Flame retardant, smoke retardant and toxicity retardant compositions for polyurethane / polyisocyanurate containing foams

Abstract

Reactive mixture comprising a flame retardant, smoke retardant and toxicity retardant (FST) composition for preparing a material comprising polyisocyanurate and / or polyurethane (PIR / PUR), the FST composition comprising: a) at least one compound having at least one ethylenically unsaturated moiety with a number average equivalent weight of <160 g / mol, and b) optionally one or more free radical initiator compounds, characterized in that the free radical polymerization onset temperature (T 起始 ) than the maximum reaction temperature (reaction exotherm (T 反应 ))2℃ as low as 2℃ to 40℃ as high as possible.

Description

Technical Field

[0001] The invention relates to a reactive mixture comprising a flame retardant, smoke retardant and / or toxicity retardant (FST) composition for preparing foams comprising polyisocyanurate (PIR) and / or polyurethane (PUR).

[0002] More particularly, the present invention relates to FST reducing compositions comprising at least one compound having at least one ethylenically unsaturated moiety and optionally a free radical initiator. Background Art

[0003] Halogen-containing additives are traditionally used as flame retardants in organic resins. That is, the additive compound contains fluorine, chlorine or bromine. The most common brominated resin is a strong oxidant. When exposed to heat, the weak bond between bromine and the rest of the resin atomic structure breaks and forms bromine free radicals, which interfere with the extremely exothermic oxidation reaction and thus suppress flames. Although it is this reaction that gives brominated resins flame retardant properties, the bromine removed by the 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 will increase. The resulting smoke is significantly more toxic than the smoke from non-halogenated resins.

[0004] In rigid polyurethane (PU) foam, for example TCPP (trichloropropyl phosphate) is widely used. In many PU applications, countries such as Canada have recently proposed restrictions for furniture and bedding applications. Similarly, the U.S. Environmental Protection Agency (EPA) is also working hard. The U.S. Consumer Product Safety Commission (CPSC) is evaluating potential regulations, or even considering banning organic-chlorinated substances as flame retardants. The European Chemicals Agency (ECHA) has opened a public consultation to consider the restrictions of TCEP, TCPP and TDCP in PU flexible foams for children's products and residential furniture, and it can be extended to other applications. In addition, there is increasing pressure on flame retardants by promoting "flame retardant-free products". For example, in California, flame retardant-free insulation boards have been promoted.

[0005] It can be seen that recent developments require the development of new solutions that not only improve the flame retardancy 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 organic halogen substances and should be suitable for use as additives in reactive mixtures for the preparation of materials containing polyisocyanurates (PIRs) and / or polyurethanes (PURs) and have no negative impact on the properties of the finally obtained materials containing PIRs and / or PURs. The compounds are referred to herein as flame, smoke and toxicity reduction (FST) compounds. Summary of the invention

[0006] The object of the present invention is to provide flame retardant, smoke retardant and / or toxicity retardant (FST) compositions for preparing reactive mixtures of materials comprising polyisocyanurates (PIRs) and / or polyurethanes (PURs), thereby avoiding or at least minimizing the use of prior art organohalogen flame retardants and further improving the flame retardancy of said materials when exposed to fire.

[0007] This object is achieved by adding the flame-retardant, smoke-retardant and / or toxicity-retardant (FST) composition of the invention to a reactive mixture for preparing a PIR / PUR-containing material.

[0008] We have surprisingly 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.

[0009] Definitions and terminology

[0010] In the context of the present invention, the following terms have the following meanings:

[0011] 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:

[0012]

[0013] 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.

[0014] It should be observed that the isocyanate index used herein is considered from the perspective of the actual polymerization process of preparing the material including the isocyanate component and the isocyanate-reactive component. Any isocyanate groups consumed in the preliminary steps of producing the modified polyisocyanate (including such isocyanate derivatives known in the art as prepolymers) or any active hydrogens consumed in the preliminary steps (e.g. reacting with isocyanates to produce modified polyols or polyamines) are not taken into account in the calculation of the isocyanate index. Only the free isocyanate groups and free isocyanate-reactive hydrogens (including those of water if water is used) present at the actual polymerization stage are taken into account.

[0015] 2) The expressions "isocyanate-reactive compound" and "isocyanate-reactive hydrogen atoms" used herein for the purpose of calculating the isocyanate index refer to the total number of active hydrogen atoms present in the hydroxyl and amine groups 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 reactive hydrogen, one primary amine group is considered to contain one reactive hydrogen, and one water molecule is considered to contain two reactive hydrogens.

[0016] 3) The term "OH value" or "hydroxyl value" is a measure of the free hydroxyl content of a chemical substance, usually expressed in units of mass (in milligrams) of potassium hydroxide (KOH) equivalent to the hydroxyl content of one gram of the 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 a pyridine solvent. After the reaction is complete, water is added and the remaining unreacted acetic anhydride is converted to acetic acid and measured by titration with potassium hydroxide.

[0017] 4) The term "average nominal hydroxyl functionality" (or simply "functionality") is used herein to indicate the number average of hydroxyl groups per molecule of a polyol or polyol composition, assuming that this is the number average functionality (number of active hydrogen atoms per molecule) of the initiator or initiators used in its preparation, although in practice it is often slightly lower due to some terminal unsaturation.

[0018] 5) Unless otherwise indicated, the word "average" refers to digital mean.

[0019] 6) "Trimerization catalyst" or "PIR catalyst" as used herein 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).

[0020] 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).

[0021] 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 prepared using an isocyanate index greater than 180, preferably greater than 250.

[0022] 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% of polyurethane. PUR-containing materials are typically prepared 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.

[0023] 10) "Functionality" generally refers to the presence of functional groups in a compound. For monomeric acrylate compounds, this refers to the amount of polymerizable acrylate groups. For isocyanate-reactive compounds, this refers to the amount of groups containing isocyanate-reactive hydrogen atoms.

[0024] 11) When disclosed in combination with a compound according to the present invention having at least one unpolymerized ethylenically unsaturated portion (also referred to herein as an ethylenically unsaturated compound), "number average equivalent weight" means the molar mass of the ethylenically unsaturated compound divided by the number of unsaturated portions in the compound, and is expressed in g / mol of unsaturated portions.

[0025] 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).

[0026] 13) "Ethylenically unsaturated compounds" or "compounds having ethylenically unsaturated moieties" are characterized as (limited to) compounds in which free radical polymerization (with or without the aid of a free radical initiator) occurs at atmospheric pressure in the temperature range of 50°C to a maximum of 160°C, preferably in the range of 90°C to a maximum of 160°C.

[0027] 14) "Free radical initiator" refers to a substance that can produce free radical species under mild conditions (e.g., by applying heat) and promote free radical reactions (e.g., free radical polymerization reactions). These substances generally have weak bonds with low bond dissociation energies. Typical examples are azo compounds / peroxide compounds (e.g., tert-butyl perbenzoate (TBPB)) and peroxides.

[0028] 15) “Activation temperature”, “Starting temperature” and “T 起始 ” 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).

[0029] 16) "Free radical polymerization" involves the formation of free radicals via decomposition of an initiator by light, temperature or redox reactions, and their reaction results in the formation of a polymer network. The initiator may be the ethylenically unsaturated compound itself (autopolymerization) or optionally it may 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 the exotherm of reactive compounds during the manufacturing process of the material (e.g. foam), or exposure to fire, optionally further activated by a free radical initiator.

[0030] 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).

[0031] 18) "DIN 4102-1" refers to the standard test which defines the fire behavior classes of building materials and specifies the requirements and test methods for each class. When the fire behavior of a material has been determined according to the standard, it divides the material into Class A and Class B building materials:

[0032]

[0033] 19) “ISO 11925” and “EN ISO 11925-2” refer to standard tests for determining the ignition properties of products by direct impingement of a small flame at zero applied irradiance using vertically oriented test specimens.

[0034] 20) The "Kleinbrenner test" (also referred to herein as the B2 test) is a small flame test in accordance with EN ISO 11925-2 in which a small flame is placed against the bottom edge of a (foam) sample for 15 seconds. A piece of the sample (see 2 in FIG. 1 ) of predetermined dimensions (e.g. measuring 19 cm x 9 cm x 2.5 cm) is cut and all sample residues resulting from the cutting are removed using pressurized air. The test is carried out in a test chamber in which the test specimen is mounted vertically. Once the foam has been placed in a metal holder (see 1 in FIG. 1 ), a 2 cm flame is placed at the bottom of the foam at a 45° angle (see A in FIG. 1 ) to ignite it.

[0035]

[0036] Figure 1

[0037] The flame is kept there for 15 seconds to observe whether the sample burns and how high it burns. Kleinbrenner test tools are also used herein to calculate the mass loss after being exposed to the flame, to quantify flame retardancy. Ideally, the test should be repeated 5 more times to obtain a reliable average value. Flame retardancy according to the present invention is measured by the weight percent mass loss of the (PIR / PUR) material after flame exposure, and the weight loss is calculated based on the gross weight of the (PIR / PUR) material before flame exposure.

[0038] The "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 production 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 irradiation level. The sample thickness should not exceed 50 mm, while the irradiation level is usually set to 25, 35 or 50 mW. The surface of the sample is heated and starts to evolve pyrolysis gases which are ignited.

[0039] The term "room temperature" refers to a temperature of about 20°C, which is meant to refer to a temperature in the range of 18°C ​​to 25°C. Such temperatures will include 18°C, 19°C, 20°C, 21°C, 22°C, 23°C, 24°C and 25°C.

[0040] Unless otherwise indicated, the weight percent of a component in a composition (expressed as % 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.

[0041] The terms "open cell" and "open cell content" refer to the open cell content of a foamed material and are expressed in volume % (vol %), calculated based on the total volume of the foam, and measured in accordance with ASTM D6226-10 (open cell content measured by pycnometer). DETAILED DESCRIPTION

[0042] The invention will be described with reference to specific embodiments.

[0043] It should be noted that the term "comprising" used in the claims should not be interpreted as being limited to the means listed thereafter; it does not exclude other elements or steps. It should therefore be interpreted as stipulating the presence of the features, steps or components mentioned, but does not exclude 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 devices consisting only of components A and B. It means that for the present invention, the only relevant components of the device are A and B.

[0044] 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. Furthermore, as will be apparent to one of ordinary skill in the art, the particular features or characteristics may be combined in any suitable manner in one or more embodiments.

[0045] 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.

[0046] The present invention provides flame retardant, smoke retardant and / or toxicity (FST) compositions for preparing reactive mixtures of materials comprising polyisocyanurate and / or polyurethane (PIR / PUR), said mixtures having improved flame retardant, smoke retardant and / or toxicity (FST) properties, thereby avoiding or at least minimizing the use of prior art organohalogen flame retardants.

[0047] It has surprisingly been observed that the incorporation of well-defined and selected compounds having ethylenically unsaturated moieties is very suitable as flame-retardant, smoke-retardant and / or toxicity-retardant (FST) compounds in PIR / PUR-containing materials.

[0048] According to the invention, these well-defined compounds are added as flame-retardant, smoke-retardant and / or toxicity-retardant (FST) compositions to the reactive mixture for the preparation of the PIR / PUR-containing material.

[0049] Therefore, the present invention discloses a class of well-defined compounds with ethylenically unsaturated moieties, which, when exposed to fire, will act as flame retardant, smoke retardant and / or toxicity retardant (FST) compounds in materials comprising PIR / PUR. This class of well-defined compounds is selected so 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 derived from the compounds with at least one ethylenically unsaturated moiety in the material comprising PIR / PUR) after the process of preparing the PIR / PUR material. This means that after the process of 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.

[0050] The well-defined class of compounds with ethylenically unsaturated moieties is chosen such that after the process for preparing the PIR / PUR containing material at least 10 wt %, preferably 10 wt % to a maximum of 90 wt %, more preferably 20 wt % to a maximum of 80 wt %, and more preferably 30 wt % to a maximum of 70 wt % of the total amount of compounds with ethylenically unsaturated moieties added has unpolymerized ethylenically unsaturated moieties.

[0051] The flame-retardant, smoke-retardant and toxicity-retardant (FST) composition according to the invention for preparing a reactive mixture of materials comprising polyisocyanurate and / or polyurethane (PIR / PUR), also referred to herein as flame-retardant composition for short, comprises:

[0052] a) at least one compound having at least one ethylenically unsaturated moiety with a number average equivalent weight <160 g / mol, preferably <120 g / mol, and

[0053] b) optionally one or more free radical initiator compounds,

[0054] It is characterized in that the free radical polymerization starting temperature (T 起始 ) than the maximum reaction temperature (reaction exotherm (T 反应 ))2℃ as low as 2℃ to 40℃ as high as possible.

[0055] Thus, the present invention discloses a reactive mixture for preparing a material comprising polyisocyanurate and / or polyurethane (PIR / PUR), the reactive mixture comprising:

[0056] - A flame retardant composition comprising

[0057] a) at least one compound having at least one ethylenically unsaturated moiety with a number average equivalent weight <160 g / mol, and

[0058] b) optionally one or more free radical initiator compounds,

[0059] It is characterized in that the free radical polymerization starting temperature (T 起始 ) than the maximum reaction temperature (reaction exotherm (T 反应 )) 2°C lower to 40°C maximum, and

[0060] - a polyisocyanate composition comprising one or more polyisocyanate compounds; and

[0061] - an isocyanate-reactive composition comprising one or more isocyanate-reactive compounds; and

[0062] - at least one catalyst compound suitable for the preparation of PIR / PUR containing materials, and

[0063] - optionally one or more blowing agents; and

[0064] -Optionally one or more surfactants, one or more antioxidants or a combination thereof.

[0065] According to an embodiment, the free radical polymerization starting temperature (T 起始 ) than the maximum reaction temperature (reaction exotherm (T 反应 )) is 2°C to 40°C at most, preferably 5°C to 30°C at most, and more preferably 5°C to 15°C at most.

[0066] According to an embodiment, the flame retardant (FST) composition according to the invention comprises essentially compounds having at least one ethylenically unsaturated moiety and having a number average equivalent weight <160 g / mol, preferably <120 g / mol.

[0067] According to an embodiment, the flame retardant (FST) composition according to the invention comprises at least 75 wt%, preferably at least 85 wt%, more preferably at least 90 wt%, based on the total weight of the FST composition, of compounds having at least one ethylenically unsaturated moiety and a number average equivalent weight of <160 g / mol, preferably <120 g / mol.

[0068] The free radical polymerization onset temperature (T 起始 ) is preferably greater than the maximum reaction temperature (reaction exotherm (T 反应 ))2℃ as low as 2℃ to 40℃ as high as possible.

[0069] In the case where a free radical initiator is used in addition to the compound having an ethylenically unsaturated portion, the free radical polymerization onset temperature (T 起始 ) is preferably greater than the maximum reaction temperature (reaction exotherm (T 反应 ))2℃ as low as 2℃ to 40℃ as high as possible.

[0070] According to an embodiment, the free radical polymerization initiation temperature (T起始 ) is preferably greater than the maximum reaction temperature (reaction exotherm (T 反应 )) is 2°C to 40°C lower, more preferably 5°C to 30°C at most, and most preferably 5°C to 15°C at most. The free radical polymerization starting temperature (T 起始 ) may be 5°C to 10°C, 10°C to 15°C, 15°C to 20°C, 20°C to 25°C, 25°C to 30°C, 30°C to 35°C lower than the maximum reaction temperature achieved during the process for preparing the PIR / PUR material.

[0071] According to an embodiment, the compound having at least one ethylenically unsaturated moiety comprises at least 1 ethylenically unsaturated moiety, preferably 2 to a maximum of 8 ethylenically unsaturated moieties.

[0072] According to an embodiment, the compound having at least one ethylenically unsaturated moiety is a monomeric compound.

[0073] According to an embodiment, the compound having at least one ethylenically unsaturated moiety is selected from acrylates, methacrylates, acrylic acid, methacrylic acid, allyl alcohol and / or maleic acid and derivatives or mixtures thereof.

[0074] According to an embodiment, the compound having at least one ethylenically unsaturated moiety is selected from the group consisting of 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.

[0075] According to an embodiment, the free radical initiator compound is selected from benzoyl peroxide, tert-butyl perbenzoate (Luperox ® P), di-tert-butyl peroxide (Luperox ® DI), tert-butyl hydroxyperoxide (Luperox ® TBH 70X) and mixtures thereof. Free radical initiators that are active at too low a temperature (e.g., too close to room temperature) should be avoided as they may result in poor foam flow in addition to handling safety issues.

[0076] According to a preferred embodiment, the compound having at least one ethylenically unsaturated moiety is selected from PETRA (pentaerythritol tetraacrylate, 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).

[0077] (I)

[0078] 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 having a 10 h half-life temperature of 121° C. ® DI (tert-butyl peroxide, see formula II) or Luperox with a half-life temperature of 103°C for 10 hours ® P (tert-butyl peroxybenzoate, see formula III).

[0079] (II)

[0080] (III)

[0081] According to a preferred embodiment, the compound having at least one ethylenically unsaturated moiety further comprises at least one isocyanate reactive moiety. During the process of 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.

[0082] According to an embodiment, the compound having at least one ethylenically unsaturated moiety has a boiling point at atmospheric pressure higher than 150°C, preferably higher than 200°C.

[0083] According to an embodiment, the amount of the flame retardant (FST) composition in the reactive mixture is such that the amount of compound having at least one ethylenically unsaturated moiety in the reactive mixture is at least 2 wt %, based on the total weight of all ingredients in the reactive mixture.

[0084] According to an embodiment, the amount of the compound having at least one ethylenically unsaturated moiety in the reactive mixture is in the range of 2 wt% to a maximum of 30 wt%, preferably in the range of 2 wt% to a maximum of 20 wt%, more preferably in the range of 2 wt% to a maximum of 15 wt%, calculated based on the total weight of the reactive mixture.

[0085] According to an embodiment, the amount of the one or more free radical initiator compounds in the reactive mixture is in the range of 0.01 wt% to at most 1 wt%, preferably in the range of 0.03 wt% to at most 0.5 wt%, calculated based on the total weight of the reactive mixture.

[0086] 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% to a maximum of 30 wt%, preferably 2 wt% to a maximum of 20 wt%, more preferably 2 wt% to a maximum of 15 wt%, based on the total weight of the reactive mixture for preparing 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 for preparing the material containing PIR / PUR.

[0087] 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 PIR / PUR material is in the range of 2 wt% to a maximum of 30 wt%, based on the total weight of the reactive mixture, and the PIR / PUR-containing material prepared using the reactive mixture contains 0.2 wt% to a maximum of 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 of preparing the PIR / PUR-containing material, 10 wt% to a maximum of 90 wt% of the total amount of the compound having ethylenically unsaturated moieties added will have unpolymerized ethylenically unsaturated moieties.

[0088] 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% to a maximum of 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% to a maximum of 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 of preparing the material comprising PIR / PUR, 20 wt% to a maximum of 80 wt% of the total amount of the compound having ethylenically unsaturated moieties added will have unpolymerized ethylenically unsaturated moieties.

[0089] 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% to a maximum of 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% to a maximum of 21 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 of preparing the material comprising PIR / PUR, 30 wt% to a maximum of 70 wt% of the total amount of the compound having ethylenically unsaturated moieties added will have unpolymerized ethylenically unsaturated moieties.

[0090] 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% to a maximum of 30 wt%, preferably in the range of 2 wt% to a maximum of 20 wt%, more preferably in the range of 2 wt% to a maximum of 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% to a maximum of 27 wt%, preferably 0.2 wt% to a maximum of 18 wt%, and more preferably 0.2 wt% to a maximum of 13.5 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 of preparing the material comprising PIR / PUR, 10 wt% to a maximum of 90 wt% of the total amount of the compound having ethylenically unsaturated moieties added will have unpolymerized ethylenically unsaturated moieties.

[0091] 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, and more preferably aromatic isocyanates such as meta- and para-phenylene diisocyanate, tolylene-2,4- and 2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, chlorophenylene-2,4-diisocyanate, naphthylene-1,5-diisocyanate, diphenylene-4,4'-diisocyanate, isocyanates, 4,4′-diisocyanate-3,3′-dimethyldiphenyl, 3-methyldiphenylmethane-4,4′-diisocyanate and diphenyl ether diisocyanate, cycloaliphatic diisocyanates such as cyclohexane-2,4- and 2,3-diisocyanate, 1-methylcyclohexyl-2,4- and 2,6-diisocyanate and mixtures thereof and bis-(isocyanatocyclohexyl-)methane, and triisocyanates such as 2,4,6-triisocyanatotoluene and 2,4,4′-triisocyanatodiphenyl ether.

[0092] According to an embodiment, the polyisocyanate compound may be selected from a mixture of polyisocyanates. For example, a mixture of tolylene diisocyanate isomers, such as a mixture of commercially available 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 of a mixture containing methylene-bridged polyphenyl polyisocyanates, the mixture including diisocyanates, triisocyanates and higher polyisocyanates and any phosgenation byproducts.

[0093] 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 as MDI) are well known in the art and have the general formula I, wherein n is 1 or greater and, in the case of a crude mixture, represents an average greater than 1. They are prepared by phosgenation of the corresponding polyamine mixtures obtained by condensation of aniline and formaldehyde.

[0094] (I)

[0095] 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 a 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 (e.g., 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.

[0096] 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.

[0097] According to the embodiment, one or more isocyanate reactive compounds include any of those known in the art for preparing rigid foams comprising polyisocyanurate and / or polyurethane. It is particularly important for preparing rigid foams that the average OH value is 50-1000 mg KOH / g (especially 150-700 mg KOH / g) and the hydroxyl (OH) functionality is 2-8 (especially 3-8) polyols and polyol mixtures. Suitable polyols have been fully described in the prior art and include polyether-based polyols, which are the reaction products of alkylene oxides (such as ethylene oxide and / or propylene oxide) and initiators containing 2-8 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 diols and higher functionality polyols with dicarboxylic acids or polycarboxylic acids in appropriate proportions. Still other suitable polymeric polyols include hydroxyl-terminated polythioethers, polyamides, polyesteramides, polycarbonates, polyacetals, polyolefins and polysiloxanes.

[0098] According to an embodiment, the material comprising PIR / PUR is a foaming 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 (e.g., pentane). The amount of the blowing agent may vary, for example, according to 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 0.5-60, more preferably 1-45 parts by weight (pbw) per hundred parts by weight of the isocyanate-reactive compound (polyol).

[0099] According to an embodiment, the PIR / PUR containing material is a foamed material, and the blowing agent comprises / contains water, and the amount of water is preferably limited to an amount of at most 15 pbw.

[0100] According to an embodiment, the catalyst compound should be present in the reactive mixture in a catalytically effective amount, preferably the catalyst compound is present in an amount such that the number of catalyst equivalents relative to the number of isocyanate equivalents ranges from 0.001-0.4, preferably in an amount of 0.01-0.26, or 0.01-0.24, or 0.02-0.2.

[0101] 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, pentamethyldipropylenetriamine, triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl)ether, tris(3-dimethylamino)propylamine or its acid-terminated derivatives, and the like, and any mixtures thereof. The catalyst compound should be present in the reactive composition in a catalytically effective amount.

[0102] 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.

[0103] According to embodiments, additional prior art flame retardant compounds such as triethylene phosphate or expandable graphite may be added to the reactive mixture used to prepare the PIR / PUR containing material.

[0104] 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 falls within the scope of the present invention.

[0105] According to embodiments, the flame retardant (FST) composition may be added to the reactive mixture as a separate stream from the isocyanate composition and from the isocyanate-reactive composition.

[0106] The amount of the one or more polyisocyanate compounds and the one or more isocyanate-reactive compounds in the reactive mixture depends on the nature of the PIR / PUR-containing material to be produced and can be readily determined by a person skilled in the art.

[0107] According to an embodiment, the PIR / PUR-containing material prepared using a reactive mixture comprising the flame retardant (FST) composition of the present invention is a polyisocyanurate (PIR)-containing foam, preferably a rigid foam containing polyisocyanurate (PIR) prepared using a reactive mixture having an isocyanate index of 180 or more, more preferably an isocyanate index above 250, and the catalyst compound used in the reactive mixture is selected from at least one trimerization catalyst.

[0108] According to an embodiment, the PIR / PUR-containing material prepared using a reactive mixture comprising the flame retardant (FST) composition of the present invention is a polyurethane (PUR)-containing foam, preferably a flexible or semi-flexible foam containing polyurethane (PUR) prepared using a reactive mixture having an isocyanate index in the range of 80-180, more preferably an isocyanate index in the range of 90-150, and the catalyst compound is selected from at least one polyurethane catalyst.

[0109] According to an embodiment, the PIR / PUR-containing material using the reactive mixture comprising the flame retardant (FST) composition of the present invention is a PIR / PUR-containing coating or adhesive.

[0110] According to an embodiment, the PIR / PUR containing material prepared using a reactive mixture containing the flame retardant (FST) composition of the present invention is a thermoplastic polyurethane (TPU) elastomer.

[0111] According to an embodiment, the PIR / PUR-containing material prepared using a reactive mixture comprising the flame retardant (FST) composition of the present invention is a PIR / PUR-containing foam having an apparent density of <200 kg / m 3 (measured according to ISO 845), and the open cell content is less than 50 wt%, preferably less than 30 wt%, more preferably less than 20 wt% by volume (calculated based on the total volume of the foam and measured according to ASTM D6226-10 (open cell content measured by pycnometer)).

[0112] According to an embodiment, the PIR / PUR containing materials prepared using the flame retardant (FST) composition of the present invention can be used in thermal insulation, acoustic insulation and / or structural panels, such as building insulation foam or appliance insulation foam (eg insulation panels). Example

[0113] Chemicals used:

[0114] -Daltolac ® R 517: polyether polyol available from Huntsman.

[0115] -Daltolac ®R 251: Polyether polyol available from Huntsman.

[0116] -Daltolac ® R 630: polyether polyol available from Huntsman.

[0117] -Daltolac ® XR 159: polyether polyol available from Huntsman.

[0118] - Cyclopentane, obtained from Merck, Germany.

[0119] - n-Pentane, obtained from Merck, Germany.

[0120] -Jeffcat ® BDMA: amine catalyst available from Huntsman.

[0121] -Jeffcat ® ZF22: amine catalyst available from Huntsman.

[0122] -Jeffcat ® TR90: amine catalyst available from Huntsman.

[0123] - K-ZERO 3000: Potassium catalyst in DMSO from Momentive Performance Materials.

[0124] - TEP: triethyl phosphate, obtained from Sigma-Aldrich.

[0125] - Neo Polyol 240 FR: an aromatic polyester polyol available from Huntsman.

[0126] -Tegostab ® B 8484: Silicone surfactant foam stabilizer available from Evonic, Germany.

[0127] -Tegostab ® B 8485: Silicone surfactant foam stabilizer available from Evonic, Germany.

[0128] -Tegostab ® B 8494: Silicone surfactant foam stabilizer available from Evonic, Germany.

[0129] - SR 444D: Pentaerythritol triacrylate (PETA) from Sartomer.

[0130] - SR 295: Pentaerythritol tetraacrylate (PETRA) from Sartomer.

[0131] - Hydroxyethyl acrylate (HEA) from Sigma-Aldrich.

[0132] - SR 351: trimethylolpropane triacrylate (TTA) from Sartomer.

[0133] - Hydroxyethyl methacrylate (HEMA) from Sigma-Aldrich.

[0134] - SR 350D: trimethylolpropane trimethacrylate (TTMA) from Sartomer.

[0135] -Genomer ® 4302: Isocyanurate trifunctional acrylate available from RAHN.

[0136] -Genomer ® 4622: Aromatic hexafunctional urethane acrylate available from RAHN.

[0137] -Genomer ® 4691: Aliphatic hexafunctional urethane acrylate available from RAHN.

[0138] - Allyl alcohol, available from Merck.

[0139] - MA: Maleic anhydride, obtained from Merck, Germany.

[0140] - SA: Succinic anhydride, available from Merck, Germany.

[0141] - TATA: 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 97%, obtained from Sigma-Aldrich.

[0142] - Lactic acid: DL-lactic acid from Sigma-Aldrich (88% in water).

[0143] -Luperox ® P: tert-Butyl peroxybenzoate, obtained from Sigma-Aldrich.

[0144] -Luperox ® Di: di-tert-butyl peroxide, obtained from Sigma-Aldrich.

[0145] -Luperox ® TBH70X: tert-butyl hydroperoxide, obtained from Sigma-Aldrich (70% in water).

[0146] - Benzoyl peroxide: dibenzoyl peroxide from Sigma-Aldrich (75% in water).

[0147] - S5025 (Suprasec ® 5025): polymeric methylene diphenyl isocyanate (MDI) from Huntsman.

[0148] -Manufacture of polyurethane (PUR) foam

[0149] Polyurethane foams were produced under free rise conditions by mixing a polyol blend (previously prepared, including all chemicals listed in the table except isocyanate) and isocyanate under high shear for 5 seconds using a Heidolph Mixer (about 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 (Tmax) of the foaming process of the PUR formulations without added ethylenically unsaturated compounds (Comparative Examples 1 and 2). 反应 ). All PUR foams were stored in a fume hood overnight before cutting and characterization.

[0150] Synthesis of MDI-HEA and MDI-PETA

[0151] MDI was placed in a three-necked round-bottom 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 at 70°C in an oil bath, and an ethylenically unsaturated compound (HEA & PETA) containing an isocyanate reactive group was added dropwise over 30 minutes. The contents in the flask were kept at 70°C for 1 hour, and the product was cooled to room temperature and stored in a sealed container.

[0152] Kleinbrenner test (B2 test)

[0153] The Kleinbrenner test is used to compare the flame retardancy (FR) performance of different samples, where a small flame is placed against the bottom edge of the foam sample for 15 seconds according to EN ISO 11925-2. A piece of foam measuring 19 cm x 9 cm x 2.5 cm is cut (see 2 in FIG. 1 ). The test is performed in a test chamber where the test specimen is mounted vertically. Once the foam has been placed in a metal holder (see 1 in FIG. 1 ), a 2 cm flame is placed at a 45° angle (see A in FIG. 1 ) at the bottom of the foam to ignite it.

[0154] The flame was held for 15 seconds to observe whether the foam burned and how high it burned. To compare the FR performance of different systems, the Kleinbrenner test was used and the foam samples were weighed before and after the test to determine the percent mass loss as an indicator of FR performance. Lower mass loss indicates better flame retardant performance.

[0155] Determination of the polymerization onset (T) of ethylenically unsaturated compounds using DSC 起始 )

[0156] In order to determine the polymerization start (T 起始 ), constant heating rate differential scanning calorimetry (DSC) was performed. DSC studies were performed using a Q2000 TA instrument. The ethylenically unsaturated compound was premixed with a free radical initiator (if applicable), and then 3-5 mg of the sample was sealed in a sealed aluminum pan and heated from 0°C to 280°C at a heating rate of 10°C / min.

[0157] The conversion of the olefinically unsaturated compounds (α) was determined using DSC:

[0158] In order to determine the amount of unreacted ethylenically unsaturated compounds (also referred to herein as compounds with unpolymerized ethylenically unsaturated parts) in PUR foam, isothermal differential scanning calorimetry (DSC) was performed. DSC research was performed using a Q2000 TA instrument. 3 mg (± 5%) ground samples were sealed in a sealed aluminum pan and heated to 70 ° C and isothermally maintained for 15 seconds at a heating rate of 60 ° C / min. The temperature balance of the DSC furnace was then maintained at 230 ° C and isothermally maintained for 20 minutes. The positive heat flow value was digitally integrated to estimate the total residual exotherm. Equation 1 was used to calculate the conversion rate:

[0159] Equation

[0160] 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 EUM is the wt% of ethylenically unsaturated compounds (EUM), and RE EUM It is pure ethylenically unsaturated compounds (EUM) plus 1 wt% Luperox ® Di's residual exotherm.

[0161] A conversion (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.

[0162] Examples 1-25 according to the present invention and comparative example 1

[0163] 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 production) measured by cone calorimetry, THR of the base formulation (Comparative Example 1), and TSP of the base formulation (Comparative Example 1). 反应 and T of ethylenically unsaturated compounds (EUM) plus initiator (if applicable) 起始 .

[0164] Table 1

[0165]

[0166]

[0167] NA = Not analyzed

[0168] 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 components used (in parts by weight (pbw)), as well as the percent mass loss of Kleinbrener (B2), the T of the base formulation (Comparative Example 1), and the relative humidity of the base formulation (Comparative Example 1). 反应 and T of ethylenically unsaturated compounds plus initiator (if applicable) 起始 .

[0169] Table 2

[0170]

[0171]

[0172] NA = Not analyzed

[0173] Examples 26-27 according to the present invention and comparative example 2

[0174] Table 3 summarizes the reactive compositions used to make Examples 26 and 27 according to the invention and Comparative Example 3 and the amounts of the components used (in parts by weight (pbw)), as well as the percent mass loss of Kleinbrener (B2), the T of the base formulation (Comparative Example 2), and the relative humidity of the base formulation (Comparative Example 2). 反应 and T of ethylenically unsaturated compounds plus initiator (if applicable) 起始 .

[0175] Table 3

[0176] Chemicals (pbw) Comparative Example 2 Embodiment 26 Embodiment 27 <![CDATA[Daltolac ® R 517]]> 30.5 30.5 30.5 <![CDATA[Daltolac ® R 251]]> 21 21 21 <![CDATA[Daltolac ® R 630]]> 21 21 21 <![CDATA[Daltolac ® XR 159]]> 16 16 16 <![CDATA[Jeffcat ® BDMA]]> 1.5 1.5 1.5 <![CDATA[Jeffcat ® ZF 22]]> 0.1 0.1 0.1 <![CDATA[Jeffcat ® TR 90]]> 0.1 0.1 0.1 TEP 6 6 6 <![CDATA[Tegostab ® B 8485]]> 0.5 0.5 0.5 <![CDATA[Tegostab ® B 8494]]> 1 1 1 water 2.3 2.3 2.3 Cyclopentane 19.5 19.5 19.5 SA 48.47 - - MA - 48.47 48.47 <![CDATA[Luperox ® Of]]> - - 0.29 <![CDATA[Suprasec ® 5025]]> 181.45 181.45 181.45 Isocyanate Index 133 133 133 Quality loss (%) 17.0 9.2 8.4 <![CDATA[T 反应 (℃)]]> 154 154 154 <![CDATA[T 起始 ]]> - NA NA

[0177] NA = Not analyzed

[0178] It is clear from Table 1 that all investigated acrylates (Examples 1-12) have reduced mass loss in B2 in the presence and absence of thermal initiator compared to Comparative Example 1. In the case of PETRA, where various free radical initiator loadings were tested (Examples 1-4) and conversion (α) evaluated, herein the conversion equal to about 59% (meaning that 41% of unpolymerized PETRA remained based on the total amount of PETRA added to the reactive mixture) was 0.04477 %. 起始 T 反应 (0.1% Luperox ® The best results (lowest mass loss in the B2 test) were obtained in the formulations with a temperature 5°C lower than Di). For all other acrylates used herein (Examples 5-12), 0.1% Luperox ® Di reduces the mass loss of B2. Cone calorimetry results also show significant improvements in total smoke production (TSP) and peak heat release rate (PHRR).

[0179] It is clear from Table 2 that at 0.1% Luperox ® In the presence of Di, all investigated ethylenically unsaturated compounds reduce the mass loss of B2, whereas in the case of TATA (which does not have a free radical initiator, 反应 Compared with it has a significantly higher T 起始 (216°C, relative to 130°C)), in Luperox ® In the presence of Di, it only improves the flame retardant properties. 起始 Lower to closer to T 反应 (130℃)136℃.

[0180] 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 about 9% in Example 26. In addition, the thermal initiator Luperox ® Di further reduced the mass loss to about 8% of Example 27.

Claims

1. A reactive mixture for preparing a material comprising polyisocyanurate and / or polyurethane (PIR / PUR), the reactive mixture comprising: - A flame retardant composition comprising: a) at least one compound having at least one ethylenically unsaturated moiety, the equivalent weight of said compound being <120 g / mol, and b) one or more free radical initiator compounds in an amount of 0.01 wt.-% to 0.1 wt.-%, based on the total weight of the material comprising the PIR / PUR, and wherein the one or more free radical initiator compounds are selected from benzoyl peroxide, tert-butyl peroxide, tert-butyl hydroperoxide and / or tert-butyl perbenzoate, It is characterized in that In the presence of the free radical initiator, the free radical polymerization initiation temperature (T 起始 ) than the maximum reaction temperature (reaction exotherm (T 反应 )) 2°C lower to 40°C maximum, and - 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 suitable for preparing said PIR / PUR containing material, and - optionally one or more blowing agents; and - optionally one or more surfactants, one or more antioxidants or a combination thereof, The compound having at least one ethylenically unsaturated portion is selected from maleic acid and its derivatives or mixtures.

2. The reactive mixture of claim 1, wherein the compound having at least one ethylenically unsaturated moiety and the starting temperature (T 起始 ) is 5° C. to 30° C. lower than the maximum reaction temperature achieved during the process for preparing the PIR / PUR material.

3. The reactive mixture of claim 1, wherein the compound having at least one ethylenically unsaturated moiety further comprises one or more isocyanate-reactive groups.

4. The reactive mixture of claim 1, wherein the compound having at least one ethylenically unsaturated moiety has a boiling point above 150°C at atmospheric pressure.

5. The reactive mixture of claim 1, wherein the amount of the compound having at least one ethylenically unsaturated moiety in the reactive mixture is in the range of 2 wt% to a maximum of 30 wt%, based on the total weight of the reactive mixture.

6. The reactive mixture of claim 2, wherein the free radical polymerization initiation temperature (Tc) of the combination of the compound having at least one ethylenically unsaturated moiety and the free radical initiator in the flame retardant composition is 起始 ) than the maximum reaction temperature (reaction exotherm (T 反应 ))Low 5℃ to 15℃.

7. The reactive mixture of claim 3, wherein the free radical polymerization initiation temperature (T 起始 ) than the maximum reaction temperature (reaction exotherm (T 反应 ))Low 5℃ to 30℃.

8. The reactive mixture of claim 4, wherein the compound having at least one ethylenically unsaturated moiety has a boiling point above 200°C at atmospheric pressure.

9. The reactive mixture of claim 5, wherein the amount of the compound having at least one ethylenically unsaturated moiety in the reactive mixture is in the range of 2 wt% to a maximum of 20 wt%, based on the total weight of the reactive mixture.

10. The reactive mixture of claim 5, wherein the amount of the compound having at least one ethylenically unsaturated moiety in the reactive mixture ranges from 2 wt% to a maximum of 15 wt%, based on the total weight of the reactive mixture.

11. Use of a reactive mixture as defined in any one of claims 1 to 10 for improving the flame retardancy of materials comprising polyisocyanurates and / or polyurethanes (PIR / PUR).

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