Thermally expandable compositions containing chemical blowing agents

Abstract

The present invention is directed to a thermally expandable composition comprising a thermoplastic polymeric and / or elastomeric compound, at least one blowing agent comprising at least one dicarboxylic acid salt of an aminoguanidine compound, optionally at least one free radical initiator and / or vulcanization system, 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, the use of the baffle and / or reinforcing element 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 reinforcing elements, which are particularly suitable for use in sealing, baffling and / or reinforcing 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 resulting from the manufacturing process and / or 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 pillars 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 into the orifices or cavities. Similarly, such members or elements often perform the additional task of strengthening the hollow structure of the product, e.g., the automotive 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, capable of expanding 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 the 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, a liquid. For example, during the manufacturing process of a vehicle, the hollow part of the metal frame can still be mostly covered by an 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 in which an intumescent 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 structure it is intended to seal, baffle or reinforce, resulting in significant weight reduction in the vehicle body and superior 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 cavity as intended and adheres to its walls. Such systems are disclosed, for example, in DE 10 2011 080 223 A1. EP 3 281 970 A1 discloses a pumpable, thermally foamable filler composition comprising a liquid epoxy resin, a polyvinyl chloride resin and / or an acrylic resin powder, and a blowing agent such as an azo compound, a nitroso compound or a hydrazine derivative. EP 3 281 970 A1 also discloses the use of dicyandiamide as a curing agent. Another EP 2 994 502 A1 discloses the use of N,N'-di-ortho-tolylguanidine as a curing accelerator in chemically foamed polyolefins.

[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 state-of-the-art compositions. Summary of the Invention [Means for solving the problem]

[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, e.g., in the range of 120-200°C, and cure to form a stable crosslinked foam structure. Additionally, the resulting foam should exhibit reduced 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 without the use of exothermic chemical blowing agents, particularly azodicarbonamide (ADCA).

[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 chemical blowing agents based on dicarboxylates of aminoguanidine compounds.Furthermore, it has been found that thermally expandable compositions containing a thermoplastic polymer component, at least one chemical blowing agent comprising at least one dicarboxylate of aminoguanidine compounds, and at least one guanidine derivative, in addition to exhibiting increased volumetric expansion ratio, also exhibit improved foam properties and stable expansion over a wide temperature range.

[0012] One advantage of the thermally expandable compositions of the present invention is that they can achieve high volumetric expansion rates 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 thermoplastic polymer component P and / or an elastomer component E, (b) at least one foaming agent BA comprising at least one dicarboxylate salt of an aminoguanidine compound; (c) optionally, at least one free radical initiator I and / or vulcanization system VS, and (d) at least one guanidine derivative G different from at least one dicarboxylate of an aminoguanidine compound; The aminoguanidine compound is represented by the following formula (I): A thermally expandable composition: [ka] (In the formula, R 1 and R 2 each independently represents a hydrogen atom or an amino group.

[0015] Material names beginning with "poly" designate materials that formally contain more than one functional group per molecule that appears in their name. For example, a polyol refers to a compound that has at least two hydroxyl groups. A 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, e.g. addition or substitution, of functional groups in a given macromolecule and which may be chemically uniform or chemically non-uniform.

[0017] The term "elastomer" refers to any natural, synthetic, or modified high molecular weight polymer or combination of polymers that can recover from large deformations, i.e., have elastic properties. Typical elastomers can be stretched or deformed to at least 200% of their original dimensions under an externally applied force, and after the external force is removed, they substantially recover their original dimensions and sustain only a small permanent set (typically about 20% or less). In particular, the term "elastomer" designates elastomers that are not chemically crosslinked. The term "chemically crosslinked" is understood to mean that the polymer chains that form the elastomer are interconnected by multiple covalent bonds that are mechanically and thermally stable.

[0018] The term "molecular weight" refers to the molar mass (g / mol) of a molecule or a portion of a molecule, also called a "moiety." The term "average molecular weight" refers to the number average molecular weight (M n Molecular weight 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.

[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 individual amounts of the thermoplastic polymers TP contained in the composition. For example, if the at least one thermoplastic polymer TP accounts for 20% by weight of the total weight of the composition, the sum of the amounts of all 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] The thermally expandable composition comprises at least one chemical blowing agent BA, which comprises at least one dicarboxylate salt of an aminoguanidine compound of formula (I).

[0022] According to one or more embodiments, the molar ratio of the amount of aminoguanidine compound of formula (I) to the amount of dicarboxylic acid in the at least one dicarboxylic acid salt of aminoguanidine compound of formula (I) (aminoguanidine compound:dicarboxylic acid) is in the range of 1:1 to 2:1, preferably in the range of 1:1 to 1.5:1, more preferably in the range of 1:1 to 1.2:1.

[0023] Thus, the at least one dicarboxylate salt of the aminoguanidine compound of formula (I) according to these embodiments may also be represented by the following formula (II): [ka] (In the formula, R 1 and R 2 has the same meaning as described further above; and m is a number ranging from 1.0 to 2.0).

[0024] The amount of the at least one chemical blowing agent BA in the thermally expandable composition is not particularly limited. The preferred amount of the at least one chemical blowing agent BA depends, inter alia, on the desired deposition expansion rate of the thermally expandable composition.

[0025] According to one or more embodiments, the at least one chemical blowing agent BA represents 0.5-35 wt.-%, preferably 1-25 wt.-%, more preferably 2.5-20 wt.-%, even more preferably 2.5-15 wt.-%, even more preferably 5-15 wt.-%, in particular 5-12.5 wt.-% of the total weight of the thermal expansion coefficient.

[0026] According to one or more embodiments, the at least one chemical blowing agent BA comprises at least 5% by weight, preferably at least 25% by weight, more preferably at least 35% by weight, even more preferably at least 45% by weight, even more preferably at least 55% by weight, in particular at least 65% by weight of at least one dicarboxylate salt of an aminoguanidine compound of formula (I).

[0027] According to one or more further embodiments, the at least one chemical blowing agent BA comprises at least 50% by weight, preferably at least 65% by weight, more preferably at least 75% by weight, even more preferably at least 85% by weight, even more preferably at least 95% by weight, in particular at least 98% by weight of at least one dicarboxylate of aminoguanidine compound of formula (I). It may also be preferred that the at least one blowing agent BA essentially consists of at least one dicarboxylate of aminoguanidine compound of formula (I). The expression "essentially consists of" is understood to mean that the at least one blowing agent comprises one or more dicarboxylates of aminoguanidine compound of formula (I), where the amount of other components is less than 0.5% by weight, more preferably less than 0.25% by weight, even more preferably less than 0.1% by weight, based on the total weight of the at least one blowing agent BA.

[0028] According to one or more embodiments, the at least one dicarboxylate salt of an aminoguanidine compound of formula (I) represents 0.1 to 35 wt. %, preferably 1 to 25 wt. %, more preferably 2.5 to 20 wt. %, even more preferably 2.5 to 15 wt. %, even more preferably 5 to 15 wt. %, and in particular 5 to 12.5 wt. % of the total weight of the thermally expandable composition.

[0029] Preferably, the at least one chemical blowing agent BA has a d of 350 μm or less, more preferably 250 μm or less, even more preferably 200 μm or less, and even more preferably 150 μm or less. 90 The term "d" refers to a solid particulate form having a particle size. 90 "Particle size" is the size at which 90% of all particles are d 90 The term "particle size" refers to a particle size smaller than the area equivalent spherical diameter of a particle. The particle size distribution can be measured by laser diffraction methods as described in the standard ISO 13320:2009.

[0030] According to one or more embodiments, the at least one chemical blowing agent BA has a d in the range of 1 to 250 μm, preferably 5 to 200 μm, more preferably 15 to 150 μm, even more preferably 25 to 150 μm, and even more preferably 35 to 125 μm. 90 It has a particle size.

[0031] According to one or more embodiments, the at least one chemical blowing agent BA has a maximum decomposition peak temperature as measured by differential scanning calorimetry (DSC) in the range of 135-250° C., preferably 145-225° C., more preferably 155-225° C., and even more preferably 160-215° 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.

[0032] 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, it is possible that the aminoguanidine compound released during the decomposition of at least one blowing agent BA at high temperature can act as a curing agent for polymers having functional groups.

[0033] According to one or more preferred embodiments, at least one dicarboxylate salt of the aminoguanidine compound of formula (I) is an oxalate salt of the aminoguanidine compound of formula (I).

[0034] According to one or more embodiments, the aminoguanidine compound of formula (I) is selected from the group consisting of aminoguanidine, diaminoguanidine, and triaminoguanidine. According to one or more preferred embodiments, the aminoguanidine compound of formula (I) is aminoguanidine.

[0035] The oxalate salt of the aminoguanidine compound of formula (I) can be obtained by reacting an aminoguanidine compound, such as a carbonate salt of an aminoguanidine compound, with oxalic acid. A detailed description of the oxalate salt of the aminoguanidine compound of formula (I) and the method for preparing them is disclosed, for example, in EP 3196270 A1.

[0036] According to one or more embodiments, the at least one chemical blowing agent BA is a microencapsulated blowing agent. The term "microencapsulated blowing agent" as used herein refers to a blowing agent having a core-shell structure.

[0037] Suitable microencapsulated blowing agents BA have a core component consisting of at least one dicarboxylate salt of an aminoguanidine compound of formula (I) or a composition containing at least the oxalate salt of an aminoguanidine compound of formula (I).

[0038] The composition of the shell component of the microencapsulated foaming agent is not particularly limited. Suitable compounds used for the shell component include, for example, polymethyl methacrylate and copolymers of methyl methacrylate and another comonomer. The shell component of the microencapsulated foaming agent may further include one or more fatty acid salts or surfactants as dispersants. Suitable comonomers used in combination with methyl methacrylate include, for example, acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and dicyclopentyl acrylate, methacrylic acid esters such as ethyl methacrylate, butyl methacrylate, and isobornyl methacrylate, acrylonitrile, methacrylonitrile, vinylidene fluoride, vinyl chloride, styrene, vinyl acetate, α-methylstyrene, chloroprene, neoprene, and butadiene.

[0039] The thermally expandable composition further comprises at least one guanidine derivative G different from the at least one dicarboxylate salt of the aminoguanidine compound of formula (I).

[0040] According to one or more embodiments, the at least one guanidine derivative G has the formula (II): [ka] (In the formula, R 3 represents a hydrogen atom, or a monovalent linear or branched alkyl group, alicyclic group, aryl group, or arylalkyl group having 1 to 10 carbon atoms, optionally further containing a nitrogen atom; R 4 represents a hydrogen atom or a monovalent linear or branched alkyl group having 1 to 10 carbon atoms; R 5 represents a hydrogen atom, or a monovalent linear or branched alkyl group having 1 to 10 carbon atoms, or an alicyclic group, an aryl group, or an arylalkyl group, which optionally further contains a nitrogen atom and / or an oxygen atom and / or a silicon atom. is a functional guanidine.

[0041] According to one or more embodiments, the at least one guanidine derivative G is 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-dicyclohexyl-3-hexylguanidine, 1,2-diisopropyl-3-phenylguanidine and 1,2-bis(2,6-diisopropylphenyl)-3-hexylguanidine. According to one or more embodiments, the at least one guanidine derivative G is cyanoguanidine.

[0042] Suitable guanidine derivatives are commercially available, for example, under the trade name Dyhard® (from AlzChem Group AG).

[0043] According to one or more embodiments, the at least one guanidine derivative G represents 0.1 to 10.0 wt. %, preferably 0.25 to 7.5 wt. %, more preferably 0.35 to 5.0 wt. %, more preferably 0.5 to 5.0 wt. %, and even more preferably 0.5 to 4.5 wt. % of the total weight of the thermally expandable composition.

[0044] According to one or more embodiments, component (a) of the thermally expandable composition comprises or consists of a thermoplastic polymer component P.

[0045] According to one or more embodiments, the thermoplastic polymer component P comprises at least 35 wt.%, preferably at least 45 wt.%, more preferably at least 55 wt.%, and even more preferably at least 60 wt.% of the total weight of the thermally expandable composition.

[0046] According to one or more embodiments, the thermoplastic polymer component P comprises 35-90 wt.%, preferably 45-90 wt.%, more preferably 45-85 wt.%, even more preferably 50-85 wt.%, and even more preferably 55-85 wt.% of the total weight of the thermally expandable composition.

[0047] Essentially all thermoplastic polymers and thermoplastic elastomers (TPEs) are suitable for use as the thermoplastic polymer component P. According to one or more embodiments, the thermoplastic polymer component P comprises at least one epoxy-functional polymer EP and / or at least one anhydride-functional polymer AP and / or at least one thermoplastic polymer TP.

[0048] According to one or more embodiments, component (a) of the thermally expandable composition comprises or is equivalent to a thermoplastic polymer component P, where the thermally expandable composition further comprises at least one free radical initiator I. In particular in those embodiments where component (a) of the thermally expandable composition consists of a thermoplastic polymer component P, it may be further preferred that component (c) of the thermally expandable composition consists of at least one free radical initiator I.

[0049] 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.

[0050] According to one or more embodiments, the at least one free radical initiator I is an azo initiator AI, preferably selected from the group consisting of azonitrile compounds, alkylazo compounds, and azoamide compounds.

[0051] 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 azo initiator AI can function not only as a free radical initiator for the crosslinking reaction, but also as a chemical blowing agent for the foaming process.

[0052] Suitable azo initiators are essentially inactive at normal 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 azo initiator AI to have an activation temperature compatible with the decomposition temperature of the at least one 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.

[0053] It may further be advantageous that the at least one azo initiator AI has a half-life of 10 h at a temperature in the range of 55-120 ° C., as measured in toluene or a similar non-polar solvent. For certain types of azo radical initiators, solvents other than toluene, such as substituted (e.g. chlorinated) benzene, methanol, or water, may be more suitable for use in measuring the half-life. The selection of a suitable solvent depends primarily on the solubility of the azo initiator in the respective solvent. It is further advantageous that the at least one azo initiator AI is compatible and / or miscible with the polymer matrix of the thermally expandable composition. In some cases, the compatibility of the azo initiator with the polymer matrix can be further improved by using processing aids and other compatibilizing additives.

[0054] Suitable azo initiators for use as the at least one azo initiator AI include, for example, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-carbonitrile) (ACHN), azobisisobutyronitrile (AIBN), 2,2'-azobis(2-methylpropionamidine), 2,2'-azobis(2-methylpropionitrile), di-tert-butyl-4,4-azobis(4-cyanoperoxypentanoate), di-tert-butyl-4,4-azobis(4-cyanoperoxyhexanoate ... cyheptanoate), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamide] tetrahydrate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide].

[0055] According to one or more embodiments, the at least one azo initiator AI is selected from the group consisting of azobisisobutyronitrile (AIBN), 1,1′-azobis(cyclohexane-1-carbonitrile) (ACHN), and 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide].

[0056] Other free radical initiators, such as peroxide initiators, are also suitable for use as the at least one free radical initiator I. According to one or more further embodiments, the at least one free radical initiator I is a peroxide initiator PI. The thermally expandable composition may also include multiple different free radical initiators, for example, at least one azo initiator AI and at least one peroxide initiator PI. However, the use of multiple different free radical initiators, although possible, is not preferred.

[0057] 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 automotive 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 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.

[0058] 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 in 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 with 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.

[0059] 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 peroxide initiators.

[0060] 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.

[0061] Preferred 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.

[0062] Particularly preferred peroxides include dicumyl peroxide, and / or di(t-butylperoxyisopropyl)benzene, and / or 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane.

[0063] 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) from Pergan; and Peroxan® PK295 (di(t-butylperoxyisopropyl)benzene) from Pergan.

[0064] It may further be advantageous for 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 organic peroxide in the thermally expandable composition. Examples of such 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 peroxide initiator, such as the organic peroxide, is immobilized.

[0065] According to one or more embodiments, the thermally expandable composition comprises at least one free radical initiator I and at least one additional crosslinking coagent 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 in this disclosure both acryloyl and methacryloyl.

[0066] 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. %, and even more preferably 0.25 to 1.5 wt. % of the total weight of the thermally expandable composition.

[0067] 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.

[0068] 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. Higher functional, hyperbranched acrylates with a functionality of 6 to 16 or more are even more suitable. Examples of such acrylates include hyperbranched polyester polyacrylates.

[0069] Epoxy-functional polymer EP According to one or more embodiments, the thermoplastic polymer component P comprises at least one epoxy-functional polymer EP. Preferably, the at least one epoxy-functional polymer EP has an average of more than one epoxy group per molecule.

[0070] Suitable epoxy-functional polymers EP include, for example, olefin glycidyl (meth)acrylate copolymers, olefin alkyl (meth)acrylate glycidyl (meth)acrylate terpolymers, epoxy resins, and epoxy-functionalized polyurethane polymers. The term "(meth)acrylate" in this disclosure designates both acrylates and methacrylates.

[0071] Suitable olefin glycidyl (meth)acrylate copolymers include, for example, copolymers of ethylene, propylene, or butylene with glycidyl acrylate (GA) or with glycidyl methacrylate (GMA). Suitable olefin (meth)acrylate glycidyl (meth)acrylate terpolymers include, for example, terpolymers, especially random terpolymers of ethylene and alkyl (meth)acrylate with glycidyl acrylate (GA) or with glycidyl methacrylate (GMA), where the alkyl group of the alkyl (meth)acrylate is preferably selected from the group consisting of methyl, ethyl, propyl, and butyl, especially methyl or butyl.

[0072] Preferred olefin alkyl (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 methacrylate glycidyl acrylate terpolymer (E / BM A / 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).

[0073] 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 EP1, 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 methyl, ethyl, propyl and butyl, in particular methyl or butyl.

[0074] According to one or more embodiments, the at least one olefin alkyl acrylate glycidyl (meth)acrylate terpolymer EP1 has a content of glycidyl methacrylate of 1 to 50% by weight, more preferably 2 to 25% by weight, and / or a melt flow index, measured according to ISO 1133 (190°C / 2.16 kg), of 100 g / 10 min or less, preferably 50 g / 10 min or less, more preferably 25 g / 10 min or less and / or a melting point, as measured by DSC measurement performed according to ISO 11357-3, of 120°C or less, preferably 110°C or less, more preferably 100°C or less.

[0075] According to one or more embodiments, the at least one epoxy-functional polymer EP is selected from the group consisting of at least one olefin alkyl acrylate glycidyl (meth)acrylate terpolymer EP1, 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 methyl, ethyl, propyl and butyl, in particular methyl or butyl.

[0076] According to one or more embodiments, the at least one epoxy-functional polymer EP comprises at least one olefin glycidyl (meth)acrylate copolymer EP2, preferably selected from the group consisting of ethylene glycidyl (meth)acrylate copolymers, in particular ethylene glycidyl methacrylate copolymers.

[0077] According to one or more embodiments, the at least one epoxy-functional polymer EP is selected from the group consisting of at least one olefin glycidyl (meth)acrylate copolymer EP2, preferably selected from the group consisting of ethylene glycidyl (meth)acrylate copolymers, in particular ethylene glycidyl methacrylate copolymers.

[0078] 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 more than one epoxy group per molecule. The term "solid epoxy resin" designates an epoxy resin that has a glass transition temperature above normal room temperature.

[0079] Suitable solid epoxy resins include those of formula (III): [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.) This includes:

[0080] Compounds of formula (III) 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.

[0081] Suitable solid epoxy resins are commercially available from, for example, Dow Chemical Company, Huntsman International LLC, Hexion Specialty Chemicals Inc., and Olin Corporation.

[0082] In particular, suitable liquid epoxy resins which can be used together with the solid epoxy resins of formula (III) include those of formula (IV) [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). This includes:

[0083] 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).

[0084] 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.).

[0085] Further suitable solid epoxy resins are the so-called novolac resins. Preferred epoxy novolac resins include those having the formula (V) [ka] in which the moiety X represents a hydrogen atom or a methyl group. The moiety W is -CH2- or of formula (VI) [ka] Represents a part of.

[0086] 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-).

[0087] Such epoxy novolac resins are commercially available, for example, under the trade names EPN®, ECN®, and Tactix® 556 (from Huntsman International LLC) and DEN® (from Dow Chemical Company).

[0088] According to one or more embodiments, the at least one epoxy-functional polymer EP comprises at least one epoxy resin EP3, preferably selected from the group consisting of solid epoxy resins of formula (III), solid epoxy resins of formula (V), and mixtures of solid epoxy resins of formula (III) and / or (V) with liquid epoxy resins of formula (IV).

[0089] According to one or more embodiments, the at least one epoxy-functional polymer EP is selected from the group consisting of at least one epoxy resin EP3, preferably selected from the group consisting of solid epoxy resins of formula (III), solid epoxy resins of formula (V) and mixtures of solid epoxy resins of formula (III) and / or (V) with liquid epoxy resins of formula (IV).

[0090] Further suitable epoxy resins to be used as the at least one epoxy-functional polymer EP include those having the formula (VII) [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 aralaliphatic (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; w represents an integer between 2 and 4. The epoxy-functional polyurethane polymers include

[0091] The linear or branched isocyanate-functional polyurethane polymer PU preferably has the formula (VIII) [ka] (wherein Y and w have the same meaning as described further above). It has a structure according to:

[0092] The isocyanate-functional polyurethane polymer PU of formula (VIII) 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.

[0093] Suitable polyols for the preparation of the isocyanate-functional polyurethane polymers PU include, for example, 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 with 2 or 3 OH groups, such as starter molecules with 2 or 3 active H atoms, such as ethylene glycol or glycerol.

[0094] 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 ).

[0095] 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 with an OH functionality of 3, such as, for example, trimethylolpropane, butoxylated trimethylolpropane (for example, Simulsol® TOMB), and / or pentaerythritol, can be added to the polyether polyol to increase the OH functionality.

[0096] 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. In this specification, OH-terminated rubbers are understood to refer, for example and preferably, to hydroxyl-terminated polybutadienes and to 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.

[0097] 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.

[0098] The OH functionality of the hydroxyl terminated rubbers is preferably in the range of 1.7 to 2.2 for types produced anionically and 2.2 to 2.8 for types produced by free radical polymerization.

[0099] Polyhydroxy-terminated acrylonitrile / butadiene copolymers, such as those commercially available from Emerald Materials under the trade name Hypro® CTBN, as well as those prepared using carboxyl-terminated acrylonitrile / butadiene copolymers, such as those prepared using epoxides or amino alcohols, are also suitable as polyols.

[0100] 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 or their anhydrides or esters, 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, and also from lactones, such as ε-caprolactone.

[0101] Further polycarbonate polyols of the type obtained by reacting the abovementioned 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 the isocyanate-functional polyurethane polymers PU. Polyols of the type obtained by reduction of dimerized fatty acids are also suitable.

[0102] 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 includes those obtained by using polyether polyol, especially polytetrahydrofuran, and polybutadiene polyol.

[0103] 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) as well as dimers thereof, where HDI, IPDI, MDI, TDI are preferred. Particularly preferred diisocyanates are aliphatic and cycloaliphatic diisocyanates, such as HDI, H12MDI and IPDI.

[0104] Suitable triisocyanates are the trimers or biurets of aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanates, in particular the isocyanurates and biurets of the aforementioned diisocyanates.

[0105] The isocyanate-functional polyurethane polymer PU is then reacted with an isocyanate-functional polyurethane polymer having the formula (IX): [ka] (wherein Z and v have the same meanings as above). is end-capped with at least one monohydroxyl epoxide compound E according to

[0106] The monohydroxyl epoxide compound E of formula (IX) is an aliphatic, cycloaliphatic, aromatic, or araliphatic (araliphatic) epoxide containing one primary or secondary hydroxyl group and one to three epoxide groups.

[0107] The monohydroxyl epoxide compounds E of formula (IX) 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, which can be separated by routine separation operations.

[0108] 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.

[0109] 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 (IV) as described above are further preferred.

[0110] 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. Furthermore, it is also possible to use a wide 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.

[0111] According to one or more embodiments, the at least one epoxy-functional polymer EP comprises at least one epoxy-functional polyurethane polymer EP4, preferably at least one epoxy-functional polyurethane polymer of formula (VII).

[0112] According to one or more embodiments, the at least one epoxy-functional polymer EP is selected from the group consisting of at least one epoxy-functional polyurethane polymer EP4, preferably at least one epoxy-functional polyurethane polymer of formula (VII).

[0113] Acid anhydride functional polymer AP According to one or more embodiments, the thermoplastic polymer component P comprises at least one anhydride-functional polymer AP. Preferably, the at least one anhydride-functional polymer AP has an average of 2 or more anhydride groups per molecule.

[0114] The at least one anhydride-functional polymer AP may contain either polymerized or grafted anhydride functionality, i.e., the anhydride moieties may be present as part of the polymer backbone or may be grafted onto the polymer as side chains.

[0115] Suitable anhydride-functional polymers AP include maleic anhydride-functional polymers and tetrahydrophthalic anhydride-functional polymers, in particular maleic anhydride-functional polymers.

[0116] Suitable maleic anhydride functional polymers include, for example, olefin-maleic anhydride copolymers and olefin-maleic anhydride terpolymers. Further suitable maleic anhydride functional polymers include maleic anhydride grafted (co)polymers, such as 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), such as maleic anhydride grafted olefin copolymer elastomers.

[0117] Suitable olefin maleic anhydride copolymers include, for example, copolymers of maleic anhydride with ethylene, propylene, or butylene. Suitable olefin maleic anhydride terpolymers include, for example, olefin alkyl (meth)acrylate maleic anhydride terpolymers, such as terpolymers of ethylene and alkyl (meth)acrylate with maleic anhydride, where the alkyl group of the alkyl (meth)acrylate is preferably selected from the group consisting of methyl, ethyl, propyl, and butyl.

[0118] 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 methyl, ethyl, propyl and butyl, more preferably methyl, ethyl and butyl.

[0119] According to one or more embodiments, the at least one olefin-alkyl acrylate maleic anhydride terpolymer AP1 has a maleic anhydride content of 0.5 to 10% by weight, preferably 1 to 7.5% by weight, more preferably 1 to 5% by weight.

[0120] According to one or more embodiments, the at least one olefin alkyl acrylate maleic anhydride terpolymer AP1 has a melt flow index, measured according to ISO 1133 (190° C. / 2.16 kg), of ≦100 g / 10 min, preferably ≦50 g / 10 min, more preferably ≦35 g / 10 min, and / or a melting point, as measured by DSC measurement performed according to ISO 11357-3, of ≦125° C., preferably ≦110° C., more preferably ≦100° C.

[0121] According to one or more embodiments, the at least one anhydride-functional polymer AP is selected from the group consisting 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 methyl, ethyl, propyl and butyl, more preferably methyl, ethyl and butyl.

[0122] According to one or more embodiments, the at least one anhydride-functional polymer AP comprises at least one olefin-maleic anhydride copolymer AP2, preferably selected from the group consisting of copolymers of ethylene, propylene and butylene with maleic anhydride, in particular ethylene-maleic anhydride copolymers.

[0123] According to one or more embodiments, the at least one anhydride-functional polymer AP is selected from the group consisting 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, in particular ethylene-maleic anhydride copolymers.

[0124] According to one or more embodiments, the at least one acid anhydride-functional polymer AP comprises at least one maleic anhydride-grafted (co)polymer AP3, 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.

[0125] According to one or more embodiments, the at least one maleic anhydride grafted (co)polymer AP3 has a maleic anhydride content 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 and in particular 0.1 to 1.5% by weight.

[0126] According to one or more embodiments, the at least one maleic anhydride grafted (co)polymer AP3 has 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 50 g / 10 min, more preferably less than or equal to 35 g / 10 min, and / or a melting point, as measured by DSC measurements performed according to ISO 11357-3, of less than or equal to 145° C., preferably less than or equal to 125° C., more preferably less than or equal to 120° C.

[0127] According to one or more embodiments, the at least one anhydride-functional polymer AP is selected from the group consisting of at least one maleic anhydride grafted (co)polymer AP3, 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 selected from the group consisting of maleic anhydride grafted olefin vinyl acetate copolymers, maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene.

[0128] Thermoplastic Polymer TP According to one or more embodiments, the thermoplastic polymer component P comprises at least one thermoplastic polymer TP, which is of course different from the at least one epoxy-functional polymer EP and the at least one anhydride-functional polymer AP.

[0129] Suitable thermoplastic polymers 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). Suitable olefin (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.

[0130] 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 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.

[0131] According to one or more embodiments, the at least one thermoplastic polymer TP is a non-functionalized thermoplastic polymer, 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 olefin (meth)acrylate copolymers and olefin alkyl (meth)acrylate copolymers, where the alkyl group of the olefin alkyl (meth)acrylate copolymer is preferably selected from the group consisting of methyl, ethyl, propyl, and butyl, more preferably butyl.

[0132] According to one or more embodiments, the at least one thermoplastic polymer TP has 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 150 g / 10 min, even more preferably less than or equal to 125 g / 10 min, and / or a melting point, 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.

[0133] 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 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 olefin (meth)acrylate copolymers and olefin alkyl (meth)acrylate copolymers, where the alkyl group of the olefin alkyl (meth)acrylate copolymer is preferably selected from the group consisting of methyl, ethyl, propyl, and butyl, more preferably butyl.

[0134] 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 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 150 g / 10 min, preferably from 30 to 100 g / 10 min.

[0135] According to one or more embodiments, the weight ratio of the amount of the at least one first non-functionalized thermoplastic polymer TP1 to the amount of the at least one second non-functionalized thermoplastic polymer TP2 is in the range of 5:1 to 1:3, preferably 3:1 to 1:2, more preferably 2.5:1 to 1:1.

[0136] According to one or more embodiments, the at least one thermoplastic polymer TP is selected from the group consisting of at least one first non-functionalized thermoplastic polymer TP1 and at least one second non-functionalized thermoplastic polymer TP2, where the 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 olefin (meth)acrylate copolymers and olefin alkyl (meth)acrylate copolymers.

[0137] According to one or more further embodiments, the thermoplastic polymer component P consists of at least one epoxy-functional polymer EP or at least one anhydride-functional polymer AP. According to one or more further embodiments, the thermoplastic polymer component P consists of at least one thermoplastic polymer TP.

[0138] According to one or more further embodiments, the thermoplastic polymer component P consists of at least one epoxy-functional polymer EP and at least one acid anhydride-functional polymer AP, where 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.

[0139] According to one or more further embodiments, the thermoplastic polymer component P consists of at least one epoxy-functional polymer EP and at least one acid anhydride-functional polymer AP, wherein the thermally expandable composition is essentially free of free-radical crosslinkers, and 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.

[0140] The expression "essentially free of free radical crosslinkers" is understood to mean that the amount of such substances capable of crosslinking the polymer by a free radical curing mechanism is preferably less than 0.2 wt. %, more preferably less than 0.1 wt. %, and even more preferably less than 0.05 wt. %, based on the total weight of the thermally expandable composition.

[0141] According to one or more further embodiments, the thermoplastic polymer component P comprises at least one epoxy-functional polymer EP or at least one anhydride-functional polymer AP and at least one thermoplastic polymer TP, where the at least one thermoplastic polymer TP preferably represents at least 50 wt.-%, more preferably at least 60 wt.-%, even more preferably at least 70 wt.-%, and even more preferably at least 75 wt.-% of the total weight of the thermoplastic polymer component P.

[0142] According to one or more further embodiments, the thermoplastic polymer component P comprises or consists of at least one epoxy-functional polymer EP, at least one anhydride-functional polymer AP and at least one thermoplastic polymer TP, where the at least one thermoplastic polymer TP preferably accounts for at least 25 wt.-%, more preferably at least 35 wt.-%, even more preferably at least 40 wt.-%, even more preferably at least 45 wt.-% and in particular at least 50 wt.-% of the total weight of the polymer component P.

[0143] According to one or more further embodiments, component (a) of the thermally expandable composition comprises or consists of a thermoplastic polymer component P, which consists of at least one thermoplastic polymer TP, where the thermally expandable composition further comprises at least one free radical initiator I and, optionally, at least one multifunctional acrylate A. In particular in these embodiments where component (a) of the thermally expandable composition consists of the polymer component P, it may be further preferred that component (c) of the thermally expandable composition consists of at least one free radical initiator I.

[0144] According to one or more further embodiments, component (a) of the thermally expandable composition comprises or consists of an elastomeric component E.

[0145] According to one or more embodiments, the elastomer component E comprises at least 2.5 wt.%, preferably at least 5 wt.%, more preferably at least 10 wt.%, and even more preferably at least 15 wt.% of the total weight of the thermally expandable composition.

[0146] According to one or more embodiments, the elastomer component E comprises 2.5 to 35 wt. %, preferably 5 to 30 wt. %, more preferably 7.5 to 25 wt. %, even more preferably 10 to 25 wt. %, even more preferably 10 to 20 wt. %, and most preferably 12.5 to 20 wt. % of the total weight of the thermally expandable composition.

[0147] Essentially all types of natural and synthetic elastomers are suitable for use as the elastomer component E. According to one or more embodiments, the elastomer component E comprises at least one solid rubber SR. The term "solid rubber" designates herein a rubber that is solid at a temperature of 25°C.

[0148] Solid Rubber SR Suitable solid rubbers SR include, for example, butyl rubber, halogenated butyl rubber, styrene-butadiene rubber (SBR), ethylene-propylene rubber (EPR), ethylene-propylene diene monomer rubber (EPDM), natural rubber, polychloroprene rubber, cis-1,4-polyisoprene, polybutadiene rubber, isoprene-butadiene rubber, styrene-isoprene-butadiene rubber, nitrile rubber, nitrile-butadiene rubber, and acrylonitrile rubber.

[0149] According to one or more embodiments, the at least one solid rubber SR is selected from the group consisting of butyl rubber, halogenated butyl rubber, styrene-butadiene rubber (SBR), ethylene-propylene rubber (EPR), ethylene-propylene diene monomer rubber (EPDM), natural rubber, cis-1,4-polyisoprene, and polybutadiene rubber.

[0150] Preferred solid rubbers SR have an average molecular weight (M) of at least 100,000 g / mol, such as at least 125,000 g / mol. n ).

[0151] According to one or more embodiments, the at least one solid rubber SR comprises at least one solid styrene-butadiene rubber SR1.

[0152] According to one or more embodiments, at least one solid styrene-butadiene rubber SR1 is emulsion polymerization styrene-butadiene rubber. These can be divided into two types, cold rubber and hot rubber, depending on the emulsion polymerization temperature, hot rubber (hot type) is preferred.

[0153] According to one or more embodiments, the at least one solid styrene-butadiene rubber SR1 has a styrene content of 1 to 60% by weight, more preferably 2 to 50% by weight, even more preferably 10 to 40% by weight, such as 15 to 40% by weight, most preferably 20 to 35% by weight.

[0154] According to one or more embodiments, the at least one solid styrene-butadiene rubber SR1 has a Mooney viscosity (ML 1+4 at 100° C.) of 25 to 150 MU (Mooney Units), more preferably of 30 to 100 MU, even more preferably of 35 to 80 MU.

[0155] Preferred solid styrene-butadiene rubbers SR1 include pre-crosslinked styrene-butadiene elastomers commercially available under the trade names, for example, Petroflex® SBR 1009A, 1009S and 1018 elastomers, produced by Petroflex / Lanxess and coagulated by the salt-acid process using either rosin or fatty acid soap as emulsifier, and SBR 1009, 1009A, 1502, and 4503 elastomers produced by Lion Elastomer by hot emulsion polymerization with divinylbenzene.

[0156] According to one or more embodiments, the at least one solid rubber SR is selected from the group consisting of at least one solid styrene-butadiene rubber SR1.

[0157] According to one or more embodiments, the at least one solid rubber SR comprises at least one solid butyl rubber SR2.

[0158] The term "butyl rubber" as used herein refers to a rubber composition that is a rubber that is made up of a major portion of C4-C7 monoolefin monomers, preferably isoolefin monomers, and a minor portion, such as up to 30% by weight, of C4-C 14 It designates a polymer derived from a monomer mixture containing a multiolefin monomer, preferably a conjugated diolefin.

[0159] Preferred C4 to C7 monoolefin monomers may be selected from the group consisting of isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 4-methyl-1-pentene, and mixtures thereof.

[0160] Preferred C4~C 14 Multiolefins are C4 to C 10 Conjugated diolefins are included. Preferred are C4-C 10The conjugated diolefin may be selected from the group including isoprene, butadiene, 2,4-dimethylbutadiene, piperylene, 3-methyl-1,3-pentadiene, 2,4-hexadiene, 2-neopentyl-1,3-butadiene, 2-methyl-1,5-hexadiene, 2,5-dimethyl-2,4-hexadiene, 2-methyl-1,4-pentadiene, 2-methyl-1,6-heptadiene, cyclopentadiene, methylcyclopentadiene, cyclohexadiene, 1-vinylcyclohexadiene, and mixtures thereof.

[0161] According to one or more embodiments, the at least one solid butyl rubber SR2 is a butyl rubber having about 80% to about 99% by weight of a C4-C7 monoolefin monomer and about 1.0% to about 20% by weight of a C4-C 14 More preferably, the monomer mixture is derived from a monomer mixture containing about 85% by weight to about 99% by weight of a C4-C7 monoolefin monomer and about 1.0% by weight to about 10% by weight of a C4-C7 multiolefin monomer. 14 Most preferably, the monomer mixture contains about 95% to about 99% by weight of C4 to C7 monoolefin monomers and about 1.0% to about 5.0% by weight of C4 to C7 multiolefin monomers. 14 and a multiolefin monomer.

[0162] Preferably, the at least one solid butyl rubber SR2 is derived from a monomer mixture containing about 97% to about 99.5% by weight of isobutylene and about 0.5% to about 3% by weight of isoprene.

[0163] It is further possible to prepare butyl terpolymers by including an optional third monomer. For example, a styrene-based monomer can be included in the monomer mixture, preferably in an amount of about 15% by weight or less of the monomer mixture. The preferred styrene-based monomer can be selected from the group including p-methylstyrene, styrene, α-methylstyrene, p-chlorostyrene, p-methoxystyrene, indene, indene derivatives, and mixtures thereof. The most preferred styrene-based monomer can be selected from the group including styrene, p-methylstyrene, and mixtures thereof. Other suitable copolymerizable termonomers will be apparent to those skilled in the art.

[0164] According to one or more embodiments, at least one solid butyl rubber SR2 has a Mooney viscosity (ML 1+8, 125°C) of 125 MU (Mooney Units), more preferably 100 MU or less, even more preferably 85 MU or less. Mooney viscosity refers to the viscosity measure of rubber. It is defined as the shear torque that resists the rotation of a cylindrical metal disk (or rotor) embedded in rubber in a cylindrical cavity. The dimensions of the shear disk viscometer, the test temperature, and the measurement procedure of Mooney viscosity are defined in the ASTM D1646 standard.

[0165] According to one or more embodiments, the at least one solid butyl rubber SR2 is a halogenated butyl rubber, preferably a chlorinated butyl rubber or a brominated butyl rubber, with brominated butyl rubber being especially preferred.

[0166] Preferred halogenated butyl rubbers contain halogen in an amount of at least 0.1% by weight, in particular 0.1 to 10.0% by weight, preferably 0.1 to 8.0% by weight, more preferably 0.5 to 8.0% by weight, even more preferably 0.5 to 4.0% by weight, and most preferably 1.5 to 3.0% by weight, based on the weight of the butyl rubber.

[0167] According to one or more embodiments, the at least one solid butyl rubber SR2 is a mixture of a solid halogenated butyl rubber and a solid non-halogenated butyl rubber, where the solid halogenated butyl rubber is preferably a brominated butyl rubber. Preferably, in these embodiments, the weight ratio of the amount of solid halogenated butyl rubber to the weight of the solid non-halogenated butyl rubber is in the range of 20 to 0.1, more preferably 15 to 0.5, even more preferably 12.5 to 1, and most preferably 10 to 1.

[0168] According to one or more embodiments, the at least one solid rubber SR is selected from the group consisting of at least one solid butyl rubber SR2.

[0169] According to one or more embodiments, the at least one solid rubber SR comprises at least one solid polybutadiene rubber SR3.

[0170] The term "polybutadiene rubber" herein designates a polymer resulting from the polymerization of 1,3-butadiene monomer. According to one or more embodiments, at least one solid polybutadiene rubber SR3 has a 1,4-cis bond content of at least 40% by weight, more preferably more than 80% by weight, and even more preferably more than 95% by weight.

[0171] According to one or more embodiments, the at least one solid polybutadiene rubber SR3 has a Mooney viscosity (M 1+4 at 100° C.) of 20 to 100 MU (Mooney Units), more preferably of 25 to 80 MU, even more preferably of 30 to 60 MU.

[0172] According to one or more embodiments, the at least one solid rubber SR is selected from the group consisting of at least one solid polybutadiene rubber SR3.

[0173] According to one or more embodiments, component (a) of the thermally expandable composition comprises or consists of elastomeric component E, where the thermally expandable composition further comprises vulcanization system VS. In particular in those embodiments where component (a) of the thermally expandable composition consists of elastomeric component E, it may be further preferred that component (c) of the thermally expandable composition consists of vulcanization system VS.

[0174] The type of vulcanization system VS is not particularly limited. Vulcanization systems based on elemental sulfur as well as those that do not contain elemental sulfur are considered suitable.

[0175] When a vulcanizing system based on elemental sulfur is used, the system preferably contains pulverulent sulfur, more preferably at least one sulfur compound selected from the group consisting of powdered sulfur, precipitated sulfur, highly dispersed sulfur, surface-treated sulfur, and insoluble sulfur.

[0176] Preferred vulcanization systems based on elemental sulfur contain 1 to 15% by weight, more preferably 5 to 10% by weight, of powdered sulfur, preferably at least one sulfur compound selected from the group consisting of powdered sulfur, precipitated sulfur, highly dispersed sulfur, surface-treated sulfur, and insoluble sulfur, based on the total weight of the vulcanization system.

[0177] According to one or more embodiments, the vulcanization system VS is an elemental sulfur-free vulcanization system.

[0178] A preferred vulcanization system without elemental sulfur comprises at least one vulcanizing agent and optionally at least one inorganic vulcanization accelerator and / or at least one inorganic vulcanization accelerator.

[0179] Suitable vulcanizing agents for vulcanizing systems without elemental sulfur include, for example, phenolic resins, bisazidoformates, polyfunctional amines, para-quinone dioxime, para-benzoquinone dioxime, para-quinone dioxime dibenzoate, p-nitrosobenzene, dinitrosobenzene, thiuram compounds, bismaleimides, dithiols, zinc oxide, as well as crosslinking systems crosslinked with (blocked) diisocyanates.

[0180] Suitable organic vulcanization accelerators for use in vulcanization systems without elemental sulfur include thiocarbamates, dithiocarbamates (in the form of their ammonium or metal salts), xanthates, thiuram compounds (monosulfides and disulfides), thiazole compounds, aldehyde-amine accelerators such as hexamethylenetetramine, and guanidine accelerators.

[0181] Suitable inorganic vulcanization accelerators for use in elemental sulfur-free vulcanization systems include, for example, zinc compounds, particularly zinc salts of fatty acids, basic zinc carbonate, and zinc oxide.

[0182] According to one or more embodiments, the vulcanization system VS is an elemental sulfur-free vulcanization system containing at least one vulcanizing agent selected from the group consisting of para-quinone dioxime, para-benzoquinone dioxime, para-quinone dioxime dibenzoate, p-nitrosobenzene, dinitrosobenzene, and thiuram compounds, preferably from the group consisting of para-quinone dioxime, para-benzoquinone dioxime, para-quinone dioxime dibenzoate, tetramethylthiuram disulfide (TMTD), and tetrabenzylthiuram disulfide (TBzTD), and preferably further containing at least one organic vulcanization accelerator and / or at least one inorganic vulcanization accelerator.

[0183] According to one or more embodiments, the at least one organic vulcanization accelerator is selected from the group consisting of cyclohexylbenzothiazole sulfonamide, mercaptobenzothiazole sulfide (MBTS), diphenyl guanidine, and zinc dimethyldithiocarbamate.

[0184] According to one or more embodiments, the at least one inorganic vulcanization accelerator is selected from the group consisting of zinc salts of fatty acids, basic zinc carbonate, and zinc oxide, more preferably zinc oxide.

[0185] According to one or more embodiments, the elemental sulfur-free vulcanization system VS comprises 1-15 wt. %, more preferably 1-12.5 wt. %, even more preferably 2-10 wt. %, and most preferably 3.5-10 wt. % of the total weight of the thermally expandable composition.

[0186] According to one or more preferred embodiments, the elemental sulfur-free vulcanization system VS comprises 10-40% by weight, preferably 20-35% by weight, of at least one vulcanizing agent, preferably selected from the group consisting of para-quinone dioxime, para-benzoquinone dioxime, para-quinone dioxime dibenzoate, tetramethylthiuram disulfide (TMTD), and tetrabenzylthiuram disulfide (TBzTD), and 10-40% by weight, preferably 20-35% by weight, of cyclohexylbenzothiazole. at least one organic vulcanization accelerator, preferably selected from the group consisting of arylsulfonamide, mercaptobenzothiazole sulfide (MBTS), diphenylguanidine, and zinc dimethyldithiocarbamate, and / or 10-40 wt. %, preferably 20-35 wt. %, of at least one inorganic vulcanization accelerator, preferably selected from the group consisting of zinc salts of fatty acids, basic zinc carbonate, and zinc oxide, more preferably zinc oxide, all percentages being based on the total weight of the vulcanization system VS.

[0187] 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.

[0188] The term "tackifying resin" as used herein designates a resin that generally enhances the adhesiveness and / or tackiness of a 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. A preferred tackifying resin provides tackiness at a temperature of 25°C. Such a tackifying resin provides good adhesion to metal substrates, especially oily metal substrates, both before and after foaming of the thermally expandable composition.

[0189] Suitable tackifying resins for use in the thermally expandable composition have a relatively low average molecular weight (M), such as 5,000 g / mole or less, in particular 3,500 g / mole or less, and preferably 2,500 g / mole or less. 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.

[0190] 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, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C210, C220, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33, C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, C44, C45, C46, ​​C47, C48, C49, C50, C51, C52, C53, C54, C55, C56, C57, C58, C59, C61, C62, C63, C64, C65, C65, C66, C67, C68, 10Exemplary aromatic monomers include styrene, alpha methyl styrene, vinyl toluene, methoxy styrene, tertiary butyl styrene, chlorostyrene, coumarone, and indene monomers such as indene and methyl indene, and combinations thereof.

[0191] Suitable synthetic resins include, for example, hydrocarbon resins, coumarone-indene resins, polyindene resins, polystyrene resins, vinyltoluene-alpha methylstyrene copolymer resins, and alpha methylstyrene resins.

[0192] 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 as "petroleum hydrocarbon resins." Hydrocarbon resins also include pure monomeric aromatic resins, which are prepared by polymerizing aromatic monomer feedstocks that have been refined to remove color-causing contaminants and to precisely control the product composition.

[0193] 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).

[0194] When used, the tackifying resin is preferably contained 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.

[0195] Suitable fillers 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.

[0196] 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.

[0197] Colorants, such as pigments or dyes, for example 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.

[0198] 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.

[0199] 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.

[0200] The thermally expandable composition according to the present invention can be prepared by mixing the components in any suitable mixing equipment, for example 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.

[0201] 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 chemical blowing agent BA and at least one free radical initiator I, if contained in the thermally expandable composition, for example by using temperature monitoring and, where appropriate, cooling of the device. The thermally expandable composition thus obtained is preferably essentially solid at standard room temperature (23° C.), meaning that it does not deform appreciably at this temperature by gravity alone, during a period of at least 24 h.

[0202] 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.

[0203] 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 system, or even a 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.

[0204] The thermally expandable composition according to the present invention is storage stable under typical storage conditions. The term "storage stable" in the present 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 refer to temperatures below 60°C, particularly below 50°C.

[0205] 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 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 on the composition of the at least one chemical blowing agent BA and the at least one free radical initiator I, if 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.

[0206] The preferences given above for the thermoplastic polymer component P, the elastomeric component E, 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 chemical blowing agent BA, the at least one free-radical initiator I, the vulcanization system VS and the at least one guanidine derivative G apply equally to all subjects of the present invention, unless stated otherwise.

[0207] Another subject of the invention is a baffle and / or reinforcing element for hollow structures comprising or consisting essentially of the thermally expandable composition of the invention.

[0208] 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.

[0209] According to one or more embodiments, the baffle and / or reinforcing element for a hollow structure consists 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 wall of the hollow structure to be baffled and / or 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.

[0210] 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 structure to be baffled and / or reinforced, 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.

[0211] The carrier of the baffle and / or reinforcing element, if used, may be made 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. 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. Also glassy or ceramic materials can be used. Any combination of such materials can also be used. It is also contemplated that such materials can be filled or foamed, for example with fibers, minerals, clays, silicates, carbonates, combinations thereof, etc.

[0212] The carrier element can further exhibit any shape or geometry. It can also consist of several, not directly connected 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, according to the intended use of the baffle and / or reinforcing element.

[0213] Another subject of the invention is a method for producing 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.

[0214] The details of the manufacturing method of the baffles and / or reinforcing elements of the present invention depend largely on the carrier material: if the carrier material 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.

[0215] 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.

[0216] 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 chemically or physically, for example by gluing, or mechanically, for example by bolting, screwing, etc.

[0217] Another subject of the invention is the use of the baffles and / or strengthening elements of the invention for sealing, baffling or strengthening cavities or hollow structures of land, water or air vehicles, preferably automotive vehicles, and / or cavities of buildings, such that the transfer of noise, vibration, humidity and / or heat is reduced and / or the structure surrounding said cavity or hollow structure is mechanically strengthened.

[0218] 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 by UV treatment, so that said cavity or hollow structure is at least partially filled by the expanded composition.

[0219] 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.

[0220] With regard to the thermal activation of components that contain thermally expandable compositions when used in the manufacture of automotive vehicles, it is advantageous to combine the thermal activation with another process step that involves 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

[0221] The following chemicals, shown in Table 1, were used to formulate the thermally expandable compositions.

[0222] [Table 1]

[0223] Preparation of Thermally Expandable Composition All inventive and non-inventive (reference (Ref)) example compositions herein were produced in standard manufacturing equipment suitable for compounding thermoplastic resins 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 then hot pressed into test specimens used for volume expansion and water absorption test procedures.

[0224] 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.

[0225] 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.

[0226] [Table 2] The present disclosure includes the following inventive aspects: <Aspect 1> 1. A thermally expandable composition comprising: (a) a thermoplastic polymer component P and / or an elastomer component E, (b) at least one chemical blowing agent BA comprising at least one dicarboxylate salt of an aminoguanidine compound; (c) optionally, at least one free radical initiator I and / or vulcanization system VS, and (d) at least one guanidine derivative G different from said at least one dicarboxylate of an aminoguanidine compound; The aminoguanidine compound is represented by the following formula (I): Thermally expandable composition: [ka] (In the formula, R 1 and R 2 each independently represents a hydrogen atom or an amino group. <Aspect 2> 2. The thermally expandable composition according to claim 1, wherein the molar ratio of the amount of said aminoguanidine compound of formula (I) to the amount of dicarboxylic acid in said at least one dicarboxylate of said aminoguanidine compound is in the range of 1:1 to 2:1. <Aspect 3> 3. The thermally expandable composition of any one of the preceding aspects, wherein the dicarboxylic acid is oxalic acid and / or the aminoguanidine compound of formula (I) is aminoguanidine. <Aspect 4> 4. The thermally expandable composition according to any one of the preceding aspects, wherein the at least one chemical foaming agent BA comprises 0.5 to 35 wt. %, preferably 1 to 25 wt. %, of the total weight of the thermally expandable composition. <Aspect 5> The thermally expandable composition according to any one of the preceding embodiments, wherein the at least one guanidine derivative G is a functional guanidine of formula (II): [ka] (In the formula, R 3 represents a hydrogen atom, or a monovalent linear or branched alkyl group, alicyclic group, aryl group, or arylalkyl group having 1 to 10 carbon atoms, optionally containing a nitrogen atom; R 4 represents a hydrogen atom or a monovalent linear or branched alkyl group having 1 to 10 carbon atoms; R 5 represents a hydrogen atom, or a monovalent linear or branched alkyl group having 1 to 10 carbon atoms, or an alicyclic group, aryl group, or arylalkyl group optionally containing nitrogen atoms and / or oxygen atoms and / or silicon atoms). <Aspect 6> 6. The thermally expandable composition according to any one of aspects 1 to 5, wherein the at least one guanidine derivative G accounts for 0.1 to 7.5 wt %, preferably 0.25 to 5.0 wt %, of the total weight of the thermally expandable composition. <Aspect 7> 7. The thermally expandable composition according to any one of the preceding claims, wherein the at least one guanidine derivative G is 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-dicyclohexyl-3-hexylguanidine, 1,2-diisopropyl-3-phenylguanidine, and 1,2-bis(2,6-diisopropylphenyl)-3-hexylguanidine, preferably cyanoguanidine. <Aspect 8> 8. The thermally expandable composition of any one of the preceding aspects, wherein the thermoplastic polymer component P comprises at least 35 wt.%, preferably at least 45 wt.%, of the total weight of the thermally expandable composition. <Aspect 9> 9. The thermally expandable composition according to any one of the preceding claims, wherein the polymer component P comprises at least one epoxy-functional polymer EP and / or at least one anhydride-functional polymer AP and / or at least one thermoplastic polymer TP. <Aspect 10> The thermally expandable composition according to any one of the first to ninth aspects, wherein the elastomer component E comprises at least one solid rubber SR preferably selected from the group consisting of butyl rubber, halogenated butyl rubber, styrene-butadiene rubber (SBR), ethylene-propylene rubber (EPR), ethylene-propylene diene monomer rubber (EPDM), natural rubber, cis-1,4-polyisoprene, and polybutadiene rubber. <Aspect 11> A baffle and / or reinforcing element for a hollow structure comprising the thermally expandable composition according to any one of the preceding aspects. <Aspect 12> 12. The baffle and / or reinforcing element of embodiment 11, further comprising a carrier on which the thermally expandable composition is deposited or attached. <Aspect 13> A method of making the baffle and / or reinforcing element of embodiment 12, wherein the thermally expandable composition is injection molded onto the carrier or co-extruded with the carrier. <Aspect 14> 13. Use of a baffle and / or strengthening element according to aspect 11 or 12 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 mechanically strengthening a structure surrounding said cavity. <Aspect 15> A method of sealing, baffling, and / or strengthening a cavity or hollow structure, comprising introducing an element comprising the thermally expandable composition according to any one of aspects 1 to 10 into said cavity or hollow structure and subsequently expanding it by heat and / or UV treatment, whereby said cavity or hollow structure is at least partially filled by said expanded composition.

Claims

1. 1. A thermally expandable composition comprising: (a) a thermoplastic polymer component P and / or an elastomer component E, (b) at least one chemical blowing agent BA comprising at least one dicarboxylate salt of an aminoguanidine compound; and (c) at least one guanidine derivative G different from said at least one dicarboxylate of an aminoguanidine compound; The aminoguanidine compound is represented by the following formula (I): Thermally expandable composition: 【Chemistry 1】 (In the formula, R １ and R ２ each independently represents a hydrogen atom or an amino group.

2. 2. The thermally expandable composition of claim 1, wherein the molar ratio of the amount of said aminoguanidine compound of formula (I) to the amount of dicarboxylic acid in said at least one dicarboxylate salt of said aminoguanidine compound is in the range of 1:1 to 2:

1.

3. 3. The thermally expandable composition of claim 1 or 2, wherein the dicarboxylic acid is oxalic acid and / or the aminoguanidine compound of formula (I) is aminoguanidine.

4. The thermally expandable composition according to any one of claims 1 to 3, wherein said at least one chemical blowing agent BA represents 0.5 to 35 wt.% of the total weight of said thermally expandable composition.

5. The thermally expandable composition according to any one of claims 1 to 4, wherein said at least one guanidine derivative G is a functional guanidine of formula (II): 【Chemistry 2】 (In the formula, R ３ represents a hydrogen atom or a monovalent linear or branched alkyl group, alicyclic group, aryl group, or arylalkyl group having 1 to 10 carbon atoms, optionally containing a nitrogen atom; R ４ represents a hydrogen atom or a monovalent linear or branched alkyl group having 1 to 10 carbon atoms; R ５ represents a hydrogen atom or a monovalent linear or branched alkyl group having 1 to 10 carbon atoms, or an alicyclic, aryl, or arylalkyl group optionally containing nitrogen and / or oxygen and / or silicon atoms).

6. The thermally expandable composition according to any one of claims 1 to 5, wherein said at least one guanidine derivative G represents 0.1 to 7.5% by weight of the total weight of said thermally expandable composition.

7. The thermally expandable composition according to any one of claims 1 to 6, wherein the at least one guanidine derivative G is 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-dicyclohexyl-3-hexylguanidine, 1,2-diisopropyl-3-phenylguanidine, and 1,2-bis(2,6-diisopropylphenyl)-3-hexylguanidine.

8. The thermally expandable composition according to any one of claims 1 to 7, wherein the thermoplastic polymer component P represents at least 35% by weight of the total weight of the thermally expandable composition.

9. The thermally expandable composition according to any one of claims 1 to 8, wherein the polymer component P comprises at least one epoxy-functional polymer EP and / or at least one anhydride-functional polymer AP and / or at least one thermoplastic polymer TP.

10. The thermally expandable composition according to any one of claims 1 to 9, wherein the elastomer component E comprises at least one solid rubber SR.

11. A baffle and / or reinforcing element for hollow structures comprising a thermally expandable composition according to any one of claims 1 to 10.

12. 12. The baffle and / or reinforcing element of claim 11, further comprising a carrier on which the thermally expandable composition is deposited or attached.

13. 13. The method of claim 12, wherein the thermally expandable composition is injection molded onto the carrier or the thermally expandable composition is co-extruded with the carrier.

14. 13. Use of a baffle and / or strengthening element according to claim 11 or 12 to seal, baffle or strengthen a cavity or hollow structure of a land vehicle, water vehicle or aircraft, and / or a building cavity, thereby reducing the transfer of noise, vibration, humidity and / or heat, and / or mechanically strengthening a structure surrounding said cavity.

15. 11. A method of sealing, baffling and / or strengthening a cavity or hollow structure, comprising introducing an element comprising a thermally expandable composition according to any one of claims 1 to 10 into said cavity or hollow structure and subsequently expanding it by heat and / or UV treatment, whereby said cavity or hollow structure is at least partially filled by said expanded composition.

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