Impact-modified polypropylene composition, molded article and method for preparing same

Abstract

The polymer composition contains a polypropylene-based polymer and a vinyl ester-containing copolymer comprising ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate. A method of making the polymer composition includes mixing the polypropylene-based polymer and the vinyl ester-containing copolymer at a temperature ranging from 20° C. to 300° C. to form the polymer composition. A molded article contains the polymer composition.

Description

[Background technology]

[0001] Polypropylene (PP) compositions have gained widespread commercial acceptance and use in numerous applications due to the relatively low cost of the polymers and the desirable properties they exhibit. PP applications include packaging, household products, automotive interior and exterior parts, and construction. Although PP has properties such as good processability, high melting temperature, and high chemical resistance, PP is generally brittle and has poor mechanical performance and, particularly, low glass transition temperature (T g ) and has low impact resistance. To address these issues, manufacturers have incorporated various additives and modifiers, such as ethylene vinyl acetate (EVA) and ethylene propylene diene monomer (EPDM), to improve the properties of PP, especially its impact resistance. Summary of the Invention [Problem to be solved by the invention]

[0002] This Summary is provided to introduce some of the concepts that are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter.

[0003] In one aspect, embodiments disclosed herein relate to polymer compositions containing a polypropylene-based polymer and a vinyl ester-containing copolymer comprising ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate.

[0004] In another aspect, embodiments disclosed herein relate to a method of making a polymer composition comprising mixing a polypropylene-based polymer and a vinyl ester-containing copolymer at a temperature ranging from 20° C. to 300° C. to form a polymer composition, wherein the vinyl ester-containing copolymer comprises ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate.

[0005] In yet another aspect, embodiments disclosed herein relate to molded articles containing the polymeric compositions.

[0006] Other aspects and advantages of the claimed subject matter will become apparent in the following specification and appended claims. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic diagram of an exemplary extruder for producing a polymeric composition according to one or more embodiments. [Diagram 2] FIG. 2 is a tan delta versus temperature graph of the polymer compositions of Examples 1-2 and Reference Example 1 according to one or more embodiments obtained by dynamic viscoelastic measurements. [Diagram 3] FIG. 3 is a tan delta versus temperature graph of the polymer compositions of Examples 3-4 and Reference Example 2 according to one or more embodiments obtained by dynamic viscoelastic measurements. [Figure 4] FIG. 4 is a tan delta versus temperature graph of the polymer compositions of Examples 5-6 and Reference Example 2 according to one or more embodiments obtained by dynamic viscoelastic measurements. [Figure 5A] FIG. 5A is an SEM image of Reference Example 2. [Figure 5B] FIG. 5B is an SEM image of the polymer composition of Example 3 according to one or more embodiments. [Figure 5C] FIG. 5C is an SEM image of the polymer composition of Example 4 according to one or more embodiments. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] In one aspect, the disclosed embodiments relate to a polymer composition comprising a polypropylene-based polymer and a vinyl ester-containing copolymer comprising ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate.

[0009] In one or more embodiments, the polymer composition may comprise a weight percent of polypropylene-based polymer ranging from a lower limit selected from any of 60%, 65%, and 70% by weight to an upper limit selected from any of 80%, 85%, 90%, 95%, and 99% by weight, where any lower limit may be paired with any upper limit.

[0010] In one or more embodiments, the polymer composition may comprise a weight percent of the vinyl ester-containing copolymer ranging from a lower limit selected from any of 1 wt%, 2 wt%, 3 wt%, 4 wt%, and 5 wt%, to an upper limit selected from any of 25 wt%, 30 wt%, 35 wt%, and 40 wt%, where any lower limit may be paired with any upper limit.

[0011] Polypropylene-based polymer The polymer composition of the present disclosure may include a polypropylene-based polymer that is a polypropylene homopolymer or a propylene copolymer. In one or more embodiments, the propylene copolymer may include propylene and up to 40% by weight of a comonomer selected from ethylene and one or more of C4 to C10 alkanes, including linear monomers, such as alpha-olefins, and comonomers with various degrees of branching. In one or more embodiments, the propylene copolymer may include propylene and up to 40%, up to 30%, up to 20%, or up to 10% by weight of a comonomer.

[0012] In one or more embodiments, the polymer composition may include a polypropylene-based polymer that is a "heterophasic polypropylene." Heterophasic polypropylene is defined as a polypropylene containing a continuous matrix (continuous phase or matrix polymer) and an elastomeric rubber phase (also known as an internal rubber phase or discontinuous phase), which is produced by incorporating the elastomeric rubber phase into the matrix polymer, which results in a polymer composition with modified bulk properties, such as significant changes in impact resistance and modulus. In one or more embodiments, the matrix polymer may be unimodal or bimodal. Materials, e.g., polymers, with a single molecular weight distribution and two different molecular weight distributions are referred to as unimodal and bimodal.

[0013] In one or more embodiments, the heterophasic polypropylene may comprise an elastomeric rubber phase prepared from propylene and propylene copolymers comprising ethylene and at least one comonomer selected from linear monomers, e.g., one or more of C4 to C10 alkanes, including alpha-olefins and comonomers with various degrees of branching. The rubbers according to the present disclosure may have various compositions and molecular weights (MW). In one or more embodiments, the rubbers have a molecular weight distribution (MWD, M) of 10 or more for both fractions as measured by GPC-3D (three detectors), light scattering, viscosity, infrared detector. w / M n In certain embodiments, the rubber may have an MWD ranging from a lower limit selected from any one of 2, 4, 6, 8, 10, and 12 to an upper limit selected from any one of 20, 23, and 26, where any lower limit may be paired with any upper limit.

[0014] In one or more embodiments, the comonomer of the elastomeric rubber phase is ethylene.

[0015] In one or more embodiments, the continuous matrix is ​​present in the heterophasic polypropylene at a weight percent of the total heterophasic propylene ranging from a lower limit selected from one of 60 wt%, 65 wt%, and 70 wt%, to an upper limit selected from one of 72 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, and 99 wt%, where any lower limit may be paired with any upper limit.

[0016] In one or more embodiments, the elastomeric rubber phase is present in the heterophasic polypropylene at a weight percent of the total heterophasic propylene ranging from a lower limit selected from any one of 1 weight percent, 5 weight percent, 10 weight percent, 15 weight percent, 20 weight percent, 25 weight percent, and 28 weight percent to an upper limit selected from any one of 30 weight percent, 35 weight percent, and 40 weight percent, where any lower limit may be paired with any upper limit.

[0017] In one or more embodiments, the elastomeric rubber phase may comprise a comonomer weight percent of the total elastomeric rubber phase ranging from a lower limit selected from any one of 1 wt%, 5 wt%, 10 wt%, and 15 wt%, to an upper limit selected from any one of 25 wt%, 30 wt%, and 35 wt%, where any lower limit may be paired with any upper limit. In one or more embodiments, the elastomeric rubber phase may contain a comonomer weight percent of 35 wt% or less. In one or more embodiments, the elastomeric rubber phase may contain a comonomer weight percent of 5 wt% or less. In one or more embodiments, the elastomeric rubber phase may contain an ethylene comonomer weight percent of 35 wt% or less.

[0018] In one or more embodiments, the heterophasic polypropylene is prepared in a multi-stage polymerization process. In one or more embodiments, the matrix polymer may be produced in a first and a second reactor, and the discontinuous rubber phase may be prepared using two or more gas phase reactors. The heterophasic polypropylene may be prepared using any suitable catalyst, such as a Ziegler-Natta catalyst, a metallocene catalyst, or other single-site catalyst. In one or more embodiments, the melt flow rate (MFR) of the matrix polymer may be controlled by adjusting the concentration of hydrogen gas present in the first reactor and available for interaction with the Ziegler-Natta catalyst, according to known polymerization methods. After polymerization, the heterophasic polypropylene may be visbroken with any suitable peroxide agent to achieve the target MFR.

[0019] Following the heterophasic polypropylene synthesis, the heterophasic polypropylene may be visbroken by adding a visbreaking agent, such as a peroxide agent, to the copolymer during extrusion to increase the melt flow rate. Visbreaking may be performed in a pelletizing extruder in one or more embodiments, and in one or more embodiments, the copolymer may be pelletized prior to visbreaking. For example, a solution of peroxide in mineral oil or alcohol may be mixed with the heterophasic polyethylene or the heterophasic polyethylene may be added at the throat of the extruder.

[0020] The extrusion temperature depends, at least in part, on the visbreaking agent used. In one or more embodiments, the visbreaking temperature should be high enough to ensure that the visbreaking agent reacts during the visbreaking process. In one or more embodiments, the extrusion temperature during visbreaking can be 120° C. or higher.

[0021] Vinyl ester-containing copolymer In one or more embodiments, the polymer composition may include a vinyl ester-containing copolymer including ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate.

[0022] The polymer composition of the embodiment may include a vinyl ester-containing copolymer incorporating various ratios of ethylene and one or more branched vinyl esters. In one or more embodiments, the vinyl ester-containing copolymer may be prepared by reacting ethylene and one or more branched vinyl esters in the presence of additional comonomers and one or more radical initiators. In other embodiments, the polymer composition may include a vinyl ester-containing copolymer that is a terpolymer. The terpolymer is prepared by reacting ethylene with a first comonomer to form a polymer resin or prepolymer, which is then reacted with a second comonomer to prepare the final polymer composition, and the first and second comonomers may be added in the same reactor or in different reactors. In one or more embodiments, the first comonomer may be one or more vinyl esters and the second comonomer may be vinyl acetate.

[0023] In one or more embodiments, the vinyl ester-containing copolymer is selected from the group consisting of 1,2-dichlorophenyl ether, ... and 1,2-dichlorophenyl ether. 1 H NMR) and carbon-13 nuclear magnetic resonance ( 13 The weight percent of ethylene, as measured by C NMR, may range from a lower limit selected from one of 10%, 20%, and 30% by weight to an upper limit selected from one of 60%, 70%, 80%, 90%, 95%, 99.9%, and 99.99% by weight, where any lower limit may be paired with any upper limit.

[0024] In one or more embodiments, the vinyl ester-containing copolymer may include branched vinyl ester monomers formed from an isomeric mixture of branched alkyl acids. The branched vinyl ester according to the present disclosure has the general formula (I): [ka] Here, R 1 , R 2 and R3 Together they have carbon numbers ranging from C3 to C20.

[0025] In one or more embodiments, R 1 , R 2 and R 3 may all, in one or more embodiments, be alkyl chains with various degrees of branching; R 1 , R 2 and R 3 may be independently selected from the group consisting of hydrogen, alkyl, or aryl in one or more embodiments.

[0026] In one or more embodiments, the vinyl ester-containing copolymer may include a branched vinyl ester monomer having the general formula (II): [ka] Here, R 4 and R 5 The polymer composition has a number average molecular weight (M) in the range of 5 kDa to 10,000 kDa as determined by GPC. n ).

[0027] In one or more embodiments, R 4 and R 5 may have a total carbon number of less than 6 or more than 7, and the polymer composition may have a M n That is, M n If is less than 5 kDa, R 4 and R 5 may have a total of less than 6 or more than 7 carbon atoms, but M n If R is greater than 5, for example in the range of 5 to 10,000 kDa, 4 and R 5 may contain a total of 6 or 7 carbon atoms. In certain embodiments, R 4 and R 5 may have a total of 7 carbon atoms, M nmay range from 5 kDa to 10000 kDa. In one or more further embodiments, the vinyl ester according to formula (II) may be used in combination with vinyl acetate.

[0028] Examples of branched vinyl ester monomers may include monomers having chemical structures including derivatives thereof. [ka]

[0029] In one or more embodiments, the branched vinyl ester monomers may include monomer and comonomer mixtures containing vinyl esters such as neononanoic acid, neodecanoic acid, etc. In one or more embodiments, the branched vinyl esters may include tertiary carboxylic acids from the Versatic® acid series, including Versatic® acid EH, Versatic® acid 9 and Versatic® acid 10, VeoVa 9®, VeoVa 10®, VeoVa EH®, prepared by Koch synthesis, commercially available from Hexion® chemicals. In one or more embodiments, the vinyl ester-containing copolymers may include branched vinyl ester monomers produced from monomers derived from petroleum and / or renewable resources.

[0030] In one or more embodiments, the vinyl ester-containing copolymer is selected from the group consisting of 1,2-dichlorophenyl ether, ... and 1,2-dichlorophenyl ether. 1 H NMR) and carbon-13 nuclear magnetic resonance ( 13 %, by weight, of branched vinyl ester monomer, e.g., of formulas (I) and (II) above, ranging from a lower limit selected from any of 0.01%, 0.1%, 1%, 5%, 10%, 20%, and 30% by weight, to an upper limit selected from any of 50%, 60%, 70%, 80%, 89.99%, and 90% by weight, as measured by C NMR, where any lower limit may be paired with any upper limit.

[0031] In one or more embodiments, the vinyl ester-containing copolymer is selected from the group consisting of 1,2-dichlorophenyl ether, ... and 1,2-dichlorophenyl ether. 1 H NMR) and carbon-13 nuclear magnetic resonance ( 13 %, 0.01%, 0.1%, 1%, 5%, 10%, 20%, and 30% by weight, to an upper limit selected from any of 50%, 60%, 70%, 80%, and 89.99% by weight of vinyl acetate, as measured by C NMR, where any lower limit may be paired with any upper limit.

[0032] In one or more embodiments, the vinyl ester-containing copolymer has a number average molecular weight (M) in kilodaltons (kDa) ranging from a lower limit selected from any of 1 kDa, 5 kDa, 10 kDa, 15 kDa, and 20 kDa to an upper limit selected from any of 40 kDa, 50 kDa, 100 kDa, 300 kDa, 500 kDa, 1000 kDa, 5000 kDa, and 10000 kDa, as measured by gel permeation chromatography (GPC). n ), where any lower limit may be paired with any upper limit.

[0033] In one or more embodiments, the vinyl ester-containing copolymer has a molecular weight distribution (M) as measured by GPC having a lower limit of any of 1, 2, 5, or 10, and an upper limit of any of 20, 30, 40, 50, or 60. n M w and any lower limit may be paired with any upper limit.

[0034] In one or more embodiments, the vinyl ester-containing copolymer has a number average molecular weight (M) in kilodaltons (kDa) ranging from a lower limit selected from any of 1 kDa, 5 kDa, 10 kDa, 15 kDa, and 20 kDa to an upper limit selected from any of 40 kDa, 50 kDa, 100 kDa, 200 kDa, 300 kDa, 500 kDa, 1000 kDa, 2000 kDa, 5000 kDa, 10000 kDa, and 20000 kDa, as measured by GPC. n ), and any lower limit may be paired with any upper limit.

[0035] In one or more embodiments, the vinyl ester-containing copolymer may include one or more radical polymerization initiators capable of generating free radicals that initiate chain polymerization of the comonomers and prepolymers in the reaction mixture. In one or more embodiments, the radical initiator may include a chemical species that decomposes spontaneously or under stimulation by temperature, pH, or other trigger to release free radicals.

[0036] In one or more embodiments, the radical initiator is a peroxide or a difunctional peroxide, such as benzoyl peroxide; dicumyl peroxide; di-tert-butyl peroxide; tert-butyl cumyl peroxide; t-butyl-peroxy-2-ethyl-hexanoate; tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate; t-butyl-peroxy-benzoate; t-butyl-peroxy-2-ethyl-hexanoate; tert-butyl 3,5,5-trimethylhexanoate peroxide; tert-butyl peroxybenzoate; 2-ethylhexyl carbonate t 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane; 1,1-di(tert-butylperoxide)-3,3,5-trimethylcyclohexane; 2,5-dimethyl-2,5-di(tert-butylperoxide)-hexyne-3; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane; butyl 4,4-di(tert-butylperoxide)valerate; di(2,4-dichlorobenzoyl)peroxide; di(4-methylbenzoyl)peroxide; peroxide di(tert-butylperoxyisopropyl)benzene, and the like.

[0037] The radical initiators were benzoyl peroxide, 2,5-di(cumylperoxy)-2,5-dimethylhexane, 2,5-di(cumylperoxy)-2,5-dimethylhexyne-3,4-methyl-4-(t-butylperoxy)-2-pentanol, 4-methyl-4-(t-amylperoxy)-2-pentanol, 4-methyl-4-(cumylperoxy)-2-pentanol, 4-methyl-4-(t-butylperoxy)-2-pentanone, 4-methyl-4-(t-amylperoxy)-2-pentanone ... 2,5-dimethyl-4-(cumylperoxy)-2-pentanone, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-amylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(t-amylperoxy)hexyne-3, 2,5-dimethyl-2-t-butylperoxy-5-hydroperoxyhexane, 2,5-dimethyl-2-cumylperoxy-5-hydroperoxyhexane, 2,5-di Methyl-2-t-amylperoxy-5-hydroperoxyhexane, m / p-alpha, alpha-di[(t-butylperoxy)isopropyl]benzene, 1,3,5-tris(t-butylperoxyisopropyl)benzene, 1,3,5-tris(t-amylperoxyisopropyl)benzene, 1,3,5-tris(cumylperoxyisopropyl)benzene, di[1,3-dimethyl-3-(t-butylperoxy)butyl]carbonate, di[1,3-dimethyl-3-(t-amylperoxy) butyl] carbonate, di[1,3-dimethyl-3-(cumylperoxy)butyl] carbonate, di-t-amyl peroxide, t-amyl cumyl peroxide, t-butyl-isopropenyl cumyl peroxide, 2,4,6-tri(butylperoxy)-s-triazine, 1,3,5-tri[1-(t-butylperoxy)-1-methylethyl]benzene, 1,3,5-tri-[(t-butylperoxy)-isopropyl]benzene, 1,3-dimethyl-3-(t-butylperoxy)butanol, 1,3-Dimethyl-3-(t-amylperoxy)butanol, di(2-phenoxyethyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, dimyristylperoxydicarbonate, dibenzylperoxydicarbonate, di(isobornyl)peroxydicarbonate, 3-cumylperoxy-1,3-dimethylbutylmethacrylate, 3-t-butylperoxy-1,3-dimethylbutylmethacrylate, 3-t-amylperoxy-1,3-dimethylbutylmethacrylate ester, tri(1,3-dimethyl-3-t-butylperoxybutyloxy)vinylsilane, 1,3-dimethyl-3-(t-butylperoxy)butyl N-[1-{3-(1-methylethenyl)-phenyl}1-methylethyl]carbamate, 1,3-dimethyl-3-(t-amylperoxy)butyl N-[1-{3-(1-methylethenyl)-phenyl}1-methylethyl]carbamate, 1,3-dimethyl-3-(cumylperoxy)butyl N-[1-{3-(1-methylethenyl)-phenyl}1-methylethyl ]carbamate, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)cyclohexane, n-butyl 4,4-di(t-amylperoxy)valerate, ethyl 3,3-di(t-butylperoxy)butyrate, 2,2-di(t-amylperoxy)propane, 3,6,6,9,9-pentamethyl-3-ethoxycarbonylmethyl-1,2,4,5-tetraoxacyclononane, n-butyl-4,4-bis(t-butylperoxy)valerate, ethyl-3, 3-Di(t-amylperoxy)butyrate, benzoyl peroxide, OO-t-butyl-O-hydrogen-monoperoxy-succinate, OO-t-amyl-O-hydrogen-monoperoxy-succinate, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane (or methyl ethyl ketone peroxide cyclic trimer), methyl ethyl ketone peroxide cyclic dimer, 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane, 2,5-dimethyl-2,5-Di(benzoylperoxy)hexane, t-butyl perbenzoate, t-butyl peroxyacetate, t-butyl peroxy-2-ethylhexanoate, t-amyl perbenzoate, t-amyl peroxyacetate, t-butyl peroxyisobutyrate, 3-hydroxy-1,1-dimethyl t-butylperoxy-2-ethylhexanoate, OO-t-amyl-O-hydrogen-monoperoxysuccinate, OO-t- Butyl-O-hydrogen-monoperoxysuccinate, di-t-butyl diperoxyphthalate, t-butylperoxy(3,3,5-trimethylhexanoate), 1,4-bis(t-butylperoxycarbo)cyclohexane, t-butylperoxy-3,5,5-trimethylhexanoate, t-butyl-peroxy-(cis-3-carboxy)propionate, 3-methyl-3-t-butylperoxybutyric acid allyl, OO-t-butyl 1,1,1-tris[2-(t-butylperoxycarbonyloxy)ethoxymethyl]propane, 1,1,1-tris[2-(t-amylperoxycarbonyloxy)ethoxymethyl]propane, 1,1,1-tris[2-(cumylperoxycarbonyloxy)ethoxymethyl]propane, OO- The peroxycarbonate may include t-amyl-O-isopropyl monoperoxycarbonate, di(4-methylbenzoyl) peroxide, di(3-methylbenzoyl) peroxide, di(2-methylbenzoyl) peroxide, didecanoyl peroxide, dilauroyl peroxide, 2,4-dibromo-benzoyl peroxide, succinic peroxide, dibenzoyl peroxide, di(2,4-dichloro-benzoyl) peroxide, and combinations thereof.

[0038] In one or more embodiments, the radical initiator may include an azo compound such as azobisisobutyronitrile (AIBN), 2,2′-azobis(amidinopropyl)dihydrochloride, and the like, and the azoperoxide initiator includes a mixture of an azodinitrile compound such as 2,2′-azobis(2-methyl-pentanenitrile), 2,2′-azobis(2-methyl-butanenitrile), 2,2′-azobis(2-ethyl-pentanenitrile), 2-[(1-cyano-1-methylpropyl)azo]-2-methyl-pentanenitrile, 2-[(1-cyano-1-ethylpropyl)azo]-2-methyl-butanenitrile, 2-[(1-cyano-1-methylpropyl)azo]-2-ethyl, and the like, and a peroxide.

[0039] In one or more embodiments, the radical initiator may include a carbon-carbon ("CC") free radical initiator, such as 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 3,4-diethyl-3,4-diphenylhexane, 3,4-dibenzyl-3,4-ditolylhexane, 2,7-dimethyl-4,5-diethyl-4,5-diphenyloctane, 3,4-dibenzyl-3,4-diphenylhexane, and the like.

[0040] In one or more embodiments, the vinyl ester-containing copolymer may comprise one or more radical initiators present in a weight percent (wt%) of the total polymerization mixture ranging from a lower limit selected from any of 0.000001% by weight, 0.0001% by weight, 0.01% by weight, 0.1% by weight, 0.15% by weight, 0.4% by weight, 0.6% by weight, 0.75% by weight, and 1% by weight, to an upper limit selected from any of 0.5% by weight, 1.25% by weight, 2% by weight, 4% by weight, and 5% by weight, where any lower limit can be used in conjunction with any upper limit.Furthermore, it is envisioned that the concentration of radical initiator may be higher or lower depending on the application of the final material.

[0041] In one or more embodiments, the vinyl ester-containing copolymer may include one or more stabilizers that can prevent polymerization in the monomer and comonomer feed lines but do not interfere with polymerization in the reactor.

[0042] In one or more embodiments, the stabilizer may include a nitroxyl derivative, such as 2,2,6,6-tetramethyl-1-piperidinyloxy, 2,2,6,6-tetramethyl-4-hydroxy-1-piperidinyloxy, 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy, 2,2,6,6-tetramethyl-4-amino-piperidinyloxy, and the like.

[0043] In one or more embodiments, the vinyl ester-containing copolymer may comprise an ethylene-based polymer polymerized in the presence of a chain transfer agent. Examples of chain transfer agents may include propylene, ethane, propane, methane, trimethylamine, dimethylamine, chloroform, and carbon tetrachloride. The chain transfer agent may be a weight percent (wt%) of the total composition ranging from a lower limit selected from any of 0.0000001% by weight, 0.000001% by weight, 0.001% by weight, 00.1% by weight, 0.02% by weight, 0.05% by weight, and 1.0% by weight to an upper limit selected from any of 2.0% by weight, 3.0% by weight, 4.0% by weight, and 5.0% by weight, where any lower limit can be used in conjunction with any upper limit.

[0044] In one or more embodiments, the vinyl ester-containing copolymer may comprise a stabilizer present in a weight percent (wt%) of the total polymerization mixture ranging from a lower limit selected from any of 0.000001% by weight, 0.0001% by weight, 0.01% by weight, 0.1% by weight, 0.15% by weight, 0.4% by weight, 0.6% by weight, 0.75% by weight, and 1% by weight, to an upper limit selected from any of 0.5% by weight, 1.25% by weight, 2% by weight, 4% by weight, and 5% by weight, where any lower limit may be paired with any upper limit.Furthermore, it is envisioned that the concentration of stabilizer may be higher or lower depending on the application of the final material.

[0045] In one or more embodiments, the vinyl ester-containing copolymer may be prepared in a reactor by polymerizing ethylene and one or more branched vinyl ester monomers. The method of reacting the comonomers in the presence of a radical initiator may include any suitable method in the art, including solution phase polymerization, pressure radical polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization.

[0046] In one or more embodiments, the reactor may be a batch or continuous reactor at a pressure below 500 bar, known as a low pressure polymerization system. In one or more embodiments, the reaction may be carried out in a low pressure polymerization process in which ethylene and one or more vinyl ester monomers are polymerized in the liquid phase of an inert solvent and / or one or more liquid monomer(s).

[0047] In one or more embodiments, the polymerization may include an amount of free radical polymerization initiator from 0.0001 to 0.01 millimoles, calculated as the total amount of free radical polymerization initiator(s) per liter of volume of the polymerization zone. The amount of ethylene in the polymerization zone may depend primarily on the total reactor pressure, which may range from about 20 bar to about 500 bar, and the temperature, which may range from about 20° C. to about 300° C.

[0048] In one or more embodiments, the pressure in the reactor may range from a lower limit of any of 20, 30, 40, 50, 75, or 100 bar to an upper limit of any of 100, 150, 200, 250, 300, 350, 400, 450, or 500 bar, and the temperature in the reactor may range from a lower limit of any of 20° C., 50° C., 75° C., or 100° C. to an upper limit of any of 150° C., 200° C., 250° C., or 300° C., where any lower limit may be paired with any upper limit.

[0049] The liquid phase of the polymerization process according to the present disclosure may comprise ethylene, one or more vinyl ester monomers, a free radical polymerization initiator, and optionally one or more inert solvents such as tetrahydrofuran (THF), chloroform, dichloromethane (DCM), dimethylsulfoxide (DMSO), dimethylcarbonate (DMC), hexane, cyclohexane, ethyl acetate (EtOAc), acetonitrile, toluene, xylene, ether, dioxane, dimethyl-formamide (DMF), benzene, or acetone. Copolymers and terpolymers produced under low pressure conditions may exhibit number average molecular weights of 1 to 300 kDa, weight average molecular weights of 1 to 1000 kDa, and MWDs of 1 to 60.

[0050] In one or more embodiments, the comonomers and one or more free radical initiators are polymerized to produce vinyl ester-containing copolymers in a continuous or batch process at temperatures above 50° C. and pressures above 1000 bar, known as high pressure polymerization systems. For example, pressures above 1000, 1100, 1200, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 3000, 5000, or 10000 bar may be used. The vinyl ester copolymers, which may be copolymers or terpolymers produced under high pressure conditions, have number average molecular weights (M) of 1 to 10000 kDa. n ), weight average molecular weight (M w The molecular weight distribution (MWD) may be determined based on the weight average molecular weight (M w ) and number average molecular weight (M n) ratio. Copolymers and terpolymers produced under high pressure conditions have MWDs between 1 and 60. GPC experiments are performed by analytical methods such as gel permeation chromatography combined with an infrared detector IR5 and a four-bridge capillary viscometer, both from PolymerChar, and a triple detector with an 8-angle light scattering detector from Wyatt. A set of four 13 μm mixed bed columns from Tosoh may be used at a temperature of 140° C. The experimental conditions may be a concentration of 1 mg / mL each, a flow rate of 1 mL / min, a dissolution temperature of 160° C. and a dissolution time of 90 minutes, and an injection volume of 200 μL. The solvent used is TCB (trichlorobenzene) stabilized with 100 ppm BHT.

[0051] In one or more embodiments, conversion during polymerization for low pressure and high pressure polymerization systems is defined as the mass or mass flow rate of polymer produced divided by the mass of the mass flow rates of monomer and comonomer, with the comonomer having a lower limit of any of 0.01%, 0.1%, 1%, 2%, 5%, 7%, or 10% and an upper limit of any of 15%, 17%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%, 99%, or 100%, where any lower limit may be paired with any upper limit.

[0052] additives The polymer composition according to the present disclosure may include fillers and additives that modify various physical and chemical properties, which are added to the polymer composition during blending. In one or more embodiments, the polymer composition may include one or more polymer additives, such as kickers, processing aids, lubricants, antistatic agents, clarifiers, nucleating agents, beta-nucleating agents, lubricants, antioxidants, antacids, light stabilizers such as HALS, IR absorbers, whitening agents, organic and / or inorganic dyes, antiblocking agents, processing aids, flame retardants, plasticizers, biocides, adhesion promoters, pigments, fillers, reinforcing agents, adhesion promoters, biocides, whitening agents, antiblocking agents, processing aids, and plasticizers.

[0053] In one or more embodiments, the polymer composition may include one or more inorganic fillers such as calcium carbonate, talc, glass fiber, marble dust, cement dust, clay, carbon black, feldspar, silica or glass, fumed silica, silicates, calcium silicate, silicic acid powder, glass microspheres, mica, metal oxide particles and nanoparticles such as magnesium oxide, antimony oxide, zinc oxide, inorganic salt particles and nanoparticles such as barium sulfate, wollastonite, alumina, aluminum silicate, titanium oxide, calcium carbonate, polyhedral silsesquioxanes (POSS).

[0054] In one or more embodiments, the polymer composition may contain a weight percent (wt%) of the total composition of one or more additives and / or fillers ranging from a lower limit of any of 0.01 wt%, 0.02 wt%, 0.05 wt%, 1.0 wt%, 5.0 wt%, 10.0 wt%, 15.0 wt%, and 20.0 wt%, to an upper limit selected from any of 25 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, and 70 wt%, where any lower limit may be used in conjunction with any upper limit.

[0055] Polymer composition properties In one or more embodiments, the polymer composition may have an Instrumented Dart Impact (IDI) puncture energy of about 10 ft-lb or greater, e.g., 10, 15, and 20 ft-lb or greater, at -20°C when tested according to ASTM D3763.

[0056] In one or more embodiments, the polymer composition may have a percent increase in instrumented dart impact (IDI) puncture energy of about 10% or more at -20°C when tested by ASTM D3763. The percent increase in IDI puncture energy refers to the percent difference between the IDI puncture energy of the polymer composition and the IDI puncture energy of a comparable polypropylene-based polymer, based on the IDI puncture energy of the polypropylene-based polymer. In one or more embodiments, the polymer composition has a percent increase in IDI puncture energy of at least 10%, 12.5%, 15%, 17.5%, and 20% at -20°C.

[0057] In one or more embodiments, the polymer composition may have a melt flow rate (MFR) according to ASTM D1238, Procedure B, Condition 230° C. / 2.16 kg in a range having a lower limit selected from any of 0.1 g / 10 min, 0.5 g / 10 min, 1 g / 10 min, 10 g / 10 min, 15 g / 10 min, 50 g / 10 min, and 100 g / 10 min, and an upper limit selected from any of 30 g / 10 min, 200 g / 10 min, 300 g / 10 min, 500 g / 10 min, and 1000 g / 10 min, where any lower limit may be paired with any upper limit.

[0058] In one or more embodiments, the polymer composition has a glass transition temperature (T) as measured by ASTM D3418 by dynamic mechanical analysis (DMA) or DSC in a range from a lower limit selected from any of −50° C., −45° C., and −40° C. to an upper limit selected from any of 30° C., 35° C., and 40° C. g ), where any lower limit and any upper limit may be paired.

[0059] In one or more embodiments, the polymer composition has a viscosity of 0.85 g / cm 3 , 0.90g / cm 3 , and 0.90 g / cm 3 From the lower limit selected from any one of 1.20 g / cm 3, 1.25g / cm 3 , and 1.30 g / cm 3 and wherein any lower limit and any upper limit may be paired.

[0060] In one or more embodiments, the polymeric composition has a tensile stress at yield (yield stress) of about 5 MPa or greater according to ASTM D638. In one or more embodiments, the polymeric composition may have a tensile stress at yield ranging from a lower limit selected from any of 5 MPa, 6 MPa, and 7 MPa to an upper limit selected from any of 40 MPa, 50 MPa, 100 MPa, and 200 MPa, where any lower limit and any upper limit may be paired.

[0061] In one or more embodiments, the polymeric composition has a tensile stress at break (stress at break) of about 5 MPa or greater according to ASTM D638. In one or more embodiments, the polymeric composition may have a tensile stress at break ranging from a lower limit selected from any of 5 MPa, 6 MPa, and 7 MPa to an upper limit selected from any of 40 MPa, 50 MPa, 100 MPa, and 200 MPa, where any lower limit and any upper limit may be paired.

[0062] In one or more embodiments, the polymer composition may have a tensile modulus (tangent modulus) according to ASTM D638 ranging from a lower limit selected from any of 0.1 GPa, 0.2 GPa, 0.3 GPa, 0.4 GPa, and 0.5 GPa to an upper limit selected from any of 3 GPa, 3.5 GPa, 4.0 GPa, and 5.0 GPa, where any lower limit and any upper limit may be paired.

[0063] In one or more embodiments, the polymeric composition has a yield strain of about 2% or greater according to ASTM D638. In one or more embodiments, the polymeric composition may have a yield strain ranging from a lower limit selected from any of 2%, 3%, 4%, and 5% to an upper limit selected from any of 10%, 15%, 20%, 30%, 50%, and 100%, where any lower limit and any upper limit may be paired.

[0064] In one or more embodiments, the polymeric composition has a break strain of about 50% or greater according to ASTM D638. In one or more embodiments, the polymeric composition may have a yield strain ranging from a lower limit selected from any of 50%, 60%, and 70% to an upper limit selected from any of 500%, 600%, 700%, 1000%, and 2000%, where any lower limit and any upper limit may be paired.

[0065] In one or more embodiments, the polymeric composition has a secant flexural modulus at 1% of about 100 MPa or greater according to ASTM D790. In one or more embodiments, the polymeric composition may have a secant flexural modulus at 1% ranging from a lower limit selected from any one of 100 MPa, 150 MPa, and 200 MPa to an upper limit selected from any one of 850 MPa, 900 MPa, 950 MPa, 1000 MPa, 1500 MPa, and 2000 MPa, where any lower limit and any upper limit may be paired.

[0066] In one or more embodiments, the polymeric composition has a Rockwell hardness of at least 25. In one or more embodiments, the polymeric composition has a Rockwell hardness ranging from about 25 to 100, e.g., from a lower limit selected from any one of 25 and 30, to an upper limit selected from any one of 70, 80, 90, and 100.

[0067] In one or more embodiments, the polymeric composition has a deflection temperature under load (HDT) of at least 50° C. when tested under ASTM D648 at a load of 66 psi. In one or more embodiments, the polymeric composition has a deflection temperature under load of at least 50, 60, 70, and 80° C.

[0068] In one or more embodiments, the polymeric composition has a biobased carbon content, as determined by ASTM D6866-18 Method B, ranging from a lower limit selected from any of 1%, 5%, 10%, and 20%, to an upper limit selected from any of 60%, 80%, 90%, and 100%, where any lower limit and any upper limit may be paired.

[0069] Method for preparing a polymer composition The polymer compositions according to the present disclosure are prepared by several possible polymer blending and formation techniques.

[0070] In one or more embodiments, the polymer composition is produced by mixing a polyethylene-based polymer and a vinyl ester-containing copolymer in a melt blending process. In one or more other embodiments, a polypropylene-based polymer and a vinyl ester-containing copolymer are combined in a dry blending process to form a powder blend of polypropylene-based polymer and vinyl ester-containing copolymer that may be particularly useful for additive manufacturing.

[0071] In one or more embodiments, the polymer composition may be mixed in a batch, semi-continuous, or continuous process, such as continuous or non-continuous extrusion. In one or more embodiments, the extrusion may include a single screw, twin screw, or multi-screw extruder.

[0072] In one or more embodiments, the polymer composition may be mixed at a temperature ranging from about 20° C. to 300° C., e.g., from a lower limit selected from any of 20° C., 30° C., 40° C., 50° C., to an upper limit of 250° C., 260° C., 280° C., and 300° C., where any lower limit may be paired with any upper limit.

[0073] In one or more embodiments, all of the components may be mixed together in a single step. In other embodiments, when more than one polypropylene-based polymer and / or vinyl ester-containing copolymer is present in the polymer composition, there may be a step of premixing selected components before mixing with the remaining components in a subsequent mixing step.

[0074] Purpose In one aspect, the present disclosure relates to a molded article comprising the polymer composition. In one or more embodiments, the molded article may be an injection molded article, a thermoformed article, a film, a foam, a blow molded article, an additive manufacturing molded article, a compression molded article, a coextrusion molded article, a laminate molded article, an injection blow molded article, a rotational molded article, an extrusion molded article, a single layer molded article, a multilayer molded article, or a pultrusion molded article, etc.

[0075] In one or more embodiments, molded articles comprising the polymeric composition include, but are not limited to, extrusion, coextrusion, extrusion coating, injection molding, compression blow molding, compression molding, injection blow molding, injection stretch blow molding, thermoforming, cast film extrusion, blown film extrusion, blown film processing, foam molding, extrusion blow molding, injection stretch blow molding, rotational molding, pultrusion, calendar molding, additive manufacturing, and lamination. EXAMPLES

[0076] The following examples are provided to illustrate embodiments of the present disclosure and are not intended, and should not be construed, to limit the scope of the invention.

[0077] Various exemplary polymer compositions were prepared based on two polypropylene heterophasic copolymers, ICP1 and ICP2, which are propylene-based polymers, and two vinyl ester-containing copolymers, DV001A and DV002B ("modifier"). ICP1 and ICP2 are polypropylene-based polymers commonly used in the automotive compounding industry. The components and properties of ICP1 and ICP2 are shown in Table 1. The xylene solubles in Table 1 indicate the amount of rubber phase in the propylene-based polymer, and the melt flow rates in Table 1 were obtained by ASTM D1238, procedure B, condition 230°C / 2.16 kg, as described above. [Table 1]

[0078] The components and properties of DV001A and DV001B are shown in Table 2. DV001A contains 5 wt% VeoVa® branched vinyl ester comonomer, 19 wt% vinyl acetate (VA), the remainder being ethylene. DV002B contains 9 wt% VeoVa® branched vinyl ester comonomer, 23 wt% vinyl acetate, the remainder being ethylene. Comonomer content was determined by NMR. [Table 2]

[0079] MFR indicates the melt flow index or melt flow rate, which was determined by ASTM D1238 as described above. Flexural modulus was determined by testing injection molded bars at room temperature using ASTM D790. Glass transition temperature (T g ) was determined using dynamic mechanical analysis (DMA) temperature sweep from -150 °C to 90 °C at a frequency of 1 Hz according to ASTM D4065. The melting temperature was determined from dynamic scanning calorimetry (DSC). The samples were tempered at 200 °C, then scanned from 200 °C to 45 °C at a ramp rate of 10 °C / min and back to 200 °C.

[0080] Example 1 An exemplary polymer composition was produced by compounding 10 wt. % DV001A, 10 wt. % talc, 3000 ppm B225 antioxidant, and the balance ICP1 at a temperature of 200° C. in a ZSK-25 extruder as shown in Figure 1. The talc generally helps to disperse the elastomer in a high melt flow matrix, and the antioxidant helps to prevent degradation of the polymer during the compounding process.

[0081] Example 2 The exemplary polymer composition of Example 2 was prepared as described in Example 1, except that DV001A was replaced with DV001B.

[0082] Example 3 The exemplary polymer composition of Example 3 was prepared as described in Example 1, except that ICP1 was replaced with ICP2.

[0083] Example 4 The exemplary polymer composition of Example 4 was prepared as described in Example 1, except that ICP1 was replaced with ICP2 and DV001A was replaced with DV001B.

[0084] Example 5 The exemplary polymer composition of Example 5 was prepared as described in Example 1, except that ICP1 was replaced with ICP2 and 10 wt. % DV001A was replaced with 20 wt. % DV001A.

[0085] Example 6 The exemplary polymer composition of Example 6 was prepared as described in Example 1, except that ICP1 was replaced with ICP2 and 10 wt % of DV001A was replaced with 20 wt % of DV001B.

[0086] (Reference example 1) In order to compare the properties with Examples 1 to 6, unmodified ICP1 was used as Reference Example 1.

[0087] (Reference example 2) In order to compare the properties with Examples 1 to 6, unmodified ICP2 was used as Reference Example 2.

[0088] The melt flow rates of Examples 1 to 6 (EX1 to 6) and Reference Examples 1 to 2 (RE1 to 2) were obtained according to ASTM D1238, as described above. The results are summarized in Table 3. [Table 3]

[0089] The physical and mechanical properties of Examples 1 to 6 and Reference Examples 1 and 2 were obtained by carrying out the tests described below.

[0090] Tensile stress at break and at yield, yield strain, break strain, and tensile modulus (tangent modulus) were determined according to ASTM D638. Secant flexural modulus at 1% was determined according to ASTM D790. Instrumented dart impact puncture energy was determined according to ASTM D3763 at -20°C. Rockwell hardness was determined according to ASTM D785. HDT at 66 psi was determined according to ASTM D648.

[0091] Tables 4-1 and 4-2 summarize the physical / mechanical properties of Examples 1-6 and Reference Examples 1-2. [Table 4-1] [Table 4-2]

[0092] Tables 4-1 and 4-2 show that the addition of DV001A and DV001B increased the puncture energy of the ICP2-based polymer composition.

[0093] DMA temperature sweep tests were performed on Examples 1-6 and Reference Examples 1-2 at a frequency of 1 Hz and temperatures from -150° C. to 90° C. Examples 1-2 and Reference Example 1, Examples 3-4 and Reference Example 2, and Examples 5-6 and Reference Example 2 are shown in Figures 2-4, respectively.

[0094] 5A to 5C show SEM images of Reference Example 2, Example 3, and Example 4, respectively. The SEM images show rubber domains of similar size, indicating good dispersion of the rubber.

[0095] Although only a few exemplary embodiments have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments without significantly departing from the present invention. Accordingly, all such modifications are intended to be included within the scope of the present disclosure as defined in the following claims. In the claims, means-plus-function clauses are intended to cover the structures described herein as performing the described function and not only structural equivalents, but also equivalent structures. Thus, nails and screws are not structural equivalents in that nails use cylindrical surfaces to fasten wooden parts together, while screws use helical surfaces, but in the context of fastening wooden parts, nails and screws may be equivalent structures. It is the applicant's intention not to invoke 35 USC § 112(f) on any claim limitation herein, except where the claim expressly uses the words "means from" with the relevant function.

Claims

1. A polymer composition, Polypropylene polymers and A polymer composition comprising ethylene, one or more branched vinyl ester monomers, and a vinyl ester-containing copolymer, optionally containing vinyl acetate.

2. The aforementioned polypropylene polymer Polypropylene homopolymer; A propylene copolymer comprising propylene and one or more comonomers selected from the group consisting of ethylene and C4 to C10 alpha-olefins; and / or A polymer composition according to claim 1, selected from heterogeneous polypropylene.

3. The polymer composition according to any one of claims 1, wherein the polymer composition has a percentage increase of 10% or more in the instrumented dart impact puncture energy at -20°C according to ASTM D3763, compared to the puncture energy of the polypropylene polymer at -20°C.

4. The one or more branched vinyl ester monomers have the structure of general formula (I), 【Chemistry 1】 R 1 , R 2 and R 3 The polymer composition according to claim 1, wherein the total number of carbon atoms is 3 to 20.

5. The one or more branched vinyl ester monomers have the structure of general formula (II), 【Chemistry 2】 R ４ and R ５ The polymer composition according to claim 1, wherein the total number of carbon atoms is 7.

6. The vinyl ester-containing copolymer is A copolymer comprising ethylene and one or more branched vinyl ester monomers; A terpolymer comprising ethylene, one or more branched vinyl ester monomers, and vinyl acetate; The vinyl acetate content is in the range of 0 to 50% by mass, based on the total amount of the vinyl ester-containing copolymer in the polymer composition; and / or The polymer composition according to claim 1, wherein the content of one or more branched vinyl ester monomers is in the range of 0.01 to 50% by mass, based on the total amount of the vinyl ester-containing copolymer in the polymer composition.

7. The aforementioned polypropylene polymer Based on the total amount of the polymer composition, it is present in an amount ranging from 60% to 99% by mass; and / or The polymer composition according to claim 1, wherein the vinyl ester-containing copolymer is present in an amount ranging from 1% by mass to 40% by mass, based on the total amount of the polymer composition.

8. The polymer composition is Melt flow rate (MFR) in the range of 0.1 g / 10 min to 1000 g / 10 min at 230°C / 2.16 kg according to ASTM D1238; Glass transition temperature (T g) in the range of -50°C to 40°C; Tensile stress at yield of 5 MPa or more according to ASTM D638; Tensile stress at fracture of 5 MPa or more according to ASTM D638; Tensile modulus in the range of 0.1 to 5 GPa according to ASTM D638; Secant flexural modulus at 1% above 100 MPa according to ASTM D790; Load deflection temperature of at least 50°C; At least 50% fracture strain; Yield strain of at least 2%; and / or The polymer composition according to claim 1, exhibiting a Rockwell hardness of at least 25.

9. The polymer composition according to claim 1, wherein the vinyl ester-containing copolymer is polymerized under conditions including a reactor pressure of more than 40 bar, preferably more than 1000 bar, and a reactor temperature of more than 50°C.

10. The polymer composition according to claim 1, further comprising one or more selected from the group consisting of antioxidants, pigments, fillers, reinforcing agents, adhesion promoters, biocides, whitening agents, nucleating agents, antistatic agents, antiblocking agents, processing aids, flame retardants, plasticizers, and light stabilizers.

11. A method for producing a polymer composition, This includes mixing a polypropylene polymer and a vinyl ester-containing copolymer at a temperature ranging from 20°C to 300°C to form a polymer composition. A method wherein the vinyl ester-containing copolymer comprises ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate.

12. The method according to claim 11, wherein the mixing includes melt mixing.

13. The method according to claim 11, wherein the polymer composition is a powder mixture of the polypropylene polymer and the vinyl ester-containing copolymer.

14. A molded article comprising the polymer composition according to any one of claims 1 to 10.

15. A molded article according to claim 14, wherein the molded article is prepared by a method selected from the group consisting of extrusion molding, co-extrusion molding, extrusion coating, injection molding, cast film extrusion, blow film extrusion, foam molding, extrusion blow molding, injection stretch blow molding, rotational molding, pultrusion, calendering, additive manufacturing, and lamination.

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