Radiation-curable polymers

Abstract

The present invention relates to radiation or radiation / moisture dual curable polymers and methods for their preparation. These polymers are useful for a variety of applications in the fields of adhesives, coatings, and sealants. The radiation curable polymers contain at least one end group of the general formula (I): -A 1 -C(=O)-CR 1 =CH2(I) (In the formula, A 1 is a divalent linking group containing at least one heteroatom; R 1 is selected from H and C1-C4 alkyl, preferably H and methyl; The polymer backbone is selected from the group consisting of polyoxyalkylenes, poly(meth)acrylates, polyesters, and combinations thereof. and optionally at least one terminal group of general formula (II) -A 2 -SiXYZ(II) (wherein X, Y, and Z are each independently selected from the group consisting of a hydroxyl group, and a C1-C8 alkyl, C1-C8 alkoxy, and C1-C8 acyloxy group, and X, Y, and Z are substituents directly bonded to the Si atom, or two of the substituents X, Y, and Z together with the Si atom to which they are bonded form a ring, and at least one of the substituents X, Y, and Z is selected from the group consisting of a hydroxyl group, a C1-C8 alkoxy, and a C1-C8 acyloxy group; A 2 is a divalent linking group containing at least one heteroatom Further includes:

Description

[Technical Field]

[0001] FIELD OF THE INVENTION The present invention is in the field of radiation or radiation / moisture dual curable polymers and methods for their preparation. [Background technology]

[0002] Radiation-curable adhesives are widely used and can crosslink (cure) upon sufficient exposure to radiation, such as electron beam radiation, or actinic radiation, such as ultraviolet (UV) radiation or visible light. It would be desirable to provide radiation-curable polymers that allow for the formation of cured materials that exhibit elastomeric properties and are resistant to high temperatures.

[0003] One-component moisture-curing adhesives and sealants, especially so-called silane-terminated adhesives and sealants, are well known and widely used in the adhesive and sealant fields. Over the years, they have played an important role in numerous technical applications. Silane-terminated adhesives and sealants have the advantage of providing broad-spectrum adhesion to a wide variety of substrates without surface pretreatment using a primer. In contrast to hot melts, silane-modified polymer compositions offer a variety of interesting properties, such as isotropic and chemically curable elastomers, and resistance to deformation at high temperatures. They can be combined with various additives to tailor the properties of the resulting product, such as mechanical properties, fire resistance, thermal conductivity, electrical conductivity, heat resistance, UV resistance, and weather resistance. Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention provides a new type of polymer that is curable by either radiation or a combination of radiation and moisture. [Means for solving the problem]

[0005] In a first aspect, the present invention provides a compound comprising at least one terminal group of general formula (I) -A1 -C(=O)-CR 1 =CH2(I) (In the formula, A 1 is a divalent linking group containing at least one heteroatom; R 1 is selected from H and C1-C4 alkyl, preferably H and methyl; The polymer backbone is selected from the group consisting of polyoxyalkylenes, poly(meth)acrylates, polyesters, and combinations thereof. The present invention relates to a radiation-curable polymer comprising: DETAILED DESCRIPTION OF THE INVENTION

[0006] In various embodiments, the radiation curable polymer comprises at least one end group of general formula (II): -A 2 -SiXYZ(II), (wherein X, Y, and Z are each independently selected from the group consisting of a hydroxyl group, and a C1-C8 alkyl, C1-C8 alkoxy, and C1-C8 acyloxy group, and X, Y, and Z are substituents directly bonded to the Si atom, or two of the substituents X, Y, and Z together with the Si atom to which they are bonded form a ring, and at least one of the substituents X, Y, and Z is selected from the group consisting of a hydroxyl group, a C1-C8 alkoxy, and a C1-C8 acyloxy group; A 2 is a divalent linking group containing at least one heteroatom Further includes:

[0007] In another aspect, the present invention provides a method for making the radiation-curable polymers described herein, comprising reacting an OH-terminated polymer with a compound of formula (Ia) OCN-R 13 -C(=O)-C(R 1 )=CH2(Ia) and optionally a compound of formula (IIa) OCN-R 23 -SiXYZ(IIa) (In the formula, R13 and R 23 are independently a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene or arylene residue having 1 to 14 carbon atoms; The polymer backbone is selected from the group consisting of polyoxyalkylenes, poly(meth)acrylates, polyesters, and combinations thereof. and reacting the compound with

[0008] This method is also referred to herein as the "one-step method."

[0009] In another aspect, the present invention provides a method for making the radiation-curable polymer described herein, comprising: (a) reacting an OH-terminated polymer with a polyisocyanate of formula (V) (OCN) p -R 2 -NCO(V) (In the formula, R 2 is a substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene or arylene residue having 1 to 14 carbon atoms; p is 1 to 3, preferably 1 or 2, more preferably 1. and reacting with; (b) reacting the resulting NCO-terminated polymer with a compound of formula (Ib) B 1 -R 13 -C(=O)-CR 1 =CH2(Ib) (In the formula, B 1 is an NCO reactive group, preferably —OH) and optionally a compound of formula (IIb) B 2 -R 23 -SiXYZ(IIb) (In the formula, B 2is an NCO reactive group, preferably —N(R″)2, where R″ can be hydrogen or an optionally substituted hydrocarbon moiety having 1 to 12 carbon atoms, preferably C1-C2 alkyl or hydrogen, more preferably hydrogen; R 13 and R 23 are independently a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene or arylene residue having 1 to 14 carbon atoms; The polymer backbone is selected from the group consisting of polyoxyalkylenes, poly(meth)acrylates, polyesters, and combinations thereof. and reacting with The present invention relates to a method comprising:

[0010] This method is also referred to herein as the "two-step method."

[0011] In yet another aspect, the present invention relates to radiation-curable polymers obtainable according to the methods described herein.

[0012] In still a further aspect, the invention also features a composition including at least one polymer of the invention.

[0013] A "composition" is understood in the context of the present invention as a mixture of at least two components.

[0014] The term "curable" should be understood to mean that the composition can transition from a relatively flexible state, optionally with plastic ductility, to a harder state under the influence of external conditions, particularly radiation present in the environment and / or provided for the purpose, and optionally moisture. Crosslinking can generally be achieved by chemical and / or physical influences, for example, by the application of energy in the form of heat, light, or other electromagnetic radiation, but also by simply contacting the composition with air, atmospheric moisture, water, or reactive components. In the context of the present invention, "curable" primarily refers to the crosslinking properties of the end groups of formula (I) and the condensation properties of the end groups of formula (II). Thus, "radiation-curable" as used herein refers to curing under the influence of radiation, e.g., electromagnetic radiation, particularly UV or visible light, e.g., exposure to radiation. UV radiation is in the range of 100 to 400 nanometers (nm). Visible light is in the range of 400 to 780 nanometers (nm). Thus, "moisture curable" as used herein refers to curing under the influence of moisture, typically moisture from ambient air.

[0015] When referring to the molecular weight of an oligomer or polymer in this application, the amount is number average, i.e., M n It does not refer to the weight average molecular weight.

[0016] As used herein, "at least one" refers to one or more, i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to components, this term refers to the type of component, not the absolute number of molecules. Thus, "at least one polymer" means, for example, that at least one type of polymer can be used, i.e., a mixture of one type of polymer or several different polymers can be used. Together with weight data, this term refers to all compounds of a given type contained in a composition / mixture, i.e., the composition does not contain other compounds of this type in excess of a given amount of the relevant compound.

[0017] All percentage data provided in connection with the compositions described herein refer in each case to % by weight, based on the relevant mixture, unless otherwise stated.

[0018] As used herein, "consisting essentially of" means that the respective composition consists primarily, i.e., at least 50% by weight, e.g., at least 60%, 70%, or 80%, of the referenced component listed below.

[0019] As used herein, "alkyl" refers to saturated aliphatic hydrocarbons, including straight-chain and branched-chain groups. The alkyl group preferably has 1 to 10 carbon atoms (when a numerical range, e.g., "1 to 10," is given herein, this means that the group, in this case the alkyl group, can have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to 10 carbon atoms). In particular, alkyl can be a medium alkyl having 5 to 6 carbon atoms, or a lower alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, tert-butyl, etc. Alkyl groups can be substituted or unsubstituted. "Substituted," as used in this context, means that one or more carbon and / or hydrogen atoms of the alkyl group have been replaced by a heteroatom or a functional group. Functional groups that can replace hydrogen atoms include, inter alia, =O, =S, -O-(C 1~10 alkyl), -O-(C 6~14 aryl), -N(C 1~10 alkyl)2, e.g., -N(CH3)2, -F, -Cl, -Br, -I, C 3~8 Cycloalkyl, C 6~14The heteroaryl group is selected from aryl, a 5- to 10-membered heteroaryl ring in which 1 to 4 ring atoms are independently nitrogen, oxygen, or sulfur, and a 5- to 10-membered heteroalicyclic ring in which 1 to 3 ring atoms are independently nitrogen, oxygen, or sulfur. Substituted alkyl includes, for example, alkylaryl groups. Heteroalkyl groups in which one or more carbon atoms are replaced by heteroatoms, particularly heteroatoms selected from O, S, N, and Si, are obtained by replacing one or more carbon atoms with heteroatoms. Examples of such heteroalkyl groups include, but are not limited to, methoxymethyl, ethoxyethyl, propoxypropyl, methoxyethyl, isopentoxypropyl, trimethoxypropylsilyl, and the like. In various embodiments, substituted alkyl is a C substituted with aryl, alkoxy, or oxyaryl. 1~10 Alkyl, preferably C 1~4 Alkyl includes, for example, propyl. As used herein, "alkylene" refers to the corresponding divalent alkyl group, i.e., alkanediyl.

[0020] As used herein, "alkenyl" refers to an alkyl group, as defined herein, consisting of at least two carbon atoms and at least one carbon-carbon double bond, e.g., ethenyl, propenyl, butenyl, or pentenyl, and structural isomers thereof, e.g., 1- or 2-propenyl, 1-, 2-, or 3-butenyl, etc. Alkenyl groups can be substituted or unsubstituted. If substituted, the substituents are as defined above for alkyl. "Alkenyloxy" refers to an alkenyl group, as defined herein, linked to the remainder of the molecule via -O-. Thus, each term includes an enoxy group, e.g., vinyloxy (HC=CH-O-). As used herein, "alkenylene" refers to the corresponding divalent alkenyl group.

[0021] As used herein, "alkynyl" refers to an alkyl group, as defined herein, consisting of at least two carbon atoms and at least one carbon-carbon triple bond, such as ethynyl (acetylene), propynyl, butynyl, or petynyl, and the structural isomers thereof described above. Alkynyl groups can be substituted or unsubstituted. If they are substituted, the substituents are as defined above for alkyl. "Alkynyloxy" refers to an alkynyl group, as defined herein, linked to the remainder of the molecule via -O-. As used herein, "alkynylene" refers to the corresponding divalent alkynyl group.

[0022] As used herein, "alicyclic group" or "cycloalkyl group" refers to a monocyclic or polycyclic group (several rings having a common carbon atom), especially of 3 to 8 carbon atoms, in which the rings do not have a completely conjugated pi-electron system, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, etc. Cycloalkyl groups can be substituted or unsubstituted. "Substituted," as used in this context, means that one or more hydrogen atoms of the cycloalkyl group have been replaced by a functional group. Functional groups that can replace hydrogen atoms include, among others, =O, =S, -O-(C 1~10 alkyl), -O-(C 6~14 aryl), -N(C 1~10 alkyl)2, for example, -N(CH3)2, -F, -Cl, -Br, -I, -COOH, -CONH2, -C 1~10 Alkyl or alkoxy, C 2~10 Alkenyl, C 2~10 Alkynyl, C 3~8 Cycloalkyl, C 6~14and 5-10 membered heteroalicyclic rings in which 1-4 ring atoms are independently nitrogen, oxygen, or sulfur. "Cycloalkyloxy" refers to a cycloalkyl group, as defined herein, linked to the remainder of the molecule via -O-. "Cycloalkylene," as used herein, refers to the corresponding divalent cycloalkyl group.

[0023] As used herein, "aryl" specifically refers to a monocyclic or polycyclic group of 6 to 14 carbon ring atoms (i.e., rings with a common adjacent carbon atom) having a completely conjugated π-electron system. Examples of aryl groups are phenyl, naphthalenyl, and anthracenyl. Aryl groups can be substituted or unsubstituted. If they are substituted, the substituents are as defined above for cycloalkyl. "Aryloxy" refers to an aryl group, as defined herein, linked to the remainder of the molecule via -O-. "Arylene," as used herein, refers to the corresponding divalent aryl group.

[0024] As used herein, a "heteroaryl" group refers to a monocyclic or polycyclic (i.e., rings which share adjacent pairs of ring atoms) aromatic ring, particularly having 5 to 10 ring atoms, in which 1, 2, 3, or 4 ring atoms are nitrogen, oxygen, or sulfur, and the remainder are carbon. Examples of heteroaryl groups include pyridyl, pyrrolyl, furyl, thienyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,3,4-triazinyl, 1,2,3-triazinyl, benzofuryl, isobenzofuryl, benzothienyl, benzotriazolyl, and the like. Heteroaryl groups are cycloalkyl, cycloalkyl, cyclopropyl, cyclopropyl, cyclopropyl- ...

[0025] As used herein, a "heteroalicyclic group" or "heterocycloalkyl group" refers to a monocyclic or fused ring system having 5 to 10 ring atoms containing one, two, or three heteroatoms selected from N, O, and S, with the remainder of the ring atoms being carbon. A "heterocycloalkenyl" group further contains one or more double bonds. However, the ring does not have a completely conjugated π-electron system. Examples of heteroalicyclic groups are pyrrolidinone, piperidine, piperazine, morpholine, imidazolidine, tetrahydropyridazine, tetrahydrofuran, thiomorpholine, tetrahydropyridine, and the like. Heterocycloalkyl groups can be substituted or unsubstituted. If substituted, the substituents are as defined above for cycloalkyl. "Heteroalicyclic" refers to a heteroalicyclic group, as defined herein, linked to the remainder of the molecule via -O-.

[0026] As used herein, "substituted" with respect to a hydrocarbon moiety has the meaning provided above depending on the type of hydrocarbon moiety. Thus, the hydrocarbon moiety may be an alkyl, alkenyl, alkynyl, alicyclic or aryl group as defined above, or a divalent or polyvalent variant thereof, which may be substituted or unsubstituted as defined above.

[0027] The polymer having at least one end group of general formula (I) is preferably a polyoxyalkylene / polyether, a polyester, or a poly(meth)acrylate, such as a poly(meth)acrylic acid (ester).

[0028] As used interchangeably herein, "polyoxyalkylene," "polyalkylene glycol," or "polyether" refers to a polymer whose organic repeating units contain ether functional groups C-O-C in the main chain. Polymers with lateral ether groups, such as cellulose ethers, starch ethers, and vinyl ether polymers, as well as polyacetals, such as polyoxymethylene (POM), are not included in the term polyethers. Examples of such polymers are polypropylene and polyethylene, as well as their copolymers.

[0029] In various embodiments, the polymer has a polyoxyethylene backbone, a polypropylene backbone, or a polyoxyethylene-polyoxypropylene backbone, preferably a polyoxypropylene backbone.

[0030] "Poly(meth)acrylic acid(esters)" is understood to be a polymer based on (meth)acrylic acid(esters) and therefore has the structural motif -CH2-CR a (COOR b )-(wherein, R a represents a hydrogen atom (acrylate ester) or a methyl group (methacrylate ester), and R b represents hydrogen or a straight chain alkyl residue, a branched alkyl residue, a cyclic alkyl residue and / or an alkyl residue containing a functional substituent, such as a methyl, ethyl, isopropyl, cyclohexyl, 2-ethylhexyl or 2-hydroxyethyl residue) as a repeating unit.

[0031] The polymer having at least one end group of general formula (I) is particularly preferably polyether.Polyether has a flexible and elastic structure, and can produce a composition with excellent elastic properties.Polyether is not only flexible in its main chain, but also strong at the same time.Therefore, for example, polyether is not attacked or decomposed by water and bacteria, unlike, for example, polyester.

[0032] The number average molecular weight M of the polyether on which the polymer is based nis preferably at least 500 g / mol, for example 500 to 100,000 g / mol (Daltons), particularly preferably at least 700 g / mol, in particular at least 1,000 g / mol. For example, the number average molecular weight M of the polyether n is 500 to 5000 g / mol, preferably 700 to 40000 g / mol, and particularly preferably 1000 to 30000 g / mol. These molecular weights are particularly advantageous because the corresponding compositions have a balanced ratio of viscosity (ease of processing), strength, and elasticity. Since lower molecular weights can result in a high concentration of urethane bonds and therefore undesirable hydrogen bonds, which can lead to the formulation being in an undesirable solid state, it is recommended that the polyether have a molecular weight M of at least 500 g / mol. n It is more preferred that the .alpha.-hydroxybenzoate has the formula:

[0033] Particularly advantageous viscoelastic properties can be achieved using polyethers with narrow molecular weight distributions and therefore low polydispersities. These can be produced, for example, by so-called double metal cyanide catalysis (DMC catalysis). Polyethers produced in this way are distinguished by particularly narrow molecular weight distributions, high average molecular weights, and a very low number of double bonds at the ends of the polymer chains.

[0034] Therefore, in a particular embodiment of the present invention, the maximum polydispersity M of the polyether on which the polymer is based is w / M n is 3, particularly preferably 1.7, most particularly preferably 1.5.

[0035] Number average molecular weight M n and weight average molecular weight M wis determined in accordance with the present invention by gel permeation chromatography (GPC, also known as SEC) at 23°C using a styrene standard. Molecular weights can be determined by gel permeation chromatography (GPC) according to DIN 55672-1:2007-08, preferably at 23°C or 35°C, using tetrahydrofuran (THF) as the eluent. The molecular weights of the monomeric compounds are calculated based on the respective molecular formulas and the known molecular weights of the individual atoms. These methods are known to those skilled in the art. Polydispersity is determined by the average molecular weight M w and M n This is derived from PD=M w / M n It is calculated as:

[0036] Ratio M w / M n The polydispersity (M) indicates the width of the molecular weight distribution and therefore the width of the different degrees of polymerization of the individual chains in a polydisperse polymer. For many polymers and polycondensates, a polydispersity value of about 2 applies. Strict monodispersity exists at a value of 1. A low polydispersity, for example less than 1.5, indicates a relatively narrow molecular weight distribution and therefore a particular expression of molecular weight-related properties, such as viscosity. Thus, in particular, in the context of the present invention, the polyether on which polymer A is based has a polydispersity (M) of less than 1.3. w / M n )

[0037] Polyesters are typically polymers obtained by the reaction of a polycarboxylic acid with a polyol, such as succinic acid or adipic acid, with butanediol or hexanediol. For polyesters, the same preferred molecular weight and polydispersity definitions apply as given above for polyethers.

[0038] In various embodiments, polyether / polyester polymers having at least one end group of general formula (I) and optionally (II) can be derived from a polyol or a mixture of two or more polyols, typically a polyether polyol or a polyester polyol.

[0039] A "polyol" is understood to be a compound containing at least two OH groups, regardless of whether the compound contains other functional groups. However, the polyols used according to the invention to prepare the polymers of the invention preferably contain only OH groups as functional groups, or, if other functional groups are present, none of these other functional groups are reactive with isocyanates, at least under the conditions prevailing during the reaction of the polyol and polyisocyanate described herein.

[0040] The polyol suitable for the present invention is preferably a polyether polyol.The above explanations regarding the molecular weight and polydispersity of polyethers apply to polyether polyols.The polyether polyol is preferably a polyalkylene oxide, particularly preferably polyethylene oxide and / or polypropylene oxide.In a preferred embodiment, a polyether or a mixture of two polyethers is used.

[0041] The polyols used according to the invention preferably have an OH number of about 5 to about 15, more preferably about 10. The content of primary OH groups should be less than about 20%, preferably less than 15%, based on all OH groups. In a particularly advantageous embodiment, the acid number of the polyethers used is less than about 0.1, preferably less than 0.05, more preferably less than 0.02.

[0042] In addition to the polyether, the polyol mixture may contain other polyols, for example, polyester polyols having a molecular weight of at least about 500 to about 50,000.

[0043] Generally, all of the above polymers can have multiple reactive terminals, such as multiple hydroxyl groups, used for the attachment of the end groups described herein, and are therefore polyols. However, it is preferred that these polymers contain two or three, preferably only two, such reactive terminal groups for attachment of the end groups of formulas (I) and (II), and are therefore linear polymers. Difunctional and trifunctional polymers, such as diols and / or triols, are particularly preferred, and difunctional polymers, such as diols, optionally combined with trifunctional polymers, such as triols, are more preferred. When trifunctional polymers, such as triols, are used, they are preferably used in combination with difunctional polymers, such as diols, for example, in a molar ratio of 1:1, more preferably in a molar ratio greater than 1:1. Thus, in some embodiments, the polymer used is a diol or a combination of diols / triols in a given ratio.

[0044] When the polymers described herein, especially polyethers, contain multifunctional polymers, i.e., polymers with more than two reactive end groups, it is generally preferred that they are present only in combination with polymers with a maximum of two reactive end groups.In such a mixture of polymers, the amount of difunctional polymers is preferably at least 50 mol%, and the amount of trifunctional or higher functional polymers is preferably less than 50 mol%, more preferably less than 45 mol%, or less than 40 mol%, or less than 35 mol%, or less than 30 mol%, or less than 25 mol%, or even less than 20 mol%.A larger amount of multifunctional polymers can cause an undesirable degree of crosslinking even during the production of the polymer of the present invention.

[0045] The radiation-curable polymers of the present invention contain at least one end group of general formula (I) -A 1 -C(=O)-CR 1 =CH2(I) (In the formula, A 1 is a divalent linking group containing at least one heteroatom; R 1is selected from H and C1-C4 alkyl, preferably H and methyl; The polymer backbone is selected from the group consisting of polyoxyalkylenes, poly(meth)acrylates, polyesters, and combinations thereof. Includes:

[0046] The presence of terminal acrylic groups confers radiation curable properties to the polymer. To obtain dual cure properties, the radiation curable polymer must contain at least one terminal group of general formula (II): -A 2 -SiXYZ(II), (wherein X, Y, and Z are each independently selected from the group consisting of a hydroxyl group, and a C1-C8 alkyl, C1-C8 alkoxy, and C1-C8 acyloxy group, and X, Y, and Z are substituents directly bonded to the Si atom, or two of the substituents X, Y, and Z together with the Si atom to which they are bonded form a ring, and at least one of the substituents X, Y, and Z is selected from the group consisting of a hydroxyl group, a C1-C8 alkoxy, and a C1-C8 acyloxy group; A 2 is a divalent linking group containing at least one heteroatom It may further include:

[0047] In various embodiments, the radiation-curable polymer may contain at least two, for example, two, three, or four or more, end groups of general formula (I). In addition, the polymer may further contain at least one, for example, one, two, or more, end groups of formula (II). In various embodiments, the polymer may contain at least one, for example, one, two, or three, end groups of formula (I) and at least one, for example, one, two, or three, end groups of formula (II). In some embodiments, the polymer is a linear polymer and therefore contains only two end groups. These may be of formula (I), or formula (I) and formula (II).

[0048] In various embodiments, the radiation-curable polymers of the present invention comprise 1 to 100 mol %, preferably 50 to 100 mol %, of end groups of Formula (I) and 99 to 0 mol %, preferably 50 to 0 mol %, of end groups of Formula (II). For a linear polymer having one end group of Formula (I) and one end group of Formula (II), the mol % of both groups would be 50%. In various embodiments, the presence of both types of end groups can be advantageous because it imparts dual-cure properties to the polymer. This is advantageous because radiation curing provides a fast cure mechanism and moisture curing provides a slower cure mechanism. While it is possible to indicate the number of end groups of each formula for a single polymer molecule, it is understood that the resulting polymer population may differ in their structure with respect to the end groups, depending on the manufacturing process, since a manufacturing process may be capable of producing polymer molecules having only end groups of Formula (I), only end groups of Formula (II), and both types of end groups. In such polymer compositions, the percentages given above regarding the percentage of each end group still apply, but now they relate to the total number of end groups in a given population of polymer molecules. In various embodiments, the molar ratio of end groups of formula (I) and (II) in the polymer of the present invention is greater than 1:1, for example, at least 1.5:1, at least 2:1, at least 2.1:1, at least 2.2:1, or at least 2.4:1. In certain embodiments, the molar ratio can be 20:1 or less, or 15:1 or less, or 10:1 or less.

[0049] Thus, in various embodiments, the radiation-curable polymer comprises (i) two or three, preferably two, end groups of formula (I), or (ii) one end group of formula (I) and one or two, preferably one, end group of formula (II), or (iii) two end groups of formula (I) and one end group of formula (II). Preferably, the polymer is a linear polymer.

[0050] In various embodiments, the divalent linking group A 1 and / or A 2The term "substituted" in reference to these groups means that a hydrogen atom present in these groups is replaced with a non-hydrogen moiety, such as an alkyl, e.g., C 1~4 It means that it can be replaced by alkyl. 1 and / or A 2 can be any one of the groups listed, but in various embodiments, they include additional structural elements, such as additional linking groups, that connect the listed functional groups to the polymer and / or end groups.

[0051] Generally, in various embodiments, the linking group A 1 and A 2 is produced in a capping reaction in which the polymer ends react with a compound to produce the end groups of formulas (I) and (II). In various embodiments, the polymer is provided in a hydroxyl (OH)-terminated form, thus providing reactive groups on the ends that can be used in the capping reaction. In various embodiments, the end groups of the polymer backbone, such as hydroxyl groups, can be first functionalized with a polyisocyanate, such as a diisocyanate or triisocyanate, such as those described below, to produce an NCO-terminated polymer. This can then be reacted in a subsequent step with a (meth)acrylate / silane containing an NCO-reactive group, such as an amino or hydroxyl group, preferably a hydroxy-modified (meth)acrylate and / or aminosilane. The urethane and urea groups resulting from such a reaction advantageously increase the strength of the polymer chain and the overall crosslinked polymer.

[0052] As used herein, "polyisocyanate" is understood to be a compound having at least two isocyanate groups -NCO. The compound need not be a polymer, but instead is often a low molecular weight compound.

[0053] Polyisocyanates suitable according to the invention include ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,4-tetramethoxybutane diisocyanate, 1,6-hexamethylene diisocyanate (HDI), cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, bis(2-isocyanatoethyl) fumarate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4- and 2,6-hexahydrotoluylene diisocyanate, hexahydro-1,3- or -1,4-phenylenediisocyanate, isocyanate, benzidine diisocyanate, naphthalene-1,5-diisocyanate, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 1,3- and 1,4-phenylene diisocyanate, 2,4- or 2,6-toluylene diisocyanate (TDI), 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, or 4,4'-diphenylmethane diisocyanate (MDI), and isomeric mixtures thereof. Also included are partially or fully hydrogenated cycloalkyl derivatives of MDI, such as fully hydrogenated MDI (H 12Also suitable are alkyl-substituted diphenylmethane diisocyanates, such as mono-, di-, tri-, or tetraalkyldiphenylmethane diisocyanates and their partially or fully hydrogenated cycloalkyl derivatives, 4,4'-diisocyanatophenyl perfluoroethane, phthalic acid bisisocyanatoethyl ester, 1-chloromethylphenyl-2,4- or 2,6-diisocyanate, 1-bromomethylphenyl-2,4- or 2,6-diisocyanate, 3,3'-bischloromethylether-4,4'-diphenyl diisocyanate, sulfur-containing diisocyanates, such as those obtainable by reacting two moles of a diisocyanate with one mole of thiodiglycol or dihydroxydihexyl sulfide, diisocyanates of dimeric fatty acids, or mixtures of two or more of the specified diisocyanates. The polyisocyanate is preferably IPDI, TDI, or MDI.

[0054] Other polyisocyanates suitable for use according to the invention are isocyanates with a functionality of three or more, obtainable, for example, by oligomerization of diisocyanates, more particularly by oligomerization of the isocyanates mentioned above. Examples of such triisocyanates and higher isocyanates are the triisocyanurates of HDI or IPDI or mixtures thereof, or mixed triisocyanurates thereof, and polyphenylmethylene polyisocyanates obtainable by phosgenation of aniline / formaldehyde condensates.

[0055] Thus, in some embodiments, A 1 is a group of formula (III) -R 11 -A 11 -(R 12 -A 12 ) n -R 13 -(III) [In the formula, R 11 , R 12 and R 13are independently a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene or arylene residue having 1 to 14 carbon atoms; A 11 and A 12 are each independently a divalent radical selected from -OC(=O)-NH-, -NH-C(=O)O-, -NH-C(=O)-NH-, -NR"-C(=O)-NH-, -NH-C(=O)-NR"-, -NH-C(=O)-, -C(=O)-NH-, -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, -SC(=O)-NH-, -NH-C(=O)-S-, -C(=O)-S-, -SC(=O)-, -SC(=O)-S-, -C(=O)-, -S-, -O-, and -NR"-, where R" can be hydrogen or an optionally substituted hydrocarbon moiety having 1 to 12 carbon atoms, preferably C-C alkyl, or hydrogen; n is 0 or 1] is.

[0056] As used herein, "(cyclo)alkylene" refers to a cycloalkylene or alkylene group.

[0057] A "bond" means that the respective moiety is essentially absent, i.e., the remaining structural element is directly attached to the next structural element. For example, R 11 is a bond, the structural element A 11 is directly bonded to the polymer main chain, and R 13 is a bond and n is 0, A 11 is the remainder of the terminal group of formula (I), i.e., -C(=O)-CR 1 = means that it is directly bonded to CH2.

[0058] "Substituted" with respect to a (cyclo)alkylene or arylene group has the same meaning as disclosed above with respect to alkyl, cycloalkyl, and aryl groups. In some embodiments, R 13is involved, it also applies when the substituent has the formula -C(=O)-CR 1 However, it is also contemplated that each group in formula (I) may be or contain another group of the structure -C(=O)-CR 1 It is preferred that the ═CH group contains only one or two groups, preferably only one. In some embodiments, R 12 is involved, it also means that the substituent has the formula -A 12 -R 13 -, and this R 13 also linked to the group of formula (I). These structures can be produced, for example, when a triisocyanate is used.

[0059] If n=0, this means that A 12 and R 12 does not exist, and A 11 R 13 This means that it is directly connected to

[0060] In either case, the orientation of the structural elements of formula (III) is R 13 is the structural element -C(=O)-CR of the group of formula (I) 1 =CH2, or A if not present 12 Or A 11 It is like connecting to

[0061] In various embodiments, R 11 is a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably an unsubstituted alkylene residue having 1 to 4 carbon atoms, such as methylene, 1,2-ethylene, 1,3-propylene or 1,4-butylene; A 11 is a divalent radical selected from -OC(=O)-NH-, -NH-C(=O)-NH- and -NR''-C(=O)-NH-, preferably -OC(=O)-NH-; R 13is a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted alkylene residue having 1 to 8 carbon atoms, such as ethylene (—CH—CH—), propylene, or butylene; n is 0 or 1.

[0062] In the above embodiment, when n is 1, R 12 may be a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene residue or arylene residue having 1 to 14 carbon atoms; A 12 may be a divalent group selected from -NH-C(=O)-O-, -NH-C(=O)-NH-, and -NH-C(=O)-NR''-, preferably -NH-C(=O)-O-.

[0063] In various embodiments, the structural element of formula (III) results from the reaction of a diisocyanate with a hydroxyl-terminated polymer, and in a second step, the reaction of the resulting NCO-terminated polymer with a hydroxyl-containing (meth)acrylate. In such embodiments, R 11 can be a bond or alkylene, A 11 is -OC(=O)-NH-, and R 12 is the NCO-containing residue of a diisocyanate, and A 12 is -NH-C(=O)-O-, and R 13 are the remaining structural elements of the hydroxy-modified (meth)acrylate ester moiety. In these embodiments, R 12 can be the divalent (1,3,3-trimethylcyclohexyl)methylene group (when IPDI is used as the diisocyanate), 1-methyl-2,4-phenylene (when TDI is used as the diisocyanate), and any other divalent group remaining when any one of the diisocyanates disclosed herein is used. In various embodiments, R 13is the remainder of the hydroxy ester group of the (meth)acrylate used, for example, ethyl when 2-hydroxyethyl (meth)acrylate is used, or n-butyl when 4-hydroxybutyl (meth)acrylate is used, or 3-(phenoxy)-2-propyl when 2-hydroxy-3-phenoxy (meth)acrylate is used.

[0064] In various embodiments, the preferred diisocyanates used include IPDI, such that R 12 is 1,3,3-trimethylcyclohexyl)methylene-4-yl.

[0065] In various embodiments, the (meth)acrylates used include, but are not limited to, 2-hydroxyethyl acrylate and -methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and 2-hydroxy-3-phenoxy acrylate, such that R 13 is preferably ethyl, propyl, butyl or 3-(phenoxy)-2-propyl.

[0066] Alternatively, other (meth)acrylates may be used, such as those based on monofunctional (meth)acrylate monomers containing reactive groups for coupling, such as hydroxyl groups, including, by way of example only and without limitation, isooctyl (meth)acrylate; tetrahydrofuranyl (meth)acrylate; cyclohexyl (meth)acrylate; dicyclopentanyl (meth)acrylate; dicyclopentanyloxyethyl (meth)acrylate; N,N-diethylaminoethyl (meth)acrylate; 2-ethoxyethyl (meth)acrylate; caprolactone-modified (meth)acrylates; isobornyl (meth)acrylate; lauryl (meth)acrylate; acryloylmorpholine; N-vinylcaprolactam; nonylphenoxy polyethylene glycol (meth)acrylate; nonylphenoxy polypropylene glycol (meth)acrylate; phenoxyethyl (meth)acrylate; phenoxydi(ethylene glycol) (meth)acrylate; and tetrahydrofuranyl (meth)acrylate. Suitable multifunctional (meth)acrylate monomers may include, by way of example and without limitation, 1,4-butylene glycol di(meth)acrylate; dicyclopentanyl di(meth)acrylate; ethylene glycol di(meth)acrylate; dipentaerythritol hexa(meth)acrylate; caprolactone-modified dipentaerythritol hexa(meth)acrylate; 1,6-hexanediol di(meth)acrylate; neopentyl glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; trimethylolpropane tri(meth)acrylate; tris(acryloyloxyethyl)isocyanurate; caprolactone-modified tris(acryloyloxyethyl)isocyanurate; tris(methylacryloyloxyethyl)isocyanurate, and tricyclodecane dimethanol di(meth)acrylate. The monofunctional (meth)acrylate monomers and the polyfunctional (meth)acrylate monomers may be used alone or in combination of two or more monomers, or the monofunctional (meth)acrylate monomers and the polyfunctional (meth)acrylate monomers may be combined together.

[0067] In other embodiments, n is 0. In such embodiments, R 11 can be a bond, and A 11 is -OC(=O)-NH-, and R 13 is typically an alkylene moiety, such as methylene, ethylene, or propylene. In such embodiments, the linking group results from the reaction of an isocyanatoacrylate with a hydroxy-terminated polymer.

[0068] In all embodiments described herein, various (meth)acrylates may be used, such as, by way of example only and without limitation, butylene glycol mono(meth)acrylate; hydroxyethyl (meth)acrylate; hydroxypropyl (meth)acrylate; hydroxybutyl (meth)acrylate; isooctyl (meth)acrylate; tetrahydrofuranyl (meth)acrylate; cyclohexyl (meth)acrylate; dicyclopentanyl (meth)acrylate; dicyclopentanyloxyethyl (meth)acrylate; N,N-diethylaminoethyl (meth)acrylate; 2-ethoxyethyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; 2-hydroxypropyl Those based on monofunctional (meth)acrylate monomers including (meth)acrylate; caprolactone-modified (meth)acrylate; isobornyl (meth)acrylate; lauryl (meth)acrylate; acryloylmorpholine; N-vinyl caprolactam; nonylphenoxy polyethylene glycol (meth)acrylate; nonylphenoxy polypropylene glycol (meth)acrylate; phenoxyethyl (meth)acrylate; phenoxyhydropropyl (meth)acrylate; phenoxydi(ethylene glycol) (meth)acrylate; polyethylene glycol (meth)acrylate and tetrahydrofuranyl (meth)acrylate can be used to provide the group of formula (I).Suitable multifunctional (meth)acrylate monomers may include, by way of example and without limitation, 1,4-butylene glycol di(meth)acrylate; dicyclopentanyl di(meth)acrylate; ethylene glycol di(meth)acrylate; dipentaerythritol hexa(meth)acrylate; caprolactone-modified dipentaerythritol hexa(meth)acrylate; 1,6-hexanediol di(meth)acrylate; neopentyl glycol di(meth)acrylate; pentaerythritol tri(meth)acrylate; polyethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; trimethylolpropane tri(meth)acrylate; tris(acryloyloxyethyl)isocyanurate; caprolactone-modified tris(acryloyloxyethyl)isocyanurate; tris(methylacryloyloxyethyl)isocyanurate, and tricyclodecane dimethanol di(meth)acrylate. Monofunctional (meth)acrylate monomers and polyfunctional (meth)acrylate monomers may be used alone or in combination of two or more monomers, or monofunctional (meth)acrylate monomers and polyfunctional (meth)acrylate monomers may be combined together. It is understood that all of the above (meth)acrylates may need to be used in the form of their derivatives, if not already present, containing additional linking groups, such as hydroxyl groups, isocyanate groups, or amine groups, to enable coupling to the polymer backbone. Specific modified acrylates that can be used include, but are not limited to, isocyanatoalkyl (meth)acrylates, such as 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 4-isocyanatobutyl (meth)acrylate, 3-isocyanatobutyl (meth)acrylate, and 2-isocyanatobutyl (meth)acrylate.

[0069] In various embodiments, A 2 is a group of formula (IV) -R 21 -A21 -(R 22 -A 22 ) m -R 23 -(IV) [In the formula, R 21 , R 22 and R 23 are independently a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene or arylene residue having 1 to 14 carbon atoms; A 21 and A 22 are each independently a divalent radical selected from -OC(=O)-NH-, -NH-C(=O)O-, -NH-C(=O)-NH-, -NR"-C(=O)-NH-, -NH-C(=O)-NR"-, -NH-C(=O)-, -C(=O)-NH-, -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, -SC(=O)-NH-, -NH-C(=O)-S-, -C(=O)-S-, -SC(=O)-, -SC(=O)-S-, -C(=O)-, -S-, -O-, and -NR"-, where R" can be hydrogen or an optionally substituted hydrocarbon moiety having 1 to 12 carbon atoms, preferably C-C alkyl, or hydrogen; m is 0 or 1] is.

[0070] Here, the same definitions of "bond" and "substituted" as disclosed above for formula (III) apply, the only difference being that "substituted" is specifically defined as R 23 The substituent is -C(=O)-CR 1 It is also encompassed that instead of =CH2, another group of formula -SiXYZ is used. Also, in various embodiments, R 22 But another -A 22 -R 23 is substituted with a moiety, 23 is linked to another group of formula (II).

[0071] If n=0, this means that A 22 and R 22 does not exist, and A 21 R 23 This means that it is directly connected to

[0072] In either case, the orientation of the structural elements of formula (IV) is R 23 is the structural element -SiXYZ of the group of formula (II), or, if absent, A 22 Or A 21 It is like connecting to

[0073] In various embodiments, R 21 is a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably an unsubstituted alkylene residue having 1 to 4 carbon atoms, such as methylene, ethylene, propylene, preferably a bond; R 23 is a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably an unsubstituted alkylene residue having 1 to 3 carbon atoms, more preferably methylene or propylene; n is 0 or 1, and when n is 0, A 21 is a divalent radical selected from -O-, -OC(=O)-NH-, -NH-C(=O)-NH-, and -NR''-C(=O)-NH-, preferably -O-, -OC(=O)-NH-, or NH-C(=O)-NH-; If n is 1, A 21 is a divalent radical selected from -O-, -OC(=O)-NH-, -NH-C(=O)-NH-, and -NR''-C(=O)-NH-, preferably -OC(=O)-NH; R 22 is a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene residue or arylene residue having 1 to 14 carbon atoms; A 22is a divalent group selected from -NH-C(=O)O-, -NH-C(=O)-NH-, and -NH-C(=O)-NR''-, preferably -NH-C(=O)-NH.

[0074] Such linking groups result from the reaction of a hydroxy-terminated polymer with a diisocyanate, as defined above for (meth)acrylate end groups, followed by the reaction of an NCO-terminated polymer with an NCO-reactive silane, such as a hydroxysilane or, preferably, an aminosilane. Suitable aminosilanes are well known in the art and include, but are not limited to, 3-aminopropyltrimethoxysilane, as well as those disclosed below with respect to the method of the present invention. Further useful isocyanate-containing alkoxysilanes that provide moisture cure include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-isocyanatopropylmethyldimethoxysilane.

[0075] In various embodiments, R in general formula (III) and / or (IV) 11 , R 21 and R 23 is selected from a bond, methylene, ethylene, or n-propylene group. 11 and R 21 is preferably a bond. 23 is preferably 1,3-propylene.

[0076] Alkoxysilane-terminated compounds having a methylene group as the bonding link to the polymer backbone, the so-called "alpha-silanes," have a particularly high reactivity of the terminal silyl groups, leading to reduced cure times and therefore extremely rapid cure of formulations based on these polymers.

[0077] Generally, increasing the length of the connecting hydrocarbon chain reduces the reactivity of the polymer. In particular, "gamma-silanes" containing unbranched propylene residues as connecting links have a balanced ratio between the required reactivity (acceptable curing time) and delayed curing (open assembly time, possibility of post-connection modification). Therefore, by carefully combining alpha-alkoxysilane-terminated building blocks with gamma-alkoxysilane-terminated building blocks, the cure rate of the system can be influenced as desired.

[0078] The substituents X, Y, and Z are independently selected from the group consisting of hydroxyl groups and C1-C8 alkyl, C1-C8 alkoxy, and C1-C8 acyloxy groups. At least one of the substituents X, Y, and Z must be a hydrolyzable group, preferably a C1-C8 alkoxy or C1-C8 acyloxy group. The substituents X, Y, and Z are directly bonded to the silicon atom, or two of the substituents X, Y, and Z, together with the silicon atom to which they are attached, form a ring. In a preferred embodiment, X, Y, and Z are directly bonded to the silicon atom. Alkoxy groups, particularly methoxy, ethoxy, i-propyloxy, and i-butyloxy groups, are preferably selected as hydrolyzable groups, since no substances irritating to mucous membranes are released during the curing of compositions containing alkoxy groups. The alcohol formed by hydrolysis of the residue is harmless in the amount released and evaporates. However, acyloxy groups, such as the acetoxy group -O-CO-CH3, can also be used as hydrolyzable groups.

[0079] In a preferred embodiment, the polymer has at least one end group of general formula (II). Thus, each polymer chain contains at least one linkage point where condensation of the polymer can be completed and hydrolysis residues can be separated in the presence of atmospheric moisture. Regular and rapid crosslinking is achieved in this way, resulting in bonds with good strength. Furthermore, depending on the amount and structure of the hydrolyzable groups, for example, by using di- or trialkoxysilyl groups, methoxy groups, or longer residues, the network configuration can be controlled, resulting in long-chain systems (thermoplastics), relatively wide-mesh three-dimensional networks (elastomers), or highly crosslinked systems (thermosets), thereby influencing, among other things, the elasticity, flexibility, and heat resistance of the resulting crosslinked composition.

[0080] In a preferred embodiment, in general formula (II), X is preferably an alkyl group, and Y and Z are each, independently of one another, an alkoxy group, or X, Y, and Z are each, independently of one another, an alkoxy group. In general, polymers containing di- or trialkoxysilyl groups have highly reactive linking points that allow for rapid curing, a high degree of crosslinking, and therefore good final strength. A particular advantage of dialkoxysilyl groups lies in the fact that, after curing, the corresponding compositions are more elastic, soft, and flexible than systems containing trialkoxysilyl groups.

[0081] On the other hand, trialkoxysilyl groups can be used to achieve a higher degree of crosslinking, which is particularly advantageous when a harder, stronger material is desired after curing. Furthermore, trialkoxysilyl groups are more reactive and therefore crosslink more quickly, thus reducing the amount of catalyst required and offering advantages in the "cold flow" - the dimensional stability of the corresponding adhesive under the influence of forces and possibly temperature.

[0082] Particularly preferably, the substituents X, Y and Z in general formula (II) are each independently selected from hydroxyl, methyl, ethyl, methoxy or ethoxy groups, and at least one of the substituents is a hydroxyl group, or a methoxy or ethoxy group, preferably a methoxy group.Methoxy and ethoxy groups, as relatively small hydrolyzable groups with low steric bulk, are highly reactive, and therefore allow rapid curing even when using little catalyst.Therefore, they are particularly interesting for systems that require rapid curing.

[0083] The combination of the two groups also opens up interesting configuration possibilities: for example, if methoxy is selected for X and ethoxy for Y in the same alkoxysilyl group, the desired reactivity of the terminal silyl group can be particularly finely tuned if a silyl group containing exclusively methoxy groups is considered too reactive, and a silyl group containing exclusively ethoxy groups is considered insufficiently reactive for the intended application.

[0084] In addition to methoxy and ethoxy groups, it is of course also possible to use larger residues as hydrolyzable groups, which are inherently less reactive. This is of particular interest when delayed cure is also achieved by the formation of alkoxy groups.

[0085] In various embodiments, in formula (II), X, Y, and Z are each independently selected from hydroxyl, methyl, ethyl, methoxy, or ethoxy groups, and at least one of the substituents is a hydroxyl group, or a methoxy or ethoxy group, and preferably all are selected from methoxy or ethoxy, more preferably methoxy. Thus, methyldimethoxysilyl, trimethoxysilyl, triethoxysilyl, and ethyldiethoxysilyl, preferably methyldimethoxysilyl and trimethoxysilyl, more preferably trimethoxysilyl, are explicitly encompassed.

[0086] The present invention also relates to methods of making the radiation-curable polymers disclosed herein.

[0087] Such a method comprises reacting a polymer capped with end groups of formula (I) and, optionally, formula (II), with an isocyanate that also contains the desired end groups, said isocyanate being a compound of formula (Ia) OCN-R 13 -C(=O)-C(R 1 )=CH2(Ia) and optionally an additional compound of formula (IIa) OCN-R 23 -SiXYZ(IIa) (In the formula, R 13 and R 23 are independently a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene or arylene residue having 1 to 14 carbon atoms; The polymer backbone is selected from the group consisting of polyoxyalkylenes, poly(meth)acrylates, polyesters, and combinations thereof. can be used.

[0088] The compounds of formula (Ia) and (IIa) may be used simultaneously, for example in a mixture, so that the reactions with the polymer occur in parallel, or may be reacted sequentially with the polymer, for example, in that the reaction with compound (Ia) is carried out first, and then the remaining reactive groups on the polymer are reacted with compound (IIa).

[0089] To enable this reaction, the polymer contains terminal NCO-reactive groups, such as hydroxyl or amino groups. In all methods described herein, it is understood that the polymer capped with the described end groups can be a mixture of polymers.

[0090] In a preferred embodiment, the polymer used is a hydroxy-terminated polymer, such as a polyol, e.g., a polyether and / or polyester polyol, that reacts with isocyanate to form a urethane bond. In such an embodiment, the definitions of polyether and polyester polyols above apply to the polymers used in these methods. This particularly relates to the molecular weight, polydispersity, and functionality defined above. Generally, all of the above polymers can have multiple reactive ends, e.g., multiple hydroxyl groups, that are used for the end group attachment described herein and are therefore polyols, but it is preferred that these polymers contain two or three, preferably only two, such reactive end groups for the attachment of the end groups of formulas (I) and (II), and are therefore linear polymers. Diols and triols are particularly preferred, with diols being more preferred. When triols are used, they are preferably used in combination with diols, for example, in a molar ratio of 1:1, more preferably a molar ratio greater than 1:1.

[0091] If the polymer contains terminal OH groups, the molar ratio of the terminal OH groups of the polymer to the NCO groups of the compounds of formula (Ia) and, optionally, formula (IIa) is in the range of 1:0.5 to 1:1.5, preferably 1:0.9 to 1:1.1, more preferably 1:0.99 to 1:1.01. If alternative NCO-reactive groups are used, the respective ratios may also be applied.

[0092] Compounds of formula (Ia) include, but are not limited to, isocyanatoalkyl(meth)acrylates, such as 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 3-isocyanatopropyl(meth)acrylate, 2-isocyanatopropyl(meth)acrylate, 4-isocyanatobutyl(meth)acrylate, 3-isocyanatobutyl(meth)acrylate, and 2-isocyanatobutyl(meth)acrylate. Compounds of formula (IIa) useful herein include, but are not limited to, isocyanate-containing alkoxysilanes that impart moisture cure, such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-isocyanatopropylmethyldimethoxysilane.

[0093] In the resulting reaction, essentially all of the hydroxy groups react with isocyanate groups to form urethane groups that link the desired end groups to the polymer backbone.

[0094] Similar to the method described above, the polymer is modified with the desired end group in only one step, and this method is also referred to herein as the one-step method.

[0095] In an alternative method for making the radiation curable polymer of the present invention, the method comprises: (a) reacting a polymer terminated with an NCO reactive group, e.g., an OH-terminated polymer, with a polyisocyanate of formula (V) (OCN) p -R 2 -NCO(V) (In the formula, R 2 is a substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene or arylene residue having 1 to 14 carbon atoms; p is 1 to 3, preferably 1 or 2, more preferably 1. and reacting the compound with the compound; (b) reacting the resulting NCO-terminated polymer with a compound of formula (Ib) B 1 -R 13 -C(=O)-CR1 =CH2(Ib) (In the formula, B 1 is an NCO reactive group, preferably —OH) and optionally a compound of formula (IIb) B 2 -R 23 -SiXYZ(IIb) (In the formula, B 2 is an NCO reactive group, preferably —N(R″)2, where R″ can be hydrogen or an optionally substituted hydrocarbon moiety having 1 to 12 carbon atoms, preferably C1-C2 alkyl or hydrogen, more preferably hydrogen; R 13 and R 23 are independently a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene or arylene residue having 1 to 14 carbon atoms; The polymer backbone is selected from the group consisting of polyoxyalkylenes, poly(meth)acrylates, polyesters, and combinations thereof. and reacting the compound with It includes two steps:

[0096] "Substituted" is R 2 As used herein, preferably, C 1~8 Alkyl, C 2~8 Alkenyl, C 3~8 Cycloalkyl, C 6~14"aryl" refers to saturated or unsaturated hydrocarbons, including straight-chain and branched chain, alicyclic, and aromatic groups, particularly (cyclo)alkylene or arylene residues having 1 to 14 carbon atoms, optionally substituted with one or more substituents selected from aryl, 5- to 10-membered heteroaryl rings in which 1 to 4 ring atoms are independently nitrogen, oxygen, or sulfur, and 5- to 10-membered heteroalicyclic rings in which 1 to 3 ring atoms are independently nitrogen, oxygen, or sulfur. Substituted alkyl includes, for example, alkylaryl groups. In some embodiments, the term "substituted alkyl" also includes groups in which one of the carbon atoms is replaced by a heteroatom, such as a heteroalkyl group. Heteroalkyl groups in which one or more carbon atoms are replaced by a heteroatom, particularly a heteroatom selected from O, S, N, and Si, are obtained by replacing one or more carbon atoms with a heteroatom. Examples of such heteroalkyl groups include, but are not limited to, methoxymethyl, ethoxyethyl, propoxypropyl, methoxyethyl, isopentoxypropyl, ethylaminoethyl, trimethoxypropylsilyl, and the like. Substituted R 2 is generally understood to depend on the isocyanate used, and preferably has a structure that renders the compound of formula (V) any one of the isocyanates specifically disclosed herein.

[0097] "Substituted" is R ’’ As used herein with respect to —O—(C 1~10 alkyl), -O-(C 6~14 aryl), -NH2, -N(C 1~10 alkyl)2, e.g., -N(CH3)2, C 1~10 Alkyl or alkoxy, C 2~10 Alkenyl, C 2~10 Alkynyl, C 3~8 Cycloalkyl, -SiXYZ, C 6~14 and a 5- to 10-membered heteroalicyclic ring in which 1 to 3 ring atoms are independently nitrogen, oxygen, or sulfur.

[0098] In various embodiments, R 2 is the above R 12 and R 22 and is the NCO-containing residue of any one of the diisocyanates disclosed above, such as IPDI, TDI, or MDI.

[0099] In these methods, the first step serves the purpose of modifying the polymer so that it is NCO-terminated. The reactive NCO termini of the polymer obtained in the first step of the reaction are then used to couple the end groups of formula (I) and, optionally, also the end groups of formula (II) to the polymer.

[0100] As described for the one-step method above, in this method too, the polymer contains terminal NCO-reactive groups, such as hydroxyl or amino groups. Also, in the two-step method described herein, the polymer reacted with a polyisocyanate and then capped with the described end groups may be a mixture of polymers. Also, in a preferred embodiment, the polymer used is a hydroxy-terminated polymer, such as a polyol, e.g., a polyether and / or polyester polyol, that reacts with an isocyanate to form a urethane bond. In such embodiments, the definitions of polyether and polyester polyols above apply to the polymers used in these methods. This particularly relates to the molecular weight, polydispersity, and functionality defined above. Generally, all of the above polymers can have multiple reactive ends, e.g., multiple hydroxyl groups, used for the attachment of the end groups described herein, and are therefore polyols. However, it is preferred that these polymers contain two or three, preferably only two, such reactive end groups for attachment of the end groups of formulae (I) and (II), and thus are linear polymers. Diols and triols are particularly preferred, with diols being more preferred. When triols are used, they are preferably used in combination with diols, for example in a molar ratio of 1:1, more preferably in a molar ratio of greater than 1:1.

[0101] In all of the methods described, i.e., the one-step and two-step methods, suitable catalysts and reaction conditions generally known to those skilled in the art can be used / utilized. When using isocyanate groups and hydroxyl groups, in principle, any compound capable of catalyzing the reaction of hydroxyl groups with isocyanato groups to form urethane bonds can be used. Some useful examples include tin carboxylates such as dibutyltin dilaurate (DBTL), dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctoate, dibutyltin dimethyl maleate, dibutyltin diethyl maleate, dibutyltin dibutyl maleate, dibutyltin diisooctyl maleate, dibutyltin ditridecyl maleate, dibutyltin dibenzyl maleate, dibutyltin maleate, dibutyltin diacetate, tin octanoate, dioctyltin distearate, dioctyltin dilaurate (DOTL), dioctyltin diethyl maleate, dioctyltin diisooctyl maleate, dioctyltin diacetate, and tin naphthenoate. tin alkoxides such as dibutyltin dimethoxide, dibutyltin diphenoxide, and dibutyltin diisoproxoxide; tin oxides such as dibutyltin oxide and dioctyltin oxide; reaction products between dibutyltin oxide and phthalic acid esters; dibutyltin bisacetylacetonate; titanates such as tetrabutyl titanate and tetrapropyl titanate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, and diisopropoxyaluminum ethylacetoacetate; chelating compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octanoate;Amine compounds or their salts with carboxylic acids, such as butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetraamine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, 2,2'-dimorpholinodiethyl ether, triethylenediamine, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, and 1,8-diazabicyclo-(5,4,0)-undecene-7 (DBU); aliphatic carboxylates or acetylacetonates of potassium, iron, indium, zinc, bismuth, titanium, cobalt, or copper. Some of these catalysts are also disclosed below as components of the present invention. Preferred catalysts are metal catalysts based on tin, bismuth, titanium, zinc, and cobalt, as well as amines. Catalysts based on tin, bismuth, titanium, and known amine catalysts are more preferred. The catalyst is preferably present in an amount of 0.005 to 3.5% by weight, based on the total composition weight.

[0102] In the two-step process, the first step, i.e., functionalization of the polymer ends with NCO groups, is preferably carried out at a temperature ranging from 0 to 120° C., more preferably from 50 to 100° C., and most preferably from 70 to 90° C. The second step, in which the NCO-terminated polymer is reacted with an NCO-reactive group-modified (meth)acrylate and a silane, is then preferably carried out at a temperature ranging from 0 to 90° C., more preferably from 10 to 50° C., and most preferably from 20 to 30° C.

[0103] The molar ratio of terminal OH groups to polyisocyanate of formula (V) can range from 1:0.5 to 1:1.5, preferably from 1:0.9 to 1:1.1, and more preferably from 1:0.99 to 1:1.01. As disclosed for the one-step process, this ratio ensures that essentially all of the hydroxy groups are reacted with the isocyanate to obtain an essentially fully NCO-terminated polymer.

[0104] In various embodiments, the unreacted NCO groups after step (a) and B 1 Groups and B 2 The molar ratio of the total of the groups is 1:0.5 to 1:1.5, preferably 1:0.9 to 1:1.0, and more preferably 1:0.94 to 1:0.96.

[0105] Therefore, the molar ratio of terminal NCO reactive groups of the polymer, such as OH groups, to the NCO groups of the polyisocyanate of formula (V) to the NCO reactive groups of the (meth)acrylate / silane, such as OH groups or amine groups, can be about 1:about 1:about 1, more preferably about 1:about 1:about 0.95. It can be preferable that the amount of (meth)acrylate / silane used, relative to the number of NCO reactive groups, is about 5% less than the amount stoichiometrically required (by calculation) for all NCO groups. When used herein with respect to a numerical value, "about" typically refers to the value ±10%, preferably ±5%.

[0106] The amounts of the compounds of formula (Ib) and (IIb) can be selected so that essentially all NCO groups react with the respective compounds. When both types of compounds are used for both types of end groups, as in all methods described herein, the second step can be subdivided into a first step in which a first compound, for example, a compound of formula (Ib), is reacted with the NCO-terminated polymer, and a second step in which the remaining NCO groups are reacted with a compound of formula (IIb).

[0107] In various embodiments, the polyisocyanate of formula (V) is selected from the group consisting of ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,4-tetramethoxybutane diisocyanate, 1,6-hexamethylene diisocyanate (HDI), cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, bis(2-isocyanatoethyl) fumarate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isocyanatomethyl) methyl ester, 1,4-isocyanato ... Isophorone diisocyanate (IPDI), 2,4- and 2,6-hexahydrotoluylene diisocyanate, hexahydro-1,3- or -1,4-phenylene diisocyanate, benzidine diisocyanate, naphthalene-1,5-diisocyanate, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 1 ,3- and 1,4-phenylene diisocyanate, 2,4- or 2,6-toluylene diisocyanate (TDI), 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), and their isomeric mixtures, partially or fully hydrogenated cycloalkyl derivatives of MDI, alkyl-substituted diphenylmethane diisocyanates, 4,4'-diisocyanatophenyl perfluoroethane, phthalic acid The diisocyanate is selected from the group consisting of bis-isocyanatoethyl ester, 1-chloromethylphenyl-2,4- or -2,6-diisocyanate, 1-bromomethylphenyl-2,4- or -2,6-diisocyanate, 3,3'-bis-chloromethylether-4,4'-diphenyl diisocyanate, sulfur-containing diisocyanates, diisocyanates of dimer fatty acids, or mixtures of two or more of the above diisocyanates, preferably IPDI, TDI and MDI.

[0108] In various embodiments, the compound of formula (Ib) is selected from the group consisting of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxybutyl acrylate, acrylic acid, and methacrylic acid. Hydroxyethyl (meth)acrylate is preferably 2-hydroxyethyl (meth)acrylate. Hydroxypropyl (meth)acrylate is preferably 2- or 3-hydroxypropyl or 2-hydroxy-1-methylethyl (meth)acrylate. Hydroxybutyl (meth)acrylate is preferably 2-, 3-, or 4-hydroxybutyl- or 2- or 3-hydroxy-1-methylpropyl (meth)acrylate. In general, unless otherwise specified, of all acrylates specifically described herein, the corresponding methacrylates may also be used, and vice versa. Furthermore, whenever acrylates are generally referred to herein, it is understood that methacrylates may also be used, and vice versa. Further modified (meth)acrylates are described above.

[0109] In various embodiments, the compound of formula (IIb) is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-(trimethoxysilyl)-n-(3-(trimethoxysilyl)propyl)-1-propanamine (CAS 82985-35-1), 3-triethoxysilyl-N-(3-triethoxysilylpropyl)propan-1-amine (CAS 13497-18-2), and N-(phenylamino)methyltrimethoxysilane.

[0110] The present invention also relates to radiation-curable polymers obtainable by any one of the methods described herein. Depending on the method and the compounds used therein, these methods result in polymers containing various amounts of end groups of formula (I), as well as polymers containing both groups of formula (I) and groups of formula (II), and polymers containing only end groups of formula (II). Such mixtures of polymers containing both types of end groups have the desired dual-cure properties described above. In either case, it is preferred that these mixtures of polymers contain polymers having end groups of formula (I) and preferably also end groups of formula (II) on the same polymer chain.

[0111] In principle, in the present invention, all features mentioned in the context of the present text, in particular embodiments, proportion ranges, components and other features of the compositions according to the invention and the uses according to the invention indicated as preferred and / or special, can be implemented in all possible non-mutually exclusive combinations, and combinations of features indicated as preferred and / or special are also considered to be preferred and / or special. All embodiments disclosed for polymers can be applied equally to the methods described herein, and vice versa. [Example]

[0112] Example 1: (Meth)acrylate-terminated polymer

[0113] Table 1 (all amounts in weight %) [Table 1] DOTL: Dioctyltin dilaurate

[0114] In the first step, polyol, isocyanate (IPDI), and catalyst (DOTL) were mixed under nitrogen at 80°C for 2.5 hours at 400 U / min. The molar ratio of OH groups to NCO groups was 1:1. After the reaction, the reaction mixture was cooled to 25°C, and then acrylate was added (an amount corresponding to a molar ratio of OH (polyol):NCO:OH (acrylate) of 1:1:1 (formulations 1, 2, and 5) and 1:1:0.95 (formulations 3, 4)). Mixing was carried out at 25°C for 3 hours. The resulting formulations were clear or slightly cloudy (formulation 2) liquids. The properties of these polymers are shown in Table 2.

[0115] [Table 2]

[0116] Example 2: Preparation of methacrylate-terminated and silane-terminated polymers In the first step, 72.8 wt% polypropylene oxide (PPG 2000), 16.2 wt% isophorone diisocyanate (IPDI), and 0.07 wt% dioctyltin dilaurate (DOTL) were mixed at 400 U / min under nitrogen for 0.5 hours at 80°C. The molar ratio of OH groups to NCO groups was 1:2. After the reaction, the reaction mixture was cooled to 25°C, and then 6.5 wt% aminopropyltrimethoxysilane (AMMO) was added. After 0.5 hours, 4.5 wt% hydroxyethyl methacrylate (HEMA) was added (corresponding to a molar ratio of OH (from polyol):NCO:NH2 (from AMMO):OH (acrylate from HEMA) of 1:2:0.5:0.48). Mixing was continued for 4.5 hours at 25°C. A methacrylate-terminated polymer, a silane-terminated polymer, and a mixture of methacrylate and silane-terminated polymers were obtained. The resulting methacrylate-terminated and silane-terminated polymers had a M (determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as eluent according to DIN 55672-1:2007-08). wThe polymer was a clear liquid with a D σ of 7400 g / mol and a viscosity of 68000 mPa.s (at 23°C, Anton Paar, Physica MCR 301, spindle PP25). Preferred aspects of the present invention include the following. [1] At least one terminal group of general formula (I) -A 1 -C(=O)-CR 1 =CH 2 (I) (In the formula, A 1 is a divalent linking group containing at least one heteroatom; R 1 H and C 1 ~C 4 alkyl, preferably selected from H and methyl; The polymer backbone is selected from the group consisting of polyoxyalkylenes, poly(meth)acrylates, polyesters, and combinations thereof. A radiation curable polymer comprising: [2] At least one terminal group of general formula (II) -A 2 -SiXYZ (II) (Wherein X, Y, and Z are each independently a hydroxyl group, and C 1 ~C 8 Alkyl group, C 1 ~C 8 Alkoxy groups, and C 1 ~C 8 acyloxy groups, wherein X, Y, and Z are substituents directly bonded to the Si atom, or two of the substituents X, Y, and Z together with the Si atom to which they are bonded form a ring, and at least one of the substituents X, Y, and Z is selected from the group consisting of a hydroxyl group, C 1 ~C 8 Alkoxy groups and C 1 ~C 8 acyloxy groups; A 2 is a divalent linking group containing at least one heteroatom The radiation-curable polymer according to [1], comprising: [3] (1) Contains at least two terminal groups of general formula (I), or contains at least one terminal group of formula (I) and at least one terminal group of formula (II); and / or (2) The radiation-curable polymer according to [1] or [2], which contains 1 to 100 mol %, preferably 50 to 100 mol %, of terminal groups of formula (I) and 99 to 0 mol %, preferably 50 to 0 mol %, of terminal groups of formula (II), and the molar ratio of the terminal groups of formula (I) to the terminal groups of formula (II) is preferably greater than 1:1, more preferably at least 2:1. [4] (1) A linear polymer having (i) two or three, preferably two, end groups of formula (I), or (ii) one end group of formula (I) and one or two, preferably one, end group of formula (II), or (iii) two end groups of formula (I) and one end group of formula (II); and / or (2) The radiation-curable polymer according to any one of [1] to [3], which has a polyoxyethylene main chain, a polypropylene main chain, or a polyoxyethylene-polyoxypropylene main chain, preferably a polyoxypropylene main chain. 〔5〕 A 1 and / or A 2 [4] The radiation-curable polymer according to any one of [1] to [4], wherein the substituted or unsubstituted ether group, amide group, carbamate group, urethane group, urea group, imino group, siloxane group, carboxylate group, carbamoyl group, amidino group, carbonate group, sulfonate group, or sulfinate group, preferably a urea group and / or a urethane group. 〔6〕 A 1 is a group of formula (III) -R 11 -A 11 -(R 12 -A 12 ) n -R 13 - (III) [In the formula, R 11 、R 12 and R 13 are independently a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene residue or arylene residue having 1 to 14 carbon atoms; A 11 and A 12 are each independently -OC(=O)-NH-, -NH-C(=O)O-, -NH-C(=O)-NH-, -NR"-C(=O)-NH-, -NH-C(=O)-NR"-, -NH-C(=O)-, -C(=O)-NH-, -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, -SC(=O)-NH-, -NH-C(=O)-S-, -C(=O)-S-, -SC(=O)-, -SC(=O)-S-, -C(=O)-, -S-, -O-, and -NR"-, where R" is hydrogen or an optionally substituted hydrocarbon moiety having 1 to 12 carbon atoms, preferably C 1 ~C 2 is a divalent group selected from (which may be alkyl or hydrogen); n is 0 or 1] The radiation-curable polymer according to any one of [1] to [5], 〔7〕 R 11 is a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably an unsubstituted alkylene residue having 1 to 4 carbon atoms; A 11 is a divalent radical selected from -OC(=O)-NH-, -NH-C(=O)-NH- and -NR''-C(=O)-NH-, preferably -OC(=O)-NH-; R 13 is a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted alkylene residue having 1 to 8 carbon atoms; n is 0 or 1, provided that when n is 1, R 12 is a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene residue or arylene residue having 1 to 14 carbon atoms; A 12 is a divalent group selected from —NH—C(═O)O—, —NH—C(═O)—NH—, and —NH—C(═O)—NR″—, preferably —NH—C(═O)O. 〔8〕 A 2 is a group of formula (IV) -R 21 -A 21 -(R 22 -A 22 ) m -R 23 -(IV) [In the formula, R 21 、R 22 and R 23 are independently a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene residue or arylene residue having 1 to 14 carbon atoms; A 21 and A 22 are each independently -OC(=O)-NH-, -NH-C(=O)O-, -NH-C(=O)-NH-, -NR"-C(=O)-NH-, -NH-C(=O)-NR"-, -NH-C(=O)-, -C(=O)-NH-, -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, -SC(=O)-NH-, -NH-C(=O)-S-, -C(=O)-S-, -SC(=O)-, -SC(=O)-S-, -C(=O)-, -S-, -O-, and -NR"-, where R" is hydrogen or an optionally substituted hydrocarbon moiety having 1 to 12 carbon atoms, preferably C 1 ~C 2 is a divalent group selected from (which may be alkyl or hydrogen); m is 0 or 1] The radiation-curable polymer according to any one of [1] to [7], 〔9〕 R 21 is a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably an unsubstituted alkylene residue having 1 to 4 carbon atoms; R 23 is a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably an unsubstituted alkylene residue having 1 to 3 carbon atoms; n is 0 or 1, provided that when n is 0, A 21 is a divalent radical selected from -O-, -OC(=O)-NH-, -NH-C(=O)-NH-, and -NR''-C(=O)-NH-, preferably -O-, -OC(=O)-NH-, or NH-C(=O)-NH-; However, if n is 1, A 21 is a divalent radical selected from -O-, -OC(=O)-NH-, -NH-C(=O)-NH-, and -NR''-C(=O)-NH-, preferably -OC(=O)-NH; R 22 is a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene residue or arylene residue having 1 to 14 carbon atoms; A 22 is a divalent group selected from —NH—C(═O)O—, —NH—C(═O)—NH—, and —NH—C(═O)—NR″—, preferably —NH—C(═O)—NH.

[10] (1) In formula (II), X, Y, and Z are each independently selected from a hydroxyl group, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and at least one of the substituents is a hydroxyl group, a methoxy group, or an ethoxy group, preferably all of which are selected from a methoxy group or an ethoxy group, more preferably a methoxy group; and / or (2) R in general formula (III) and / or (IV) 11 、R 21 and R 23 [9] The radiation-curable polymer according to any one of [1] to [9], wherein is selected from a bond, a methylene group, an ethylene group, or an n-propylene group.

[11] A method for producing the radiation-curable polymer according to any one of [1] to

[10] , comprising: OCN-R 13 -C(=O)-C(R 1 )=CH 2 (Ia) and optionally a compound of formula (IIa) OCN-R 23 -SiXYZ(IIa) (In the formula, R13 and R 23 are independently a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene residue or arylene residue having 1 to 14 carbon atoms; The polymer backbone is selected from the group consisting of polyoxyalkylenes, poly(meth)acrylates, polyesters, and combinations thereof. The method of claim 1, wherein the reactant is a hydroxybenzoate.

[12] (i) the molar ratio of terminal OH groups to NCO groups in the polymer is in the range of 1:0.5 to 1:1.5, preferably 1:0.9 to 1:1.1, more preferably 1:0.99 to 1:1.01; and / or (ii) The method according to

[11] , wherein the reaction is carried out in the presence of a suitable catalyst.

[13] A method for producing the radiation-curable polymer according to any one of [1] to

[10] , comprising: (a) reacting an OH-terminated polymer with a polyisocyanate of formula (V) (OCN) p -R 2 -NCO(V) (In the formula, R 2 is a substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene residue or arylene residue having 1 to 14 carbon atoms; p is 1 to 3, preferably 1 or 2, more preferably 1. reacting with; and (b) The resulting NCO-terminated polymer is reacted with a compound of formula (Ib) B 1 -R 13 -C(=O)-CR 1 =CH 2 (Ib) (In the formula, B 1 is an NCO reactive group, preferably —OH) and optionally a compound of formula (IIb) B 2 -R 23 -SiXYZ(IIb) (In the formula, B 2 is an NCO reactive group, preferably -N(R'') 2 and R″ is hydrogen or an optionally substituted hydrocarbon moiety having 1 to 12 carbon atoms, preferably C 1 ~C 2 may be alkyl or hydrogen, more preferably hydrogen; R 13 and R 23 are independently a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene residue or arylene residue having 1 to 14 carbon atoms; The polymer backbone is selected from the group consisting of polyoxyalkylenes, poly(meth)acrylates, polyesters, and combinations thereof. To react with A method comprising:

[14] (i) the molar ratio of the terminal OH group to the polyisocyanate of formula (V) is 1:0.5 to 1:1.5, preferably 1:0.9 to 1:1.1, more preferably 1:0.99 to 1:1.01; and / or (ii) Unreacted NCO groups after step (a) and B1 Groups and B 2 the molar ratio of the total of the aryl groups to the total of the aryl groups is 1:0.5 to 1:1.5, preferably 1:0.9 to 1:1.0, more preferably 1:0.94 to 1:0.96; and / or (iii) The polyisocyanate of formula (V) is selected from the group consisting of ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,4-tetramethoxybutane diisocyanate, 1,6-hexamethylene diisocyanate (HDI), cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, bis(2-isocyanatoethyl) fumarate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone), Diisocyanate, IPDI), 2,4- and 2,6-hexahydrotoluylene diisocyanate, hexahydro-1,3- or -1,4-phenylene diisocyanate, benzidine diisocyanate, naphthalene-1,5-diisocyanate, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 1,3- and and 1,4-phenylene diisocyanate, 2,4- or 2,6-toluylene diisocyanate (TDI), 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), and their isomeric mixtures, partially or fully hydrogenated cycloalkyl derivatives of MDI, alkyl-substituted diphenylmethane diisocyanates, 4,4'-diisocyanatophenyl perfluoroethane, bis-isocyanated phthalates, diisocyanates selected from the group consisting of anthraquinone ethyl ester, 1-chloromethylphenyl-2,4- or -2,6-diisocyanate, 1-bromomethylphenyl-2,4- or -2,6-diisocyanate, 3,3'-bis-chloromethylether-4,4'-diphenyl diisocyanate, sulfur-containing diisocyanates, diisocyanates of dimeric fatty acids, or mixtures of two or more of the aforementioned diisocyanates, preferably IPDI, TDI and MDI; and / or (iv) the compound of formula (Ib) is selected from the group consisting of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxybutyl acrylate, acrylic acid and methacrylic acid; and / or (v) the compound of formula (IIb) is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-(trimethoxysilyl)-n-(3-(trimethoxysilyl)propyl)-1-propanamine (CAS 82985-35-1), 3-triethoxysilyl-N-(3-triethoxysilylpropyl)propan-1-amine (CAS 13497-18-2), and N-(phenylamino)methyltrimethoxysilane; and / or (vi) The method according to

[13] , wherein the reaction is carried out in the presence of a suitable catalyst.

[15] A radiation-curable polymer obtainable according to any one of

[11] to

[14] .

Claims

1. At least one terminal group of general formula (I) -A １ -C(=O)-CR １ =CH ２ (I) (In the formula, A １ is a divalent linking group containing at least one heteroatom; R １ is H and C １ ~C ４ alkyl) Here, A １ is a group of formula (III)  １１ . １１ () １２ . １２ ) ｎ  １３ ().) [In the formula, R １１ , R １２ and R １３ are independently a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; A １１ and A １２ are each independently a divalent group selected from —O—C(═O)—NH—, —NH—C(═O)O—, —NH—C(═O)—NH—, —NR″—C(═O)—NH—, —NH—C(═O)—NR″—, —NH—C(═O)—, —C(═O)—NH—, —C(═O)—O—, —O—C(═O)—, —O—C(═O)—O—, —S—C(═O)—NH—, —NH—C(═O)—S—, —C(═O)—S—, —S—C(═O)—, —S—C(═O)—S—, —C(═O)—, —S—, —O—, and —NR″-, where R″ is hydrogen or an optionally substituted hydrocarbon moiety having 1 to 12 carbon atoms; n is 0 or 1. That is, 1. A radiation / moisture dual curable polymer comprising: the polymer has a polyoxyethylene backbone or a polyoxyethylene-polyoxypropylene backbone; The polymer has at least one end group of general formula (II) -A ２ -SiXYZ (II) (Wherein X, Y, and Z are each independently a hydroxyl group, and C １ ~C ８ Alkyl group, C １ ~C ８ Alkoxy groups, and C １ ~C ８ acyloxy groups, wherein X, Y, and Z are substituents directly bonded to the Si atom, or two of the substituents X, Y, and Z form a ring together with the Si atom to which they are bonded, and at least one of the substituents X, Y, and Z is selected from the group consisting of a hydroxyl group, C １ ~C ８ Alkoxy groups and C １ ~C ８ acyloxy groups; A ２ is a divalent linking group containing at least one heteroatom 1. A radiation / moisture dual curable polymer comprising:

2. The radiation / moisture dual curable polymer of claim 1 , wherein the polymer comprises at least two end groups of general formula (I).

3. R １１ is a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; A １１ is a divalent group selected from —O—C(═O)—NH—, —NH—C(═O)—NH—, and —NR″—C(═O)—NH—; R １３ is a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; n is 0 or 1, provided that when n is 1, R １２ is a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; A １２ The radiation / moisture dual curable polymer of claim 1 or 2, wherein is -NH-C(=O)O-, -NH-C(=O)-NH-, and -NH-C(=O)-NR''-.

4. A ２ is a group of formula (IV) -R ２１ -A ２１ -(R ２２ -A ２２ ) ｍ -R ２３ -(IV) [In the formula, R ２１ , R ２２ and R ２３ are independently a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; A ２１ and A ２２ are each independently a divalent group selected from —O—C(═O)—NH—, —NH—C(═O)O—, —NH—C(═O)—NH—, —NR″—C(═O)—NH—, —NH—C(═O)—NR″—, —NH—C(═O)—, —C(═O)—NH—, —C(═O)—O—, —O—C(═O)—, —O—C(═O)—O—, —S—C(═O)—NH—, —NH—C(═O)—S—, —C(═O)—S—, —S—C(═O)—, —S—C(═O)—S—, —C(═O)—, —S—, —O—, and —NR″-, where R″ can be hydrogen or an optionally substituted hydrocarbon moiety having 1 to 12 carbon atoms; m is 0 or 1.

4. The radiation / moisture dual curable polymer of claim 1, wherein

5. R ２１ is a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; R ２３ is a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; n is 0 or 1, provided that when n is 0, A ２１ is a divalent group selected from —O—, —O—C(═O)—NH—, —NH—C(═O)—NH—, and —NR″—C(═O)—NH—; However, when n is 1, A ２１ is a divalent group selected from —O—, —O—C(═O)—NH—, —NH—C(═O)—NH—, and —NR″—C(═O)—NH—; R ２２ is a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; A ２２ is a divalent group selected from -NH-C(=O)O-, -NH-C(=O)-NH-, and -NH-C(=O)-NR''-.

6. (1) In formula (II), X, Y, and Z are each independently selected from a hydroxyl group, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and at least one of the substituents is a hydroxyl group, or a methoxy or ethoxy group; and / or (2) R in general formula (III) and / or (IV) １１ , R ２１ and R ２３ The radiation / moisture dual curable polymer of any one of claims 1 to 5, wherein is selected from a bond, a methylene group, an ethylene group, or an n-propylene group.

7. A method for producing the radiation / moisture dual curable polymer of any one of claims 1 to 6, comprising reacting an OH-terminated polymer with a compound of formula (Ia) OCN-R １３ -C(=O)-C(R １ )=CH ２ (Ia) and optionally a compound of formula (IIa) OCN-R ２３ -SiXYZ(IIa) (In the formula, R １３ and R ２３ are independently a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms. wherein the polymer has a polyoxyethylene backbone or a polyoxyethylene-polyoxypropylene backbone, The method of claim 1, wherein the reactant is a hydroxybenzoate.

8. (i) the molar ratio of terminal OH groups to NCO groups of the polymer is in the range of 1:0.5 to 1:1.5; and / or (ii) The method of claim 7, wherein the reaction is carried out in the presence of a suitable catalyst.

9. A method for producing the radiation / moisture dual curable polymer of any one of claims 1 to 6, comprising the steps of: (a) reacting an OH-terminated polymer with a polyisocyanate of formula (V) (OCN) ｐ -R ２ -NCO(V) (In the formula, R ２ is a substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; p is 1 to 3. reacting with; and (b) treating the resulting NCO-terminated polymer with a compound of formula (Ib) B １ -R １３ -C(=O)-CR １ =CH ２ (Ib) (In the formula, B １ is an NCO reactive group) and optionally a compound of formula (IIb) B ２ -R ２３ -SiXYZ(IIb) (In the formula, B ２ is an NCO-reactive group, and R″ can be hydrogen or an optionally substituted hydrocarbon moiety having 1 to 12 carbon atoms; R １３ and R ２３ are independently a bond or a divalent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms. wherein the polymer has a polyoxyethylene backbone or a polyoxyethylene-polyoxypropylene backbone, To react with A method comprising:

10. (i) the molar ratio of terminal OH groups to the polyisocyanate of formula (V) is from 1:0.5 to 1:1.5; and / or (ii) Unreacted NCO groups after step (a) and B １ Groups and B ２ and / or (iii) The polyisocyanate of formula (V) is selected from the group consisting of ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,4-tetramethoxybutane diisocyanate, 1,6-hexamethylene diisocyanate (HDI), cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, bis(2-isocyanatoethyl)fumarate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylsilane, and the like. Diisocyanate (isophorone diisocyanate, IPDI), 2,4- and 2,6-hexahydrotoluylene diisocyanate, hexahydro-1,3- or -1,4-phenylene diisocyanate, benzidine diisocyanate, naphthalene-1,5-diisocyanate, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, xylylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), 1,3- and 1,4-phenylene diisocyanate, 2,4- or 2,6-toluylene diisocyanate (TDI), 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), and isomeric mixtures thereof, partially or fully hydrogenated cycloalkyl derivatives of MDI, alkyl-substituted diphenylmethane diisocyanates, 4,4'-diisocyanatophenylperfluoroethane, phthalic acid bis-isocyanatoethyl ester, 1-chloromethylphenyl-2,4- or -2,6-diisocyanate, 1-bromomethylphenyl-2,4- or -2,6-diisocyanate, 3,3'-bis-chloromethylether-4,4'-diphenyl diisocyanate, sulfur-containing diisocyanates, diisocyanates of dimer fatty acids, or the aforementioned diisocyanates; and / or (iv) the compound of formula (Ib) is selected from the group consisting of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxybutyl acrylate, acrylic acid and methacrylic acid; and / or (v) the compound of formula (IIb) is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-(trimethoxysilyl)-n-(3-(trimethoxysilyl)propyl)-1-propanamine (CAS 82985-35-1), 3-triethoxysilyl-N-(3-triethoxysilylpropyl)propan-1-amine (CAS 13497-18-2), and N-(phenylamino)methyltrimethoxysilane; and / or (vi) The method of claim 9, wherein the reaction is carried out in the presence of a suitable catalyst.

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