Thermally expandable composition containing endothermic blowing agent

Abstract

The present invention is directed to a thermally expandable composition comprising at least one epoxy-functional polymer, at least one endothermic chemical blowing agent, at least one free-radical initiator, and at least one guanidine derivative. The present invention also relates to a baffle and / or reinforcing element for a hollow structure comprising the thermally expandable composition, a method for making the baffle and / or reinforcing element, a method for sealing, baffling, or reinforcing a cavity or hollow structure, and a method for sealing, baffling, and / or reinforcing a cavity or hollow structure.

Description

[Technical field]

[0001] The present invention relates to a thermally expandable composition and its use for providing baffles and / or reinforcement elements, which are particularly suitable for use in sealing, baffling and / or reinforcement of cavities in hollow structures, such as hollow structural parts of automotive vehicles. [Background technology]

[0002] Products often contain orifices and cavities or other hollow parts that result from the manufacturing process and / or are designed into the product for various purposes, such as weight reduction. Automobile vehicles contain several such orifices and cavities throughout the vehicle, such as in the structural columns of the vehicle and in the sheet metal of the vehicle doors. It is often desirable to seal such orifices and cavities to minimize the passage of noise, vibration, smoke, dust, water, humidity, etc. from one area to another in the vehicle by means of sealing members or baffle elements incorporated in the orifices or cavities. Similarly, such members or elements often perform the additional task of strengthening the hollow structure of the product, for example, an automobile part, so that it becomes more resistant to mechanical stresses, while still maintaining the low weight advantage of the hollow structure.

[0003] Such elements used for sealing, baffling or reinforcement often consist of a carrier made of plastic, metal or another rigid material and one or more layers of thermoplastic material attached to the carrier that can expand its volume when heat or another physical or chemical form of energy is applied, but they can also be made entirely of intumescent material. With appropriate design, it is possible to insert the baffle or reinforcement element into the hollow part of the structure during the manufacturing process, but also to leave the inner wall of the structure accessible (or passable through the cavity) by, for example, liquid. For example, during the manufacturing process of a vehicle, the hollow part of the metal frame may still be mostly covered by electrocoating ("e-coat") liquid, while the baffle or reinforcement element is already inserted, and then, during the heat treatment step, the intumescent thermoplastic material of the baffle or reinforcement element expands to fill the cavity as intended.

[0004] The development of such baffles or reinforcing elements has resulted in highly advanced systems where an expandable material can increase its volume by up to several hundred percent, form a stable cross-linked foam-like structure that fills a cavity and adheres to the walls of the seal, baffle or structure it is intended to reinforce. This has resulted in significant weight reduction in the vehicle body and excellent damping of noise or vibration, particularly in automotive manufacturing.

[0005] Thermally expandable compositions currently used often consist of polymers such as ethylene-vinyl acetate polymers that can be crosslinked by radical initiators, most commonly peroxides. To obtain foams, these compositions further contain blowing agents, the most widely used being azodicarbonamide (also called azodicarboxamide or azobisformamide) and 4,4'-oxydibenzenesulfonylhydrazide (abbreviated OBSH). Under activation conditions, such as high temperature, hardening of the crosslinked network occurs, with simultaneous decomposition of the blowing agent and release of gas. This leads to the above-mentioned volume expansion and the formation of a stable foam, which in the ideal case fills the cavities as intended and adheres to their walls. Such systems are disclosed, for example, in DE 10 2011 080 223 A1.

[0006] One of the problems associated with the established solutions described above is the fact that the most commonly used exothermic blowing agents, particularly azodicarbonamide (ADCA), are increasingly facing regulatory challenges regarding health and safety issues.

[0007] It would therefore be desirable to have a thermally expandable thermoplastic composition that overcomes the above-discussed problems associated with prior art compositions. Summary of the Invention [Problem to be solved by the invention]

[0008] It is an object of the present invention to provide a storage stable thermally expandable composition that can expand uniformly over a wide range of temperatures, for example in the range of 120-200° C., and cure to form a stable foam structure. Additionally, the resulting foam should exhibit reduced water uptake (water uptake) and good adhesion to metal, even oily, surfaces and other substrates commonly used in products, particularly automotive vehicles.

[0009] Another object of the present invention is to provide a thermally expandable composition that does not use an exothermic blowing agent, particularly azodicarbonamide (ADCA). [Means for solving the problem]

[0010] The subject of the present invention is a thermally expandable composition as defined in claim 1.

[0011] Surprisingly, it has been found that guanidine derivatives can be used as activators for endothermic chemical blowing agents, particularly for organic acids.Furthermore, it has been found that thermally expandable compositions containing endothermic chemical blowing agents, at least one epoxy-functional polymer, and at least one guanidine derivative exhibit reduced water absorption in addition to improved volume expansion coefficient.

[0012] One advantage of the thermally expandable compositions of the present invention is that good expansion rates can be achieved over a wide range of temperatures without the use of exothermic blowing agents, particularly without the use of azodicarbonamide.

[0013] Further subject matter of the invention is set out in the other independent claims. Preferred embodiments of the invention are set out in the dependent claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The subject of the present invention is a thermally expandable composition comprising: (a) a polymer component P comprising: (a1) at least one epoxy-functional polymer EP, (a2) optionally at least one anhydride-functional polymer AP, and (a3) optionally at least one thermoplastic polymer TP, (b) at least one endothermic chemical blowing agent BA; (c) at least one free radical initiator I, and (d) at least one guanidine derivative G.

[0015] Substance names beginning with "poly" designate substances that formally contain more than one functional group per molecule that appears in their name. For example, polyol refers to a compound that has at least two hydroxyl groups. Polyether refers to a compound that has at least two ether groups.

[0016] The term "polymer" refers to a collection of chemically uniform macromolecules produced by polyreactions (polymerization, polyaddition, polycondensation), where the macromolecules differ with respect to their degree of polymerization, molecular weight and chain length. The term also includes derivatives of said collection of macromolecules resulting from polyreactions, i.e. compounds obtained by reactions, for example addition or substitution, of functional groups in a given macromolecule, and which may or may not be chemically uniform.

[0017] The term "molecular weight" refers to the molar mass (g / mol) of a molecule or a portion of a molecule, also referred to as a "moiety." The term "average molecular weight" refers to the number average molecular weight (M n Molecular weights may be measured by conventional methods, preferably at 35° C., by gel permeation chromatography (GPC) using polystyrene as standards, styrene-divinylbenzene gels with porosities of 100 Angstroms, 1000 Angstroms and 10000 Angstroms as columns, and tetrahydrofuran as solvent.

[0018] The term "melting temperature" refers to the temperature at which a material undergoes a transition from a solid state to a liquid state. m ) is preferably measured by differential scanning calorimetry (DSC) according to the ISO 11357-3 standard using a heating rate of 2° C. / min. The measurement can be carried out using a Mettler Toledo DSC 3+ device, T m The value can be determined from the measured DSC curve using DSC software. If the measured DSC curve shows several peak temperatures, the first peak temperature coming from the lower temperature side of the thermograph is the melting temperature (T m ) is adopted.

[0019] The "amount or content of at least one component X" in a composition, such as the "amount of at least one thermoplastic polymer TP", refers to the sum of all the individual amounts of the thermoplastic polymers TP contained in the composition. For example, if the at least one thermoplastic polymer TP represents 20% by weight of the total weight of the composition, then the sum of the amounts of all the thermoplastic polymers TP contained in the composition is equal to 20% by weight.

[0020] The term "room temperature" designates a temperature of 23°C.

[0021] Preferably, the polymer component P represents at least 35% by weight of the total weight of the thermally expandable composition, more preferably at least 45% by weight, even more preferably at least 55% by weight, even more preferably at least 60% by weight, especially at least 70% by weight, such as at least 65% by weight.

[0022] According to one or more embodiments, the polymer component P comprises 35-95 wt.%, preferably 45-90 wt.%, more preferably 50-90 wt.%, even more preferably 55-85 wt.%, even more preferably 60-85 wt.%, and most preferably 65-85 wt.% of the total weight of the thermally expandable composition.

[0023] The thermally expandable composition comprises at least one endothermic chemical blowing agent BA. Chemical blowing agents are, for example, organic or inorganic compounds that decompose under the influence of temperature or humidity, while at least one of the decomposition products formed is a gas.

[0024] Despite the fact that exothermic blowing agents have been widely used in thermally expandable compositions, especially in the automotive industry, they are not preferred for use in the thermally expandable compositions of the present invention. Exothermic blowing agents are not preferred because they have been found to have the potential to cause respiratory hypersensitivity, and are generally unsafe from a toxicological point of view or have the risk of explosion. Furthermore, by-products such as ammonia, formamide, formaldehyde or nitrosamines are released during the decomposition of exothermic blowing agents, and these substances are classified as hazardous substances and are prohibited from use in automotive manufacturing.

[0025] According to one or more embodiments, the thermally expandable composition is substantially free of ADCA (azodicarbonamide) and OBSH (4,4'-oxybis(benzenesulfonic acid hydrazide)), and preferably essentially free of exothermic blowing agents, in particular ADCA, OBSH, DNPT (dinitrosopentamethylenetetramine), PTSS (p-toluenesulfonyl semicarbazide), BSH (benzene-4-sulfonyl hydrazide), TSH (4-toluenesulfonyl hydrazide) and 5-PT (5-phenyltetrazole). The expression "essentially free" is understood to mean that the thermally expandable composition may only contain trace amounts of the above-listed compounds, such as less than 0.25% by weight, preferably less than 0.1% by weight, more preferably less than 0.01% by weight, based on the total weight of the thermally expandable composition.

[0026] Endothermic chemical blowing agents have the advantage that they are not hazardous or explosive and fewer volatile organic compounds (VOCs) are produced during their decomposition. The decomposition products are essentially carbon dioxide and water.

[0027] According to one or more embodiments, the at least one endothermic chemical blowing agent BA comprises at least one organic acid. Suitable organic acids include, for example, monocarboxylic acids, such as acetic acid and propionic acid, and solid polycarboxylic acids, such as citric acid, tartaric acid, malic acid, fumaric acid, and maleic acid, for example solid hydroxy-functionalized or unsaturated dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, or polycarboxylic acids.

[0028] According to one or more embodiments, the at least one blowing agent BA comprises at least 85 wt.-%, preferably at least 90 wt.-%, more preferably at least 95 wt.-%, even more preferably at least 97.5 wt.-%, and even more preferably at least 99 wt.-% of the at least one organic acid, based on the total weight of the at least one blowing agent.

[0029] According to one or more embodiments, the at least one organic acid is a polyfunctional organic acid having at least two acidic functional groups, preferably at least two carboxyl groups. Partially esterified polyfunctional organic acids having at least one free acidic functional group, particularly at least one free carboxyl group, are also suitable. According to one or more embodiments, the at least one organic acid has a molecular weight of 1000 g / mol or less, preferably 750 g / mol or less, more preferably 500 g / mol or less.

[0030] According to one or more embodiments, the at least one organic acid is selected from the group consisting of citric acid, tartaric acid, malic acid, fumaric acid and maleic acid, preferably from citric acid. According to one or more embodiments, the at least one endothermic chemical blowing agent BA comprises exactly one single organic acid, preferably selected from the group consisting of citric acid, tartaric acid, malic acid, fumaric acid and maleic acid, preferably from citric acid.

[0031] Although some of the compounds used in the present invention are characterized as being useful for specific functions, it should be understood that the use of these compounds is not limited to their typical functions. For example, at least one organic acid, when heated to high temperatures, can also function as a curing agent for functional polymers, such as for at least one epoxy-functional polymer EP.

[0032] The at least one organic acid may be present in the thermally expandable composition in the free acid form, i.e., in the protonated acidic functional group, or as a salt of the deprotonated acidic functional group, e.g., as a carboxylate salt or as a mixture thereof. Suitable cations for the carboxylate salt include, for example, Li + , Na + , K + , NH4 + , Ca 2+ , Mg 2+ etc. are included.

[0033] According to one or more embodiments, the at least one organic acid is present in the thermally expandable composition in its free acid form.

[0034] According to one or more embodiments, the at least one endothermic chemical blowing agent BA has a maximum decomposition peak temperature as measured by differential scanning calorimetry (DSC) in the range of 135-200° C., preferably 150-200° C., more preferably 155-200° C., and even more preferably 160-200° C. Preferably, the maximum decomposition peak as measured by DSC is measured with a Mettler-Toledo DSC822e differential scanning calorimeter by holding the sample at 25° C. for 2 minutes, then heating the sample from 25° C. to 280° C. at a rate of 5° C. / min, then holding the sample at 280° C. for 2 minutes, and finally cooling the sample from 280° C. to 25° C. at a rate of 10° C. / min.

[0035] According to one or more embodiments, the at least one endothermic chemical blowing agent BA comprises 1 to 35 wt. %, preferably 5 to 25 wt. %, more preferably 10 to 25 wt. %, and even more preferably 12.5 to 20 wt. % of the total weight of the thermally expandable composition.

[0036] According to one or more embodiments, the at least one organic acid comprises 1 to 35 wt. %, preferably 5 to 25 wt. %, more preferably 10 to 25 wt. %, and even more preferably 12.5 to 20 wt. % of the total weight of the thermally expandable composition.

[0037] The at least one chemical blowing agent BA may contain one or more activators which are used to lower the decomposition temperature of the at least one organic acid. Commonly used activators for organic acids include hydrogen carbonates (bicarbonates) and carbonates, especially those of the formula XHCO3 or X2CO3, where X is Na + , K + , NH4 + , 1 / 2Zn 2+ , 1 / 2Mg 2+ and 1 / 2Ca 2+ , especially Na + and K + These types of activators, however, have the disadvantage that they tend to remain in the resulting foam and that they are water soluble, thus increasing the water absorption of the foam, which is particularly undesirable in the automotive sector where foaming compositions are used to achieve improved corrosion resistance and long term durability.

[0038] According to one or more embodiments, the thermally expandable composition is substantially free of sodium and potassium bicarbonate, and preferably has the formula XHCO3, where X is a common cation, particularly Na + , K + , NH4 + , 1 / 2Zn 2+ , 1 / 2Mg 2+ or 1 / 2Ca 2+and more preferably bicarbonates of the formula XHCO3 and carbonates of the formula X2CO3, where X is a common cation, in particular Na + , K + , NH4 + , 1 / 2Zn 2+ , 1 / 2Mg 2+ or 1 / 2Ca 2+ The expression "substantially free" is understood to mean that the thermally expandable composition may only contain trace amounts of the aforementioned compounds, such as less than 0.5 wt. %, preferably less than 0.25 wt. %, more preferably less than 0.1 wt. %, even more preferably less than 0.05 wt. %, and even more preferably less than 0.01 wt. %, based on the total weight of the thermally expandable composition.

[0039] According to one or more embodiments, the at least one guanidine derivative G is a functionalized guanidine of formula (I): [ka] (In the formula, R 1 represents a hydrogen atom, or a monovalent linear or branched alkyl group, alicyclic group, or aryl or arylalkyl group having 1 to 10 carbon atoms, optionally further containing a nitrogen atom; R 2 represents a hydrogen atom or a monovalent linear or branched alkyl group having 1 to 10 carbon atoms; R 3 represents a hydrogen atom, or a monovalent linear or branched alkyl group having 1 to 10 carbon atoms, or an alicyclic group optionally further containing nitrogen atoms and / or oxygen atoms and / or silicon atoms).

[0040] According to one or more embodiments, the at least one guanidine derivative G is selected from the group of functional guanidines of formula (I), preferably selected from the group consisting of cyanoguanidine, methylguanidine, dimethylguanidine, trimethylguanidine, tetramethylguanidine, acetylacetoneguanidine, 1,3-di-o-tolylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, 1,2-diisopropyl-3-phenylguanidine, 1,2-bis(2,6-diisopropylphenyl)-3-hexylguanidine, more preferably from cyanoguanidine.

[0041] Suitable guanidine derivatives are commercially available, for example, under the trade name Dyhard® (from AlzChem Group AG).

[0042] According to one or more embodiments, the at least one guanidine derivative G represents 0.01 to 5 wt. %, preferably 0.025 to 4.5 wt. %, more preferably 0.1 to 3.5 wt. %, even more preferably 0.15 to 2.5 wt. %, and even more preferably 0.2 to 1 wt. % of the total weight of the thermally expandable composition.

[0043] The thermally expandable composition further comprises at least one free radical initiator I. In principle, all types of free radical initiators known to undergo decomposition upon exposure to a sufficient amount of energy, such as radiation, heat, etc., to generate radicals capable of initiating the desired curing (crosslinking) reaction, are considered suitable for use as the at least one free radical initiator I.

[0044] According to one or more embodiments, the at least one free radical initiator I is a peroxide initiator PI, i.e. the thermally expandable composition comprises at least one peroxide initiator PI, preferably an organic peroxide.

[0045] Suitable peroxide initiators are essentially inactive at room temperature (23° C.) and exhibit an activation temperature suitable for the intended purpose. For example, if the thermally expandable composition is used to provide baffles and / or reinforcing elements in automobile manufacturing, an activation temperature in the range of 90-250° C. is typically preferred. Furthermore, it is advantageous for the at least one peroxide initiator PI to have an activation temperature that is compatible with the decomposition temperature of the at least one endothermic chemical blowing agent BA. If the two aforementioned temperatures differ too greatly, it may be more difficult to obtain a thermally expandable composition with optimal performance and stability.

[0046] It may further be advantageous for the at least one peroxide initiator PI to have a half-life of 10 h at a temperature in the range of 90-130° C., as measured in benzene or a similar non-polar solvent. For certain types of peroxide initiators, solvents other than benzene may be more suitable for use in measuring the half-life, such as, for example, toluene, triethyl phosphate or dibutyl phthalate. For ultra-low temperature embodiments, i.e., those optimized for expansion at 120° C. to 150° C., peroxide initiators having a half-life of 10 h at a temperature in the range of 50-100° C. are preferred. It is further advantageous for the at least one peroxide initiator PI to be compatible and / or miscible with the polymer matrix of the thermally expandable composition. In some cases, the compatibility of the peroxide initiator with the polymer matrix can be further improved by using processing aids and other compatibilizing additives.

[0047] Suitable peroxide initiators include in particular organic peroxides: in principle, all types of organic peroxides known to undergo thermal decomposition to generate radicals capable of initiating the desired curing (crosslinking) reaction are considered suitable for use as the at least one peroxide initiator PI.

[0048] According to one or more embodiments, the at least one peroxide initiator PI is an organic peroxide, preferably selected from the group consisting of ketone peroxides, diacyl peroxides, peresters, perketals, and hydroperoxides. Examples of preferred peroxides include cumene hydroperoxide, t-butyl peroxide, bis(t-butylperoxy)-diisopropylbenzene, di(t-butylperoxyisopropyl)benzene, dicumyl peroxide, t-butyl peroxybenzoate, dialkyloxydicarbonate, diperoxyketals (such as 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane), ketone peroxides (such as methyl ethyl ketone peroxide), and 4,4-di-t-butylperoxy-n-butylvalerate.

[0049] Particularly suitable organic peroxides include 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di(t-butylperoxyisopropyl)benzene, dicumyl peroxide, butyl-4,4-di(t-butylperoxy)valerate, t-butylperoxy-2-ethylhexyl carbonate, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, t-butylperoxybenzoate, di(4-methylbenzoyl)peroxide, and dibenzoyl peroxide.

[0050] According to one or more embodiments, the at least one peroxide initiator PI is selected from the group consisting of dicumyl peroxide, and / or di(t-butylperoxyisopropyl)benzene, and / or 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane.

[0051] These are commercially available, for example, under the trade names Perkadox® BC-40B-PD from Akzo Nobel and Peroxan® DC-40 PK (dicumyl peroxide) from Pergan; Perkadox® 14-40B-PD from Akzo Nobel and Peroxan® BIB-40 P (di(t-butylperoxyisopropyl)benzene); and Peroxan® PK295 (di(t-butylperoxyisopropyl)benzene) from Pergan.

[0052] According to one or more embodiments, the at least one peroxide initiator PI comprises 0.01-10 wt.-% of the total weight of the thermally expandable composition, preferably 0.025-7.5 wt.-%, more preferably 0.05-5 wt.-%, even more preferably 0.1-3.5 wt.-%, even more preferably 0.15-3.5 wt.-%, and most preferably 0.25-3 wt.-%.

[0053] It may further be advantageous for the at least one peroxide initiator PI to be present in the thermally expandable composition so as to be immobilized on a support material, such as silica, kaolin, and / or calcium carbonate, or other suitable material. This approach may facilitate handling, use, and uniform distribution of the at least one peroxide initiator PI in the thermally expandable composition. Examples of immobilized organic peroxides include, for example, 40 wt. % dicumyl peroxide on calcium carbonate, 40 wt. % di(t-butylperoxyisopropyl)benzene on clay and silica, and 40 wt. % 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane on calcium carbonate. In these embodiments, the expression "amount of at least one peroxide initiator PI" refers to the amount of active material contained in the thermally expandable composition excluding the amount of the support material on which the at least one peroxide initiator PI, such as the organic peroxide, is immobilized.

[0054] According to one or more embodiments, the thermally expandable composition comprises at least one co-agent containing at least two (meth)acryloyl groups, preferably at least one multifunctional acrylate A, preferably having a molecular weight of less than 2,500 g / mol, more preferably less than 1,000 g / mol, and preferably having an acrylate functionality of at least 2 or 3, preferably at least 4 or 5, or more. The term "(meth)acryloyl" designates both acryloyl and methacryloyl in this disclosure.

[0055] Such multifunctional acrylates can improve the crosslinking of the polymer components contained in the thermally expandable composition and help to obtain a stable foam structure. When used, the at least one multifunctional acrylate A preferably accounts for 0.05 to 3.5 wt.%, more preferably 0.1 to 2.5 wt.%, even more preferably 0.25 to 2.0 wt.%, and even more preferably 0.25 to 1.5 wt.% of the total weight of the thermally expandable composition.

[0056] Suitable multifunctional acrylates A with a functionality of 2 include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tripropylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,10-dodecanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, and polybutylene glycol dimethacrylate, and hexanediol diacrylate. The most preferred acrylate with a functionality of 2 is hexanediol diacrylate.

[0057] Suitable multifunctional acrylates A with a functionality of 3 or more include glycerol triacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane tetraacrylate, di-(trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri(2-methacryloxyethyl) trimellitate, tri(2-acryloxyethyl) isocyanurate, and their ethoxylated or propoxylated derivatives. The most preferred multifunctional acrylate with a functionality of 5 is dipentaerythritol pentaacrylate. Furthermore, highly functional, hyperbranched acrylates with a functionality of 6 to 16 or more are suitable. Examples of such acrylates include hyperbranched polyester polyacrylates.

[0058] According to one or more embodiments, the sum of the amounts of the at least one free radical initiator I and the at least one multifunctional acrylate A, when present in the thermally expandable composition, represents 0.25 to 7.5 wt. %, preferably 0.25 to 5.0 wt. %, more preferably 0.5 to 3.5 wt. %, and even more preferably 0.75 to 2.5 wt. %, based on the total weight of the thermally expandable composition.

[0059] According to one or more embodiments, the weight ratio of the amount of at least one free radical initiator I to the amount of at least one multifunctional acrylate A, when present in the thermally expandable composition, is in the range of 0.1:1 to 10:1, preferably 0.1:1 to 5:1, more preferably 0.2:1 to 5:1, even more preferably 0.3:1 to 3:1.

[0060] Epoxy-functional polymer EP The thermally expandable composition comprises at least one epoxy-functional polymer EP. Preferably, the at least one epoxy-functional polymer EP has an average of 2 or more epoxy groups per molecule. Furthermore, the at least one epoxy-functional polymer EP can contain either polymerized or grafted epoxy functionality, i.e., the epoxide moiety can be present as part of the polymer backbone or grafted onto the polymer as a side chain.

[0061] Suitable epoxy-functional polymers for use as the at least one epoxy-functional polymer EP include, for example, olefin glycidyl (meth)acrylate copolymers, olefin alkyl (meth)acrylate glycidyl (meth)acrylate terpolymers, glycidyl methacrylate grafted (co)polymers, epoxy resins and epoxy-functionalized polyurethane polymers. The term "(meth)acrylate" in this disclosure designates both acrylate and methacrylate.

[0062] Suitable olefin glycidyl (meth)acrylate copolymers to be used as the at least one epoxy-functional polymer EP include, for example, copolymers of ethylene, propylene or butylene with glycidyl acrylate (GA) or with glycidyl (meth)acrylate (GMA).

[0063] According to one or more embodiments, the at least one epoxy-functional polymer EP preferably comprises at least one olefin glycidyl (meth)acrylate copolymer EP1 selected from the group consisting of ethylene glycidyl (meth)acrylate copolymer, propylene glycidyl (meth)acrylate copolymer and butylene glycidyl (meth)acrylate copolymer, more preferably from the group consisting of ethylene glycidyl (meth)acrylate copolymer, in particular ethylene glycidyl methacrylate copolymer. In general, the expression "at least one component X comprises at least one component XN", such as "at least one epoxy-functional polymer EP comprises at least one olefin glycidyl (meth)acrylate copolymer EP1", is understood in the context of the present disclosure to mean that the thermally expandable composition comprises one or more olefin glycidyl (meth)acrylate copolymers EP1 as representative of at least one epoxy-functional polymer EP.

[0064] According to one or more embodiments, the at least one olefin glycidyl (meth)acrylate copolymer EP1 is a content of glycidyl methacrylate ranging from 1 to 50% by weight, more preferably from 2 to 25% by weight, and / or a melt flow index, measured according to ISO 1133 (190 ° C / 2.16 kg), of less than or equal to 100 g / 10 min, preferably less than or equal to 75 g / 10 min, more preferably less than or equal to 50 g / 10 min, and / or - a melting temperature (T) as measured by DSC measurement performed according to ISO 11357-3 of not more than 150 ° C, preferably not more than 135 ° C, in particular in the range of 75 to 150 ° C, preferably 85 to 135 ° C, more preferably 90 to 125 ° C. m ) has.

[0065] According to one or more embodiments, the at least one epoxy-functional polymer EP is preferably composed of at least one olefin glycidyl (meth)acrylate copolymer EP1 selected from the group consisting of ethylene glycidyl (meth)acrylate copolymers, propylene glycidyl (meth)acrylate copolymers and butylene glycidyl (meth)acrylate copolymers, more preferably from the group consisting of ethylene glycidyl (meth)acrylate copolymers, in particular ethylene glycidyl methacrylate copolymers. In general, the expression "at least one component X is composed of at least one component XN", such as "at least one epoxy-functional polymer EP is composed of at least one olefin glycidyl (meth)acrylate copolymer EP1", is understood in the context of the present disclosure to mean that the at least one epoxy-functional polymer EP is selected from the group consisting of at least one olefin glycidyl (meth)acrylate copolymer EP1.

[0066] Suitable olefin alkyl (meth)acrylate glycidyl (meth)acrylate terpolymers to be used as the at least one epoxy-functional polymer EP include, for example, terpolymers, in particular random terpolymers of ethylene and alkyl (meth)acrylate with glycidyl acrylate (GA) or glycidyl methacrylate (GMA), where the alkyl group of the alkyl (meth)acrylate is preferably selected from the group consisting of methylene, ethylene, propylene and butylene, in particular methylen or butylene.

[0067] Preferred olefin alkyl (meth)acrylate glycidyl (meth)acrylate terpolymers include ethylene methyl acrylate glycidyl acrylate terpolymer (E / MA / GA), ethylene ethyl acrylate glycidyl acrylate terpolymer (E / EA / GA), ethylene propyl acrylate glycidyl acrylate terpolymer (E / PA / GA), ethylene butyl acrylate glycidyl acrylate terpolymer (E / BA / GA), ethylene methyl methacrylate glycidyl acrylate terpolymer (E / MMA / GA), ethylene ethyl methacrylate glycidyl acrylate terpolymer (E / EMA / GA), ethylene propyl methacrylate glycidyl acrylate terpolymer (E / PMA / GA), ethylene butyl ...butyl methacrylate glycidyl acrylate terpolymer (E / PMA / GA), ethylene butyl methacrylate glycidyl acrylate terpolymer (E / PMA / GA), ethylene butyl methacrylate glycidyl acrylate terpolymer (E / PMA / GA), ethylene butyl methacrylate glycidyl acrylate terpolymer (E / PMA / GA), ethylene butyl methacrylate glycidyl acrylate terpolymer (E / PMA / GA), ethylene butyl methacrylate glycidyl acrylate terpolymer (E / PMA / GA), ethylene butyl methacrylate glycidyl acrylate terpolymer (E ethylene methyl acrylate glycidyl methacrylate terpolymer (E / BMA / GA), ethylene methyl acrylate glycidyl methacrylate terpolymer (E / MA / GMA), ethylene ethyl acrylate glycidyl methacrylate terpolymer (E / EA / GMA), ethylene propyl acrylate glycidyl methacrylate terpolymer (E / PA / GMA), ethylene butyl acrylate glycidyl methacrylate terpolymer (E / BA / GMA), ethylene methyl methacrylate glycidyl methacrylate terpolymer (E / MMA / GMA), ethylene ethyl methacrylate glycidyl methacrylate terpolymer (E / EMA / GMA), ethylene propyl methacrylate glycidyl methacrylate terpolymer (E / PMA / GMA), ethylene butyl methacrylate glycidyl methacrylate terpolymer (E / BMA / GMA).

[0068] According to one or more embodiments, the at least one epoxy-functional polymer EP comprises at least one olefin alkyl acrylate glycidyl (meth)acrylate terpolymer EP2, preferably selected from the group consisting of random terpolymers of ethylene, alkyl (meth)acrylate and glycidyl methacrylate, where the alkyl group of the alkyl (meth)acrylate is preferably selected from the group consisting of methylene, ethylene, propylene and butylene, in particular methylene or butylene.

[0069] According to one or more embodiments, the at least one olefin alkyl acrylate glycidyl (meth)acrylate terpolymer EP2 is a content of glycidyl methacrylate ranging from 1 to 50% by weight, more preferably from 2 to 25% by weight, and / or a melt flow index, measured according to ISO 1133 (190 ° C / 2.16 kg), of less than or equal to 100 g / 10 min, preferably less than or equal to 75 g / 10 min, more preferably less than or equal to 50 g / 10 min, and / or - a melting temperature (T) as measured by DSC measurement performed according to ISO 11357-3 of not more than 150 ° C, preferably not more than 135 ° C, in particular in the range of 75 to 150 ° C, preferably 85 to 135 ° C, more preferably 90 to 125 ° C. m ) has.

[0070] According to one or more embodiments, the at least one epoxy-functional polymer EP consists of at least one olefin alkyl acrylate glycidyl (meth)acrylate terpolymer EP2, preferably selected from the group consisting of random terpolymers of ethylene, alkyl (meth)acrylate and glycidyl methacrylate, where the alkyl group of the alkyl (meth)acrylate is preferably selected from the group consisting of methylene, ethylene, propylene and butylene, in particular methylene or butylene.

[0071] Suitable glycidyl (meth)acrylate grafted (co)polymers to be used as the at least one epoxy-functional polymer EP include, for example, glycidyl methacrylate grafted olefin vinyl acetate copolymers, glycidyl methacrylate grafted ethylene-α-olefin copolymers, glycidyl methacrylate grafted propylene-α-olefin copolymers, glycidyl methacrylate grafted polyethylene, glycidyl methacrylate grafted polypropylene and glycidyl methacrylate grafted olefin copolymer elastomers, glycidyl (meth)acrylate grafted styrene butadiene copolymers and glycidyl (meth)acrylate grafted styrene ethylene butylene styrene terpolymers.

[0072] According to one or more embodiments, the at least one epoxy-functional polymer EP comprises at least one glycidyl methacrylate grafted (co)polymer EP3 preferably selected from the group consisting of glycidyl methacrylate grafted olefin vinyl acetate copolymers, glycidyl methacrylate grafted ethylene-α-olefin copolymers, glycidyl methacrylate grafted propylene-α-olefin copolymers, glycidyl methacrylate grafted polyethylene, glycidyl methacrylate grafted polypropylene, glycidyl (meth)acrylate grafted styrene butadiene copolymers and glycidyl (meth)acrylate grafted styrene ethylene butylene styrene terpolymers.

[0073] According to one or more embodiments, the at least one glycidyl methacrylate grafted (co)polymer EP3 is a content of glycidyl methacrylate (GMA) of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.1 to 3.5% by weight, even more preferably 0.1 to 2.5% by weight, in particular 0.1 to 1.5% by weight, and / or a melt flow index, measured according to ISO 1133 (190 ° C / 2.16 kg), of less than or equal to 100 g / 10 min, preferably less than or equal to 75 g / 10 min, more preferably less than or equal to 50 g / 10 min, and / or - a melting temperature (T) as measured by DSC measurement performed according to ISO 11357-3 of not more than 150 ° C, preferably not more than 135 ° C, in particular in the range of 75 to 150 ° C, preferably 85 to 135 ° C, more preferably 90 to 125 ° C. m ) has.

[0074] According to one or more embodiments, the at least one epoxy-functional polymer EP consists of at least one glycidyl methacrylate grafted (co)polymer EP3 preferably selected from the group consisting of glycidyl methacrylate grafted olefin vinyl acetate copolymers, glycidyl methacrylate grafted ethylene-α-olefin copolymers, glycidyl methacrylate grafted propylene-α-olefin copolymers, glycidyl methacrylate grafted polyethylene, glycidyl methacrylate grafted polypropylene, glycidyl (meth)acrylate grafted styrene butadiene copolymers and glycidyl (meth)acrylate grafted styrene ethylene butylene styrene terpolymers.

[0075] Suitable epoxy resins for use as the at least one epoxy-functional polymer EP include solid and liquid epoxy resins and mixtures thereof having an average of two or more epoxy groups per molecule. The term "solid epoxy resin" designates an epoxy resin that has a glass transition temperature above normal room temperature.

[0076] Suitable solid epoxy resins include those of formula (II): [ka] (wherein the substituents R′ and R″ each independently represent either a hydrogen atom or a methyl group, and the index s has a value of 1 or more, preferably 1.5 or more, more preferably 2 to 12).

[0077] Compounds of formula (II) having an index s in the range of from greater than 1 to 1.5 are known to those skilled in the art as semi-solid epoxy resins, and for the purposes of this disclosure, they are considered to be solid epoxy resins as well.

[0078] Suitable solid epoxy resins are commercially available from, for example, Dow Chemical Company, Huntsman International LLC, Hexion Specialty Chemicals Inc., and Olin Corporation.

[0079] In particular, suitable liquid epoxy resins that can be used together with the solid epoxy resins of formula (II) include those of formula (III): [ka] (wherein the substituents R''' and R'''' represent, independently of one another, either a hydrogen atom or a methyl group, and the index r has a value between 0 and 1, preferably between 1 and less than 0.2).

[0080] Preferred liquid epoxy resins are therefore the diglycidyl ethers of bisphenol A (DGEBA), of bisphenol F and of bisphenol A / F (the expression "A / F" refers herein to the mixture of acetone and formaldehyde used as reactants in its preparation).

[0081] Suitable liquid epoxy resins are commercially available, for example, under the trade names Araldite® GY 250, Araldite® PY 304 and Araldite® GY 282 (from Huntsman International LLC), as well as under the trade names DER® 331 or DER® 330 (from Dow Chemical Company), and under the trade names Epikote® 828 or Epikote® 862 (from Hexion Specialty Chemicals Inc.).

[0082] Further suitable solid epoxy resins are the so-called novolac resins. Preferred epoxy novolac resins include those of formula (IV): [ka] In the formula, the moiety X represents a hydrogen atom or a methyl group. The moiety W represents -CH- or a group represented by the formula (V): [ka] (representing part of).

[0083] Preferably, the index z represents a value between 0 and 7, in particular a value greater than or equal to 3. In particular, they are phenol or cresol novolaks (W represents -CH2-).

[0084] Such epoxy novolac resins are commercially available, for example, under the EPN®, ECN® and Tactix® 556 trade names (from Huntsman International LLC) and DEN® trade name (from Dow Chemical Company).

[0085] According to one or more embodiments, the at least one epoxy-functional polymer EP comprises or consists of at least one epoxy resin EP4, preferably selected from the group consisting of solid epoxy resins of formula (II), solid epoxy resins of formula (IV) and mixtures of solid epoxy resins of formula (II) and / or (IV) with liquid epoxy resins of formula (III). The thermally expandable compositions according to these embodiments are particularly suitable for use as structural foams, in particular for the reinforcement of hollow structures.

[0086] Further suitable epoxy resins to be used as the at least one epoxy-functional polymer EP include epoxy-functional polyurethane polymers of formula (VI): [ka] (wherein Y represents the w-valent radical of a linear or branched isocyanate-functional polyurethane polymer PU after removal of the w terminal isocyanate groups; Z represents a (1+v)-valent radical of an aliphatic, cycloaliphatic, aromatic or araliphatic epoxide E containing a hydroxyl group and a primary or secondary hydroxyl group after removal of the v epoxide groups; v represents an integer having a value of 1, 2 or 3, preferably 2; and w represents an integer having a value of 2 to 4.

[0087] The linear or branched isocyanate-functional polyurethane polymer PU preferably has a structure according to formula (VII): [ka] (wherein Y and w have the same meaning as described further above).

[0088] The isocyanate-functional polyurethane polymer PU of formula (VII) can be obtained from the reaction of at least one polyisocyanate, preferably a diisocyanate or triisocyanate, with at least one polyol, in which the isocyanate groups are in stoichiometric excess over the hydroxyl groups. This reaction can be carried out by known methods, preferably at temperatures between 50 and 150° C., optionally in the presence of a catalyst.

[0089] Suitable polyols for the preparation of the isocyanate-functional polyurethane polymers PU include, for example, the polyoxyalkylene polyols, also known as polyether polyols, which are the polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, tetrahydrofuran or mixtures thereof, optionally polymerized with water or compounds having 2 or 3 OH groups, such as starter molecules having 2 or 3 active H atoms, such as ethylene glycol or glycerol.

[0090] Preferred polyether polyols are the polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, tetrahydrofuran or mixtures thereof, with polypropylene oxide and polytetrahydrofuran being particularly preferred. Suitable polytetrahydrofurans are commercially available, for example, from BASF under the trade name PolyTHF®, such as PolyTHF® 2000, PolyTHF® 2500 CO and PolyTHF® 3000 CO. Suitable polypropylene oxides are commercially available, for example, from Shell under the trade name Caradol®, such as Caradol® 2000 and Caradol® ED56, and from Bayer under the trade name Acclaim®, such as Acclaim® Polyol 2200, Acclaim® Polyol 12200 and Acclaim® Polyol 4200. Further suitable polyether polyols are commercially available from Dow Chemicals under the trade names Voranol® 1010L, Voranol® EP1900 and Voranol® CP4755. A particularly preferred polyether polyol is polytetrahydrofuran. Preferred polyester polyols have, for example, a weight average molecular weight (M) in the range of 500 to 5000 g / mol, more preferably 1000 to 3000 g / mol, particularly preferably 1500 to 2500 g / mol. w ).

[0091] The OH functionality of the polyether polyols used is preferably in the range of approximately 2, for example in the range of 1.9 to 2.1. Optionally, compounds having an OH functionality of 3, such as trimethylolpropane, butoxylated trimethylolpropane (for example Simulsol® TOMB) and / or pentaerythritol, can be added to the polyether polyol to increase the OH functionality.

[0092] Further suitable polyols include hydroxyl-terminated rubbers.One or more OH-terminated rubbers can be used, where the use of two OH-terminated rubbers, particularly two OH-terminated polybutadienes, is preferred.Herein, OH-terminated rubbers are understood to refer, for example and preferably, to hydroxyl-terminated polybutadienes and castor oil-based polyols, where hydroxyl-terminated polybutadienes are particularly preferred.Castor oil-based polyols include various grades of castor oil and castor oil derivatives.

[0093] Commercially available hydroxyl terminated polybutadienes are commercially available from Cray valley under the trade names Poly bd and Krasol, such as Krasol LBH-P 2000 or Poly bd R45V; from Evonik under the trade name Polyvest HT; from Emerald materials under the trade name Hypro 2800X95 HTB. Castor oil-based polyols are commercially available from Alberdingk Boley under the trade name Albodur; from Baker Castor Oil Company under the trade name Polycine, such as Polycine GR80.

[0094] The OH functionality of the hydroxyl terminated rubbers preferably ranges from 1.7 to 2.2 for types produced anionically and from 2.2 to 2.8 for types produced by free radical polymerization.

[0095] Polyhydroxy-terminated acrylonitrile / butadiene copolymers, such as those commercially available from Emerald Materials under the tradename Hypro® CTBN, as well as those prepared using carboxyl-terminated acrylonitrile / butadiene copolymers, such as those prepared using epoxides or aminoalcohols, are also suitable as polyols.

[0096] Further suitable polyols for the preparation of the isocyanate-functional polyurethane polymers PU include polyester polyols prepared, for example, from dihydric to trihydric alcohols, such as, for example, 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, glycerol, 1,1,1-trimethylolpropane or mixtures of the aforementioned alcohols, and organic dicarboxylic acids, such as, for example, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and hexahydrophthalic acid or mixtures of the aforementioned acids, or their acid anhydrides or esters, and also polyester polyols from lactones, such as ε-caprolactone.

[0097] Further polycarbonate polyols of the type obtained by reacting the above-mentioned alcohols, i.e. those used to synthesize the polyester polyols, with dialkyl carbonates, diaryl carbonates or phosgene are suitable as polyols for the preparation of isocyanate-functional polyurethane polymers PU. Polyols of the type obtained by reduction of dimerized fatty acids are also suitable.

[0098] The isocyanate-functional polyurethane polymer PU can be obtained by using only one type of polyol. The preferred polyol for these embodiments is polyether polyol, especially polytetrahydrofuran. However, it may be advantageous to use a mixture of different types of polyols for the preparation of the polyurethane polymer PU. According to one or more embodiments, the isocyanate-functional polyurethane polymer PU can be obtained by using polyether polyol, especially polytetrahydrofuran and polybutadiene polyol.

[0099] Suitable polyisocyanates for the preparation of the isocyanate-functional polyurethane polymer PU include diisocyanates and triisocyanates. Suitable diisocyanates are aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanates, in particular those commercially available such as methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), toluidine diisocyanate (TODI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), 2,5- or 2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 1,5-naphthalene diisocyanate (NDI), dicyclohexylmethyl diisocyanate (H12MDI), p-phenylene diisocyanate (PPDI), m-tetramethylxylylene diisocyanate (TMXDI) and dimers thereof, where HDI, IPDI, MDI, TDI are preferred. Particularly preferred diisocyanates are aliphatic and cycloaliphatic diisocyanates, such as HDI, H12MDI and IPDI.

[0100] Suitable triisocyanates are the trimers or biurets of aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanates, in particular the isocyanurates and biurets of the aforementioned diisocyanates.

[0101] The isocyanate-functional polyurethane polymer PU is then endcapped with at least one monohydroxyl epoxide compound E according to formula (VIII): [ka] (wherein Z and v have the same meanings as above).

[0102] The monohydroxyl epoxide compounds E of formula (VIII) are aliphatic, cycloaliphatic, aromatic or araliphatic epoxides containing one primary or secondary hydroxyl group and 1 to 3 epoxide groups.

[0103] The monohydroxyl epoxide compounds E of formula (VIII) can be obtained, for example, by reacting a polyol with epichlorohydrin. Depending on the reaction regime, the reaction of a polyol with epichlorohydrin produces by-products containing different concentrations of the corresponding monohydroxyl epoxide compounds. These can be separated by routine separation operations.

[0104] However, generally speaking, it is sufficient to use the product mixture obtained in the glycidylation reaction of polyol, which contains fully reacted polyol and partially reacted polyol to form glycidyl ether.Examples of this type of hydroxyl-containing epoxide compound are butanediol monoglycidyl ether (contained in butanediol diglycidyl ether), hexanediol monoglycidyl ether (contained in hexanediol diglycidyl ether), cyclohexanedimethanol glycidyl ether, trimethylolpropane diglycidyl ether (contained as a mixture in trimethylolpropane triglycidyl ether), glycerol diglycidyl ether (contained as a mixture in glycerol triglycidyl ether), pentaerythritol triglycidyl ether (contained as a mixture in pentaerythritol tetraglycidyl ether).It is preferable to use trimethylolpropane diglycidyl ether, which occurs in a relatively high fraction in the customarily prepared trimethylolpropane triglycidyl ether.

[0105] However, it is also possible to use other similar hydroxyl-containing epoxides, especially glycidol, 3-glycidyloxybenzyl alcohol or hydroxymethylcyclohexene oxide. Liquid epoxy resins of formula (III) as described above are further preferred.

[0106] The preference for end-capping of isocyanate-functional polyurethane polymers PU extends to the distillation residues obtained in the preparation of high-purity, distilled liquid epoxy resins. This type of distillation residue has a concentration of hydroxyl-containing epoxides up to three times higher than that of commercially available non-distilled liquid epoxy resins. Such resins are commercially available, for example, under the trade name Epilox® M850 from Leuna-Harze. It is also possible to use a variety of β-hydroxyether group-containing epoxides prepared by reaction of (poly)epoxides with stoichiometric amounts of monofunctional nucleophiles such as carboxylic acids, phenols, thiols or secondary amines.

[0107] According to one or more embodiments, the at least one epoxy-functional polymer EP comprises or consists of at least one epoxy-functional polyurethane polymer EP5, preferably at least one epoxy-functional polyurethane polymer of formula (VI).

[0108] According to one or more embodiments, the at least one epoxy-functional polymer EP comprises at least one olefin glycidyl (meth)acrylate copolymer EP1, and / or at least one olefin alkyl acrylate glycidyl (meth)acrylate terpolymer EP2, and / or at least one glycidyl (meth)acrylate grafted (co)polymer EP3.

[0109] According to one or more preferred embodiments, the at least one epoxy-functional polymer EP is selected from the group consisting of olefin glycidyl (meth)acrylate copolymers, olefin alkyl (meth)acrylate glycidyl (meth)acrylate terpolymers, and glycidyl (meth)acrylate grafted (co)polymers, and epoxy-functionalized polyurethane polymers, preferably from the group consisting of at least one olefin glycidyl (meth)acrylate copolymer EP1, at least one olefin alkyl (meth)acrylate glycidyl (meth)acrylate terpolymer EP2, at least one glycidyl (meth)acrylate grafted (co)polymer EP3 and at least one epoxy-functionalized polyurethane polymer EP4, more preferably from the group consisting of at least one olefin glycidyl (meth)acrylate copolymer EP1, at least one olefin alkyl (meth)acrylate glycidyl (meth)acrylate terpolymer EP2 and at least one glycidyl (meth)acrylate grafted (co)polymer EP3.

[0110] Acid anhydride functional polymer AP The polymer component P of the thermally expandable composition can further comprise at least one anhydride-functional polymer AP. The preferred anhydride-functional polymer AP has an average of more than one anhydride group per molecule. Furthermore, the at least one anhydride-functional polymer AP can contain either polymerized or grafted anhydride functionality, i.e., the anhydride moiety can be present as part of the polymer backbone or grafted onto the polymer as a side chain.

[0111] Suitable anhydride-functional polymers for use as the at least one anhydride-functional polymer AP include maleic anhydride-functional polymers and tetrahydrophthalic anhydride-functional polymers, in particular maleic anhydride-functional polymers. Suitable maleic anhydride-functional polymers include, for example, olefin-maleic anhydride copolymers, olefin-alkyl (meth)acrylate-maleic anhydride terpolymers, and maleic anhydride-grafted (co)polymers.

[0112] Suitable olefin alkyl acrylate maleic anhydride terpolymers to be used as the at least one anhydride-functional polymer AP include, for example, terpolymers, in particular random terpolymers, of ethylene, alkyl (meth)acrylate and maleic anhydride, in which the alkyl group of the alkyl (meth)acrylate is preferably selected from the group consisting of methylene, ethylene, propylene and butylene.

[0113] According to one or more embodiments, the at least one anhydride-functional polymer AP comprises at least one olefin-alkyl acrylate-maleic anhydride terpolymer AP1, preferably selected from the group consisting of random terpolymers of ethylene, alkyl (meth)acrylate and maleic anhydride, where the alkyl groups of the alkyl (meth)acrylate are preferably selected from the group consisting of methylene, ethylene, propylene and butylene, more preferably methylene, ethylene and butylene.

[0114] According to one or more embodiments, the at least one olefin alkyl acrylate maleic anhydride terpolymer AP1 is a content of maleic anhydride ranging from 0.5 to 10% by weight, preferably from 1 to 7.5% by weight, more preferably from 1 to 5% by weight, and / or a melt flow index, measured according to ISO 1133 (190 ° C / 2.16 kg), of less than or equal to 100 g / 10 min, preferably less than or equal to 75 g / 10 min, more preferably less than or equal to 50 g / 10 min, and / or - a melting temperature (T) as measured by DSC measurement performed according to ISO 11357-3 of not more than 150 ° C, preferably not more than 135 ° C, in particular in the range of 75 to 150 ° C, preferably 85 to 135 ° C, more preferably 90 to 125 ° C. m ) has.

[0115] According to one or more embodiments, the at least one anhydride-functional polymer AP consists of at least one olefin-alkyl acrylate-maleic anhydride terpolymer AP1, preferably selected from the group consisting of random terpolymers of ethylene, alkyl (meth)acrylate and maleic anhydride, where the alkyl groups of the alkyl (meth)acrylate are preferably selected from the group consisting of methylene, ethylene, propylene and butylene, more preferably methylene, ethylene and butylene.

[0116] Suitable olefin-maleic anhydride copolymers to be used as the at least one anhydride-functional polymer AP include, for example, copolymers of maleic anhydride with ethylene, propylene or butylene.

[0117] According to one or more embodiments, the at least one anhydride-functional polymer AP comprises or consists of at least one olefin-maleic anhydride copolymer AP2 preferably selected from the group consisting of copolymers of ethylene, propylene and butylene with maleic anhydride, more preferably ethylene-maleic anhydride copolymers.

[0118] Suitable maleic anhydride grafted (co)polymers to be used as the at least one acid anhydride functional polymer AP include, for example, maleic anhydride grafted olefin alkyl (meth)acrylate copolymers, maleic anhydride grafted olefin vinyl acetate copolymers, maleic anhydride grafted ethylene-α-olefin copolymers, maleic anhydride grafted propylene-α-olefin copolymers, maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene and maleic anhydride grafted ethylene propylene rubber (EPR) and other maleic anhydride grafted olefin copolymer elastomers.

[0119] According to one or more embodiments, the at least one acid anhydride-functional polymer AP preferably comprises at least one maleic anhydride-grafted (co)polymer AP3 selected from the group consisting of maleic anhydride grafted olefin alkyl (meth)acrylate copolymers, maleic anhydride grafted olefin vinyl acetate copolymers, maleic anhydride grafted ethylene-α-olefin copolymers, maleic anhydride grafted propylene-α-olefin copolymers, maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene and maleic anhydride grafted olefin copolymer elastomers, more preferably from the group consisting of maleic anhydride grafted olefin vinyl acetate copolymers, maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene.

[0120] According to one or more embodiments, the at least one maleic anhydride grafted (co)polymer AP3 is a content of maleic anhydride of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.1 to 3.5% by weight, even more preferably 0.1 to 2.5% by weight, in particular 0.1 to 1.5% by weight, and / or a melt flow index, measured according to ISO 1133 (190 ° C / 2.16 kg), of less than or equal to 100 g / 10 min, preferably less than or equal to 75 g / 10 min, more preferably less than or equal to 50 g / 10 min, and / or - a melting temperature (T) as measured by DSC measurement performed according to ISO 11357-3 of not more than 150 ° C, preferably not more than 135 ° C, in particular in the range of 75 to 150 ° C, preferably 85 to 135 ° C, more preferably 90 to 125 ° C. m ) has.

[0121] According to one or more embodiments, the at least one anhydride-functional polymer AP is preferably selected from the group consisting of maleic anhydride grafted olefin alkyl (meth)acrylate copolymers, maleic anhydride grafted olefin vinyl acetate copolymers, maleic anhydride grafted ethylene-α-olefin copolymers, maleic anhydride grafted propylene-α-olefin copolymers, maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene and maleic anhydride grafted olefin copolymer elastomers, more preferably from the group consisting of maleic anhydride grafted olefin vinyl acetate copolymers, maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene.

[0122] According to one or more embodiments, the at least one anhydride-functional polymer AP comprises at least one olefin-alkyl acrylate-maleic anhydride terpolymer AP1, and / or at least one olefin-maleic anhydride copolymer AP2, and / or at least one maleic anhydride grafted (co)polymer AP3.

[0123] According to one or more preferred embodiments, the at least one anhydride-functional polymer AP is selected from the group consisting of olefin-alkyl acrylate-maleic anhydride terpolymers, olefin-maleic anhydride copolymers, maleic anhydride grafted (co)polymers, preferably from the group consisting of at least one olefin-alkyl acrylate-maleic anhydride terpolymer AP1, at least one olefin-maleic anhydride copolymer AP2 and at least one maleic anhydride grafted (co)polymer AP3, more preferably from the group consisting of at least one olefin-alkyl acrylate-maleic anhydride terpolymer AP1 and at least one olefin-maleic anhydride copolymer AP2.

[0124] According to one or more embodiments, the polymer component P of the thermally expandable composition further comprises, in addition to the at least one epoxy-functional polymer EP, at least one acid anhydride-functional polymer AP, wherein the ratio of the amount of the at least one epoxy-functional polymer EP to the amount of the at least one acid anhydride-functional polymer AP is preferably in the range of 0.3:1 to 3:1, more preferably 0.5:1 to 2:1, and wherein the at least one epoxy-functional polymer EP preferably consists of at least one olefin glycidyl (meth)acrylate copolymer EP1, and / or at least one olefin alkyl acrylate glycidyl (meth)acrylate terpolymer EP2, and / or at least one glycidyl (meth)acrylate grafted (co)polymer EP3, and wherein the at least one acid anhydride-functional polymer AP preferably consists of at least one olefin alkyl acrylate maleic anhydride terpolymer AP1, and / or at least one olefin maleic anhydride copolymer AP2, and / or at least one maleic anhydride grafted (co)polymer AP3.

[0125] Thermoplastic Polymers According to one or more embodiments, the polymer component P of the thermally expandable composition further comprises at least one thermoplastic polymer TP. In principle all thermoplastic polymers and thermoplastic elastomers (TPEs) are suitable as the at least one thermoplastic polymer TP. It goes without saying that the at least one thermoplastic polymer TP is different from the at least one epoxy-functional polymer EP and the at least one acid anhydride-functional polymer AP.

[0126] Suitable polymers for use as the at least one thermoplastic polymer TP include, for example, styrene-butadiene copolymers, styrene-isoprene copolymers, ethylene-vinyl acetate copolymers (EVA), olefin (meth)acrylate copolymers, olefin alkyl (meth)acrylate copolymers, olefin (meth)acrylic acid copolymers, polyolefins and halogenated polyolefins such as polyvinyl chloride (PVC). Particularly suitable olefin alkyl (meth)acrylate copolymers and olefin alkyl (meth)acrylate copolymers include, for example, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer (EBA) and ethylene-2-ethylhexyl acrylate copolymer.

[0127] Suitable thermoplastic polymers TP may contain unsaturated olefinic bonds and they may also contain functional groups other than epoxide or anhydride groups, such as halogen, nitrile, thiol, hydroxyl or carboxyl groups. However, it is preferred that the at least one thermoplastic polymer TP does not contain functional groups that may interfere with the curing mechanism of the thermally expandable composition. This approach provides better controllability of the curing mechanism and secondary properties, such as adhesive properties.

[0128] According to one or more embodiments, the at least one thermoplastic polymer TP is preferably a non-functionalized thermoplastic polymer selected from the group consisting of ethylene-vinyl acetate copolymers, olefin (meth)acrylate copolymers, olefin alkyl (meth)acrylate copolymers and olefin (meth)acrylic acid copolymers, more preferably from the group consisting of ethylene-vinyl acetate copolymers, olefin alkyl (meth)acrylate copolymers and olefin alkyl (meth)acrylate copolymers, even more preferably from the group consisting of olefin alkyl (meth)acrylate copolymers and olefin alkyl (meth)acrylate copolymers.

[0129] According to one or more embodiments, the at least one thermoplastic polymer TP is a melt flow index, measured according to ISO 1133 (190 ° C / 2.16 kg), of less than or equal to 200 g / 10 min, preferably less than or equal to 175 g / 10 min, even more preferably less than or equal to 155 g / 10 min, and / or a melting temperature (T) as measured by DSC measurements performed according to ISO 11357-3 of less than or equal to 125° C., preferably less than or equal to 110° C., more preferably less than or equal to 100° C. m ) has.

[0130] According to one or more embodiments, the at least one thermoplastic polymer TP comprises at least one first non-functionalized thermoplastic polymer TP1 and at least one second non-functionalized thermoplastic polymer TP2 different from the at least one first non-functionalized thermoplastic polymer TP1, where the at least one first and second non-functionalized thermoplastic polymers TP1 and TP2 are preferably selected from the group consisting of ethylene-vinyl acetate copolymers, olefin (meth)acrylate copolymers, olefin alkyl (meth)acrylate copolymers and olefin (meth)acrylic acid copolymers, more preferably from the group consisting of ethylene-vinyl acetate copolymers, olefin (meth)acrylate copolymers and olefin alkyl (meth)acrylate copolymers, even more preferably from the group consisting of olefin (meth)acrylic acid copolymers and olefin alkyl (meth)acrylate copolymers.

[0131] According to one or more embodiments, the at least one first non-functionalized thermoplastic polymer TP1 has a melt flow index, measured according to ISO 1133 (190°C / 2.16 kg) of 25 g / 10 min or less, more preferably 15 g / 10 min or less, even more preferably 10 g / 10 min or less, in particular from 1 to 10 g / 10 min, preferably from 1 to 7.5 g / 10 min, and / or the at least one second non-functionalized thermoplastic polymer TP2 has a melt flow index, measured according to ISO 1133 (190°C / 2.16 kg) of at least 15 g / 10 min, more preferably at least 20 g / 10 min, even more preferably at least 25 g / 10 min, in particular from 25 to 200 g / 10 min, preferably from 30 to 175 g / 10 min.

[0132] According to one or more embodiments, the weight ratio of the total amount of the at least one first non-functionalized thermoplastic polymer TP1 and the at least one second non-functionalized thermoplastic polymer TP2 ranges from 5:1 to 1:3, preferably from 3:1 to 1:2, more preferably from 2.5:1 to 1:1.

[0133] According to one or more embodiments, the at least one thermoplastic polymer TP consists of at least one first non-functionalized thermoplastic polymer TP1 and at least one second non-functionalized thermoplastic polymer TP2, where the at least one first and second non-functionalized thermoplastic polymers TP1 and TP2 are preferably selected from the group consisting of ethylene-vinyl acetate copolymers, olefin (meth)acrylate copolymers, olefin alkyl (meth)acrylate copolymers and olefin (meth)acrylic acid copolymers, more preferably from the group consisting of ethylene-vinyl acetate copolymers, olefin (meth)acrylate copolymers and olefin alkyl (meth)acrylate copolymers, even more preferably from the group consisting of olefin (meth)acrylic acid copolymers and olefin alkyl (meth)acrylate copolymers.

[0134] According to one or more embodiments, the polymer component P of the thermally expandable composition further comprises, in addition to the at least one epoxy-functional polymer EP, at least one thermoplastic polymer TP, where the at least one epoxy-functional polymer EP preferably comprises or consists of at least one olefin-glycidyl (meth)acrylate copolymer EP1, and / or at least one olefin-alkyl acrylate-glycidyl (meth)acrylate terpolymer EP2, and / or at least one glycidyl (meth)acrylate-grafted (co)polymer EP3, where the at least one thermoplastic polymer TP preferably comprises at least one first It comprises or consists of a non-functionalized thermoplastic polymer TP1 and at least one second non-functionalized thermoplastic polymer TP2 different from the at least one first non-functionalized thermoplastic polymer TP1, wherein the at least one first and second non-functionalized thermoplastic polymers TP1 and TP2 are preferably selected from the group consisting of ethylene-vinyl acetate copolymers, olefin (meth)acrylate copolymers, olefin alkyl (meth)acrylate copolymers and olefin (meth)acrylic acid copolymers, more preferably from the group consisting of ethylene-vinyl acetate copolymers, olefin alkyl (meth)acrylate copolymers and olefin alkyl (meth)acrylate copolymers.

[0135] According to one or more embodiments, the polymer component P of the thermally expandable composition comprises or consists of at least one epoxy-functional polymer EP and at least one acid anhydride-functional polymer AP and at least one thermoplastic polymer TP, where the at least one thermoplastic polymer TP preferably represents at least 35 wt.-%, more preferably at least 45 wt.-%, even more preferably at least 55 wt.-% of the total weight of the polymer component P, where the at least one epoxy-functional polymer EP preferably comprises or consists of at least one olefin-glycidyl (meth)acrylate copolymer EP1, and / or at least one olefin-alkyl acrylate-glycidyl (meth)acrylate terpolymer EP2, and / or at least one glycidyl (meth)acrylate-grafted (co)polymer EP3, where the at least one acid anhydride-functional polymer AP preferably represents at least one olefin-alkyl acrylate-glycidyl (meth)acrylate terpolymer EP4, and / or at least one glycidyl (meth)acrylate-grafted (co)polymer EP5. The at least one thermoplastic polymer TP preferably comprises or consists of at least one first non-functionalized thermoplastic polymer TP1 and at least one second non-functionalized thermoplastic polymer TP2 different from the at least one first non-functionalized thermoplastic polymer TP1, and wherein the at least one first and second non-functionalized thermoplastic polymers TP1 and TP2 are preferably selected from the group consisting of ethylene-vinyl acetate copolymers, olefin (meth)acrylate copolymers, olefin alkyl (meth)acrylate copolymers and olefin (meth)acrylic acid copolymers, more preferably from the group consisting of ethylene-vinyl acetate copolymers, olefin alkyl (meth)acrylate copolymers and olefin alkyl (meth)acrylate copolymers.

[0136] According to one or more embodiments, the polymer component P of the thermally expandable composition consists of at least one epoxy-functional polymer EP, which preferably comprises or consists of at least one olefin glycidyl (meth)acrylate copolymer EP1, and / or at least one olefin alkyl acrylate glycidyl (meth)acrylate terpolymer EP2, and / or at least one glycidyl (meth)acrylate grafted (co)polymer EP3, more preferably at least one olefin glycidyl (meth)acrylate copolymer EP1 and / or at least one olefin alkyl acrylate glycidyl (meth)acrylate terpolymer EP2.

[0137] According to one or more embodiments, the thermally expandable composition is substantially free of epoxy resins, in particular free of solid epoxy resins of formula (II), liquid epoxy resins of formula (III) and solid epoxy resins of formula (IV). The expression "substantially free" is understood to mean that the amount of epoxy resins in the thermally expandable composition is 1.5% by weight or less, preferably 1.0% by weight or less, more preferably 0.5% by weight or less, even more preferably 0.25% by weight or less, in particular 0.1% by weight or less, based on the total weight of the thermally expandable composition. The thermally expandable compositions according to these embodiments are particularly suitable for use in sealing and baffling hollow structures.

[0138] According to one or more embodiments, the thermally expandable composition comprises less than 3.5 wt%, preferably less than 2.5 wt%, more preferably less than 1.5 wt%, even more preferably less than 1.0 wt%, and even more preferably less than 0.5 wt% rubber. The term "rubber" in this disclosure designates a natural, synthetic, or modified high molecular weight polymer or combination of polymers that can recover from large deformations, i.e., have elastic properties. A typical rubber can be stretched or deformed to at least 200% of its original dimensions under an externally applied force, and will substantially recover its original dimensions and sustain only a small permanent set (typically about 20% or less) after the external force is removed.

[0139] According to one or more further embodiments, the thermally expandable composition is substantially free of rubber. The expression "substantially free" is understood to mean that the thermally expandable composition may only contain trace amounts of rubber, such as less than 0.25 wt. %, preferably less than 0.1 wt. %, more preferably less than 0.01 wt. %, based on the total weight of the thermally expandable composition.

[0140] In addition to the essential and optional components listed above, the thermally expandable composition may contain other compounds commonly used in such compositions and known to those skilled in the art, including, for example, tackifying resins, fillers, colorants, dispersing aids or homogenizers, stabilizers, and the like.

[0141] The term "tackifying resin" as used herein designates a resin that generally enhances the adhesiveness and / or tackiness of the composition. The term "tackiness" as used herein refers to the property of a material being tacky or adhesive by simple contact, which can be measured, for example, as loop tack. Preferred tackifying resins are tacky at a temperature of 25°C. Such tackifying resins provide good adhesion to metal substrates, especially oily metal substrates, both before and after foaming of the thermally expandable composition.

[0142] Suitable tackifying resins for use in the thermally expandable composition have a relatively low average molecular weight (M n ) and a softening point, measured by the ring and ball method according to DIN EN 1238, of not more than 180° C., preferably not more than 160° C., more preferably not more than 150° C. Suitable tackifying resins include in particular synthetic resins, natural resins and chemically modified natural resins.

[0143] The term "synthetic resin" in this disclosure designates a compound resulting from a controlled chemical reaction, such as polyaddition or polycondensation, between well-defined reactants that do not have resinous properties themselves. Monomers that can be polymerized to synthesize a synthetic resin can include aliphatic monomers, cycloaliphatic monomers, aromatic monomers or mixtures thereof. Suitable aliphatic monomers can include C4, C5 and C6 paraffins, olefins and conjugated diolefins. Examples of aliphatic or cycloaliphatic monomers include butadiene, isobutylene, 1,3-pentadiene, 1,4-pentadiene, cyclopentane, 1-pentene, 2-pentene, 2-methyl-1-pentene, 2-methyl-2-butene, 2-methyl-2-pentene, isoprene, cyclohexane, 1-3-hexadiene, 1-4-hexadiene, cyclopentadiene and dicyclopentadiene. Examples of aromatic monomers include C8, C9 and C10. 10 Exemplary aromatic monomers include styrene, alpha methyl styrene, vinyl toluene, methoxy styrene, tertiary butyl styrene, chlorostyrene, coumarone, and indene monomers such as indene and methylindene, and combinations thereof.

[0144] Suitable synthetic resins include, for example, hydrocarbon resins, coumarone-indene resins, polyindene resins, polystyrene resins, vinyltoluene-alpha methylstyrene copolymer resins, and alpha methylstyrene resins.

[0145] The term "hydrocarbon resin" in this disclosure designates synthetic resins made by polymerizing a mixture of unsaturated monomers obtained from petroleum-based feedstocks, such as by-products of cracking natural gas liquids, gas oil, or petroleum naphtha. These types of hydrocarbon resins are also known as "petroleum resins" or "petroleum hydrocarbon resins." Hydrocarbon resins also include pure monomeric aromatic resins, which are prepared by polymerizing aromatic monomer feedstocks that have been purified to remove color-causing contaminants and to precisely control the product composition.

[0146] Suitable hydrocarbon resins are commercially available, for example, under the trade names Wingtack®, Wingtack® Plus, Wingtack® Extra and Wingtack® STS (all manufactured by Cray Valley); under the trade names Escorez® 1000 series, Escorez® 2000 series and Escorez® 5000 series (all manufactured by ExxonMobil Chemical); under the trade names Novares® T series, Novares® TT series, Novares® TD series, Novares® TL series, Novares® TN series, Novares® TK series and Novares® TV series (all manufactured by RUETGERS Novares GmbH); and under the trade names Kristalex®, Plastolyn®, Piccotex®, Piccolastic® and Endex® (all manufactured by Eastman Chemicals).

[0147] When used, the tackifying resin is preferably included in the thermally expandable composition in an amount of 2 to 20% by weight, preferably 4 to 15% by weight, and more preferably 5 to 10% by weight, based on the total weight of the thermally expandable composition.

[0148] Suitable fillers for use in the thermally expandable composition include, for example, ground or precipitated calcium carbonate, lime, calcium-magnesium carbonate, talc, gypsum, graphite, barite, calcined or precipitated silica, silicates, mica, wollastonite, kaolin, feldspar, chlorite, bentonite, montmorillonite, dolomite, quartz, cristobalite, calcium oxide, aluminum hydroxide, magnesium oxide, hollow ceramic spheres, hollow glass spheres, hollow organic spheres, glass spheres, functionalized alumoxanes and carbon black. Suitable fillers include commercially available organically coated and also uncoated forms of the fillers included in the list presented above. Particularly suitable fillers include ground or precipitated calcium carbonate, calcium-magnesium carbonate, talc, gypsum, graphite, barite, calcined or precipitated silica, silicates, mica, wollastonite, carbon black and mixtures thereof.

[0149] When used, the filler is preferably incorporated into the thermally expandable composition in an amount of 1 to 20 weight percent, more preferably 1 to 15 weight percent, and even more preferably 2.5 to 15 weight percent, based on the total weight of the thermally expandable composition.

[0150] Colorants or dyes, such as pigments based on carbon black, may also be included in the expandable composition, preferably in an amount of 0.1 to 1% by weight, based on the total weight of the expandable composition.

[0151] Preferably, the thermally expandable composition after curing has a volume increase of at least 100%, preferably at least 150%, more preferably at least 250% compared to the uncured composition, where the volume increase is measured using the DIN EN ISO 1183 method of density determination (Archimedes principle) in deionized water in combination with the sample mass measured by a precision balance.

[0152] According to one or more embodiments, the thermally expandable composition after curing has a volume increase in the range of 100 to 3000%, preferably 150 to 2500%, more preferably 250 to 2000%, and even more preferably 250 to 1750% compared to the uncured composition.

[0153] The thermally expandable composition according to the invention can be prepared by mixing the components in any suitable mixing device, for example in a dispersion mixer, a planetary mixer such as a planetary roller, an extruder such as a twin screw extruder, a kneader such as a Buss, Banbury or roller kneader or a two-roll mill.

[0154] It may be advantageous to heat the components before or during mixing, either by applying an external heating source or by friction generated by the mixing process itself, in order to facilitate processing of the components into a homogeneously mixed mixture by reducing the viscosity and / or melting the individual components. However, care must be taken not to exceed the activation temperature of the at least one endothermic chemical blowing agent BA and of the at least one free radical initiator I, for example by using temperature monitoring and, where appropriate, device cooling. The thermally expandable composition thus obtained is preferably essentially solid at standard room temperature (23° C.), meaning that it does not appreciably deform at this temperature only by gravity during a period of at least 24 hours.

[0155] After mixing of the components of the thermally expandable composition, the composition thus obtained can be shaped into its desired form, for example, by extrusion, blow molding, pelletizing, injection molding, compression molding, punching or stamping, or using any other suitable process.

[0156] The thermally expandable composition of the present invention may be manufactured in a substantially one-step process, including adding all components sequentially and / or simultaneously. However, it may also be advantageous to provide the thermally expandable composition as a two-part or even multi-part system. In these cases, the components of the thermally expandable composition are provided in separate air- and moisture-impermeable packages or compartments of a single package, which are mixed with each other and optionally with other compounds at or immediately before the use of the thermally expandable composition. Such an approach may be taken, for example, to increase the shelf life of the thermally expandable composition in locations with harsh conditions (such as abnormally high temperatures), to optimize storage requirements and shipping weights, or to make it possible to provide modular compositions suitable for different applications.

[0157] The thermally expandable composition according to the present invention is storage stable under typical storage conditions. The term "storage stable" in this disclosure refers to a material that can be stored under the specified storage conditions for an extended period of time, such as at least one month, particularly at least three months, without any significant change in the application-related properties of the material. "Typical storage conditions" in this specification refers to temperatures below 60°C, particularly below 50°C.

[0158] The expansion of the thermally expandable composition of the present invention is triggered by heating. This means that the thermally expandable composition is activated by a heating step that exceeds its activation temperature and exhibits a sufficiently long duration for the decomposition of the at least one endothermic chemical blowing agent BA (resulting in gas formation) to proceed until the expandable material expands and hardens to its intended final (fully expanded and stable) state. The optimal temperature and duration (residence time) of the heating step depends on the embodiment of the thermally expandable composition, in particular the composition of the at least one endothermic chemical blowing agent BA and the at least one free radical initiator I contained in the thermally expandable composition. The thermally expandable composition may have an activation temperature in the range of 120-250°C, preferably 140-220°C, and a residence time of the heating step in the range of 5-90 minutes, preferably 10-60 minutes.

[0159] The preferences given above for the polymer component P, the at least one epoxy-functional polymer EP, the at least one anhydride-functional polymer AP, the at least one thermoplastic polymer TP, the at least one endothermic chemical blowing agent BA, the at least one free-radical initiator I and the at least one guanidine derivative apply equally to all subject matters of the present invention, unless stated otherwise.

[0160] Another subject of the invention is a baffle and / or reinforcing element for a hollow structure, comprising or consisting essentially of the thermally expandable composition of the invention.

[0161] Such elements are used to seal, baffle and / or reinforce cavities in hollow structures, such as hollow structural parts of automobiles, which may include body components (e.g., panels), frame components (e.g., hydroformed tubes), frame structures (e.g., A, B, C or D pillars), bumpers, roofs, etc.

[0162] According to one or more embodiments, the baffles and / or reinforcing elements for hollow structures consist essentially of the thermally expandable composition of the present invention. In these embodiments, it is advantageous to provide the element with a shape that allows it to be easily incorporated into and attached to the walls of the baffles and / or hollow structures to be reinforced. Such shaped elements can be provided from the thermally expandable composition, for example, by injection molding, punching or stamping, or extrusion through a shaped mold.

[0163] According to one or more further embodiments, the baffle and / or reinforcing element further comprises a carrier on which the thermally expandable composition is deposited or attached. Such a design may be more cost-effective and it may facilitate fastening of the baffle and / or reinforcing element to the wall of the baffle and / or reinforced structure, for example, by incorporation of pins, bolts or hooks into the carrier element. Furthermore, suitable design of the carrier element may improve the mechanical performance and stability of the baffle and / or reinforcing element.

[0164] The carrier of the baffle and / or reinforcing element, if used, may consist of any material that can be processed into a shape. Preferred materials for the carrier include polymeric materials such as plastics, elastomers, thermoplastics, blends thereof, etc. Preferred thermoplastic materials include polymers such as polyurethane, polyamide, polyester, polyolefin, polysulfone, polyethylene terephthalate (PET), polyvinyl chloride (PVC), chlorinated polyolefins, etc., without limitation. High temperature stable polymers such as poly(phenyl ether), polysulfone, polyethersulfone, polyamide, especially polyamide 6, polyamide 6,6, polyamide 11, polyamide 12 and mixtures thereof are especially preferred. Other suitable materials for the carrier include metals, especially aluminum or steel, or naturally growing organic materials such as wood or other (pressed) fibrous materials. Glassy or ceramic materials may also be used. Any combination of such materials may also be used. It is also contemplated that such materials may be filled or foamed, for example with fibers, minerals, clays, silicates, carbonates, combinations thereof, etc.

[0165] The carrier element can further exhibit any shape or geometry. It can also consist of several directly unconnected parts. For example, it can be a block, hollow or foam structure, or it can exhibit a lattice-like structure. The surface of the carrier element can typically be smooth, rough or textured, depending on the intended use of the baffle and / or reinforcing element.

[0166] Another subject of the invention is a process for manufacturing the baffles and / or reinforcing elements of the invention, in which a thermally expandable composition is injection molded onto a carrier or coextruded with a carrier.

[0167] The details of the manufacturing process of the baffles and / or reinforcing elements of the present invention depend largely on the material of the carrier: if the material of the carrier can be (injection) molded or extruded, the baffles and / or reinforcing elements can be manufactured in a two-step injection molding process or by co-extruding the carrier and the thermally expandable composition.

[0168] In the case of a two-stage injection molding process, the first stage involves injecting the carrier material into the mold. After solidification, the cavity of the injection molding tool is enlarged or adjusted, or the injection molded piece is transferred to another tool, followed by the second stage, which involves the injection of the thermally expandable composition.

[0169] If the carrier cannot be shaped by injection molding or extrusion, for example because it is made of a metal or alloy, the carrier can first be manufactured by a suitable process and then introduced into an injection molding tool. The thermally expandable composition can then be injection molded into the tool in front of the carrier. Another possibility is to extrude the thermally expandable composition onto a previously manufactured carrier element. Of course, there is also the possibility of manufacturing the carrier and the element of the thermally expandable composition separately by any suitable process and then attaching the element of the thermally expandable composition to the carrier by any suitable means, such as chemical or physical, such as gluing, or mechanically, such as bolting, screwing, etc.

[0170] Another subject of the invention is the use of the baffles and / or reinforcing elements of the invention for sealing, baffling or reinforcing cavities or hollow structures of land, water or air vehicles, preferably automotive vehicles, and / or cavities of buildings, such that the transmission of noise, vibration, humidity and / or heat is reduced and / or the structure surrounding said cavities or hollow structures is mechanically reinforced.

[0171] Yet another subject of the invention is a method for sealing, baffling and / or strengthening a cavity or hollow structure, in which an element comprising a thermally expandable composition according to the invention is introduced into said cavity or hollow structure and then expanded by heat and / or UV treatment so that said cavity or hollow structure is at least partially filled by the expanded composition.

[0172] The temperature of the thermal expansion step is preferably 140 to 250° C., more preferably 150 to 220° C., and even more preferably 150 to 200° C. The preferred duration of the thermal expansion step, i.e., the preferred baking time of the thermally expandable composition, is 5 to 90 minutes, more preferably 10 to 60 minutes, and even more preferably 10 to 30 minutes.

[0173] With regard to the thermal activation of components containing thermally expandable compositions when used in the manufacture of automotive vehicles, it is advantageous to combine the thermal activation with another process step involving heat treatment. An example of such a process step is the electrochemical deposition (cathodic dip painting / coating) of the chassis of a car body. EXAMPLES

[0174] The following chemicals, shown in Table 1, were used to formulate the thermally expandable compositions.

[0175] [Table 1]

[0176] Preparation of Thermally Expandable Composition All inventive and non-inventive compositions herein were manufactured in standard manufacturing equipment suitable for compounding thermoplastics with temperature control, i.e. twin screw extruder, Buss kneader or Banbury mixer. The polymers were mixed until homogeneous at a temperature of 100-110°C, after which the system was cooled below the activation of the thermally reactive raw materials (below 90°C). The thermally reactive raw materials were then mixed into the system until homogeneous. The resulting material was subsequently hot pressed into test specimens used for volume expansion and water absorption test procedures.

[0177] Volume expansion Expansion properties were tested for all samples by heat treating (baking) the individual samples in an oven for 10 and 20 minutes at temperatures of 155 and 195° C., respectively. The heat ramp from room temperature (23° C.) to each baking temperature was 15 minutes (to 155° C.) or 10 minutes (to 195° C.). The magnitude of expansion (in % of the original volume before expansion) at the temperatures and corresponding baking temperatures is shown in Table 2.

[0178] The amount of swelling was determined for each sample by measuring the density before and after swelling. The density was determined according to DIN EN ISO 1183 using the water immersion method in deionized water (Archimedes principle) and a precision balance to measure the mass.

[0179] water absorption The water absorption properties of the thermally expansive material were tested using samples with approximate dimensions of 20 mm x 20 mm x 4 mm. The samples were prepared by following the procedure as described above, and expanded and cured by heat treatment using the cycle described above. The heat-treated test samples were then conditioned at standard room conditions (23°C, 50% relative humidity) for 24 hours, and the initial weight before water absorption was measured.

[0180] The conditioned test specimens were kept for 24 hours in a container filled with water (water bath) having a water temperature of 23° C. The specimens were kept submerged in the water approximately 15 cm below the water surface. After underwater storage, the test specimens were removed from the water bath, dried on the surface with an absorbent cloth, dried for 2 hours, and then weighed after water absorption.

[0181] The water absorption value (wt%) was then calculated according to the following equation:

number

[0182]

Table 2

change

Claims

1. 1. A thermally expandable composition comprising: (a) a polymer component P comprising: (a1) at least one epoxy-functional polymer EP, (a2) optionally at least one anhydride-functional polymer AP, and (a3) optionally at least one thermoplastic polymer TP, (b) at least one endothermic chemical blowing agent BA; (c) at least one free radical initiator I, and (d) at least one guanidine derivative G, A thermally expandable composition, wherein said at least one endothermic chemical blowing agent BA comprises at least one organic acid, wherein said at least one organic acid is preferably a polyfunctional organic acid having at least two acidic functional groups, preferably at least two carboxyl groups.

2. 2. The thermally expandable composition of claim 1, wherein said polymer component P comprises at least 45 wt.%, preferably at least 55 wt.%, of the total weight of said thermally expandable composition and / or said at least one endothermic chemical blowing agent BA comprises 1-35 wt.%, preferably 5-25 wt.%, of the total weight of said thermally expandable composition.

3. 3. The thermally expandable composition of claim 1 or 2, which is substantially free of azodicarbonamide (ADCA) and 4,4'-oxybis(benzenesulfonic acid hydrazide) (OBSH).

4. 4. The thermally expandable composition of claim 1, wherein the at least one organic acid is present in the thermally expandable composition in free acid form.

5. The thermally expandable composition of any one of claims 1 to 4, which is essentially free of sodium and potassium bicarbonate.

6. The thermally expandable composition according to any one of claims 1 to 5, wherein the at least one guanidine derivative G is a functional guanidine of formula (I): 【Chemistry 1】 (In the formula, R １ represents a hydrogen atom, or a monovalent linear or branched alkyl group, alicyclic group, or aryl or arylalkyl group having 1 to 10 carbon atoms, optionally further comprising a nitrogen atom; R ２ represents a hydrogen atom or a monovalent linear or branched alkyl group having 1 to 10 carbon atoms; R ３ represents a hydrogen atom or a monovalent linear or branched alkyl group having 1 to 10 carbon atoms or an alicyclic group optionally further comprising nitrogen and / or oxygen and / or silicon atoms).

7. 7. The thermally expandable composition according to any one of claims 1 to 6, wherein said at least one guanidine derivative G represents 0.01 to 5 wt.%, preferably 0.025 to 4.5 wt.%, more preferably 0.1 to 3.5 wt.% of the total weight of said thermally expandable composition.

8. The thermally expandable composition according to any one of claims 1 to 7, wherein said at least one free radical initiator I is a peroxide initiator PI, preferably an organic peroxide.

9. 9. The thermally expandable composition according to any one of claims 1 to 8, further comprising at least one multifunctional acrylate A, preferably having a molecular weight of less than 2,500 g / mol, more preferably less than 1,000 g / mol, and preferably having an acrylate functionality of at least 2 or 3, more preferably at least 4 or 5, or more.

10. 10. The thermally expandable composition according to any one of claims 1 to 9, wherein said at least one epoxy-functional polymer EP comprises at least one olefin glycidyl (meth)acrylate copolymer EP1 and / or at least one olefin alkyl acrylate glycidyl (meth)acrylate terpolymer EP2 and / or at least one glycidyl (meth)acrylate graft (co)polymer EP3.

11. The thermally expandable composition according to any one of claims 1 to 10, wherein the polymer component P further comprises at least one thermoplastic polymer TP, wherein the at least one thermoplastic polymer TP is selected from the group consisting of ethylene-vinyl acetate copolymers, olefin (meth)acrylate copolymers, olefin alkyl (meth)acrylate copolymers, and olefin (meth)acrylic acid copolymers.

12. A baffle or reinforcing element for hollow structures comprising a thermally expandable composition according to any one of claims 1 to 11.

13. 13. The baffle or reinforcing element of claim 12, further comprising a carrier onto which the thermally expandable composition is deposited or attached.

14. 14. A method of making a baffle or reinforcing element according to claim 13, wherein the thermally expandable composition is injection molded onto or co-extruded with the carrier.

15. 14. Use of a baffle or strengthening element according to claim 12 or 13 for sealing, baffling or strengthening a cavity or hollow structure of a land, water or aircraft vehicle, preferably an automotive vehicle, and / or a building cavity, thereby reducing the transfer of noise, vibration, humidity and / or heat, and / or for mechanically strengthening a structure surrounding said cavity.

16. 12. A method for sealing, baffling or strengthening a cavity or hollow structure, comprising introducing into said cavity or hollow structure an element comprising a thermally expandable composition according to any one of claims 1 to 11 and subsequently expanding by heat, whereby said cavity or hollow structure is at least partially filled by said expanded composition.

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