wt%, and most preferably more than 85 wt% polyurethane. PUR-containing materials are typically obtained using an isocyanate index below 180, preferably using an isocyanate index in the range of 80-180, and more preferably using an isocyanate index in the range of 90-150.

[0025] 10) "Functionality" generally refers to the functional groups present in a compound. For monomeric acrylate compounds, this refers to the number of polymerizable acrylate groups. For isocyanate-reactive compounds, this refers to the number of groups containing iso-reactive hydrogen atoms.

[0026] 11) When disclosed in combination with compounds according to the present invention having at least one unpolymerized ethylenically unsaturated moiety (also referred to herein as ethylenically unsaturated compounds), "number average equivalent weight" refers to the molar mass of the ethylenically unsaturated compound divided by the number of unsaturated moieties in the compound and expressed in g / mol of unsaturated moieties.

[0027] 12) "Free-rise density" means the density measured according to ISO 845 on a foam sample prepared under atmospheric conditions (in the presence of a blowing agent).

[0028] 13) "Ethylenically unsaturated compounds" or "compounds having ethylenically unsaturated moieties" are characterized as (restricted to) compounds wherein free radical polymerization (with or without the aid of a free radical initiator) is produced in the temperature range of 50°C up to 160°C, preferably in the range of 90°C up to 160°C at atmospheric pressure.

[0029] 14) "Free radical initiator" refers to a substance that can generate free radical species under mild conditions (e.g., by heating) and promote free radical reactions such as free radical polymerization. These substances usually have weak bonds with low bond dissociation energy. Typical examples are azo compounds, peroxide compounds such as tert-butyl perbenzoate (TBPB), and peroxides.

[0030] 15) “Activation temperature”, “Starting temperature” and “T 起始 (T onset")" refers to the temperature at which the ethylenically unsaturated compound starts to homopolymerize (free radical polymerization) and can be determined by differential scanning calorimetry (DSC).

[0031] 16) "Free radical polymerization" involves the formation of free radicals by decomposition of an initiator under light, temperature or redox reactions, whose reaction leads to the formation of a polymer network. The initiator can be the ethylenically unsaturated compound itself (autopolymerization) or optionally it can be another free radical forming compound added to the system (referred to herein as a free radical initiator). In the context of the present invention, free radical polymerization of acrylates is preferably initiated by temperature, such as exotherm of the reactive compounds in the manufacturing process of the material (e.g. foam) or exposure to fire, optionally further activated by a free radical initiator.

[0032] 17) “Reaction exotherm” and “T 反应 ” refers to the temperature generated by the exotherm of reaction during a process (e.g., a process for forming a foam comprising PUR and / or PIR according to the present invention).

[0033] 18) "DIN 4102-1" refers to a standard test that defines the fire performance classes of building materials and specifies the requirements and test methods for each class. When the fire performance of a material has been determined according to the standard, the material is divided into Class A and Class B building materials:

[0034] .

[0035] 19) “ISO 11925” and “EN ISO 11925-2” refer to standard tests for determining the flammability of products by direct impingement of a small flame at zero applied irradiance using vertically oriented test specimens.

[0036] 20) The "Kleinbrenner test" (also referred to herein as the B2 test) is a small flame test according to EN ISO 11925-2 where a small flame is placed on the bottom edge of a (foam) sample for 15 seconds. A piece of sample with predetermined dimensions (e.g. dimensions of 19 cm x 9 cm x 2.5 cm) is cut (see 2 in Figure 1) and all sample residues from the cut are removed using pressurized air. The test is performed in a test chamber with the test sample mounted vertically. After the foam is placed in a metal holder (see 1 in Figure 1), a 2 cm flame is placed at a 45° angle (see A in Figure 1) on the bottom of the foam to ignite it.

[0037]

[0038] Figure 1.

[0039] The flame is kept there for 15 seconds to observe whether the sample burns and how high it burns. The Kleinbrenner test device is also used herein to calculate the mass loss after flame exposure to quantify flame retardancy. Ideally, the test should be repeated 5 more times to obtain a reliable average value. The flame retardancy according to the present invention is measured as the weight percentage mass loss of the (PIR / PUR) material after flame exposure, and the weight loss is calculated based on the total weight of the (PIR / PUR) material before flame exposure.

[0040] 21) "Cone calorimetry test" refers to a test method for evaluating the reaction of materials to fire. The method follows the procedure given in the international standard ISO 5660-1:1993(E). In addition, measurements of smoke generation and toxic gas production can be made during the test. A test sample (foam) with predetermined dimensions (e.g. 100 mm x 100 mm) is subjected here to a specific irradiance level. The sample thickness should not exceed 50 mm, while the irradiance level is usually set to 25, 35 or 50 mW. The sample surface is heated and starts to release pyrolytic gases which are ignited.

[0041] 22) The term "room temperature" refers to a temperature of about 20°C, which means a temperature in the range of 18°C ​​to 25°C. Such temperatures would include 18°C, 19°C, 20°C, 21°C, 22°C, 23°C, 24°C and 25°C.

[0042] 23) Unless otherwise indicated, the weight percentage of a component in a composition (expressed as % weight or weight percent (%wt or wt%)) refers to the weight of the component relative to the total weight of the composition in which it is present and is expressed as a percentage.

[0043] 24) The terms "open cell" and "open cell content" refer to the open cell content of a foam material and are expressed as volume percent (vol %) based on the total volume of the foam and measured in accordance with ASTM D6226-10 (pycnometer open cell content).

[0044] Detailed description

[0045] The present invention will be described in terms of specific embodiments.

[0046] It should be noted that the term "comprising" used in the claims should not be interpreted as being limited to what is listed thereafter; it does not exclude other elements or steps. It should therefore be interpreted as specifying the presence of the features, steps or components mentioned, but not excluding the presence or addition of one or more other features, steps or components or groups thereof. Thus, the scope of the expression "a device comprising means A and B" should not be limited to a device consisting only of components A and B. This means that for the present invention, the only relevant components of the device are A and B.

[0047] Throughout this specification, reference is made to "one embodiment" or "an embodiment". Such reference indicates that a particular feature described in relation to the embodiment is included in at least one embodiment of the present invention. Thus, the phrases "in one embodiment" or "in an embodiment" appearing in various places throughout this specification are not necessarily all referring to the same embodiment, although they may be. Furthermore, it will be apparent to one of ordinary skill in the art that the particular features or characteristics may be combined in any suitable manner in one or more embodiments.

[0048] It should be understood that although preferred embodiments and / or materials have been discussed to provide embodiments in accordance with the present invention, various modifications or changes may be made without departing from the scope and spirit of the invention.

[0049] The present invention provides polyisocyanurate and / or polyurethane (PIR / PUR) containing materials having improved flame, smoke and / or toxicity retardant properties (FST), thereby avoiding or at least minimizing the use of prior art organohalogen flame retardants.

[0050] Surprisingly, it has been observed that the addition of well-defined and selected compounds with ethylenically unsaturated moieties is very suitable as a compound for flame, smoke and / or toxicity retardant properties (FST) in PIR / PUR containing materials. According to the present invention, these well-defined compounds are added to the reaction mixture to prepare the PIR / PUR containing material.

[0051] Thus, the present invention discloses a class of well-defined compounds with ethylenically unsaturated moieties which will act as flame retardant, smoke and / or toxicant (FST) compounds in materials comprising PIR / PUR. This class of well-defined compounds is selected such that these compounds with ethylenically unsaturated moieties will retain at least 10 wt.-% of unpolymerized ethylenically unsaturated moieties, based on the total weight of all compounds in the material comprising PIR / PUR which originate from said compounds with at least one ethylenically unsaturated moiety. This means that after the process for preparing the material comprising PIR / PUR, at least 10 wt.-% of the total amount of compounds with ethylenically unsaturated moieties added still have unpolymerized ethylenically unsaturated moieties.

[0052] According to an embodiment, the well-defined class of compounds with ethylenic unsaturation is selected such that after the process for preparing the PIR / PUR-containing material at least 10 wt.-%, preferably 10 wt.-% up to 90 wt.-%, more preferably 20 wt.-% up to 80 wt.-%, even more preferably 30 wt.-% up to 70 wt.-% of the total amount of compounds with ethylenic unsaturation added have unpolymerized ethylenic unsaturation.

[0053] The well-defined class of compounds having ethylenically unsaturated moieties preferably has an onset temperature (T 起始 ), which starting temperature is preferably higher than the highest reaction temperature (reaction exotherm (T 反应 )) Low 2℃ to high 40℃.

[0054] If a free radical initiator is used in addition to the compound having an ethylenically unsaturated moiety, the free radical polymerization onset temperature (T 起始 ) than the maximum reaction temperature (reaction exotherm (T 反应 )) Low preferably 2°C up to 40°C.

[0055] According to an embodiment, the free radical polymerization initiation temperature (T 起始 ) than the maximum reaction temperature (reaction exotherm (T 反应 )) is preferably 2°C to 40°C, more preferably 5°C to 30°C, and most preferably 5°C to 15°C. The starting temperature (T) of free radical polymerization of compounds having ethylenically unsaturated moieties with or without free radical initiators is 起始 ) than the maximum reaction temperature (reaction exotherm (T反应 ))Low 5℃ - 10℃, 10℃ - 15℃, 15℃ - 20℃, 20℃ - 25℃, 25℃ - 30℃, 30℃ - 35℃.

[0056] According to an embodiment, the amount of the compound having an ethylenically unsaturated moiety according to the present invention added to the reactive mixture for preparing the material containing PIR / PUR is in the range of 2 wt% up to 30 wt%, preferably 2 wt% up to 20 wt%, more preferably 2 wt% up to 15 wt%, based on the total weight of the reactive mixture for preparing the material of PIR / PUR. Examples of preferred amounts of the compound having an ethylenically unsaturated moiety added to the reactive mixture are 8 wt%, 9 wt%, 10 wt%, 11 wt% and 12 wt%, based on the total weight of the reactive mixture for making the PIR / PUR material.

[0057] Thus, the present invention discloses a PIR / PUR containing material with improved flame retardant, smoke and / or toxic barrier properties (FST), the material comprising at least 0.2 wt% of a compound having at least one unpolymerized ethylenically unsaturated moiety and optionally one or more free radical initiator compounds. When exposed to fire and / or elevated temperatures (typically above 200° C.), at least 0.2 wt% of the compound having at least one unpolymerized ethylenically unsaturated moiety will act as an agent for flame retardant, smoke and / or toxic barrier properties (FST).

[0058] According to an embodiment, the PIR / PUR-containing material according to the present invention having improved flame retardant, smoke and / or toxicant properties (FST) comprises 0.2 wt.-% up to 27 wt.-%, preferably 0.4 wt.-% up to 24 wt.-%, more preferably 0.6 wt.-% up to 18 wt.-%, of a compound having at least one unpolymerized ethylenically unsaturated moiety, based on the total weight of the PIR / PUR-containing material and optionally one or more free radical initiator compounds.

[0059] According to an embodiment, the PIR / PUR-containing material according to the present invention comprises:

[0060] at least 0.2% by weight of compounds having a number average equivalent weight of <160 g / mol, preferably <120 g / mol, and at least one unpolymerized ethylenically unsaturated moiety, based on the total weight of the PIR / PUR-containing material, and

[0061] - optionally 0.01 wt. % up to 1 wt. % of one or more free radical initiator compounds, based on the total weight of the PIR / PUR-containing material, and

[0062] According to an embodiment, the compound having at least one unpolymerized ethylenically unsaturated portion is selected from or derived from the following compounds: compounds having at least one ethylenically unsaturated portion and having a free radical polymerization onset temperature (T 起始 ) than the maximum reaction temperature (reaction exotherm (T 反应 )) is preferably 2°C to 40°C, more preferably 5°C to 30°C, most preferably 5°C to 15°C.

[0063] According to an embodiment, the total amount of compounds having at least one unpolymerized ethylenically unsaturated moiety and compounds derived from compounds having at least one ethylenically unsaturated moiety in the PIR / PUR-containing material is in the range of 2 wt.-% up to 30 wt.-%, preferably in the range of 2 wt.-% up to 20 wt.-%, more preferably in the range of 2 wt.-% up to 15 wt.-%, based on the total weight of the PIR / PUR-containing material.

[0064] According to an embodiment, the amount of the compound having an ethylenically unsaturated moiety according to the present invention added to the reactive mixture for preparing the PIR / PUR material is in the range of 2 wt.-% up to 30 wt.-%, based on the total weight of the reactive mixture and the PIR / PUR containing material made using the reactive mixture contains 0.2 wt.-% up to 27 wt.-%, based on the total weight of the PIR / PUR containing material, of the compound having at least one unpolymerized ethylenically unsaturated moiety, taking into account that after the process for preparing the PIR / PUR containing material, 10 wt.-% up to 90 wt.-% of the total amount of the compound having an ethylenically unsaturated moiety added will have unpolymerized ethylenically unsaturated moieties.

[0065] According to an embodiment, the amount of the compound having an ethylenically unsaturated moiety according to the present invention added to the reactive mixture for preparing the material comprising PIR / PUR is in the range of 2 wt.-% up to 30 wt.-%, based on the total weight of the reactive mixture and the material comprising PIR / PUR prepared using the reactive mixture contains 0.4 wt.-% up to 24 wt.-%, based on the total weight of the material comprising PIR / PUR, of the compound having at least one unpolymerized ethylenically unsaturated moiety, taking into account that after the process for preparing the material comprising PIR / PUR, 20 wt.-% up to 80 wt.-% of the total amount of the compound having an ethylenically unsaturated moiety added will have an unpolymerized ethylenically unsaturated moiety.

[0066] According to an embodiment, the amount of the compound having ethylenically unsaturated moieties according to the present invention added to the reactive mixture for preparing the material comprising PIR / PUR is in the range of 2 wt.-% up to 30 wt.-%, based on the total weight of the reactive mixture and the material comprising PIR / PUR prepared using the reactive mixture contains 0.6 wt.-% up to 21 wt.-%, based on the total weight of the material comprising PIR / PUR, of compounds having at least one unpolymerized ethylenically unsaturated moiety, taking into account that after the process for preparing the material comprising PIR / PUR, 30 wt.-% up to 70 wt.-% of the total amount of the compounds having ethylenically unsaturated moieties added will have unpolymerized ethylenically unsaturated moieties.

[0067] According to an embodiment, the amount of the compound having ethylenically unsaturated moieties according to the invention added to the reactive mixture for preparing the material comprising PIR / PUR is in the range of 2 wt.-% up to 30 wt.-%, preferably in the range of 2 wt.-% up to 20 wt.-%, more preferably in the range of 2 wt.-% up to 15 wt.-%, based on the total weight of the reactive mixture, and the material comprising PIR / PUR made using the reactive mixture contains 0.2 wt.-% up to 27 wt.-%, preferably 0.2 wt.-% up to 18 wt.-%, more preferably 0.2 wt.-% up to 13.5 wt.-%, based on the total weight of the material comprising PIR / PUR, of compounds having at least one unpolymerized ethylenically unsaturated moiety, taking into account that after the process for preparing the material comprising PIR / PUR, 10 wt.-% up to 90 wt.-% of the total amount of the compounds having ethylenically unsaturated moieties added will have unpolymerized ethylenically unsaturated moieties.

[0068] According to an embodiment, the PIR / PUR-containing material according to the invention comprises at least 0.2 wt.-%, based on the total weight of the PIR / PUR-containing material, of a compound having at least one unpolymerized ethylenically unsaturated moiety and optionally one or more free radical initiator compounds, wherein the number average equivalent weight of the compound having at least one unpolymerized ethylenically unsaturated moiety is <160 g / mol, preferably <120 g / mol.

[0069] According to an embodiment, the PIR / PUR-containing material according to the present invention comprises at least 0.2 wt.-%, based on the total weight of the PIR / PUR-containing material, of a compound having at least one unpolymerized ethylenically unsaturated moiety and optionally one or more free radical initiator compounds, wherein the compound having at least one unpolymerized ethylenically unsaturated moiety is a monomeric compound.

[0070] According to an embodiment, the PIR / PUR-containing material according to the present invention comprises at least 0.2 wt.-%, based on the total weight of the PIR / PUR-containing material, of a compound having at least one unpolymerized ethylenically unsaturated moiety and optionally one or more free radical initiator compounds, wherein the compound having at least one unpolymerized ethylenically unsaturated moiety is selected from acrylates, methacrylates, acrylic acid, methacrylic acid, allyl alcohol and / or maleic acid and derivatives or mixtures thereof.

[0071] According to an embodiment, the PIR / PUR-containing material according to the present invention comprises at least 0.2 wt.-%, based on the total weight of the PIR / PUR-containing material, of a compound having at least one unpolymerized ethylenically unsaturated moiety and optionally one or more free radical initiator compounds, wherein the compound having at least one unpolymerized ethylenically unsaturated moiety is selected from or derived from pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate (PETRA), ethylene glycol diacrylate (EGDA), hydroxyethyl acrylate (HEA), diethylene glycol diacrylate (DEGDA), hydroxyethyl methacrylate (HEMA), ethylene glycol dimethacrylate (EGDMA) and diethylene glycol dimethacrylate (DEGDMA), and mixtures thereof.

[0072] According to an embodiment, the PIR / PUR-containing material according to the invention comprises at least 0.2 wt.-%, based on the total weight of the PIR / PUR material, of a compound having at least one unpolymerized ethylenically unsaturated moiety and a free radical initiator compound selected from the group consisting of benzoyl peroxide, tert-butyl peroxybenzoate (Luperox ® P), di-tert-butyl peroxide (Luperox ® DI), tert-butyl hydroxyperoxide (Luperox ® TBH 70X) and mixtures thereof.

[0073] According to a preferred embodiment, the compound having at least one ethylenically unsaturated moiety is selected from PETRA (Penta Erythritol Tetra Acrylate, see formula I), which is a tetrafunctional acrylate having no reactive OH groups and a molecular weight of 352 g / mol (equivalent molecular weight of 88 g / eq).

[0074] .

[0075] According to another preferred embodiment, the compound having at least one ethylenically unsaturated moiety is selected from PETRA (PentaErythritol TetraAcrylate, see formula I) and the free radical initiator used in combination with PETRA is selected from Luperox® DI (tert-butyl peroxide, see formula II), which has a half-life of 10 hours at a temperature of 121° C. or Luperox® DI (tert-butyl peroxide, see formula II). ® P (tert-butyl peroxybenzoate, see formula III), which has a half-life of 10 hours at a temperature of 103°C.

[0076]

[0077]

[0078] According to a preferred embodiment, the compound having at least one ethylenically unsaturated moiety also comprises at least one isocyanate reactive moiety. During the process for preparing the PIR / PUR-containing material, the isocyanate reactive moiety can react with the isocyanate groups in the polyisocyanate compound and the compound having at least one ethylenically unsaturated moiety will be incorporated (crosslinked) into the PIR / PUR matrix of the PIR / PUR-containing material.

[0079] According to an embodiment, the PIR / PUR-containing material according to the present invention comprises at least 0.2 wt.-%, based on the total weight of the PIR / PUR-containing material, of a compound having at least one unpolymerized ethylenically unsaturated moiety, and optionally one or more free radical initiator compounds, wherein the compound having at least one unpolymerized ethylenically unsaturated moiety comprises at least 1, preferably 2 up to 8 unpolymerized ethylenically unsaturated moieties.

[0080] According to an embodiment, the PIR / PUR-containing material according to the invention comprises at least 0.2 wt.-%, based on the total weight of the PIR / PUR-containing material, of a compound having at least one unpolymerized ethylenically unsaturated moiety, and optionally one or more free radical initiator compounds, wherein the compound having at least one unpolymerized ethylenically unsaturated moiety is linked to the PIR / PUR matrix of the PIR / PUR-containing material. The linkage of the compound having at least one unpolymerized ethylenically unsaturated moiety is formed during the process for preparing the PIR / PUR-containing material, for example during foaming, the reaction taking place between the isocyanate-reactive groups present in the compound having at least one unpolymerized ethylenically unsaturated moiety and the isocyanate.

[0081] According to an embodiment, the PIR / PUR-containing material according to the present invention comprises at least 0.2 wt.-%, based on the total weight of the PIR / PUR-containing material, of a compound having at least one unpolymerized ethylenically unsaturated moiety and optionally one or more free radical initiator compounds, wherein the compound having at least one unpolymerized ethylenically unsaturated moiety has a boiling point at atmospheric pressure of above 150° C., preferably above 200° C.

[0082] According to an embodiment, the PIR / PUR-containing material according to the invention comprises at least 0.2% by weight of a compound having at least one unpolymerized ethylenically unsaturated moiety and at least 0.01% by weight up to 1% by weight, preferably 0.01% by weight up to 0.5% by weight of one or more free radical initiator compounds, based on the total weight of the PIR / PUR-containing material. Preferably, the free radical initiator is selected from peroxides, preferably from peroxides selected from benzoyl peroxide, tert-butyl peroxide and tert-butyl perbenzoate, based on the total weight of the PIR / PUR-containing material. The use of free radical initiators that are active at too low a temperature (e.g. too close to room temperature) should be avoided, because, in addition to the above handling safety issues, it may also lead to poor foam flowability.

[0083] According to an embodiment, the PIR / PUR-containing material according to the invention is a polyisocyanurate (PIR)-containing foam, preferably a rigid polyisocyanurate (PIR)-containing foam.

[0084] According to an embodiment, the PIR / PUR-containing material according to the present invention is a polyurethane (PUR)-containing foam, preferably a flexible or semi-flexible polyurethane (PUR)-containing foam.

[0085] According to an embodiment, the PIR / PUR-containing material according to the invention is a PIR / PUR-containing coating or an adhesive.

[0086] According to an embodiment, the PIR / PUR-containing material according to the invention is a thermoplastic polyurethane (TPU) elastomer.

[0087] The present invention further discloses a method for improving the flame retardant, smoke retardant and / or poison retardant properties (FST) of a material containing polyisocyanurate and / or polyurethane (PIR / PUR), the method comprising combining and mixing at least the following ingredients to form a material containing PIR / PUR, including:

[0088] - a polyisocyanate composition comprising one or more polyisocyanate compounds; and

[0089] - an isocyanate-reactive composition comprising one or more isocyanate-reactive compounds; and

[0090] - at least one catalyst compound selected from trimerization (PIR) catalysts and / or polyurethane (PUR) forming catalysts, and

[0091] at least one compound having at least one ethylenically unsaturated moiety and a number average equivalent weight <160 g / mol, preferably <120 g / mol, and

[0092] - optionally one or more free radical initiator compounds, and

[0093] - optionally a blowing agent; and

[0094] -Optionally one or more surfactants, one or more flame retardants, one or more antioxidants or a combination thereof

[0095] Characterized in that the amount of the compound having at least one ethylenically unsaturated moiety is at least 2% by weight, based on the total weight of all ingredients used to prepare the material containing PIR / PUR and the free radical polymerization start temperature (T 起始 ) than the maximum reaction temperature (reaction exotherm (T 反应 )) is preferably 2°C to 40°C, more preferably 5°C to 30°C, most preferably 5°C to 15°C.

[0096] According to an embodiment, the free radical polymerization starting temperature (T 起始 ) than the maximum reaction temperature (reaction exotherm (T 反应 )) is preferably 2°C to 40°C, more preferably 5°C to 30°C, most preferably 5°C to 15°C.

[0097] According to an embodiment, the amount of the compound having at least one ethylenically unsaturated moiety used to prepare the material containing PIR / PUR according to the present invention is in the range of 2 wt% up to 30 wt%, preferably in the range of 2 wt% up to 20 wt%, more preferably in the range of 2 wt% up to 15 wt%, based on the total weight of all ingredients used to make the material containing PIR / PUR. Examples of preferred amounts of the compound having an ethylenically unsaturated moiety added to the reactive mixture are 8 wt%, 9 wt%, 10 wt%, 11 wt% and 12 wt%, based on the total weight of the reactive mixture used to prepare the material containing PIR / PUR.

[0098] According to an embodiment, the amount of the compound having ethylenically unsaturated moieties according to the invention added to the reactive mixture for preparing the material comprising PIR / PUR is in the range of 2 wt.-% up to 30 wt.-%, based on the total weight of the reactive mixture and the material comprising PIR / PUR prepared using the reactive mixture contains 0.2 wt.-% up to 27 wt.-%, based on the total weight of the PIR / PUR material, of the compound having at least one unpolymerized ethylenically unsaturated moiety, taking into account that after the process for preparing the PIR / PUR material, 10 wt.-% up to 90 wt.-% of the total amount of the compound having ethylenically unsaturated moieties added will have unpolymerized ethylenically unsaturated moieties.

[0099] According to an embodiment, the amount of the compound having an ethylenically unsaturated moiety according to the present invention added to the reactive mixture for preparing the material comprising PIR / PUR is in the range of 2 wt.-% up to 30 wt.-%, based on the total weight of the reactive mixture and the material comprising PIR / PUR prepared using the reactive mixture contains 0.4 wt.-% up to 24 wt.-%, based on the total weight of the material comprising PIR / PUR, of the compound having at least one unpolymerized ethylenically unsaturated moiety, taking into account that after the process for preparing the material comprising PIR / PUR, 20 wt.-% up to 80 wt.-% of the total amount of the compound having an ethylenically unsaturated moiety added will have an unpolymerized ethylenically unsaturated moiety.

[0100] According to an embodiment, the amount of the compound having ethylenically unsaturated moieties according to the invention added to the reactive mixture for preparing the material comprising PIR / PUR is in the range of 2 wt.-% up to 30 wt.-%, based on the total weight of the reactive mixture and the PIR / PUR material prepared using the reactive mixture contains 0.6 wt.-% up to 21 wt.-%, based on the total weight of the material comprising PIR / PUR, of compounds having at least one unpolymerized ethylenically unsaturated moiety, taking into account that after the process for preparing the material comprising PIR / PUR, 30 wt.-% up to 70 wt.-% of the total amount of the compounds having ethylenically unsaturated moieties added will have unpolymerized ethylenically unsaturated moieties.

[0101] According to an embodiment, the amount of the compound having ethylenically unsaturated moieties according to the invention added to the reactive mixture for preparing the material comprising PIR / PUR is in the range of 2 wt.-% up to 30 wt.-%, preferably in the range of 2 wt.-% up to 20 wt.-%, more preferably in the range of 2 wt.-% up to 15 wt.-%, based on the total weight of the reactive mixture, and the material comprising PIR / PUR prepared using the reactive mixture contains 0.2 wt.-% up to 27 wt.-%, preferably 0.2 wt.-% up to 18 wt.-%, more preferably 0.2 wt.-% up to 13.5 wt.-%, based on the total weight of the material comprising PIR / PUR, of compounds having at least one unpolymerized ethylenically unsaturated moiety, taking into account that after the process for preparing the material comprising PIR / PUR, 10 wt.-% up to 90 wt.-% of the total amount of the compounds having ethylenically unsaturated moieties added will have unpolymerized ethylenically unsaturated moieties.

[0102] According to an embodiment, the PIR / PUR containing material is a polyisocyanurate (PIR) containing material, preferably a rigid foam containing polyisocyanurate (PIR), and the method for forming the PIR containing material is carried out at an isocyanate index of 180 or more, more preferably an isocyanate index above 250 and the catalyst compound is selected from at least one trimerization catalyst.

[0103] According to an embodiment, the PIR / PUR containing material is a polyurethane (PUR) containing material, preferably a polyurethane (PUR) containing foam, and the method for forming the PUR containing material is carried out at an isocyanate index in the range of 80-180, more preferably at an isocyanate index in the range of 90-150 and the catalyst compound is selected from at least one polyurethane catalyst.

[0104] According to an embodiment, the PIR / PUR-containing material has an apparent density measured according to ISO 845 < 200 kg / m 3 And a PIR / PUR-containing foam having an open cell content of less than 50% by weight, preferably less than 30% by weight, more preferably less than 20% by weight, the open cell content being calculated by volume based on the total volume of the foam and measured according to ASTM D6226-10 (open cell content by pycnometer).

[0105] According to an embodiment, the polyisocyanate compound according to the present invention is selected from organic polyisocyanate compounds containing multiple isocyanate groups, including aliphatic isocyanates such as hexamethylene diisocyanate, more preferably aromatic isocyanates such as m- and p-phenylene diisocyanate, toluene-2,4- and 2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, chlorophenyl-2,4-diisocyanate, naphthyl-1,5-diisocyanate, diphenyl-4,4'-diisocyanate, 4,4'-diisocyanate-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate and diphenyl ether diisocyanate, alicyclic diisocyanates such as cyclohexane-2,4- and 2,3-diisocyanate, 1-methylcyclohexyl-2,4- and 2,6-diisocyanate. 6-diisocyanate and mixtures thereof as well as bis-(isocyanatocyclohexyl-)methane and triisocyanates such as 2,4,6-triisocyanatotoluene and 2,4,4'-triisocyanatodiphenyl ether.

[0106] According to an embodiment, the polyisocyanate compound may be selected from a mixture of polyisocyanates. For example, a mixture of toluene diisocyanate isomers, such as a commercial mixture of 2,4- and 2,6-isomers, and a mixture of diisocyanates and higher polyisocyanates produced by phosgenation of aniline / formaldehyde condensates. Such mixtures are well known in the art and include crude phosgenation products containing a mixture of methylene-bridged polyphenyl polyisocyanates, including diisocyanates, triisocyanates and higher polyisocyanates and any phosgenation byproducts.

[0107] Preferred polyisocyanate compositions of the invention are those in which the polyisocyanate is an aromatic diisocyanate or a higher functionality polyisocyanate, in particular a crude mixture of methylene-bridged polyphenyl polyisocyanates containing diisocyanates, triisocyanates and higher functionality polyisocyanates. Methylene-bridged polyphenyl polyisocyanates (e.g. methylene diphenyl diisocyanate, abbreviated to MDI) are well known in the art and have the general formula I, wherein n is 1 or more and represents an average value greater than 1 in the case of a crude mixture. They are prepared by phosgenating a corresponding mixture of polyamines obtained by condensation of aniline and formaldehyde.

[0108]

[0109] Other suitable polyisocyanate compounds may include isocyanate-terminated prepolymers prepared by reacting an excess of diisocyanate or a higher functionality polyisocyanate with a hydroxyl-terminated polyester or hydroxyl-terminated polyether and products obtained by reacting an excess of diisocyanate or a higher functionality polyisocyanate with a monomeric polyol or a mixture of monomeric polyols, such as ethylene glycol, trimethylolpropane or butanediol. A preferred class of isocyanate-terminated prepolymers is an isocyanate-terminated prepolymer of a crude mixture of methylene-bridged polyphenyl polyisocyanates containing diisocyanates, triisocyanates and higher functionality polyisocyanates.

[0110] According to an embodiment, the polyisocyanate compound is selected from toluene diisocyanate, methylene diphenyl diisocyanate or a polyisocyanate composition comprising methylene diphenyl diisocyanate or a mixture of such polyisocyanates.

[0111] According to an embodiment, one or more isocyanate reactive compounds include any of those known in the art for preparing rigid foams containing polyisocyanurates and / or polyurethanes. Particularly important for preparing rigid foams are polyols and polyol mixtures having an average OH value of 50-1000 mg KOH / g, especially 150-700 mg KOH / g, and a hydroxyl (OH) functionality of 2-8, especially 3-8. Suitable polyols have been fully described in the prior art, including polyether-based polyols, which are the reaction products of alkylene oxides such as ethylene oxide and / or propylene oxide with initiators containing 2 to 8 active hydrogen atoms per molecule. Suitable initiators include: polyols, such as glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol and sucrose; polyamines, such as ethylenediamine, toluenediamine (TDA), diaminodiphenylmethane (DADPM) and polymethylene polyphenylene polyamines; and amino alcohols, such as ethanolamine and diethanolamine; and mixtures of such initiators. Other suitable polyols include polyester-based polyols obtained by condensing appropriate proportions of diols and higher functionality polyols with dicarboxylic acids or polycarboxylic acids. Still further suitable polymeric polyols include hydroxyl-terminated polythioethers, polyamides, polyesteramides, polycarbonates, polyacetals, polyolefins and polysiloxanes.

[0112] The amount of polyisocyanate compound(s) and isocyanate-reactive compound(s) to be reacted will depend on the nature of the PIR / PUR-containing material to be produced and can be readily determined by one skilled in the art.

[0113] According to an embodiment, the material comprising PIR / PUR is a foam material and the blowing agent may be selected from isobutylene, dimethyl ether, water, methylene chloride, acetone, chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), hydrofluoroolefins (HFOs) and hydrocarbons such as pentane. The amount of blowing agent used may vary based on, for example, the intended use and application of the foam product and the desired foam hardness and density. The blowing agent may be present in an amount of 0.5 to 60, more preferably 1 to 45 parts by weight (pbw) per 100 parts by weight of the isocyanate-reactive compound (polyol).

[0114] According to an embodiment, the PIR / PUR containing material is a foam material, and the blowing agent comprises / contains water, and the amount of water is preferably limited to an amount of up to 15 pbw.

[0115] According to an embodiment, the catalyst compound should be present in the reactive composition in a catalytically effective amount, preferably, the catalyst compound is present in an amount such that the ratio of the number of catalyst equivalents to the number of isocyanate equivalents is 0.001 to 0.4, preferably 0.01 to 0.26, or 0.01 to 0.24, or 0.02 to 0.2.

[0116] According to an embodiment, one or more polyurethane catalyst compounds suitable for use herein include, but are not limited to, metal salt catalysts such as organic tin, and amine compounds such as triethylenediamine (TEDA), N-methylimidazole, 1,2-dimethylimidazole, N-methylmorpholine, N-ethylmorpholine, triethylamine, N,N'-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, 2,4,6-tris(dimethylaminomethyl)phenol, N-methyldicyclohexylamine, pentamethyldipropylenetriamine, N-methyl-N'-(2-dimethylamino)-ethyl-piperazine, tributylamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexylamine, pentamethyldipropylene-triamine, triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl)ether, tris(3-dimethylamino)propylamine, or acid-blocked derivatives thereof, and any mixtures thereof. The catalyst compound should be present in the reactive composition in a catalytically effective amount.

[0117] According to an embodiment, one or more polyisocyanurate catalyst compounds (trimerization catalysts) suitable for use herein include, but are not limited to, quaternary ammonium hydroxides and salts, alkali metal and alkaline earth metal hydroxides, alkoxides and carboxylates, such as potassium acetate and potassium 2-ethylhexanoate, certain tertiary amines and non-alkaline metal carboxylates. The catalyst compound should be present in the reactive composition in a catalytically effective amount.

[0118] According to embodiments, additional prior art flame retardant compounds such as triethyl phosphate or expandable graphite may be added to the reactive composition used to make the PIR / PUR containing material.

[0119] There are many different orders of adding and mixing the ingredients to form a PIR / PUR containing material. One skilled in the art will recognize that varying the order of addition of the compounds is within the scope of the present invention.

[0120] According to embodiments, at least one compound having at least one ethylenically unsaturated moiety and optionally one or more free radical initiator compounds may be added to the isocyanate composition prior to combining and mixing the isocyanate composition with the isocyanate-reactive composition.

[0121] According to embodiments, at least one compound having at least one ethylenically unsaturated moiety and optionally one or more free radical initiator compounds may be added to the isocyanate-reactive composition prior to combining and mixing the isocyanate composition with the isocyanate composition.

[0122] According to embodiments, the at least one compound having at least one ethylenically unsaturated moiety and optionally one or more free radical initiator compounds may be added to the reactive composition as separate streams from the isocyanate composition and the isocyanate-reactive composition.

[0123] According to an embodiment, the PIR / PUR-containing material according to the invention can be used for thermal insulation, acoustic insulation and / or structural panels, such as building insulation foam or appliance insulation foam in insulation panels. Example

[0124] Chemicals used :

[0125] -Daltolac ® R 517: Polyether polyol from Huntsman.

[0126] -Daltolac ® R 251: Polyether polyol from Huntsman.

[0127] -Daltolac ® R 630: Polyether polyol from Huntsman.

[0128] -Daltolac ® XR 159: Polyether polyol from Huntsman.

[0129] -Cyclopentane, from Merck, Germany.

[0130] -n-Pentane, from Merck, Germany.

[0131] -Jeffcat ® BDMA: Amine catalyst from Huntsman.

[0132] -Jeffcat ® ZF22: Amine catalyst from Huntsman.

[0133] -Jeffcat ® TR90: Amine catalyst from Huntsman.

[0134] -K-ZERO 3000: Potassium catalyst in DMSO from Momentive Performance Materials.

[0135] -TEP: triethyl phosphate from Sigma-Aldrich.

[0136] - Neopolyol 240 FR: an aromatic polyester polyol from Huntsman.

[0137] -Tegostab ® B 8484: Silicone surfactant foam stabilizer from Evonic, Germany.

[0138] -Tegostab ® B 8485: Silicone surfactant foam stabilizer from Evonic, Germany.

[0139] -Tegostab ® B 8494: Silicone surfactant foam stabilizer from Evonic, Germany.

[0140] - SR 444D: Pentaerythritol triacrylate (PETA) from Sartomer.

[0141] - SR 295: Pentaerythritol tetraacrylate (PETRA) from Sartomer.

[0142] - Hydroxyethyl acrylate (HEA) from Sigma-Aldrich.

[0143] - SR 351: trimethylolpropane triacrylate (TTA) from Sartomer.

[0144] - Hydroxyethyl methacrylate (HEMA) from Sigma-Aldrich.

[0145] - SR 350D: trimethylolpropane trimethacrylate (TTMA) from Sartomer.

[0146] -Genomer ® 4302: Isocyanurate trifunctional acrylate from RAHN.

[0147] -Genomer ® 4622: Aromatic hexafunctional urethane acrylate from RAHN.

[0148] -Genomer ® 4691: Aliphatic hexafunctional urethane acrylate from RAHN.

[0149] -Allyl alcohol, from Merck.

[0150] -MA: Maleic anhydride, from Merck, Germany.

[0151] -SA: Succinic anhydride from Merck, Germany.

[0152] -TATA: 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 97% from Sigma-Aldrich.

[0153] -Lactic acid: DL-lactic acid (88% in water) from Sigma-Aldrich.

[0154] -Luperox ® P: tert-Butyl perbenzoate from Sigma-Aldrich.

[0155] -Luperox ® Di: Di-tert-butyl peroxide from Sigma-Aldrich.

[0156] -Luperox ® TBH70X: tert-Butyl hydroperoxide (70% in water) from Sigma-Aldrich.

[0157] -Benzoyl peroxide: dibenzoyl peroxide (75% in water) from Sigma-Aldrich.

[0158] -S5025 (Suprasec ® 5025): polymeric methylene diphenyl isocyanate (MDI) from Huntsman.

[0159] Manufacturing of polyurethane (PUR) foam

[0160] Polyurethane foams were produced under free foaming conditions by mixing a polyol mixture (previously prepared, including all chemicals listed in the table except isocyanate) and isocyanate under high shear for 5 seconds using a Heidolph mixer (~2500 rpm). A thermocouple with a diameter of 1.5 mm was placed in the middle of the foaming mold, 5 cm from the bottom, to record the maximum exotherm temperature (T) of the foaming process for the PUR formulation without the addition of ethylenically unsaturated compounds. 反应 ) (Comparative Examples 1 & 2). All PUR foams were stored overnight in a fume hood before cutting and characterization.

[0161] Synthesis of MDI-HEA and MDI-PETA

[0162] MDI was placed in a three-necked round flask equipped with a mechanical stirrer and nitrogen purge, and 3 ppm of thionyl chloride was added as a trimerization inhibitor. The flask was heated to 70°C in an oil bath, and olefinically unsaturated compounds containing iso-reactive groups (HEA and PETA) were added dropwise over 30 minutes. The contents of the flask were kept at 70°C for 1 hour, and the product was cooled to room temperature and stored in a closed container.

[0163] Kleinbrenner test (B2 test)

[0164] According to EN ISO 11925-2, the Kleinbrenner test is used to compare the flame retardant (FR) properties of different samples, where a small flame is placed against the bottom edge of the foam sample for 15 seconds. A piece of foam measuring 19cm x 9cm x 2.5cm is cut (see 2 in Figure 1). The test is performed in a test chamber where the test sample is mounted vertically. After the foam is placed in a metal holder (see 1 in Figure 1), a 2cm flame is placed at a 45° angle (see A in Figure 1) at the bottom of the foam to ignite it.

[0165] The flame was held there for 15 seconds to see if the foam burned and how high it burned. To compare the flame retardant FR performance of the different systems, the Kleinbrenner test was used and the foam samples were weighed before and after the test to determine the percentage of mass loss as an indicator of flame retardant FR performance. Lower mass loss indicates better flame retardant performance.

[0166] The polymerization initiation (T) of ethylenically unsaturated compounds was determined by DSC. onset (T 起始 )) :

[0167] In order to determine the polymerization start (T onset), constant heating rate differential scanning calorimetry (DSC) was performed. DSC investigations were performed using a Q2000 TA instrument. The ethylenically unsaturated compound was premixed with a free radical initiator (if used), and then 3-5 mg of the sample was sealed in a sealed aluminum pan and heated from 0 to 280 °C at a heating rate of 10 °C / min.

[0168] Determination of the conversion of olefinically unsaturated compounds by DSC (α) :

[0169] In order to determine the amount of unreacted ethylenically unsaturated compounds (also referred to herein as compounds with unpolymerized ethylenically unsaturated moieties) in PUR foams, isothermal differential scanning calorimetry (DSC) was performed. The DSC investigations were performed using a Q2000TA instrument. 3 mg (±5%) of ground sample were sealed in a sealed aluminum pan and heated to 70 °C at a heating rate of 60 °C / min and kept isothermal for 15 seconds. The temperature of the DSC furnace was then equilibrated at 230 °C and kept isothermal for 20 minutes. The positive heat flow values ​​were numerically integrated to estimate the total residual exotherm. The conversion was calculated using the following formula:

[0170] Equation 1

[0171] Where α is the conversion of ethylenically unsaturated compounds (EUM), RE S is the residual exotherm of the sample, RE ref is the residual exotherm of the reference foam (same formulation, without added ethylenically unsaturated compound (EUM)), C EUMs is the weight % of ethylenically unsaturated compounds (EUM), and RE EUMs Pure ethylenically unsaturated compounds (EUM) plus 1 wt% Luperox ® The remaining exotherm of Di.

[0172] A conversion rate (α) of 60% means that 40% of the ethylenically unsaturated compounds, based on the total amount of the ethylenically unsaturated compounds added to the reactive composition, are unpolymerized ethylenically unsaturated compounds.

[0173] Examples 1-25 according to the present invention and comparative example 1

[0174] Table 1 summarizes the reactive compositions used to make Examples 1-12 according to the present invention and Comparative Example 1 and the amounts of the ingredients used in parts by weight (pbw) as well as the Kleinbrener (B2) mass loss percentage, THR (total heat release), PHRR (peak heat release rate) and TSP (total smoke generation) from cone calorimetry, T 反应(Comparative Example 1) and T of ethylenically unsaturated compound (EUM) plus initiator (if used) 起始 .

[0175] .

[0176] Table 2 summarizes the reactive compositions used to make Examples 13-25 according to the invention and Comparative Example 1 and the amounts of the ingredients used in parts by weight (pbw) as well as the Kleinbrener (B2) mass loss percentage, T of the base formulation 反应 (Comparative Example 1) and T of ethylenically unsaturated compound (EUM) plus initiator (if used) 起始 .

[0177]

[0178] Examples 26-27 according to the present invention and Comparative Example 2

[0179] Table 3 summarizes the reactive compositions used to make Examples 26 and 27 according to the invention and Comparative Example 2 and the amounts of the ingredients used in parts by weight (pbw) as well as the Kleinbrener (B2) mass loss percentage, T 反应 (Comparative Example 2) and T of ethylenically unsaturated compound (EUM) plus initiator (if used) 起始 .

[0180] Table 3

[0181] Chemicals (pbw) Comparative Example 2 Embodiment 26 Embodiment 27 Daltolac R 517 30.5 30.5 30.5 Daltolac R 251 21 21 21 Daltolac R 630 21 21 21 Daltolac XR 159 16 16 16 Jeffcat BDMA 1.5 1.5 1.5 Jeffcat ZF 22 0.1 0.1 0.1 Jeffcat TR 90 0.1 0.1 0.1 TEP 6 6 6 Tegostab B 8485 0.5 0.5 0.5 Tegostab B 8494 1 1 1 water 2.3 2.3 2.3 Cyclopentane 19.5 19.5 19.5 S 48.47 - - MA - 48.47 48.47 <![CDATA[Luperox ® Of]]> - - 0.29 Suprasec 5025 181.45 181.45 181.45 Iso Index 133 133 133 Quality loss (%) 17.0 9.2 8.4 <![CDATA[T 反应 (°C)]]> 154 154 154 <![CDATA[T 起始 ]]> - NA NA

[0182] NA = not analyzed.

[0183] As can be clearly seen from Table 1, all investigated acrylates (Examples 1-12) reduced the mass loss in B2 both in the presence and absence of thermal initiator compared to Comparative Example 1. In the case of PETRA, various supported free radical initiators (Examples 1-4) were tested and the conversion (α) evaluated, with the best results (lowest mass loss in the B2 test) being those in which T 起始 T 反应 (0.1% Luperox ® Di) was obtained in a formulation 5°C lower, with a conversion equal to ca. 59% (meaning that 41% of unpolymerized PETRA remained, based on the total amount of PETRA added to the reactive formulation). For all other acrylates used here (Examples 5-12), 0.1% Luperox ®Di reduced the mass loss of B2. Cone calorimetry results also showed significant improvements in total smoke production (TSP) and peak heat release rate (PHRR).

[0184] It can be clearly seen from Table 2 that at 0.1% Luperox ® In the presence of Di, all investigated ethylenically unsaturated compounds reduced the mass loss of B2, whereas in the case of TATA, in the absence of free radical initiators, the mass loss of B2 decreased compared to that of T 反应 Compared with the significantly higher T 起始 (216°C vs. 130°C) - It is only available in Luperox ® The flame retardant properties are improved in the presence of Di, thereby 起始 Lower to closer to T 反应 (130℃) 136℃.

[0185] Table 3 shows that by replacing succinic anhydride (SA) with maleic anhydride (MA), which has a similar structure to SA plus olefinic unsaturation, the mass loss of B2 is reduced from 17% in Comparative Example 2 to ca. 9% in Example 26. In addition, the thermal initiator Luperox ® Di further reduced the mass loss to ca. 8% for Example 27.

Claims

1. A material comprising polyisocyanurate and / or polyurethane (PIR / PUR) having at least improved flame retardancy according to ISO 11925-2 using the Kleinbrenner test and measuring the weight percent mass loss of the PIR / PUR material after exposure to flame, calculated based on the total weight of the PIR / PUR material before exposure to flame, said material comprising: - at least 0.2% by weight, based on the total weight of the PIR / PUR-containing material, of ethylenically unsaturated compounds having a number average equivalent weight of <160 g / mol and having at least one unpolymerized ethylenically unsaturated moiety, and 0.01 wt.-% up to 0.1 wt.-% of one or more free radical initiator compounds, based on the total weight of the PIR / PUR-containing material, wherein the free radical initiator compound is selected from benzoyl peroxide, tert-butyl peroxide, tert-butyl hydroperoxide and / or tert-butyl perbenzoate, The compound characterized in that it has at least one unpolymerized ethylenically unsaturated portion is selected from or derived from the following compounds: compounds having at least one ethylenically unsaturated portion and having a free radical polymerization starting temperature (T 起始 ) is greater than the maximum reaction temperature (T 反应 ) from 2°C to 40°C, wherein the compound having at least one unpolymerized ethylenically unsaturated portion is selected from maleic acid and derivatives or mixtures, and characterized in that after the process for preparing a PIR / PUR-containing material, from 10% by weight to 90% by weight of the total amount of ethylenically unsaturated compounds used to prepare the PIR / PUR-containing material has unpolymerized ethylenically unsaturated portions.

2. The material comprising polyisocyanurate and / or polyurethane (PIR / PUR) according to claim 1, wherein the compound having at least one unpolymerized ethylenically unsaturated portion is selected from or derived from the following compounds: compounds having at least one ethylenically unsaturated portion and having a free radical polymerization onset temperature (T 起始 ) than the maximum reaction temperature (T 反应 ) Low 5℃ to high 30℃.

3. A material comprising polyisocyanurate and / or polyurethane (PIR / PUR) according to claim 1 or 2, wherein the total amount of compounds having at least one unpolymerized ethylenically unsaturated moiety and compounds derived from compounds having at least one ethylenically unsaturated moiety in the material comprising PIR / PUR is in the range of 2 wt.-% up to 30 wt.-%, based on the total weight of the material comprising PIR / PUR.

4. The polyisocyanurate and / or polyurethane (PIR / PUR) containing material according to claim 1 or 2, wherein the amount of the compound having at least one unpolymerized ethylenically unsaturated moiety is in the range of 0.2 wt.-% up to 27 wt.-%, based on the total weight of the PIR / PUR containing material.

5. The polyisocyanurate- and / or polyurethane-containing (PIR / PUR) material according to claim 1 or 2, wherein the compound having at least one unpolymerized ethylenically unsaturated moiety is selected from monomeric compounds.

6. The polyisocyanurate and / or polyurethane (PIR / PUR) containing material according to claim 1 or 2, wherein the compound having at least one unpolymerized ethylenically unsaturated moiety contains 2 up to 8 unpolymerized ethylenically unsaturated moieties.

7. A material comprising polyisocyanurates and / or polyurethanes (PIR / PUR) according to claim 1 or 2, wherein the compound having at least one unpolymerized ethylenically unsaturated portion and / or a compound derived from a compound having at least one ethylenically unsaturated portion is derived from a compound comprising at least one isocyanate-reactive portion.

8. The polyisocyanurate and / or polyurethane (PIR / PUR) containing material according to claim 1 or 2, wherein the compound having at least one unpolymerized ethylenically unsaturated moiety has a boiling point above 150°C at atmospheric pressure.

9. The material comprising polyisocyanurate and / or polyurethane (PIR / PUR) according to claim 1, wherein the number average equivalent weight of the compounds is <120 g / mol.

10. The material comprising polyisocyanurate and / or polyurethane (PIR / PUR) according to claim 4, wherein the compound having at least one unpolymerized ethylenically unsaturated portion is selected from or derived from the following compounds: compounds having at least one ethylenically unsaturated portion and having a free radical polymerization onset temperature (T 起始 ) than the maximum reaction temperature (T 反应 ) Low 5℃ to high 30℃.

11. The material comprising polyisocyanurate and / or polyurethane (PIR / PUR) according to claim 2, wherein the compound having at least one unpolymerized ethylenically unsaturated portion is selected from or derived from the following compounds: compounds having at least one ethylenically unsaturated portion and having a free radical polymerization onset temperature (T 起始 ) than the maximum reaction temperature (T 反应 ) Low 5℃ to high 15℃.

12. The polyisocyanurate and / or polyurethane (PIR / PUR) containing material according to claim 3, wherein the total amount of compounds having at least one unpolymerized ethylenically unsaturated moiety and compounds derived from compounds having at least one ethylenically unsaturated moiety in the PIR / PUR containing material is in the range of 2 wt.-% up to 20 wt.-%, based on the total weight of the PIR / PUR containing material.

13. The polyisocyanurate and / or polyurethane (PIR / PUR) containing material according to claim 3, wherein the total amount of compounds having at least one unpolymerized ethylenically unsaturated moiety and compounds derived from compounds having at least one ethylenically unsaturated moiety in the PIR / PUR containing material is in the range of 2 wt.-% up to 15 wt.-%, based on the total weight of the PIR / PUR containing material.

14. The polyisocyanurate and / or polyurethane (PIR / PUR) containing material according to claim 4, wherein the amount of the compound having at least one unpolymerized ethylenically unsaturated moiety is in the range of 0.4 wt.-% up to 24 wt.-%, based on the total weight of the PIR / PUR containing material.

15. The polyisocyanurate and / or polyurethane (PIR / PUR) containing material according to claim 4, wherein the amount of the compound having at least one unpolymerized ethylenically unsaturated moiety is in the range of 0.6 wt.-% up to 21 wt.-%, based on the total weight of the PIR / PUR containing material.

16. The polyisocyanurate and / or polyurethane (PIR / PUR) containing material according to claim 9, wherein the compound having at least one unpolymerized ethylenically unsaturated moiety has a boiling point above 200°C at atmospheric pressure.

17. A method for improving the flame, smoke and / or toxicity (FST) performance of a material comprising polyisocyanurate and / or polyurethane (PIR / PUR), the method comprising combining and mixing at least the following ingredients to form a material comprising PIR / PUR, the material comprising: - a polyisocyanate composition comprising one or more polyisocyanate compounds; and - an isocyanate-reactive composition comprising one or more isocyanate-reactive compounds; and - at least one catalyst compound selected from trimerization polyisocyanurate catalysts and / or polyurethane (PUR) forming catalysts, and - at least one compound having at least one ethylenically unsaturated moiety and a number average equivalent weight of <160 g / mol, and - one or more free radical initiator compounds, wherein the free radical initiator compound is selected from benzoyl peroxide, tert-butyl peroxide, tert-butyl hydroperoxide and / or tert-butyl perbenzoate, and - optionally a blowing agent; and - optionally one or more surfactants, one or more flame retardants, one or more antioxidants or combinations thereof characterized in that the amount of the compound having at least one ethylenically unsaturated moiety is at least 2 wt.%, based on the total weight of all ingredients used to prepare the material comprising PIR / PUR and the free radical polymerization start temperature (T 起始) than the maximum reaction temperature (reaction exotherm (T 反应 )) from 2°C to 40°C, wherein the compound having at least one unpolymerized ethylenically unsaturated portion is selected from maleic acid and derivatives or mixtures thereof; and Characteristically, after the process for preparing the PIR / PUR containing material, 10% up to 90% by weight of the total amount of ethylenically unsaturated compounds used to prepare the PIR / PUR containing material has unpolymerized ethylenically unsaturated moieties.

18. The method of claim 17, wherein the free radical polymerization initiation temperature (T 起始 ) than the maximum reaction temperature (reaction exotherm (T 反应 )) Low 5℃ to high 30℃.

19. The method according to claim 17 or 18, wherein the amount of the compound having at least one ethylenically unsaturated moiety ranges from 2 wt% up to 30 wt%, based on the total weight of all ingredients used to make the PIR / PUR containing material.

20. The method of claim 17 or 18, wherein the PIR / PUR containing material is a polyisocyanurate (PIR) containing material, and the process for forming the PIR containing material is carried out at an isocyanate index of 180 or more and the catalyst compound is selected from at least one trimerization catalyst.

21. The method according to claim 17 or 18, wherein the PIR / PUR containing material is a polyurethane containing (PUR) material having an open cell content of less than 50% by volume, based on the total volume of the foam, and the method for forming the PUR containing material is carried out at an isocyanate index in the range of 80-180, and the catalyst compound is selected from at least one polyurethane catalyst.

22. The method according to claim 17, wherein the number average equivalent weight is <120 g / mol.

23. The method of claim 18, wherein the free radical polymerization initiation temperature (T 起始 ) than the maximum reaction temperature (reaction exotherm (T 反应 )) Low 5℃ to high 15℃.

24. The method of claim 19, wherein the amount of the compound having at least one ethylenically unsaturated moiety ranges from 2 wt% up to 20 wt%, based on the total weight of all ingredients used to make the PIR / PUR containing material.

25. The method of claim 19, wherein the amount of the compound having at least one ethylenically unsaturated moiety ranges from 2 wt% up to 15 wt%, based on the total weight of all ingredients used to make the PIR / PUR containing material.

26. The method of claim 20, wherein the PIR / PUR containing material is a rigid foam containing polyisocyanurate (PIR).

27. The method of claim 20, wherein the process for forming the PIR-containing material is conducted at an isocyanate index above 250 and the catalyst compound is selected from at least one trimerization catalyst.

28. The method of claim 21, wherein the process for forming the PUR-containing material is conducted at an isocyanate index in the range of 90-150 and the catalyst compound is selected from at least one polyurethane catalyst.

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