Hot melt adhesive comprising siloxy-functionalized polyolefin

Abstract

The invention relates to a hot melt adhesive comprising a polar group-containing olefin copolymer having a number average molecular weight (Mn) of 10 to 50 kg / mol, preferably 20 to 50 kg / mol, a crystallinity (Xc) content of less than 30%, preferably less than 15%, more preferably less than 10%, an enthalpy (H) of 5 to 65 J / g, preferably 5 to 30 J / g, a polydispersity index # imgabs0 # of 2 to 6, preferably 3 to 6, more preferably 4 to 6, a melting temperature (Tm) of 40 to 120 DEG C, the present invention relates to a composition comprising at least 80 mol% of a constituent unit represented by the following formula (1), optionally a constituent unit represented by the following formula (2), and 0.1 to 1 mol%, preferably 0.1 to 0.5 m%, of a constituent unit represented by the following formula (3) wherein: R1 is H or CH3; r2 is selected from the list comprising: hydrocarbyl groups having 0 to 10, preferably 1 to 6 and more preferably 1 or 6, when R1 = H, and preferably 0, 2, 4 or 6 carbon atoms, when R1 = CH3, R3 is selected from the list comprising: hydrocarbyl groups having 2 to 10, preferably 2 to 8, preferably 4 to 8, more preferably 4 or 6 carbon atoms, r4, R5, R6 may be the same or different and are selected from the list comprising: hydrocarbyl groups having 0 to 10 carbon atoms, preferably 2 to 6, and more preferably 6 carbon atoms. # imgabs1 #

Description

Technical Field

[0001] The present invention relates to hot melt adhesives comprising siloxy-functionalized polyolefins. Background Art

[0002] Hot melt adhesives (HMA), also known as hot melt glues, are thermoplastic adhesive resins that are solid at ambient temperature and can be melted to apply them to surfaces. Most commonly, HMAs contain EVA or polyolefin elastomers. Other examples are thermoplastic polyurethanes (TPU), styrene block copolymers (SBC), polyamides or polyesters.

[0003] HMA is produced in several forms such as rods, pellets, beads, granules, ingots, sheets, plugs, flyers, mats, blocks, films or sprays and is used in various applications like packaging, hygiene, furniture, footwear, fabrics and leather, electronics, bookbinding and graphics, building and construction, consumer DIY.

[0004] HMAs offer several advantages over solvent-based adhesives. Volatile organic compounds are reduced or eliminated, and the drying or curing step typically required for two-component adhesives is eliminated. In addition, HMAs typically have high mileage, low odor, and are thermally stable. HMAs have a long shelf life and can generally be handled without special precautions. In addition, because they are thermoplastics, HMA bonds can be simply reversed by heating the substrate. The obvious drawback of this reversible bond is the loss of bond strength at higher temperatures until the adhesive is completely melted. Therefore, the use of HMAs is limited to applications that are not exposed to high temperatures.

[0005] Polyolefin-based HMAs exhibit good adhesion to low surface energy materials, such as untreated polyolefins, or they can be applied to porous materials such as paper, paperboard, or wood, where adhesion is achieved by physically containing the HMA within the porous material. However, these polyolefin-based HMAs typically exhibit low bond strength to polar materials such as metals, glass, and polar polymeric materials.

[0006] EP1186619 discloses the use of polyolefin-based HMAs having more than 13 carbon atoms. 13 Polar functionalized monomers are used to improve adhesion to polar substrates such as polycarbonate and aluminum.

[0007] However, HMA containing such functionalized monomers have limited adhesive strength.

[0008] An object of the present invention is to provide a hot melt adhesive comprising a siloxy-functionalized olefin copolymer, which has excellent adhesion properties to metals or polar resins and non-polar resins.

[0009] There is a need for new hot melt adhesives having at least one of the following adhesive properties:

[0010] ●Lap shear strength of steel and steel above 3MPa,

[0011] ●Aluminum-aluminum lap shear strength above 3MPa,

[0012] ●1MPa or more, preferably 3MPa or more, lap shear strength of aluminum and polyolefin,

[0013] ●Over 3MPa lap shear strength between steel and polyolefin,

[0014] ●Over 3MPa lap shear strength between polyolefins. Summary of the invention

[0015] This object is achieved by the present invention. The hot melt adhesive comprises an olefin polymer containing polar groups. The olefin polymer containing polar groups has:

[0016] ● At least 80 mol% of the constituent unit represented by the following formula (1),

[0017] ●Optional constituent units represented by the following formula (2), and

[0018] 0.1 to 1 mol%, preferably 0.1 to 0.5 mol%, of a constituent unit represented by the following formula (3):

[0019]

[0020] in:

[0021] ●R 1 It is H or CH3.

[0022] ●R 2 Select from the list consisting of: 0 to 10, in R 1 =H, preferably 1 to 6 and more preferably 1 or 6, and in R 1 =CH3 is preferably a hydrocarbon group having 0, 2, 4 or 6 carbon atoms,

[0023] ●R 3 is selected from the list comprising: a hydrocarbon group having 1 to 10, preferably 2 to 8, preferably 4 to 8, more preferably 4 or 6 carbon atoms,

[0024] ●R 4 , R 5 , R 6 The may be the same or different and are selected from the list comprising hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 6 and more preferably 1 to 4 carbon atoms, or a combination of 1 and / or 3 and / or 4 carbon atoms.

[0025] In some embodiments, the polar group-containing olefin polymer has at least one of the following, preferably two, more preferably four, more preferably three, and more preferably all of the following:

[0026] a number average molecular weight (Mn) of 5 to 50 kg / mol, preferably 10 to 50 kg / mol, preferably 20 to 50 kg / mol, as measured by the method described in the "Size Exclusion Chromatography (SEC)" section of the Measurement Methods section of the present disclosure,

[0027] The crystallinity (X) is less than 30%, preferably less than 15%, more preferably less than 10%. c ) content, measured by the method described in the "Differential Scanning Calorimetry (DSC)" section of the Measurement Methods section of this disclosure,

[0028] Enthalpy (ΔH) of 5 to 65 J / g, preferably 5 to 30 J / g, as measured by the method described in the "Differential Scanning Calorimetry (DSC)" section of the Measurement Methods section of this disclosure,

[0029] A polydispersity index of 2 to 6, preferably 3 to 6, more preferably 4 to 6 Measured by the method described in the "Size Exclusion Chromatography (SEC)" section of the Measurement Methods section of this disclosure,

[0030] ● Melting temperature (T 40 to 120°C) m ), measured by the method described in the "Differential Scanning Calorimetry (DSC)" section of the Measurement Methods section of this disclosure.

[0031] In some embodiments, the constituent unit represented by the following formula (3) is a polymerized unit derived from one of the following monomers selected from the group consisting of: (allyloxy)trimethylsilane, (allyloxy)triethylsilane, (allyloxy)triisopropylsilane, tert-butyl(allyloxy)dimethylsilane, (allyloxy)dimethylphenylsilane, (but-3-en-1-yloxy)trimethylsilane, (but-3-en-1-yloxy)triethylsilane, (but-3-en-1-yloxy)triisopropylsilane, tert-butyl(but-3-en-1-yloxy)dimethylsilane, (but-3-en-1-yloxy)dimethylphenylsilane, (hex-5-en-1-yloxy)trimethylsilane , (hex-5-en-1-yloxy)triethylsilane, (hex-5-en-1-yloxy)triisopropylsilane, tert-butyl(hex-5-en-1-yloxy)dimethylsilane, (hex-5-en-1-yloxy)dimethylphenylsilane, trimethyl(undec-10-en-1-yloxy)silane, triethyl(undec-10-en-1-yloxy)silane, triisopropyl(undec-10-en-1-yloxy)silane, tert-butyldimethyl(undec-10-en-1-yloxy)silane, dimethylphenyl(undec-10-en-1-yloxy)silane, preferably (hex-5-en-1-yloxy)trimethylsilane and tert-butyl(hex-5-en-1-yloxy)dimethylsilane.

[0032] In some embodiments, the polymerization of the polar group-containing olefin polymer has been carried out using a solution process.

[0033] In some embodiments, a siloxy-functionalized C3 to C 12 Monomers, preferably C4 to C 10 , preferably C6 to C 10 , preferably C6 to C8 olefin monomers.

[0034] In some embodiments, the hot melt adhesive resin is prepared by treating the corresponding hydroxyl-functionalized copolymer or terpolymer with a silylating agent, wherein the hydroxyl-functionalized copolymer or terpolymer has been previously prepared by solution polymerization of one or more olefin monomers and a hydroxyl-functionalized olefin monomer that was previously protected with a trialkylaluminum.

[0035] In some embodiments, the hot melt adhesive according to the present invention has at least one of the following adhesive properties, preferably two, more preferably three, more preferably four, and more preferably all, which have been measured by the method described in the "lap shear strength" section of the measurement method section, wherein the Zwick Z020 type tensile testing machine equipped with a 10kN load cell is used for measurement. Before measurement, the sample is conditioned at room temperature for 7 days. Tested on a specimen (10cm×2.5cm) with a 12.5mm overlapping surface. Use a 140mm chuck to separate from the chuck. The sample is prestressed to 3N, and then 100mm·min -1 Constant crosshead speed loading. To calculate lap shear strength, report the force value divided by the bond surface of the specimen (25 mm x 12.5 mm); the reported value is the average of at least 5 measurements for each composition:

[0036] ● Steel-to-steel lap shear strength of 3 MPa or more, preferably 4.5 MPa or more, more preferably 5 MPa or more, even more preferably 6 MPa or more,

[0037] ● Aluminum-aluminum lap shear strength of 3 MPa or more, preferably 4.5 MPa or more, more preferably 5 MPa or more, even more preferably 6 MPa or more,

[0038] ●Over 3MPa lap shear strength between steel and polyolefin,

[0039] ●1MPa or more, preferably 2.5MPa or more, more preferably 3MPa of lap shear strength between aluminum and polyolefin,

[0040] ●Over 3MPa lap shear strength between polyolefins.

[0041] In some embodiments, the hot melt adhesive according to the present invention comprises:

[0042] a. 16-100% by weight, preferably 30-50% by weight, of the polymer portion of the hot melt adhesive,

[0043] b. 0-70% by weight, preferably 20-40% by weight, of a hot melt adhesive,

[0044] c. 0-40 wt. %, preferably 10-40 wt. % of a hot melt adhesive, of a plasticizer such as a processing oil and a wax,

[0045] d. 0-10% by weight of filler of hot melt adhesive,

[0046] e. 0-3% by weight of an antioxidant based on the hot melt adhesive,

[0047] f. 0-1% by weight of pigment of hot melt adhesive,

[0048] The hot melt adhesive further comprises the polar group-containing olefin polymer according to the present invention, and the polar group-containing olefin polymer is at least a part of the polymer part, more preferably 100% of the polymer part, and the remainder of the polymer part, if any, is another polymer, preferably an olefin polymer.

[0049] Another aspect of the present invention is an olefin polymer containing a polar group according to the following formula (4):

[0050]

[0051] in

[0052] ● z is 0.1 to 1 mol %

[0053] ● x is at least 80 mol %

[0054] ●y is 0 or 100-(x+z)mol%,

[0055] ●R 1 is H or CH3,

[0056] ●R 2 Select from the list consisting of: 0 to 10, in R 1 =H, preferably 1 to 6 and more preferably 1 or 6, and in R 1 =CH3 is preferably a hydrocarbon group having 0, 2, 4 or 6 carbon atoms,

[0057] ●R 3 is a hydrocarbon group having 1 to 10, preferably 2 to 8, preferably 4 to 8, more preferably 4 or 6 carbon atoms,

[0058] ●R 4 , R 5 , R 6 The same or different and selected from the list comprising hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 6 and more preferably 1 to 4 carbon atoms, or a combination of 1 and / or 3 and / or 4 carbon atoms.

[0059] In some embodiments, the polymerization of the polar group-containing olefin polymer has been carried out using a solution process, preferably using a catalyst system comprising a metal catalyst or catalyst precursor containing a metal from Groups 3-8, more preferably from Groups 3-6, and / or wherein the metal catalyst comprises a metal selected from the group consisting of Ti, Zr, Hf, V, Cr, Fe, Co, Ni, Pd, preferably Zr or Hf, preferably a homogeneous single-site catalyst, more preferably a hafnium complex of a polyvalent aryloxy ether or a zirconium complex of a polyvalent aryloxy ether.

[0060] In some embodiments, the polar group-containing olefin polymer according to the preceding claims has at least one of the following, preferably two of the following, more preferably three, more preferably four, more preferably all:

[0061] a number average molecular weight (Mn) of 5 to 50 kg / mol, preferably 10 to 50 kg / mol, preferably 20 to 50 kg / mol, as measured by the method described in the "Size Exclusion Chromatography (SEC)" section of the Measurement Methods section of the present disclosure,

[0062] ● Crystallinity (X) lower than 30%, preferably lower than 15%, more preferably lower than 10% c ) content, measured by the method described in the "Differential Scanning Calorimetry (DSC)" section of the Measurement Methods section of this disclosure,

[0063] Enthalpy (ΔH) of 5 to 65 J / g, preferably 5 to 30 J / g, as measured by the method described in the "Differential Scanning Calorimetry (DSC)" section of the Measurement Methods section of this disclosure,

[0064] A polydispersity index of 2 to 6, preferably 3 to 6, more preferably 4 to 6 Measured by the method described in the "Size Exclusion Chromatography (SEC)" section of the Measurement Methods section of this disclosure,

[0065] ● Melting temperature (T 40 to 120°C) m ), measured by the method described in the "Differential Scanning Calorimetry (DSC)" section of the Measurement Methods section of this disclosure.

[0066] Another aspect of the present invention is the use of the polar group-containing olefin polymer according to the present invention for the manufacture of hot melt adhesives, photovoltaic sealants, asphalt binders, surface modifiers for polyolefins, preferably for automobiles and household appliances, and compatibilizers.

[0067] A further aspect of the invention is the use of the hot-melt adhesive according to the invention for gluing together metal, glass, stone, wood, polar polymers or metal to glass, metal to stone, metal to wood, metal to polar polymers, glass to stone, glass to wood, glass to polar polymers, stone to wood, stone to polar polymers, wood to polar polymers, metal to polyolefins, glass to polyolefins, stone to polyolefins, wood to polyolefins or polar polymers to polyolefins, wherein the stone is a mineral material such as granite, basalt, limestone, or an artificial stone such as concrete or masonry.

[0068] A final aspect of the invention is the use of the hot-melt adhesive according to the invention for gluing together metal, glass, stone, wood, polar polymers or metal to glass, metal to stone, metal to wood, metal to polar polymers, glass to stone, glass to wood, glass to polar polymers, stone to wood, stone to polar polymers, wood to polar polymers, metal to polyolefins, glass to polyolefins, stone to polyolefins, wood to polyolefins or polar polymers to polyolefins, wherein the stone is a mineral material such as granite, basalt, limestone, or an artificial stone such as concrete or masonry. DETAILED DESCRIPTION

[0069] The present invention preferably relates to a polyolefin-based hot melt adhesive resin which is an olefin polymer containing polar groups, preferably containing siloxy functional groups as polar groups.

[0070] According to the present invention, the polyolefin-based hot melt adhesive resin is at least one first olefin monomer and a siloxy-functional C2 to C 12 , preferably C4 to C 12 , more preferably C4 to C 10 A copolymer of olefin monomers and according to formula (4),

[0071]

[0072] in

[0073] z is 0.1 to 1 mol %.

[0074] x is at least 80 mol %.

[0075] y is 0 or 100-(x+z)mol%,

[0076] R 1 is H or CH3,

[0077] R 2 Select from the list consisting of: 0 to 10, in R 1 =H, preferably 1 to 6 and more preferably 1 or 6, and in R 1 =CH3 is preferably a hydrocarbon group having 0, 2, 4 or 6 carbon atoms,

[0078] R 3 is a hydrocarbon group having 1 to 10, preferably 2 to 8, preferably 4 to 8, more preferably 4 or 6 carbon atoms,

[0079] R 4 , R 5 , R 6The may be the same or different and are selected from the list comprising hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 6 and more preferably 1 to 4 carbon atoms, or a combination of 1 and / or 3 and / or 4 carbon atoms.

[0080] In some embodiments, the polar group-containing olefin polymer has at least one of the following, preferably two, more preferably four, more preferably three, and more preferably all of the following:

[0081] a number average molecular weight (Mn) of 5 to 50 kg / mol, preferably 10 to 50 kg / mol, preferably 20 to 50 kg / mol, as measured by the method described in the "Size Exclusion Chromatography (SEC)" section of the Measurement Methods section of the present disclosure,

[0082] The crystallinity (X) is less than 30%, preferably less than 15%, more preferably less than 10%. c ) content, measured by the method described in the "Differential Scanning Calorimetry (DSC)" section of the Measurement Methods section of this disclosure,

[0083] Enthalpy (ΔH) of 5 to 65 J / g, preferably 5 to 30 J / g, as measured by the method described in the "Differential Scanning Calorimetry (DSC)" section of the Measurement Methods section of this disclosure,

[0084] A polydispersity index of 2 to 6, preferably 3 to 6, more preferably 4 to 6 Measured by the method described in the "Size Exclusion Chromatography (SEC)" section of the Measurement Methods section of this disclosure,

[0085] ● Melting temperature (T 40 to 120°C) m ), measured by the method described in the "Differential Scanning Calorimetry (DSC)" section of the Measurement Methods section of this disclosure.

[0086] In some embodiments, the first olefin monomer is ethylene or propylene, preferably propylene.

[0087] In some embodiments, the hot melt adhesive resin according to the present invention is a polyolefin-based copolymer, preferably a terpolymer, which is composed of a first olefin monomer and an optional olefin monomer selected from ethylene or C3 to C 12 The second olefin monomer of the list of olefin monomers and the second olefin monomer selected from the group consisting of C3 to C 12 , preferably C4 to C 10 The list of olefin monomers is produced by polymerization of a functionalized third olefin monomer.

[0088] In some embodiments, when the first olefin monomer is ethylene, preferably the second olefin monomer is propylene, 1-butene, 1-hexene, or 1-octene, more preferably propylene or 1-octene.

[0089] In some embodiments, when the first olefin monomer is propylene, preferably the second olefin monomer is ethylene, 1-butene, 1-hexene, or 1-octene.

[0090] In some embodiments, the third monomer is a siloxy-functionalized olefin monomer, preferably selected from the group consisting of (allyloxy)trimethylsilane, (allyloxy)triethylsilane, (allyloxy)triisopropylsilane, tert-butyl(allyloxy)dimethylsilane, (allyloxy)dimethylphenylsilane, (but-3-en-1-yloxy)trimethylsilane, (but-3-en-1-yloxy)triethylsilane, (allyloxy)triisopropylsilane, tert-butyl(allyloxy)dimethylsilane, (allyloxy)dimethylphenylsilane, (but-3-en-1-yloxy)trimethylsilane, (but-3-en-1-yloxy)triethylsilane, (allyloxy)triisopropylsilane, tert-butyl(allyloxy)dimethylsilane, (allyloxy)dimethylphenylsilane, tert-butyl(but-3-en-1-yloxy)triisopropylsilane, tert-butyl(but-3-en-1-yloxy)dimethylsilane, (but-3-en-1-yloxy)dimethylphenylsilane, (hex-5-en-1-yloxy)trimethylsilane, (hex-5-en-1-yloxy)triethylsilane, (hex-5-en-1-yloxy)triisopropylsilane, tert-butyl(hex-5-en-1-yloxy)dimethylsilane, (hex-5-en-1-yloxy)triethylsilane, 1-yloxy)dimethylphenylsilane, trimethyl(undec-10-en-1-yloxy)silane, triethyl(undec-10-en-1-yloxy)silane, triisopropyl(undec-10-en-1-yloxy)silane, tert-butyldimethyl(undec-10-en-1-yloxy)silane, dimethylphenyl(undec-10-en-1-yloxy)silane, more preferably (hex-5-en-1-yloxy)trimethylsilane, tert-butyl(hex-5-en-1-yloxy)dimethylsilane, preferably (hex-5-en-1-yloxy)trimethylsilane, (hex-5-en-1-yloxy)triethylsilane, (hex-5-en-1-yloxy)triisopropylsilane or tert-butyl(hex-5-en-1-yloxy)dimethylsilane, more preferably (hex-5-en-1-yloxy)trimethylsilane or tert-butyl(hex-5-en-1-yloxy)dimethylsilane.

[0091] In some embodiments, the hot melt adhesive resin is prepared in a solution process using a siloxy-functional C3 to C 12 Monomers, preferably C4 to C 10 , preferably C6 to C 10 , preferably obtained from C6 to C8 olefin monomers.

[0092] In some embodiments, the hot melt adhesive resin is prepared by treating the corresponding hydroxyl-functionalized copolymer or terpolymer with a silylating agent, wherein the hydroxyl-functionalized copolymer or terpolymer has been previously prepared by polymerization of one or more olefin monomers and a hydroxyl-functionalized olefin monomer, wherein the hydroxyl-functionalized olefin monomer has previously been protected with a trialkylaluminum, as described in PCT / EP2021 / 082511.

[0093] Direct use of siloxy-functionalized C3 to C 12 The monomeric embodiment of the process is preferred because it does not require a purification step to remove the protecting agent from the hydroxyl functional groups of the copolymer or terpolymer.

[0094] The tunable functionality of these functionalized olefin terpolymers HMAs makes them well suited for gluing like or different polar substrates such as metal, glass, stone, wood and polar polymers.

[0095] The generally non-polar character of the functionalized olefin terpolymer HMAs additionally provides excellent adhesion to low surface energy substrates such as polyolefins (i.e., HDPE, LDPE, LLDPE, PP), making these HMAs very suitable for gluing polyolefins to polyolefins, or for gluing polyolefins to polar substrates such as metals, glass, wood, and polar polymers.

[0096] The hot melt adhesive comprises an olefin polymer containing a polar group, wherein the olefin polymer containing a polar group has:

[0097] ● At least 80 mol% of the constituent unit represented by the following formula (1),

[0098] ●Optional constituent units represented by the following formula (2), and

[0099] 0.1 to 1 mol%, preferably 0.1 to 0.5 mol%, of a constituent unit represented by the following formula (3):

[0100]

[0101] in:

[0102] ●R 1 is H or CH3,

[0103] ●R 2 Select from the list consisting of: 0 to 10, in R 1 =H, preferably 1 to 6 and more preferably 1 or 6, and in R 1 =CH3 is preferably a hydrocarbon group having 0, 2, 4 or 6 carbon atoms,

[0104] ●R 3 is selected from the list comprising: a hydrocarbon group having 1 to 10, preferably 2 to 8, preferably 4 to 8, more preferably 4 or 6 carbon atoms,

[0105] ●R 4 , R 5 , R 6The may be the same or different and are selected from the list comprising hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 6 and more preferably 1 to 4 carbon atoms, or a combination of 1 and / or 3 and / or 4 carbon atoms.

[0106] The hot melt adhesive according to the present invention comprises:

[0107] a. 16-100% by weight, preferably 30-50% by weight, of the polymer portion of the hot melt adhesive,

[0108] b. 0-70% by weight, preferably 20-40% by weight, of a hot melt adhesive,

[0109] c. 0-40 wt. %, preferably 10-40 wt. % of a hot melt adhesive, of a plasticizer such as a processing oil and a wax,

[0110] d. 0-10% by weight of filler of hot melt adhesive,

[0111] e. 0-3% by weight of an antioxidant based on the hot melt adhesive,

[0112] f. 0-1% by weight of pigment of hot melt adhesive,

[0113] The hot melt adhesive further comprises the polar group-containing olefin polymer according to the present invention, and the polar group-containing olefin polymer is at least a part of the polymer part, more preferably 100% of the polymer part, and the remainder of the polymer part, if any, is another polymer, preferably an olefin polymer.

[0114] A catalyst system suitable for the polymerization process of an olefin polymer containing a polar group according to the present invention.

[0115] The process according to the invention is carried out in the presence of a suitable catalyst system comprising at least:

[0116] Catalyst

[0117] ●Promoter

[0118] ●Optional scavenger

[0119] ●Optional chain transfer agent

[0120] catalyst

[0121] The catalyst is a metal catalyst or catalyst precursor comprising a metal from Group 3-10, preferably from Group 3-8 of the IUPAC Periodic Table of Elements, and / or wherein the metal catalyst comprises a metal selected from the group consisting of Ti, Zr, Hf, V, Cr, Fe, Co, Ni, Pd, preferably Zr or Hf, preferably a homogeneous single-site catalyst.

[0122] In some embodiments, the catalyst is a ligand-metal complex having a bridged bis-bi-aryl structure. In particular, the ligand is a di-anionic chelating ligand that can occupy up to four coordination sites of the metal precursor atom, and more specifically has a bridged-bis-bi-aryl structure.

[0123] In some embodiments, the metal ligand complex used in the present invention can be characterized by the general formula: (4,0)MLn'(VI), wherein (4,0) is a dianionic ligand having at least 4 atoms that are oxygen and chelated to the metal M through oxygen atoms at 4 coordination sites, wherein two of the bonds between the oxygen and the metal are covalent in nature and two of the bonds are coordination in nature; M is a metal selected from the group consisting of Group 4 of the Periodic Table of Elements, more specifically, selected from Hf or Zr, preferably Hf; L is independently selected from the group consisting of: halides (F, Cl, Br, I), optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, alkylthio, arylthio, nitro, hydride, borohydride, allyl, diene, phosphine, carboxylate, 1,3-diketonate, oxalate, carbonate, nitrate, sulfate, ether, thioether and combinations thereof; and optionally two or more L groups can be linked together to form a ring structure; n' is 1, 2, 3 or 4.

[0124] In some embodiments, the metal-ligand complexes of the present invention may be characterized by the following general formula:

[0125]

[0126] in

[0127] ●R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 and R 29independently selected from the group consisting of hydrogen, halogen, and optionally substituted hydrocarbon, heteroatom-containing hydrocarbon, alkoxy, aryloxy, silyl, boron, phosphino, amino, alkylthio, arylthio, thioxy, seleno, nitro, and combinations thereof; optionally, two or more R groups may be combined together to form a ring structure, wherein such a ring structure has from 3 to 100 atoms in the ring excluding hydrogen atoms,

[0128] ●M is metal Hf or Zr,

[0129] ● L is a structural part that forms a covalent bond, a coordinate bond or an ionic bond with M; and n' is 1, 2, 3 or 4,

[0130] X, X', Y 2 and Y 3 is an oxygen atom,

[0131] • B is a bridging group having 1 to 50 atoms excluding hydrogen atoms, preferably B is a propane bridge.

[0132] In some preferred embodiments, the ligand-metal complex must be a hafnium or zirconium complex of a polyvalent aryloxyether selected from the group consisting of at least:

[0133] Bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl dimethyl hafnium(IV), bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl dichlorohafnium(IV), bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl dibenzyl hafnium(IV), bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl dichlorohafnium(IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyldimethyl hafnium (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyldibenzyl hafnium (IV), bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldimethyl hafnium (IV), bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldimethyl hafnium (IV), bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyl hafnium (IV) dichloride, bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyl dibenzyl hafnium (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyl dimethyl hafnium (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyl dichloride 3-(Dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldibenzyl hafnium (IV), bis((2-oxyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethyl hafnium (IV), bis((2-oxyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldichlorohafnium (IV), bis((2-oxyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldichlorohafnium (IV),4-Pentanediyldibenzyl hafnium (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethyl hafnium (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldichlorohafnium (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldibenzyl hafnium (IV), bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl) -methylene trans-1,2-cyclohexanediyl dimethyl hafnium (IV), bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl dichlorohafnium (IV), bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl dibenzyl hafnium (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl dimethyl hafnium (IV ), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl hafnium (IV) dichloride, and bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl dibenzyl hafnium (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,3-propyl dibenzyl hafnium (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,4-n-butyl dimethyl hafnium (IV), bis((2- bis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propyldimethyl hafnium (IV), bis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propyldimethyl hafnium (IV), bis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propyldibenzyl hafnium (IV), bis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butyldimethyl hafnium (IV), bis((2-oxy-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butyldimethyl hafnium (IV),1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butyldibenzylhafnium (IV), bis((2-oxyl-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butyldimethylhafnium (IV), bis((2-oxyl-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butyldibenzylhafnium (IV), bis((2-oxyl-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butyldibenzylhafnium (IV), bis((2-oxyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,2-ethyldimethylhafnium (IV), bis((2-oxyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)- bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,3-propyldimethyl hafnium(IV); (OC-6-33)-[[2,2"'-[1,4-butanediylbis(oxy-κO)]bis[3",5',5"-tris(1,1-dimethylethyl)[1,1':3',1"-terphenyl]-2'-O(olato)-κO]](2-)]bis(phenylmethyl) hafnium; bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethylzirconium(IV); bis((2-oxy-3 -(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylzirconium dichloride (IV), bis((2-oxyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium dichloride (IV), bis((2-oxyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium dichloride (IV), bis((2-oxyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium dichloride (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium dichloride (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium dichloride (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium dichloride (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium dichloride (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium dichloride (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylzirconium dichloride (IV), bis((2-oxy-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-Butanediylzirconium dimethyl (IV), bis((2-oxyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylzirconium dichloride (IV), bis((2-oxyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylzirconium dibenzyl (IV), bis((2-oxyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylzirconium dimethyl (IV), bis((2-oxyl-3-(dibenzo-1H-pyrrol-1 -yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylzirconium dichloride, bis((2-oxyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldibenzylzirconium (IV), bis((2-oxyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethylzirconium (IV), bis((2-oxyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethylzirconium (IV), bis((2-oxyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldichloride, bis( (2-oxyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldibenzylzirconium (IV), bis((2-oxyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldibenzylzirconium (IV), bis((2-oxyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyldimethylzirconium (IV), bis((2-oxyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)- 5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl zirconium dichloride (IV), bis((2-oxyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl dibenzyl zirconium (IV), bis((2-oxyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl dimethyl zirconium (IV), bis((2-oxyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl dimethyl zirconium (IV),2-cyclohexanediylzirconium dichloride (IV), and bis((2-oxyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyldibenzylzirconium (IV), bis((2-oxyl-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butyldimethylzirconium (IV), bis((2-oxyl-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butyldibenzylzirconium (IV), bis((2-oxyl-3-(4-methoxy-3,5-bis(1,1-dimethylethyl)phenyl)phenyl)-2-phenoxy)-1,4-n-butyldibenzylzirconium (IV), bis((2-oxyl-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyldibenzylzirconium (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,2-ethyldibenzylzirconium(IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,3-propyldimethylzirconium(IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,3-propyldibenzylzirconium(IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,4-n-butyldimethylzirconium(IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,4-n-butyldimethylzirconium(IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)phenyl)-2-phenoxy)-1,4-butyldimethylzirconium(IV), bis((2-oxyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propyldimethylzirconium (IV), bis((2-oxyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propyldimethylzirconium (IV), bis((2-oxyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butyldimethylzirconium (IV), bis((2-oxyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,3-propyldibenzylzirconium (IV), bis((2-oxyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2-phenoxy)-1,4-n-butyldimethylzirconium (IV), bis((2-oxyl-3-(3,6-bis(1,1-dimethylethyl)-9H-carbazolyl)phenyl)-2 bis((2-oxyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethylzirconium (IV), bis((2-oxyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethylzirconium (IV), bis((2-oxyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-Pentanediylzirconium dichloride, bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyl hafnium (IV) dimethyl, bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyl hafnium (IV) dichloride, bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyl dibenzyl Hafnium (IV), more preferably bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethyl hafnium (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldichlorohafnium (IV), bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldibenzyl hafnium (IV).

[0134] Catalyst

[0135] The cocatalyst is selected from the group consisting of MAO, DMAO, MMAO, SMAO or trityl or ammonium salts of fluorinated tetraarylborates, preferably MAO, MMAO, dimethylanilinium trityl tetrakis(pentafluorophenyl)borate or tri(alkyl)ammonium tetrakis(pentafluorophenyl)borate, such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, methyldi(alkyl)ammonium tetrakis(pentafluorophenyl)borate. More examples can be found in the review articles Bochmann Organometallics 2010, 29, 4711-4740 and Chen and Marks Chem. Rev. 2000, 100, 1391-1434.

[0136] Methylaluminoxane or MAO as used in the present specification may mean a compound derived from the partial hydrolysis of trimethylaluminum, which acts as a co-catalyst catalyzing the polymerization of olefins.

[0137] Supported methylaluminoxane or SMAO as used in the present specification may mean: methylaluminoxane bound to a solid support.

[0138] Depleted methylaluminoxane or DMAO as used in this specification may mean: methylaluminoxane from which free trimethylaluminum has been removed.

[0139] Modified methylaluminoxane or MMAO as used in the present specification may mean modified methylaluminoxane, ie, a product obtained after partial hydrolysis of trimethylaluminum plus another trialkylaluminum such as triisobutylaluminum or tri-n-octylaluminum.

[0140] The fluorinated aryl borate as used in the present specification may mean a borate compound having four fluorinated (preferably perfluorinated) aryl ligands.

[0141] Optional scavenger

[0142] A scavenger may optionally be added to the catalyst system to react with impurities present in the polymerization reactor and / or in the solvent and / or monomer feed. The scavenger prevents catalyst poisoning during the olefin polymerization process. The optional scavenger is selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, preferably triethylaluminum.

[0143] Surprisingly, triethylaluminum does not cause severe chain transfer and does not inhibit catalysts comprising ligand-metal complexes as described above. This feature allows the use of triethylaluminum instead of triisobutylaluminum, which is a huge cost benefit.

[0144] Optional chain transfer agent

[0145] The optional chain transfer agent is selected from the group consisting of dihydrogen or AlR 10 3. BR 10 3 or ZnR 10 2, where each R 10 Independently selected from hydrogen or C1-C10 hydrocarbon group.

[0146] The use of such a catalyst system in combination with the ratio of comonomers and polymerization conditions, such as temperature and pressure, and / or the presence of chain transfer agents, will allow a person skilled in the art to adjust the properties of the polymer to obtain an olefin polymer containing polar groups according to the present invention, thereby satisfying the requirements described above:

[0147] ●Number average molecular weight (M n ),

[0148] ●Crystallinity (X c ),

[0149] Enthalpy (△H),

[0150] ●Polydispersity index

[0151] ● Melting temperature (T m ),

[0152] Example

[0153] The following examples are not limiting examples and have been implemented using the following monomers: ethylene (C2), propylene (C3), 1-hexene (C6), 1-octene (C8) and 5-hexene-1-ol (C6OH). However, other monomers may be used to implement the present invention.

[0154] Synthesis of propylene copolymer, poly(propylene-co-1-hexene) (poly(C3-co-C6)). A stainless steel tube filled with pentamethylheptane (PMH) solvent (1 L) was used. Reactor (2L), using a stirring speed of 600rpm for polymerization experiments. Catalyst and comonomer solutions were prepared in a glove box under an inert dry nitrogen atmosphere. The reactor was first heated to 40°C, and then TiBA (1.0M toluene solution, 2mL) and 1-hexene (30mL, 240mmol) were added. Gaseous propylene (100g, 2.38mol) was charged to the reactor at 40°C, and the reactor was heated to the desired polymerization temperature of 130°C, resulting in a propylene partial pressure of about 15 bar. Once the set temperature was reached, the polymerization reaction was initiated by injecting the preactivated catalyst precursor bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-propane-diyldimethylhafnium(IV) [CAS 958665-18-4] (Hf-O4, 1.5μmol) in MAO (30wt% toluene solution, 11.2mmol). The reaction was stopped by pouring the polymer solution into a container flask containing demineralized water / iPrOH (50 wt%, 1 L) and Irganox 1010 (1.0 M, 2 mmol). The resulting suspension was filtered and dried in a vacuum oven at 80°C, and then Irganox 1010 was added as an antioxidant. The yield of poly(propylene-co-hexene) was 29.5 g (CEX1, Table 1).

[0155] Hydroxy-functionalized propylene terpolymer, poly(propylene-co-1-hexene-co-5-hexene-1-ol ) (poly(C3-co-C6-co-C6OH)). A stainless steel tube filled with pentamethylheptane (PMH) solvent (1 L) was used. Reactor (2L), using a stirring speed of 600rpm for polymerization experiments. Catalyst and comonomer solutions were prepared in a glove box under an inert dry nitrogen atmosphere. The reactor was first heated to 40°C, and then TiBA (1.0M toluene solution, 2mL), 1-hexene (neat 10mL, 80mmol) and triethylaluminum (TEA) passivated 5-hexene-1-ol (1.0M toluene solution, TEA:5-hexene-1-ol (molar ratio) = 1, 10mL, 10mmol) were added. Gaseous propylene (100g, 2.38mol) was charged into the reactor at 40°C, and the reactor was heated to the desired polymerization temperature of 130°C, resulting in a propylene partial pressure of about 15 bar. Once the set temperature was reached, the polymerization reaction was initiated by injecting the preactivated catalyst precursor bis((2-oxy-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethylhafnium(IV) [CAS 958665-18-4] (Hf-O4, 2 μmol) in MAO (30 wt% solution in toluene, 11.2 mmol). The reaction was stopped by pouring the polymer solution into a container flask containing demineralized water / iPrOH (50 wt%, 1 L) and Irganox 1010 (1.0 M, 2 mmol). The resulting suspension was filtered and dried in a vacuum oven at 80°C, and then Irganox 1010 was added as an antioxidant. The yield of poly(propylene-co-1-hexene-co-5-hexen-1-ol) was 25.6 g.

[0156] Purification procedure for the hydroxyl-functionalized propylene terpolymer, poly(C3-co-C6-co-C6OH). The copolymer obtained from the solution process can be purified to remove traces of aluminum residues. To this end, the copolymer (10 g) was dispersed in a mixture of dry toluene (400 mL) and concentrated HCl (37%, 10 mL) and heated under reflux. Once the polymer was properly dissolved, methanol (250 mL) was added to the hot mixture and the mixture was heated at 90-100° C. for another hour under stirring. The polymer was then precipitated in cold methanol, filtered and washed twice with methanol (CEX2, Table 2).

[0157] Siloxy functionalization protocol to obtain Poly(C3-co-C6-co-C6OSiMe3) 。 Reactions were performed under nitrogen atmosphere using standard Schlenk techniques. Reagent grade commercial chemicals were used as received. Deashed and degassed poly(C3-co-C6-co-C6OH) (0.5% mol OH; M n =32.0kg·mol -1 ;3.2·10 -4mol, 10.2 g) was dissolved in 300 mL of toluene at 60 °C. The mixture was stirred until a clear solution was obtained. ClSiMe3 (274 mg, 2.5·10 -3 mol) and NEt3 (511 mg, 5.0·10 -3 mol) solution and transferred to the polymer solution at 40°C through a sealed rubber septum. The reaction mixture was stirred for about 10 minutes, and then 4-dimethylaminopyridine (DMAP) (8.2 mg, 0.7·10 -4 mol). After this step, the solution became opaque and was stirred at 40°C overnight. The mixture was then precipitated into cold methanol (yield 90%, EX1, Table 2).

[0158] Direct synthesis of siloxy-functionalized propylene terpolymer, poly(C3-co-C6-co-C6OSiMe3). A stainless steel tube filled with heptane solvent (10 L) was used. Reactor (20 L), using a stirring speed of 600 rpm for terpolymerization experiments. Catalyst and comonomer solutions were prepared in a glove box. For example, for EX2 (Table 2), the reactor was first heated to 40 ° C, and then TiBA (1.0 M toluene solution, 20 mL), neat 1-hexene (300 mL, 2.4 mol) and neat (hex-5-ene-1-yloxy) trimethylsilane (34.5 g, 200 mmol) were added. Gaseous propylene (1000 g) was loaded into the reactor at 40 ° C and heated to the desired polymerization temperature of 80 ° C. Once the set temperature was reached, the polymerization reaction was initiated by injecting the preactivated catalyst rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 (9 mg, 15 μmol) in MAO (30 wt% toluene solution, 45 mmol). The reaction was stopped by pouring the polymer solution into a 20 L stainless steel container containing acidified isopropanol (2.5% v / v HCl, 3 L) and Irganox 1010 (1.0 M, 5 mmol). The resulting suspension was stirred for 4 h, filtered, washed with demineralized water / iPrOH (50 wt%, 2×2 L), and dried in a vacuum oven at 80° C. before adding Irganox 1010 as an antioxidant.

[0159] Direct Synthesis of Siloxy-Functionalized Propylene Terpolymer, Poly(C3-co-C6-co-C6OSiMe2tBu) become.The same terpolymerization procedure described for the synthesis of poly(C3-co-C6-co-C6OSiMe3) was applied to prepare poly(C3-co-C6-co-C6OSiMe2tBu) (EX3, Table 2) and poly(C3-co-C8-co-C6OSiMe2tBu) (EX4, Table 2) using rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 (6 mg, 10 μmol) which was injected after the TiBA scavenger (1.0 M toluene solution, 20 mL), neat 1-hexene (300 mL, 2.4 mol) or neat 1-octene (200 mL, 1.3 mol) and neat tert-butyl(hex-5-en-1-yloxy)dimethylsilane (42.9 g, 200 mmol).

[0160] Direct Synthesis of Siloxy-Functionalized Propylene Terpolymer, Poly(C3-co-C2-co-C6OSiMe2tBu) become. In a stainless steel tube filled with heptane solvent (1 L) The terpolymerization experiments were carried out in a reactor (2 L) with a stirring speed of 600 rpm. The catalyst and comonomer solutions were prepared in a glove box. For EX5 (Table 2), the reactor was first heated to 40° C., then TiBA (1.0 M toluene solution, 2 mL) and neat tert-butyl (hex-5-en-1-yloxy) dimethylsilane (4.3 g, 20 mmol) were added. The reactor was saturated with a gaseous propylene / ethylene mixture (weight ratio = 90 / 10) at 40° C. and heated to the desired polymerization temperature of 80° C., resulting in a total pressure of 9 bar. Once the set temperature was reached, the reaction was initiated by injecting a preactivated catalyst precursor rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 (0.7 mg, 1 μmol) in MAO (30 wt % toluene solution, 4.5 mmol). The pressure was kept constant at 9 bar while continuously feeding a gaseous propylene / ethylene mixture (weight ratio = 90 / 10). The reaction was stopped by pouring the polymer solution into a conical flask containing acidified isopropanol (2.5% v / v HCl, 500 mL) and Irganox 1010 (1.0 M, 0.5 mmol). The resulting suspension was stirred for 4 h, filtered, washed with demineralized water / iPrOH (50 wt%, 2×500 mL), and dried in a vacuum oven at 80° C., then Irganox 1010 was added as an antioxidant.

[0161] Table 1. Characteristics of comparative poly(C3-co-C6) and poly(C3-co-C6-co-C6OH) polymers prepared according to the above protocol.

[0162]

[0163] *mol%, standard deviation = 0.1mol%

[0164] Table 2. Characteristics of copolymers and terpolymers according to the invention of different compositions prepared according to the above described protocol.

[0165]

[0166] *mol%, standard deviation = 0.1mol%

[0167] Table 3. Lap shear test results of terpolymers with different compositions prepared according to the above protocol

[0168]

[0169] The hot melt adhesive according to the present invention has at least one of the following adhesive properties, preferably two, more preferably three, more preferably four, and more preferably all, which have been measured by the method described in the "lap shear strength" section of the measurement method section, wherein the Zwick Z020 type tensile tester equipped with a 10kN load cell is used for measurement. Before measurement, the sample is conditioned at room temperature for 7 days. Tested on a specimen (10cm×2.5cm) with a 12.5mm overlapping surface. Use a 140mm chuck to separate from the chuck. The sample is prestressed to 3N and then 100mm·min -1 Constant crosshead speed loading. To calculate lap shear strength, report the force value divided by the bond surface of the specimen (25 mm x 12.5 mm); the reported value is the average of at least 5 measurements for each composition:

[0170] ● Steel-to-steel lap shear strength of 3 MPa or more, preferably 4.5 MPa or more, more preferably 5 MPa or more, even more preferably 6 MPa or more,

[0171] ● Aluminum-aluminum lap shear strength of 3 MPa or more, preferably 4.5 MPa or more, more preferably 5 MPa or more, even more preferably 6 MPa or more,

[0172] ●Over 3MPa lap shear strength between steel and polyolefin,

[0173] ●1MPa or more, preferably 2.5MPa or more, more preferably 3MPa of lap shear strength between aluminum and polyolefin,

[0174] ●Over 3MPa lap shear strength between polyolefins.

[0175] Measurement

[0176] Size Exclusion Chromatography (SEC).

[0177] SEC measurements were performed at 150 °C on a Polymer Char Spectrometer built around an Agilent 7890 GC oven equipped with an autosampler and an integrated detector IR4. 1,2-Dichlorobenzene (o-DCB) was used as the eluent at a flow rate of 1 mL / min. The GPC software was used Process the data. Calculate molecular weight (M) relative to polyethylene or polystyrene standards n , M w ) and polydispersity

[0178] Liquid 1 H NMR.

[0179] 1 H NMR and 13C NMR spectra were performed at room temperature or 80 °C. 1 H and 13 C were recorded on a Varian Mercury Vx spectrometer operating at Larmor frequencies of 400 MHz and 100.62 MHz, respectively. 1 For the H NMR experiment, the spectral width was 6402.0 Hz, the acquisition time was 1.998 s, and the number of scans recorded was equal to 64. 13 C NMR spectra were recorded using a spectral width of 24154.6 Hz, an acquisition time of 1.3 s, and 256 scans.

[0180] The percentage of functionalization was determined by 1H NMR analysis carried out at 130°C using deuterated tetrachloroethane (TCE-D2) as solvent and recorded on a Varian Mercury spectrometer operating at a frequency of 400 MHz in a 5 mm tube.

[0181] Differential Scanning Calorimetry (DSC).

[0182] Melting (T) was measured using a differential scanning calorimeter Q100 from TA Instruments. m ) temperature and the enthalpy of the melting point of the transition (△H[J·g -1 ]). At 10℃·min -1 The heating and cooling rates were measured from -50 °C to 240 °C. The transformations were deduced from the secondary heating and cooling curves.

[0183] DSC has been used to determine the degree of crystallinity (X) by comparing the enthalpy of the melting transition of a sample to that of 100% crystalline polypropylene. c )content.

[0184] Compression molding experiment.

[0185] Film samples for lap shear tests were prepared via compression molding on a LabEcon 600 high temperature press (Fontijne Presses, The Netherlands) using the PP ISO setting. That is, films of functionalized polyolefin (25 mm × 12.5 mm × 0.5 mm) were loaded with an overlapping surface of 12.5 mm between substrates: PP-PP, steel-steel, aluminum-aluminum or their combination. Then, a compression molding cycle was applied: heating to 130 °C, stabilization without force for 3 min, 100 kN (0.63 MPa) normal force for 5 min, and 10 °C min -1 and 100 kN (0.63 MPa) normal force and cooled to 40°C.

[0186] Lap shear strength.

[0187] The measurements were performed using a Zwick Z020 tensile testing machine equipped with a 10 kN load cell. The samples were conditioned at room temperature for 7 days before measurement. The test was performed on a specimen (10 cm x 2.5 cm) with an overlap surface of 12.5 mm. A 140 mm grip was used to separate the grip from the grip. The sample was prestressed to 3 N and then tensioned with 100 mm min -1 Constant crosshead speed loading. To calculate lap shear strength, report the force value divided by the bond surface of the specimen (25 mm x 12.5 mm). The reported value is the average of at least 5 measurements for each composition.

Claims

1. A hot melt adhesive comprising an olefin polymer containing a polar group, wherein the olefin polymer containing a polar group has: ● At least 80 mol% of the constituent unit represented by the following formula (1), ●Optional constituent units represented by the following formula (2), and 0.1 to 1 mol%, preferably 0.1 to 0.5 mol%, of a constituent unit represented by the following formula (3): in: ●R 1 is H or CH3, ●R 2 Select from the list consisting of: 0 to 10, in R 1 =H, preferably 1 to 6 and more preferably 1 or 6, and in R 1 =CH3 is preferably a hydrocarbon group having 0, 2, 4 or 6 carbon atoms, ●R 3 is selected from the list comprising: a hydrocarbon group having 1 to 10, preferably 2 to 8, preferably 4 to 8, more preferably 4 or 6 carbon atoms, ●R 4 , R 5 , R 6 The may be the same or different and are selected from the list comprising hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 6 and more preferably 1 to 4 carbon atoms, or a combination of 1 and / or 3 and / or 4 carbon atoms.

2. The hot melt adhesive according to claim 1, wherein the polar group-containing olefin polymer has at least one of the following, preferably two, more preferably four, more preferably three, and more preferably all of the following: The number average molecular weight (M) is 5 to 50 kg / mol, preferably 10 to 50 kg / mol, preferably 20 to 50 kg / mol. n ), measured by the method described in the "Size Exclusion Chromatography (SEC)" section of the Measurement Methods section of this disclosure, The crystallinity (X) is less than 30%, preferably less than 15%, more preferably less than 10%. c ) content, measured by the method described in the "Differential Scanning Calorimetry (DSC)" section of the Measurement Methods section of this disclosure, Enthalpy (ΔH) of 5 to 65 J / g, preferably 5 to 30 J / g, as measured by the method described in the "Differential Scanning Calorimetry (DSC)" section of the Measurement Methods section of this disclosure, A polydispersity index of 2 to 6, preferably 3 to 6, more preferably 4 to 6 Measured by the method described in the "Size Exclusion Chromatography (SEC)" section of the Measurement Methods section of this disclosure, ● Melting temperature (T 40 to 120°C) m ), measured by the method described in the "Differential Scanning Calorimetry (DSC)" section of the Measurement Methods section of this disclosure.

3. The hot melt adhesive according to claim 1 or 2, wherein the constituent unit represented by the following formula (3) is a polymerized unit derived from one of the following monomers selected from the group consisting of (allyloxy)trimethylsilane, (allyloxy)triethylsilane, (allyloxy)triisopropylsilane, tert-butyl(allyloxy)dimethylsilane, (allyloxy)dimethylphenylsilane, (but-3-en-1-yloxy)trimethylsilane, (but-3-en-1-yloxy)triethylsilane, (but-3-en-1-yloxy)triisopropylsilane, tert-butyl(but-3-en-1-yloxy)dimethylsilane, (but-3-en-1-yloxy)dimethylphenylsilane, (hex-5-en-1-yloxy) )trimethylsilane, (hex-5-en-1-yloxy)triethylsilane, (hex-5-en-1-yloxy)triisopropylsilane, tert-butyl(hex-5-en-1-yloxy)dimethylsilane, (hex-5-en-1-yloxy)dimethylphenylsilane, trimethyl(undec-10-en-1-yloxy)silane, triethyl(undec-10-en-1-yloxy)silane, triisopropyl(undec-10-en-1-yloxy)silane, tert-butyldimethyl(undec-10-en-1-yloxy)silane, dimethylphenyl(undec-10-en-1-yloxy)silane, preferably (hex-5-en-1-yloxy)trimethylsilane and tert-butyl(hex-5-en-1-yloxy)dimethylsilane.

4. The hot melt adhesive according to any one of the preceding claims, wherein the polymerization of the polar group-containing olefin polymer has been carried out using a solution process.

5. The hot melt adhesive according to any one of the preceding claims, wherein siloxy-functional C3 to C 12 Monomers, preferably C4 to C 10 , preferably C6 to C 10 , preferably C6 to C8 olefin monomers.

6. A hot melt adhesive according to any one of the preceding claims, wherein the hot melt adhesive resin is prepared by treating the corresponding hydroxyl-functionalized copolymer or terpolymer with a silylating agent, wherein the hydroxyl-functionalized copolymer or terpolymer has been previously prepared by solution polymerization of one or more olefin monomers and a hydroxyl-functionalized olefin monomer, the hydroxyl-functionalized olefin monomer previously being blocked with a trialkylaluminum.

7. A hot melt adhesive according to any one of the preceding claims, wherein it has at least one of the following adhesive properties, preferably two, more preferably three, more preferably four, and more preferably all, which have been measured by the method described in the "Overlap Shear Strength" section of the measurement method section, wherein the measurement is performed using a Zwick Z020 tensile testing machine equipped with a 10kN load cell. Prior to measurement, the sample was conditioned at room temperature for 7 days. The test was performed on a specimen (10cm×2.5cm) with an overlapping surface of 12.5mm. The chuck was separated from the chuck using a 140mm chuck. The sample was prestressed to 3N and then tested with 100mm·min -1 Constant crosshead speed loading. To calculate lap shear strength, report the force value divided by the bond surface of the specimen (25 mm x 12.5 mm); the reported value is the average of at least 5 measurements for each composition: ● Steel-to-steel lap shear strength of 3 MPa or more, preferably 4.5 MPa or more, more preferably 5 MPa or more, even more preferably 6 MPa or more, ● Aluminum-aluminum lap shear strength of 3 MPa or more, preferably 4.5 MPa or more, more preferably 5 MPa or more, even more preferably 6 MPa or more, ●Over 3MPa lap shear strength between steel and polyolefin, ●1MPa or more, preferably 2.5MPa or more, more preferably 3MPa of lap shear strength between aluminum and polyolefin, ●Over 3MPa lap shear strength between polyolefins.

8. The hot melt adhesive according to any one of the preceding claims, further comprising a. 16-100 wt. %, preferably 30-50 wt. % of the polymer portion of the hot melt adhesive, b. 0-70% by weight, preferably 20-40% by weight, of the hot melt adhesive, c. 0-40 wt. %, preferably 10-40 wt. %, of the hot melt adhesive in an amount of a plasticizer such as a processing oil or wax, d. 0-10% by weight of filler of the hot melt adhesive, e. 0-3% by weight of the hot melt adhesive antioxidant, f. 0-1% by weight of a pigment of the hot melt adhesive, The hot melt adhesive further comprises an olefin polymer containing polar groups according to the present invention, and the olefin polymer containing polar groups is at least a part of the polymer part, more preferably it is 100% of the polymer part, and the rest of the polymer part, if any, is another polymer, preferably an olefin polymer.

9. An olefin polymer containing a polar group according to the following formula (4): in: ● z is 0.1 to 1 mol % ● x is at least 80 mol % ●y is 0 or 100-(x+z)mol%, ●R 1 is H or CH3, ●R 2 Select from the list consisting of: 0 to 10, in R 1 =H, preferably 1 to 6 and more preferably 1 or 6, and in R 1 =CH3 is preferably a hydrocarbon group having 0, 2, 4 or 6 carbon atoms, ●R 3 is a hydrocarbon group having 1 to 10, preferably 2 to 8, preferably 4 to 8, more preferably 4 or 6 carbon atoms, ●R 4 , R 5 , R 6 The same or different and selected from the list comprising hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 6 and more preferably 1 to 4 carbon atoms, or a combination of 1 and / or 3 and / or 4 carbon atoms.

10. The polar group-containing olefin polymer according to the preceding claims, wherein the polymerization of the polar group-containing olefin polymer has been carried out using a solution process, preferably with a catalyst system comprising a metal catalyst or catalyst precursor comprising a metal from Groups 3 to 8, more preferably from Groups 3 to 6, and / or wherein the metal catalyst comprises a metal selected from the group consisting of Ti, Zr, Hf, V, Cr, Fe, Co, Ni, Pd, preferably Zr or Hf, preferably a homogeneous single site catalyst, more preferably a hafnium complex of a polyvalent aryloxy ether or a zirconium complex of a polyvalent aryloxy ether.

11. The polar group-containing olefin polymer according to any one of the preceding claims, wherein it has at least one of the following, preferably two, more preferably three, more preferably four, more preferably all of the following: The number average molecular weight (M) is 5 to 50 kg / mol, preferably 10 to 50 kg / mol, preferably 20 to 50 kg / mol. n ), measured by the method described in the "Size Exclusion Chromatography (SEC)" section of the Measurement Methods section of this disclosure, The crystallinity (X) is less than 30%, preferably less than 15%, more preferably less than 10%. c ) content, measured by the method described in the "Differential Scanning Calorimetry (DSC)" section of the Measurement Methods section of this disclosure, Enthalpy (ΔH) of 5 to 65 J / g, preferably 5 to 30 J / g, as measured by the method described in the "Differential Scanning Calorimetry (DSC)" section of the Measurement Methods section of this disclosure, A polydispersity index of 2 to 6, preferably 3 to 6, more preferably 4 to 6 Measured by the method described in the "Size Exclusion Chromatography (SEC)" section of the Measurement Methods section of this disclosure, ● Melting temperature (T 40 to 120°C) m ), measured by the method described in the "Differential Scanning Calorimetry (DSC)" section of the Measurement Methods section of this disclosure.

12. Use of the polar group-containing olefin polymer according to any of the preceding claims for the manufacture of hot melt adhesives, photovoltaic sealants, asphalt binders, surface modifiers for polyolefins, preferably for automobiles and household appliances, and compatibilizers.

13. Use of a hot melt adhesive according to any of the preceding claims for gluing together metal, glass, stone, wood, polar polymers or metal to glass, metal to stone, metal to wood, metal to polar polymers, glass to stone, glass to wood, glass to polar polymers, stone to wood, stone to polar polymers, wood to polar polymers, metal to polyolefins, glass to polyolefins, stone to polyolefins, wood to polyolefins or polar polymers to polyolefins, wherein the stone is a mineral material such as granite, basalt, limestone, or an artificial stone such as concrete or masonry.

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