TWI729501B - Strain hardened polypropylene copolymer compositions - Google Patents

Abstract

The present disclosure relates to compositions including copolymers, and methods for making compositions. In an embodiment, a composition includes the product of a copolymer comprising at least 50 mol% propylene and at least 1 wt% of at least one of ethylene or a C₄ to C₁₀ α-olefin, based on the total weight of the copolymer; and an organic peroxide. The copolymer has Mw_MALLS /Mn_MALLS of from 1 to 5. In an embodiment, a process to form a composition includes introducing a copolymer with an organic peroxide, the copolymer comprising at least 50 mol% propylene and at least 1 wt% of at least one of ethylene or a C₄ to C₁₀ α-olefin, based on the total weight of the copolymer; and obtaining a composition comprising a product of the copolymer and the organic peroxide. The copolymer has Mw_MALLS /Mn_MALLS of from 1 to 5.

Description

Strain-hardened polypropylene copolymer composition

The present disclosure relates to a composition including a copolymer and a method of manufacturing the composition. priority

This application claims the priority of U.S. Provisional Application No. 62/736,645 filed on September 26, 2018 and European Patent Application No. 18199601.8 filed on October 10, 2018. The disclosure of these applications is by reference The method is incorporated into this article.

The current rising global demand for high-quality thermoplastic polymers for both domestic and industrial applications has promoted the development of new polymer compositions with customized properties such as high melt strength and high elongation strain hardening.

Common linear polyolefin (such as polypropylene) grades that are widely used in manufacturing show low melt strength and lack the strain hardening performance under elongational flow required for foaming, and copolymers are used for toughness, softness, and Flexible application. Some applications, especially those requiring melt strength and strain hardening such as foams, can benefit from polymers that also provide elasticity and toughness for some applications.

Polypropylene has limited applicability in industrial operations involving both shearing and extensional flow (including thermoforming, fiber drawing/spinning, blown film, and foam). This is partly due to the low melt strength and lack of strain hardening in common linear polypropylene. The industry has tried many ways to improve the melt strength and strain hardening of polypropylene, including increasing the polymer molecular weight, broadening the molecular weight distribution, and/or adding ultra-high molecular weight tails.

The lack of strain hardening results in lower viscosity pore walls during bubble expansion during the foaming process, bubble coalescence, and the formation of open-cell foams. Previous efforts to modify linear polypropylene by introducing long-chain branches through reactive extrusion with organic peroxides (such as peroxydicarbonates) have resulted in increased strain hardening, but the level of strain hardening alone is not sufficient to produce closures. Cellular foam.

Therefore, polymer compositions with high melt strength and strain hardening are required to form commercially viable foamed objects, such as foamed food containers.

Related publications include US 6,323,289; US 2018/0016414; US 2018/0051160; US 2018/0016414; US 5,047,485; US 5,416,169; US 5,883,151; US 6,956,067; US 6,875,826 A1; US 6,573,343; US 6,350,828; US 6,323,289; US 8,153,745; US 9,068,030; US 9,200,095; US 2002/0043643; US 2003/0157286 A1; US 2012/245302; EP 1179544; EP 2679630 A1; EP 2000504 A1; WO 1994/005707 A1; WO 00/00520; WO 2014/070386; WO 2015/200586; WO 2016/175942; and WO 2019/013872; and MH Wagner et al. in 39 RHEOL. ACTA 97-109 (2000) "The strain-hardening behaviour of linear and long-chain-branched polyolefin melts in extensional Flows"; RP Lagendijk et al. in 42 POLYMER 10035-10043 (2001) "Peroxydicarbonate modification of polypropylene and extensional flow properties"; P. Spitael et al. in 44(11) POLY. ENG. & SCI. 2090-2100 (2004) ) Of "Strain hardening in polypropylenes and its role in extrusion foaming"; K. Jayaraman et al. in SPE PLASTICS RESEARCH ONLINE (2011) "Entangling additives enhance polypropylene foam quality"; P. Iacobucci, "High melt strength polypropylene through reactive extrusion with Perkadox 24L", SPE POLYOLEFINS CONFERENCE, Houston, TX (February 2004); H. Pol et al. in SPE PLASTICS RESEARCH ONLINE (2014) "Microstructure and rheology of high-melt-strength poly-(propylene) impact copolymer"; M. Ratzsch et al. Of 27 PROG. POLYM. SCI. 27 1195 (2002); and N. Spisakova et al. in 15 J. MACRM. SCI. & APP. CHEM. 37 (2000).

The present disclosure relates to a composition including a copolymer and a method of manufacturing the composition. In one embodiment, the composition includes the following products: at least 50 mole% of propylene and at least 1% by weight of ethylene or C ₄ to C ₁₀ alpha olefin based on the total weight of the copolymer Copolymers of one; and organic peroxides. The copolymer has a Mw _MALLS /Mn _{MALLS of} 1 to 5. In one embodiment, the method of forming the composition includes introducing a copolymer and an organic peroxide, the copolymer comprising at least 50 mole% of propylene and at least 1% by weight of ethylene based on the total weight of the copolymer Or _{at least one of C 4} to C ₁₀ alpha olefins; and obtaining a composition comprising the copolymer and the product of the organic peroxide. The copolymer has a Mw _MALLS /Mn _{MALLS of} 1 to 5.

The present disclosure relates to a composition including a copolymer and a method of manufacturing the composition. The present disclosure further relates to an improved method for solid-state blending and post-reactor reaction of copolymer compositions with improved properties (such as melt strength or extensional strain hardening) and no substantial loss in mechanical properties compared to linear polypropylene , So that the composition is suitable for foamed objects.

The present disclosure relates to a composition including a copolymer that has been peroxide-treated, such as an ethylene-propylene copolymer. For example, this document discloses a copolymer composition having a high molecular weight portion (ie, a high molecular weight tail) modified by reactive extrusion with an organic peroxide to introduce long chain branches. Treatment of low-temperature decomposition peroxides such as peroxydicarbonate, and, for example, ethylene-propylene elastic copolymers in the form of granules or pellets such as Vistamaxx ^TM polymer (from ExxonMobil Chemical Company) can provide melt strength improvement and extensional strain hardening strengthen. The copolymers of the present disclosure can be treated with organic peroxides to form 1×10 ³ Pa. s to 1×10 ⁶ Pa. The peak elongation viscosity of s (which is an indicator of long chain branching) and the copolymer composition with increased weight average molecular weight, thus providing excellent strain hardening elongation viscosity for the copolymer composition. Without being bound by theory, the increase in crosslinking appears to be due to the presence of ethylene in the copolymer backbone.

The composition of the present disclosure may include one or more copolymers (such as copolymers) and at least one peroxide (such as organic peroxide) in an amount of 0.01% to 3% by weight based on the weight of copolymer and organic peroxide. Oxide) product. The copolymer composition may further include alkyl radical scavengers, such as tocopherols, lactones, hydroxylamines, and/or one or more additives, such as stabilizers, acid scavengers, and/or nucleating agents.

The copolymer composition of the present disclosure may have one or more of the following: the melt flow rate (MFR, ASTM D1238, condition L, 230°C and 2.16 kg) is 1g/10min to 10g/10min, and the ethylene content is 1 weight % To 50% by weight, the melt strength is 1cN to 15cN, and the peak elongation viscosity is 1×10 ³ Pa. s to 1×10 ⁶ Pa. s, the complex viscosity is 100Pa. s to 100,000Pa. s, Mn value is 50,000g/mol to 140,000g/mol, Mw is 100,000g/mol to 300,000g/mol, Mz is 200,000g/mol to 850,000g/mol, Mv _MALLS is 100,000g/mol to 300,000g/ mol, molecular weight distribution (Mw _DRI /Mn _DRI ) from 1 to 2.5 (narrow PDI), intrinsic viscosity [η] from 1dL/g to 1.6dL/g, branching index g'vis from 0.7 to 1, and Mz _MALLS / Mw _MALLS is 1 to 3.

Also disclosed is a method comprising the following steps: combining polyolefin particles and/or pellets having a melt flow rate (such as MFR1), wherein the temperature of the polyolefin particles and/or pellets is maintained at least at room temperature (such as 23°C +/- 5℃); convey the polyolefin particles to the homogenizer while maintaining the temperature of the particles and/or pellets at least at room temperature; and make the polyolefin particles at a temperature lower than the melting temperature of the polyolefin particles and/or pellets And/or the pellets and the organic peroxide are mixed in a homogenizer for a residence time of 30 seconds or longer, such as 30 seconds to 180 seconds, to form a polymer with a melt flow rate (for example, MFR2, such as MFR1 is greater than MFR2). Olefin products. The residence time is the time between the addition of the solid peroxide to the homogenizer and the kneading section of the extruder when the temperature rise is estimated to be rapid and peroxide decomposition has occurred.

As used herein, "composition" can include components (such as copolymers) as well as contact products of components and/or reaction products of components.

For the purpose of this disclosure, ethylene should be regarded as an alpha olefin.

Unless otherwise specified, all melting points (Tm) are DSC second melt.

The following abbreviations may be used herein: Mn is the number average molecular weight, Mw is the weight average molecular weight, Mz is the z average molecular weight, and Mv is the viscosity average molecular weight. Unless specifically stated, the Mn, Mw, Mz, and Mv mentioned are determined by DRI as described herein. The symbol "weight%" means weight percentage, mole% means mole percentage, MWD means molecular weight distribution, PDI means polydispersity index, MFR means melt flow rate, MAO means methylalumoxane, RT means room Temperature, and DRI is a differential refractive index detector. LS refers to light scattering, and MALLS refers to multi-angle light scattering. LS and MALLS are used interchangeably in this article.

"Polymer" has two or more units of the same or different monomers ("mer"). "Homopolymer" is a polymer with the same monomer unit. "Copolymer" is a polymer having two or more monomer units that are different from each other. "Terpolymers" are polymers with three different monomer units. The "different" used to refer to the monomer units means that the monomer units are different from each other by at least one atom or different isomers. Therefore, the definition of copolymer as used herein includes terpolymers.

As used herein, "hybrid" refers to combining solid polyolefins such as ethylene-propylene copolymers with organic peroxides that may be solid. In at least any embodiment, a homogenizer is used for this mixing. A "homogenizer" is a mechanical device that combines two or more different materials (such as one or all in solid form) by physical methods, such as mixing, rotating, agitating, vibrating, or some combination thereof. Suitable homogenizers can generally be divided into horizontal conveyors, in which a screw or screw-like mechanism transports polymer particles and/or pellets and additive mixtures along the length of the homogenizer; and a vertical or horizontal blender, which is agitated Or some other non-delivery member homogenizes the polymer particles and/or pellets and additive mixture. In at least any embodiment, the homogenizer maintains the material being mixed in a solid and/or liquid form, and does not generate a molten material such as heating the polymer to its melting point temperature.

Therefore, in at least any embodiment, the present disclosure describes a method including the following steps: combining polyolefin particles and/or pellets with MFR1, wherein the temperature of the polyolefin particles and/or pellets is maintained at least at room temperature; Conveying the polyolefin particles to the homogenizer while maintaining the temperature of the particles and/or pellets; and homogenizing the polyolefin particles and/or pellets with the organic peroxide at a temperature lower than the melting temperature of the polyolefin particles and/or pellets Mix in the machine for a residence time of at least 30 seconds, such as 50 seconds, such as 60 seconds, such as 70 seconds, such as 30 seconds to 180 seconds, to form a copolymer composition with MFR2, such as below the melting point temperature of the polyolefin particles The temperature, such as room temperature or higher, such as the range of 45°F to 80°C (176°F), such as room temperature to 71°C (160°F), for example 59°C, MFR1 is greater than MFR2. The copolymer composition may have a peak elongation viscosity of ^{1×10 3} Pa∙s to 1×10 ^{6 Pa∙s.}

The term "polypropylene" ("PP") refers to a polymer or a mixture of polymers containing at least 50% by weight of polymerized propylene. The polymerization catalyst can be Ziegler-Natta, metallocene or other types of catalysts that can provide stereospecific polymerization of propylene. In this respect, homopolymers of propylene can be used; random, alternating, or block copolymers of propylene and other olefins; or random, alternating, or block terpolymers. Generally, the propylene copolymer or terpolymer will contain one or more other olefins, such as ethylene, butene, pentene, hexene, heptene, or octene, but it may also include other olefinic unsaturated monomers or such Combinations, such as acrylic esters, styrene, styrene derivatives, acrylonitrile, vinyl acetate, vinylidene chloride, and vinyl chloride. In at least any one aspect, the polyolefin polymer used to prepare the copolymer composition is a copolymer.

"Linear" means that the polymer has a few long chain branches (if any) and has a g'vis value of 1. The more branches, the lower the g'vis. Therefore, g'vis may be 0.98 or lower, such as 0.97 or lower, such as 0.96 or lower.

As used herein, "elastomer" or "elastomer composition" refers to any polymer or polymer composition (such as a blend of polymers) consistent with the definition of ASTM D1566. Elastomers include mixed blends of polymers, such as melt blends of polymers and/or reactor blends. Elastomers are elastic polymers, such as polymers with viscoelastic properties (both viscosity and elasticity).

As used herein, "shear viscosity reduction" describes fluids that have reduced viscosity when subjected to shear strain; therefore, polymers exhibiting "shear viscosity reduction" are easier to process when exposed to shear stress. So it has improved processability. The ARES-G2B (TA Instruments) rheometer can be used to measure the shear viscosity reduction of polymer samples.

As used herein, "strain hardening" is the strengthening of a polymer when exposed to deformation forces. An Anton-Paar MCR 501 mechanical spectrometer was used to measure the strain hardening of polypropylene samples.

As used herein, "melt strength" refers to the resistance of the polymer melt to stretching. Without being bound by theory, it is generally believed that the melt strength of a material is related to the entanglement of the molecular chains of the polymer and its resistance to loosening under strain. The polymer properties that affect the resistance to loosening are molecular weight, molecular weight distribution (MWD), and molecular branching. In this paper, an extensional rheometer is used to measure at 190°C.

The "melt flow rate" (MFR) is measured in accordance with ASTM D1238 at 230°C and a load of 2.16 kg.

"Peak elongation viscosity" or "PEV" is the difference between the highest value of elongation viscosity (y-axis in Figures 3 to 8) and the linear viscoelastic limit "LVE". The copolymer composition of the present disclosure may have improved strain hardening, as evidenced by the increased peak elongation viscosity, as shown in Figures 3 to 8. Copolymer

In at least any embodiment, the copolymer is a _{random copolymer having units derived from ethylene or C 4} to C ₁₀ alpha olefins and optionally diene derived units, and the remainder of the polymer is units derived from propylene. The copolymer contains at least 50% by weight of propylene-derived units based on the weight of the copolymer.

Based on the total weight of the copolymer, the copolymer contains more than 50% by weight, such as more than 60% by weight, such as more than 65% by weight, such as more than 75% by weight and up to 99% by weight of propylene-derived units. In at least any embodiment, the content of the propylene-derived unit of the copolymer is 75% to 95% by weight, such as 75% to 92.5% by weight, such as 82.5% by weight, based on the weight of the copolymer. To 92.5% by weight, such as 82.5% to 90% by weight. Therefore, the _{amount of units or comonomers derived from at least one of ethylene or C 4} to C ₁₀ alpha olefins is 1% by weight, 5% by weight, or 10% by weight, or 14% by weight based on the weight of the copolymer. % To 16% by weight, 18% by weight, 22% by weight, or 25% by weight.

The comonomer content can be adjusted so that the copolymer has a heat of fusion of 100 J/g or lower, such as 75 J/g or lower, and a melting point (T _m ) of 100°C or lower, such as 90°C or lower, And the crystallinity of the same row polypropylene of 2% to 65%, and the MFR of less than 800 g/10 min measured at 230°C and 2.16 kg weight.

The copolymer may include more than one comonomer. In at least any aspect, the copolymer has more than one comonomer, including propylene-ethylene-octene, propylene-ethylene-hexene, and propylene-ethylene-butene copolymers.

In embodiments where there is more than one comonomer derived from ethylene or _{at least one of C 4} to C ₁₀ alpha olefins, the amount of each comonomer may be less than 5% by weight of the copolymer, but the comonomer The combined amount of the body is 5% by weight or more based on the weight of the copolymer.

In at least any embodiment, the comonomer is ethylene, 1-hexene, or 1-octene, such as the amount of which is 5% by weight, or 10% by weight, or 14% by weight based on the weight of the copolymer % To 16% by weight, 18% by weight, 22% by weight, or 25% by weight.

In at least any embodiment, the copolymer includes ethylene-derived units. The copolymer may include 5 wt%, or 10 wt%, or 14 wt% to 16 wt%, 18 wt%, 22 wt%, or 25 wt% of ethylene-derived units based on the weight of the copolymer. In at least any of the embodiments, the copolymer consists essentially of units derived from propylene and ethylene, that is, the copolymer does not include the amount or amount of impurities present in the ethylene and/or propylene feed stream used during polymerization. Any other comonomers that will severely affect the heat of fusion, melting point, crystallinity, or melt flow rate of the copolymer, or any other comonomers deliberately added to the polymer process.

In at least any one aspect, the diene comonomer unit is included in the copolymer. Examples of dienes include, but are not limited to, dicyclopentadiene, 1,3-cyclopentadiene, divinylbenzene, 1,4-hexadiene, 1,4-cyclohexadiene, 1,5-hexadiene Diene, 5-methyl-1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 3,7-dimethyl-1,6-octadiene, 1, 9-decadiene, 1,11-dodecadiene, 1,13-tetradecadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, or a combination thereof. The amount of diene comonomer, based on the weight of the copolymer, is equal to or more than 0.01% by weight, or 0.5% by weight, or 1% by weight, or 1.5% by weight, and less than or equal to 5% by weight, Or 4% by weight, or 3% by weight or 2% by weight.

The copolymer has a differential scanning calorimetry ("DSC") measurement of 100 J/g or less, such as 75 J/g or less, such as 70 J/g or less, such as 50 J/g or Lower, such as a heat of fusion ("H _f ") of 35 J/g or lower. _{The copolymer may have a lower limit H f of} 0.5 J/g, 1 J/g, or 5 J/g. For example, the H _f value may be 1 J/g to 75 J/g, such as 1.5 J/g to 70 J/g, such as 3 to 60 J/g, such as 4 J/g to 50 J/g, such as 6 J/g g to 40 J/g, such as any value from 7 J/g to 30 J/g.

The copolymer may have a crystallinity percentage of the same row polypropylene as measured according to the DSC process of 2% to 65%, such as 0.5% to 40%, such as 1% to 30%, such as 5% to 35%. The thermal energy of the highest grade propylene (ie, 100% crystallinity) is estimated to be 189 J/g. In at least any embodiment, the copolymer has a crystallinity of in-line polypropylene in the range of 0.25% to 25%, such as 0.5% to 22%.

The crystallization and melting temperature of the copolymer and composition of the present disclosure can be measured on a Pyris ^TM 1 DSC at 10° C./min by differential scanning calorimetry. The DSC heating and cooling rates of both heating and cooling are 10°C/min. The measurement system is performed as follows: 1) keep at -20.0℃ for 10.0 min; 2) heat from -20.0℃ to 200.0℃ at 10.0℃/min; 3) keep at 200.0℃ for 10.0 min; 4) keep at 10.0℃/min from 200.0℃ Cool to -20.0°C; 5) Keep at -20.0°C for 10.0 min; and 6) Heat from -20.0°C to 200.0°C at 10.0°C/min.

In at least any embodiment, the propylene-derived units of the copolymer have 50% to 99%, such as 65% to 97%, such as 75% to 97% of the same row triad portion. For example, the first polymer may have, as ^{measured by 13} C NMR, 75% or greater, such as 80% or greater, such as 82% or greater, such as 85% or greater, such as 90% Or larger three-dimensional regularity of the triplet. The ternary stereoregularity of a polymer is the relative stereoregularity of the sequence of three adjacent propylene units (chains composed of head-to-tail bonds), expressed as a binary combination of m and r sequences. It is usually expressed as the ratio of the number of units with specified stereoregularity to all propylene triads in the first polymer. The triad stereoregularity (mm part) of the propylene copolymer can be determined from the ¹³ C NMR spectrum of the propylene copolymer. The calculation of the three-dimensional regularity of triads is described in US 5,504,172, the complete content of which is incorporated herein by reference.

The copolymer may have a unimodal melting transition determined by DSC. In at least any embodiment, the copolymer has a main peak transition of 90°C or lower, and the broad end of its melting transition is 110°C or higher. The peak "melting point"("T _m ") is defined as the temperature of the maximum heat absorption within the melting range of the sample. However, the copolymer may show a secondary melting peak adjacent to the main peak and/or at the end of the melting transition. For the purpose of this disclosure, the melting peaks are regarded as a single melting point together, and the highest of these peaks is regarded as the T _{m of the} copolymer. _{The copolymer may have a T m of} 100°C or lower, such as 90°C or lower, such as 80°C or lower, such as 70°C or lower. _{In at least any embodiment, the copolymer has a T m of} 25°C to 100°C, such as 25°C to 85°C, such as 25°C to 75°C, such as 25°C to 65°C. At least one embodiment of any aspect, the copolymer having a 30 deg.] C to 80 ℃, such as a T _m 30 ℃ to 70 deg.] C of.

In at least any one embodiment, the copolymer has a Munner viscosity [ML (1+ at 125°C) as determined by ASTM D-1646 to be less than 100, such as less than 75, such as less than 60, such as less than 30 4)].

The copolymer has a measurement in accordance with ASTM D-1505 at room temperature of 0.850 g/cm ³ to 0.920 g/cm ³ , such as 0.860 g/cm ³ to 0.900 g/cm ³ , such as 0.860 g/cm ³ to 0.890 g/cm ³ The density.

Suitable copolymers may have a weight average molecular weight ("Mw") of 5,000 to 5,000,000 g/mole, such as 10,000 g/mole to 1,000,000 g/mole, such as 50,000 g/mole to 400,000 g/mole; 2,500 G/mole to 2,500,00 g/mole, such as 10,000 g/mole to 250,000 g/mole, such as number average molecular weight ("Mn") from 25,000 g/mole to 200,000 g/mole; and/ Or 10,000 g/mole to 7,000,000 g/mole, such as 80,000 to 700,000 g/mole, such as 100,000 g/mole to 500,000 g/mole of z average molecular weight ("Mz"). The copolymer may have a molecular weight distribution (Mw/Mn, or "MWD") of 1.5 to 20, or 1.5 to 15, such as 1.5 to 5, such as 1.8 to 5, such as 1.8 to 4.

The copolymer may have an elongation at break of 200% to 2000%, such as 500% to 1000%, such as 800% to 900%, as measured according to ASTM D412.

The copolymer may have crystalline regions interrupted by non-crystalline regions and in the range of 5% to 25% by weight based on the weight of the copolymer. Without wishing to be bound by any theory, it is generally believed that the amorphous region may be formed from non-crystallizable polypropylene fragment regions and/or including comonomer units. By introducing errors (stereo and regional defects) in the propylene insertion and/or by the presence of comonomers, the crystallinity and melting point of copolymers that can be propylene-based elastomers are lower than those of high-condensation polypropylene. In at least any embodiment, the copolymer is a copolymer with limited crystallinity due to adjacent propylene units in the same row. In other embodiments, the copolymer generally lacks any substantial intermolecular heterogeneity in terms of stereoregularity and comonomer composition, and generally lacks any substantial heterogeneity in terms of intramolecular composition distribution.

Content of the copolymer of the present disclosure may include Vistamaxx ^TM Commercial examples of propylene-based elastomer, which is from ExxonMobil Chemical Company in the propylene - ethylene copolymer; Tafmer ^TM elastomers from the Mitsui Chemicals; and Versify ^TM elastomers from The Dow Chemical Company .

For example, Vistamaxx ^TM propylene-based elastomers are polymers that expand the performance and processability of films, compounds, non-woven fabrics, and molded/extruded products. The free-flowing pellets of Vistamaxx ^TM acrylic elastomer are easy to combine, and the wide compatibility allows dry blending operations. Vistamaxx ^TM acrylic elastomer provides a series of applications, such as 1) non-woven fabric (elasticity, softness and toughness; with drop-in processing performance); 2) film (elasticity, tightness, toughness) And adhesiveness); 3) polymer modification and compounds (impact strength, transparency, flexibility/stiffness, softness, high filler loading). Vistamaxx ^TM copolymer is a copolymer of propylene and ethylene. Vistamaxx ^TM propylene-based elastomer is rich in propylene (>80%) and is a semi-crystalline material with high amorphous content.

Vistamaxx ^™ 3000 propylene-ethylene performance polymer ("VM3000") is available from ExxonMobil Chemical Company. VM3000 has an ethylene content of 11% by weight, with the remainder being propylene. The properties of VM3000 include: density of 0.873 g/cm ³ (ASTM D1505); melt index of 3.7 g/10 min (ASTM D1238; 190℃, 2.16 kg); melt mass flow rate of 8 g/10 min (230℃) , 2.16 kg); Shore D hardness is 27 (ASTM D2240); and Vicat softening temperature (VST) is 65.1°C.

Vistamaxx ^™ 3588 propylene-based elastomer ("VM3588") is available from ExxonMobil Chemical Company. VM3588 has an ethylene content of 4% by weight, and the rest is propylene. The properties of VM3588 include: density of 0.889 g/cm ³ (ASTM D1505); melt mass flow rate of 8 g/10 min (230°C, 2.16 kg); Shore D hardness of 50 (ASTM D2240); and Ficat softening The temperature (VST) is 103°C.

Vistamaxx ^™ 3980 propylene-based elastomer ("VM3980") is available from ExxonMobil Chemical Company. VM3020 has an ethylene content of 9% by weight, with the remainder being propylene. The properties of VM3980 include: density of 0.879 g/cm ³ (ASTM D1505); melt index of 3.6 g/10 min (ASTM D1238; 190℃, 2.16 kg); melt mass flow rate of 8 g/10 min (230℃, 2.16 kg); Shore D hardness (Shore D hardness) is 34 (ASTM D2240); and Fikka softening temperature (VST) is 77.3°C.

Examples of suitable polymerization methods for forming the copolymers of the present disclosure include contacting catalysts and olefins in a gas phase reactor, stirred tank reactor, loop reactor, or other reactor. The polymerization can be carried out in the gas phase, as a solution, or as a slurry. Hydrogen may be present in the reactor to adjust the molecular weight of the copolymer being manufactured. In at least any embodiment, if hydrogen is combined with a single catalyst during polymerization, it is combined at a fixed level. This means that during the production of the copolymer, the total hydrogen concentration in the reactor remains constant.

In at least any embodiment, the polymerization is a "single-stage" polymerization method, which means that during the entire production process of polymer particles, olefins, catalysts, and optionally hydrogen are under the same or similar conditions, such as in a single Reactor, or contact in parallel or series multiple reactors that maintain a fixed level of temperature, pressure, monomer concentration, and hydrogen concentration (without parameter changes exceeding ±5% or ±10%). Therefore, for example, if the reactor conditions are maintained at a fixed level, even if it is carried out in two or more loop slurry reactors connected in parallel, the polymerization is a single stage.

The term "slurry polymerization method" or "slurry polymerization reactor" refers to a method or reactor that processes polymers that are only partially or completely insoluble in the medium (monomers, solvents, or both), such as those with polymer , The weight of monomer and diluent is at least 20% by weight of suspended or insoluble polymer. In a suitable solution or slurry polymerization method, the catalyst components, solvents, monomers, and hydrogen (when used) are delivered to one or more polymerization reactors under pressure. The catalyst component can be delivered to the polymerization reactor as a mixture in an aliphatic hydrocarbon solvent, a mixture in an oil, a mixture thereof, or as a dry powder. In at least any of the embodiments, the polymerization method uses ethylene/propylene as the sole solvent (bulk polymerization).

In any case, the temperature of the reactor is controlled by the catalyst addition rate (polymerization rate), the temperature of the solvent/monomer feed stream, and/or the use of the heat transfer system. For olefin polymerization, the reactor temperature can range from 50°C to 120°C or higher, while the pressure is usually higher than 300 psig, or in the range of 300 psig to 1000 psig, or 1200 psig. These processing conditions are conducive to in-situ catalyst activation, because high temperature enhances the solubility of catalysts and activators in aliphatic hydrocarbon solvents. In at least any embodiment, the polymerization temperature, that is, the temperature at which the polymerization reaction proceeds, such as the environment of the polymerization vessel or reactor, is at least 50°C, such as at least 60°C, such as at least 70°C, or at 50°C to 170°C. Within the range of °C, such as 60°C to 160°C, such as 70°C to 150°C, such as 80°C to 140°C, such as 90°C to 130°C, such as 100°C to 120°C. The vessel or reactor can be a loop reactor, or a stirred tank reactor, a gas phase reactor, or any other suitable reactor.

Propylene, ethylene, and other C ₄ to C ₁₂ alpha olefins and/or dienes if present are dissolved/dispersed in the solvent before delivery to the polymerization reactor (for gaseous monomers, the monomers can be delivered to the reactor To dissolve in the reaction mixture). Before mixing, solvents and monomers are usually purified to remove potential catalyst poisons. The feedstock can be heated or cooled before being delivered to the first reactor. Additional monomer and solvent can be added to the second reactor, and it can be heated or cooled.

The catalyst/activator can be delivered to one polymerization reactor or distributed to two or more reactors. In solution or slurry polymerization, the produced polymer can be melted and maintained dissolved or partially dissolved in a solvent under reactor conditions to form a polymer solution. The catalyst can be delivered to the reactor in solid form or as a slurry/suspension in a solvent. Alternatively, the catalyst suspension can be premixed with the solvent in the feed stream of the polymerization reaction. The catalyst can be activated on the production line, or activated by an activator co-carried with it. In some instances, premixing is required to provide some reaction time before the catalyst components enter the polymerization reactor. The monomer may or may not be present to carry out the so-called "prepolymerization", but this step may not be present. The catalyst activity may be 40,000 kg or more polymer per kilogram of catalyst, such as 400,000 kg or more polymer per kilogram of catalyst, such as 1,000,000 kg or more polymer per kilogram of catalyst.

In at least any embodiment, the solution or slurry polymerization method of the present disclosure includes a stirred reactor system including one or more stirred polymerization reactors. Generally, the reactor should be operated under conditions that result in a thorough mixing of the reactants. In a dual reactor system, the reactors can be operated at the same or different temperatures and fluidly connected in series, but they can be measured at the same temperature or at the same temperature by internal thermocouples in the polymerization medium or inside the walls of each reactor that are consistent with each other. Operate within ±2℃, or ±4℃. The residence time in each reactor will depend on the design and capacity of the reactor. In at least any embodiment, two or more reactors are otherwise operated under the same conditions.

In at least any embodiment, the solution or slurry polymerization process is carried out in one or more loop-type reactors, such as two fluid connections in series. This reactor system includes a single reactor and multiple reactors in series or parallel configuration, such as those disclosed in US 2007/0022768. The solvent/monomer (such as pure propylene) flow in these reactors can be maintained using pumps and/or pressure systems, and can be fed from one point with monomer and catalyst and withdrawn from another point (such as downstream thereof) The formed polymer is operated continuously. The temperature, catalyst concentration, hydrogen concentration, and monomer concentration conditions in each loop reactor can be the same or different, and can be customized as needed to suit the desired final product.

In at least any embodiment, the solution polymerization method of the present disclosure uses a heat exchanger type reactor in which polymerization is performed. The reactor can be one or multiple shell and tube heat exchangers, or one or multiple spiral heat exchangers.

In any case, the formed copolymer is then discharged from the reactor as an effluent stream, and the polymerization reaction is inhibited, such as with a coordinated polar compound, to prevent further polymerization. When leaving the reactor system, the polymer solution is delivered through the heat exchanger system on the way to the devolatization system and the final polymer processing procedure. Under certain temperature and pressure conditions, the polymer solution can be phase separated into a polymer-poor phase and a polymer-rich phase. Copolymer particles and pellets can be recovered from the effluent by coagulation with a non-solvent, such as isopropanol, acetone, or n-butanol, or the copolymer can be recovered by stripping the solvent or other media with heat or steam . One or more conventional additives such as antioxidants can be incorporated into the copolymer during the final processing process. Possible antioxidants include phenyl-β-naphthylamine; di-tertiary butylhydroquinone, triphenyl phosphate, heptanoate diphenylamine, 2,2'-methylene-bis(4-methyl-6-tris Grade butyl)phenol, and 2,2,4-trimethyl-6-phenyl-1,2-dihydroquinoline, and/or stabilizers, such as tocopherols (described further below) or lactones , Or other agents described in WO 2009/007265. "Copolymer particles" are the solid copolymer products of the polymerization reaction between propylene and comonomers such as ethylene. The particles are made in the reactor. On the other hand, the pellets of the present disclosure can be formed by melting the pellets in a final processing extruder and then passing through a template (usually under water) with a pelletizing machine blade at the end of the final processing extruder.

The resulting copolymer particles may have a polymer weight of 0.1% to 50% by weight, such as 0.1% to 25% by weight, such as 0.1% to 20% by weight, such as 0.1% to 18% by weight, such as A copolymer with an ethylene content (ethylene-derived unit) of 0.5% to 16% by weight, such as 1% to 15% by weight, such as 2% to 12% by weight, such as 3% to 11% by weight.

Then, the copolymer particles manufactured as described in at least any one of the embodiments are mixed with an organic peroxide to manufacture a copolymer composition. The copolymer composition may include a contact product/reaction product between the copolymer and the organic peroxide. The copolymer composition may include the copolymer pellets described herein, and the copolymer pellets are expected to have the same comonomer content as the particles.

It is desirable to control the particle size of the copolymer particles from the reactor. One way to achieve this is to control the particle size of the catalyst itself. The key is to keep the particle size and pellet size as small as possible in order to maximize the surface area used for reactions that occur in the solid state. The particle size is usually controlled by the catalyst carrier. Therefore, in at least any embodiment, the average particle size of the catalyst can be reduced from an average diameter of 50 microns or less to, for example, an average diameter of 20 to 45 microns. For example, in the case of a preferred catalyst-containing catalyst, the size of the catalyst is 45 microns, but using different catalyst supports can be as small as 22 microns. In at least any embodiment, the average particle size of the copolymer particles is reduced from an average diameter of at least 1500 micrometers, or 2000 micrometers, to an average diameter of 100 micrometers to 2,000 micrometers, or 1,200 micrometers to 2,000 micrometers. For example, the particles made from the preferred catalysts are 1,939 microns on average, but can be smaller with different supports (for example, 1,222 microns on average). The copolymer can also be in the form of pellets by having an average diameter greater than 1,000 microns, such as 2,000 microns to 5,000 microns, such as 2,500 microns to 4,000 microns. The pellet size is controlled at the final processing extruder/underwater pelletizing machine. In at least any embodiment, the copolymer has a pellet size ranging from 35 pellets/g to 65 pellets/g.

For the purpose of the present disclosure, a copolymer such as Vistamaxx ^™ in the form of granules and/or pellets is used and further mixed with peroxide under an inert atmosphere in a post-reactor process.

Catalyst used to form copolymer

Copolymers can be synthesized by using appropriate polymerization techniques, such as but not limited to conventional Chi-nano type polymerization, and catalysis using "single site" organometallic catalysts (including but not limited to metallocene catalysts) . The copolymer particles described herein can be produced by any olefin polymerization method.

Since the size of the particles or pellets affects the efficiency of the method of the present disclosure (the smaller the particle/pellet size, the greater the strain hardening and melt strength), it would be desirable to control the particle size of the copolymer particles or pellets from the reactor.

The method of the present disclosure can be carried out with any suitable catalyst, such as Chi-Na catalyst and metallocene catalyst.

For the purpose of this disclosure, the term "metallocene" refers to a transition containing one or more cyclopentadienyl (Cp) moieties combined with the periodic table of elements Catalyst compounds of metals. Suitable metallocenes may contain transition metals from groups 3 to 10 of the periodic table; and at least one co-ligand that remains bonded to the transition metal during polymerization. In at least any embodiment, the transition metal is used in a cationic state and stabilized by a co-catalyst or activator. In at least any embodiment, the transition metal is a transition metal or a metallocene of Group 4 of the periodic table, such as titanium, hafnium, or zirconium, which is used in polymerization in a monovalent cation state, and has one or two Auxiliary ligand. The important feature of this catalyst for coordination polymerization will be the ligand that can be abstracted, and the ligand that can be inserted into the ethylene (olefin group).

Suitable metallocene catalysts can be used in combination with auxiliary catalysts, and the auxiliary catalyst can be an aluminoxane, such as methyl aluminoxane. In at least any embodiment, the aluminoxane can be modified to provide solubility in linear alkanes or used in slurry, but it can usually be used from a toluene solution. This solution can include unreacted trialkylaluminum and the aluminoxane concentration can be expressed as the number of moles per liter of aluminoxane (molAl.L ^-1 ), which includes any trioxane that has not yet reacted to form oligomers Base aluminum. When aluminoxane is used as a co-catalyst, it can be used in excess relative to the molar ratio of the transition metal, and the molar ratio is 50 or higher, such as 100 or higher, such as 1000 or lower, such as 500 or lower.

Preferably, "metallocene" includes a group 4 metal (Ti, Zr, Hf) and one, two or more ligands, preferably two ligands, which are selected from cyclopentadienyl and Isolobal with cyclopentadienyl; or consists of them. More preferably, the heterogeneous single-site catalyst contains asymmetric metallocene, which means that there is only one cyclopentadienyl ligand; or two cyclopentadienyl groups that are different from each other and/or have different substitution patterns from each other . In any embodiment, the cyclopentadienyl group is selected from the group consisting of indenyl, stilbene, cyclopenta[ b ]naphthyl, cyclopenta[ a ]naphthyl, cyclopenta[ l ]phenanthrene Group, cyclopenta[ b ]anthryl, cyclopenta[ a ]anthryl, indeno[1,2- b ]anthryl, dibenzo[ b,h ] anthryl, benzo[ b ] anthryl, other The hydrogenated form, its substituted form (for example, a group having pendant groups such as alkyl, aryl, halogen or hydroxy and bonded to a cyclopentadienyl group), its heterocyclic form (meaning that it binds a non-carbon atom such as oxygen) , Nitrogen, sulfur, etc.).

When using the above catalysts, the total catalyst system will additionally include one or more organometallic compounds as scavengers. The compound used in this application must include a compound that effectively removes polar impurities from the reaction environment and improves catalyst activity. Impurities can be introduced inadvertently along with any polymerization reaction components, such as solvents, monomers and catalyst feeds, and have an adverse effect on catalyst activity and stability. It can result in reduced or even eliminated catalytic activity, such as when free anion precursors activate the catalyst system. Impurities or catalyst poisons include water, oxygen, polar organic compounds, metal impurities, etc. In at least one embodiment, the poison is removed before being introduced into the reaction vessel, such as by chemical treatment or careful separation techniques after or during the synthesis or preparation of various components, but some trace organometallic compounds will generally still be used for polymerization The program itself. Method of forming copolymer composition

For the purpose of this disclosure, organic peroxides (for example, dihexadecyl peroxydicarbonate) and copolymers (for example, Vistamaxx ^TM propylene elastomer), optionally alkyl radical scavengers, and visual In some cases, the additives are blended or "combined" to coat the copolymer pellets or particles to promote the coupling of the copolymer pellets or particles, for example, to facilitate the crosslinking reaction. As used herein, the reactor pellets of the copolymer and/or the extruded pellets of the copolymer can be used to make the copolymer composition. In at least any aspect, when mixed with organic peroxides, the reactor pellets of the copolymers used herein provide significantly enhanced strain hardening and melt strength results compared to extruded pellets. These copolymers, such as ethylene-propylene copolymer particles, flakes or pellets, can be dry blended with the organic peroxide before being "combined" in the reactive extrusion procedure described below. This can be done in any type of suitable dry blending equipment that can blend the ingredients, such as mixing and/or stirring the ingredients before combining in a reactive extrusion process to enhance contact therebetween. In at least any embodiment, before or simultaneously with the dry blending of the organic peroxide, it can be used in any form (granules or pellets) at a temperature lower than the melting point of the copolymer, for example, at a temperature close to or equal to room temperature. Copolymer. In at least any embodiment, the organic peroxide and ethylene-propylene copolymer are combined at this temperature for 10 seconds to 30 minutes, such as 30 seconds to 10 minutes, such as 30 seconds to 180 seconds, such as 90 seconds, and then as follows The melt extrusion.

In at least any embodiment, the amount of organic peroxide combined with, contacted or "mixed" with the copolymer particles and/or pellets is based on the ratio of the ethylene-propylene copolymer particles and/or pellets and the organic peroxide. The weight is in the range of 0.4% to 2% by weight, such as 0.5% to 1.5% by weight, such as 0.6% to 1.4% by weight, such as 0.8% to 1.2% by weight, such as 0.9% to 1% by weight. In at least any embodiment, the mixing occurs in the presence of an inert gas, for example, in the presence of a stream of nitrogen or argon. In at least any embodiment, the mixing is in a homogenizer and occurs at a rate of at least 50,000 pounds of polymer/hour, such as 60,000 pounds of polymer/hour, such as 80,000 pounds of polymer/hour.

Finally, in this procedure, whether it is any or all of the individual steps, there is the use of cooling equipment or any type of cooling tool. Therefore, the combining and mixing steps can occur below the polymerization temperature, where cooling can be applied during the mixing step to further cool the temperature so that the reaction can occur at or near room temperature.

For manufacturing purposes, the resulting copolymer composition formed by mixing dihexadecyl peroxydicarbonate and a copolymer (such as Vistamaxx ^TM propylene-based elastomer) can be stored in the form of pellets. Alkyl radical scavenger

The polymers and polymer compositions herein may include one or more alkyl radical scavengers. "Alkyl radical scavenger" is a compound or a combination of compounds selected from the group consisting of hydroxylamine, hydroxylamine-containing compound, lactone, lactone-containing compound, chromanol, and chromanol-containing compound , And can react with alkyl radicals to make them neutral (there is no center of radicals). In at least any embodiment, the alkyl radical scavenger is selected from compounds containing 6-chromanol, such as tocopherol and its derivatives (for example, α, β, γ, δ, and C ₁₀ to C ₂₆ side chain).

In at least any embodiment, the alkyl radical scavenger is present in the composition or blend used in the method described herein, and is in the range of 5 ppm to 4000 ppm, such as 20 ppm to 3000 ppm, such as 50 ppm to 2000 ppm, such as 100 ppm to 1000 ppm, such as 125 ppm to 800 ppm, such as 130 ppm to 400 ppm, such as 135 ppm to 200 ppm, such as 140 ppm to 160 ppm.

其中各R¹ 、R² 、R³ 及R⁶ /R'⁶ 係獨立地選自氫及C₁ 至C₁₀ 直鏈烷基或分支烷基，諸如氫及C₁ 至C₅ 直鏈及分支烷基，諸如R¹ 、R² 、R³ 及R⁶ /R'⁶ 係選自氫及甲基；以及各R⁴ 及R⁵ (以及R⁴ '及R⁵ ')係獨立地選自氫及C₁ 至C₃₀ 直鏈或分支烷基；諸如，R⁴ 或R⁵ (以及R⁴ '及R⁵ ')之任一者係獨立地選自C₈ 至C₂₄ 分支烷基，諸如R⁴ 或R⁵ (以及R⁴ '及R⁵ ')之任一者係獨立地選自C₁₀ 至C₂₀ 分支烷基，其中，R⁴ 或R⁵ (以及R⁴ '及R⁵ ')之另一者為氫。例如，各R¹ 、R² 及R³ 可為甲基，而R⁵ 及R⁶ 為氫，且R⁴ 為分支C₁₆ 基，諸如使用α-生育酚之情況。於R⁴ 之立體化學可為手性中心之混合物。In at least any one aspect, the alkyl radical scavenger is selected from compounds containing 6-chromanol. The alkyl radical scavenger can be selected from tocopherols and derivatives thereof (for example, α, β, γ, δ, and C ₁₀ to C ₂₆ side chains). For example, the alkyl radical scavenger can be represented by formula (I):

Wherein each of R ¹ , R ² , R ³ and R ⁶ /R' ⁶ is independently selected from hydrogen and C ₁ to C ₁₀ linear or branched alkyl, such as hydrogen and C ₁ to C ₅ linear and branched Alkyl groups, such as R ¹ , R ² , R ³ and R ⁶ /R' ⁶ are selected from hydrogen and methyl; and each of R ⁴ and R ⁵ (and R ⁴ 'and R ⁵ ') is independently selected from hydrogen And C ₁ to C ₃₀ linear or branched alkyl groups; such as R ⁴ or R ⁵ (and R ⁴ ′ and R ⁵ ′) are independently selected from C ₈ to C ₂₄ branched alkyl groups, such as R ^{Any one of 4} or R ⁵ (and R ⁴ 'and R ⁵ ') is independently selected from C ₁₀ to C ₂₀ branched alkyl, wherein R ⁴ or R ⁵ (and R ⁴ ' and R ⁵ ') are The other is hydrogen. For example, each of R ¹ , R ² and R ³ may be a methyl group, while R ⁵ and R ⁶ are hydrogen, and R ⁴ is a branched C ₁₆ group, such as in the case of using α-tocopherol. The stereochemistry at R ⁴ can be a mixture of chiral centers.

The substitution or branching on the longer R ⁴ and/or R ⁵ can be any alkyl group on at least one carbon along the main carbon chain, such as a methyl group. In at least any embodiment, the alkyl radical scavenger is derived from dl-α-tocopherol and/or its salt and C ₁ to C ₃ (any R ¹ to R ⁴ and/or R ^{6 group)} Things. additive

The copolymer composition of the present disclosure may further include an "additive", which is in the range of 0.01% to 1% by weight based on the weight of the copolymer composition, or 2% by weight, or 3% by weight, or 4% by weight %, or 5% by weight, this additive may include one or more fillers, antioxidants (for example, hindered phenols, such as Irganox ^TM 1010 or Irganox ^TM 1076, available from Ciba-Geigy), phosphites (for example, Irganox ^TM 168 can be obtained from Ciba-Geigy), free radical scavengers such as vitamin E, anti-cling agents, adhesives (such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal And glyceryl stearate, and hydrogenated rosin), UV stabilizer, heat stabilizer, anti-caking agent, release agent, antistatic agent, pigment, colorant, silicon dioxide, titanium dioxide, polydimethylsiloxane , Talc, dye, wax, calcium stearate, carbon black, low molecular weight resin and glass beads, or a combination thereof, and these additives can be present in 0.1 ppm to 1000 ppm. Neutralizers, lubricants, surfactants and/or nucleating agents may also be present. In at least any embodiment, the copolymer composition may include at most 0.5% by weight based on the weight of the composition of one or more antioxidants, or one or more antioxidants and one or more foaming agents.

In at least any embodiment, if a colorant (dye, pigment, brightener, carbon black, etc.) is required as part of the copolymer composition, the colorant can have a peak melting point temperature in the range of 110°C to 140°C. Inner or 145°C or 150°C copolymer granules or pellets are blended. The colorant and the particles/pellets of the copolymer can be blended dry, or blended with other additives such as antioxidants and nucleating agents, and then melt blended in an extruder. For example, suitable copolymers may have a range of 1 g/10 min to 10 g/10 min, such as 1.2 g/10 min to 9 g/10 min, such as 1.4 g/10 min to 8 g/10 min Melt flow rate (ASTM D1238, 230°C, 2.16 kg). The colorant may be present at up to 60 to 90% by weight based on the weight of the colorant and the copolymer composition, which is limited by the ability of the copolymer to retain the colorant and the energy required for kneading/extrusion. Then, the copolymer/colorant concentrate or "masterbatch" (for example, 0.1% to 3% by weight, or 0.1% to 5% by weight) can be combined with the copolymer and the organic peroxide or the resulting composition , In order to produce the coloring form of the desired composition.

One or more conventional additives such as antioxidants can be incorporated into the polymer composition during the final processing process. Possible antioxidants include phenyl-β-naphthylamine; di-tertiary butylhydroquinone, triphenyl phosphate, heptanoate diphenylamine, 2,2'-methylene-bis(4-methyl-6-tris Grade butyl) phenol, and 2,2,4-trimethyl-6-phenyl-1,2-dihydroquinoline, and/or stabilizers, such as tocopherols or lactones, or WO 2009/ Other agents described in 007265.

In at least one aspect of the present invention, the additive is an auxiliary agent that can affect the melt flow rate of the copolymer and/or enhance the degree of modification of the copolymer. Without being bound by theory, adjuvants are generally understood as polyfunctional reactive additives, such as polyunsaturated compounds, which will react rapidly with polymer radicals, will overcome steric hindrance effects, and minimize unwanted side reactions. More information on additives is described in 61 RUBBER CHEMISTRY AND TECHNOLOGY, 238-254 (1988), and W. Hofmann, Progress in 1(2) RUBBER AND PLASTICS TECHNOLOGY, 18-50 (1985).

A variety of suitable additives are commercially available, including di- and triallyl compounds, di- and tri(meth)acrylate compounds, bismaleimide compounds, 1,3-di Isopropene benzene and its oligomers, vinyl toluene, vinyl pyridine, parachinone dioxime, 1,2-cis-polybutadiene and its derivatives. In at least any embodiment, the auxiliary agent includes triallyl cyanurate, triallyl isocyanate, ethylene glycol dimethacrylate, and trimethylolpropane trimethacrylate And other bifunctional agents, such as divinylbenzene, isoprene, or polyisobutylene and other conjugated dienes. Additional examples of bifunctional agents are those having moieties such as hydroxyl, thiol, thioether, and imidinyl groups, including 1,4-benzenediol and sulfurized furfuryl groups. Examples of dienes used as auxiliary agents include, but are not limited to, dicyclopentadiene, 1,3-cyclopentadiene, divinylbenzene, 1,4-hexadiene, 1,4-cyclohexadiene, 1,5-hexadiene, 5-methyl-1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 3,7-dimethyl-1,6-octane Diene, 1,9-decadiene, 1,13-tetradecadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl- 2-Norcampoene, or a combination thereof.

Incorporating an effective amount of one or more of these additives into the copolymer composition can affect the melt flow rate of the copolymer composition and improve the characteristics of strain hardening and long chain branching. Organic peroxide

The copolymer composition of the present disclosure, such as the ethylene-propylene copolymer composition, can be made into granules and/or pellets by mixing the copolymer and organic peroxide. "Copolymer composition" is the product (contact product and/or reaction product) of organic peroxide and copolymer particles or pellets. The copolymers and copolymer compositions described herein are expected to have the same comonomer content as the particles.

"Organic peroxide" is any organic compound that includes at least one -(O)COO- group and/or -OO- group, and can have a low level as determined in aromatic and/or halogenated aromatic solvents. At 100°C, such as lower than 85°C, such as lower than 75°C, such as lower than 65°C, a 1-hour half-life temperature ( ¹ T _1/2 ), such as having a temperature in the range of 25°C to 100°C ( ¹ T _{1 /2} ), such as 35°C to 80°C, such as 45°C to 65°C.

其中，各「R」基團係獨立地選自氫、C₁ 或C₅ 至C₂₄ 或C₃₀ 直鏈烷基、C₁ 或C₅ 至C₂₄ 或C₃₀ 二級烷基、C₁ 或C₅ 至C₂₄ 或C₃₀ 三級烷基、C₇ 至C₃₄ 烷基芳基、C₇ 至C₃₄ 芳基烷基、及其經取代之改型。In at least any embodiment, the organic peroxide is selected from compounds represented by one or more structures selected from (a) and (b):

Wherein, each "R" group is independently selected from hydrogen, C ₁ or C ₅ to C ₂₄ or C ₃₀ linear alkyl, C ₁ or C ₅ to C ₂₄ or C ₃₀ secondary alkyl, C ₁ or C ₅ to C ₂₄ or C ₃₀ tertiary alkyl, C ₇ to C ₃₄ alkyl aryl, C ₇ to C ₃₄ aryl alkyl, and substituted modifications thereof.

In at least any embodiment, the organic peroxide is selected from the structure represented by formula (a). "Substituted" means that the hydrocarbon "R" group has substituents such as halogens, carboxylates, hydroxyl groups, amines, thiols, and phosphorus-containing groups. In at least any embodiment, each "R" group is independently selected from C ₈ to C ₂₀ or C ₂₄ linear, secondary, or tertiary alkyl groups, such as octyl, decyl, lauryl, Myristyl, cetyl, peanut, rolyl, 13-dochenyl and insect wax, and their linear, secondary or tertiary forms. Organic peroxides may include di-secondary butyl peroxydicarbonate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis(4-tertiarybutylcyclohexyl) peroxydicarbonate Ester, dihexadecyl peroxydicarbonate, dibutyl peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, didodecyl peroxydicarbonate, diicosyl peroxydicarbonate , And bis-tetracosyl peroxydicarbonate.

In at least any embodiment, the melting point of the organic peroxide is in the range of 30°C to 75°C, such as 40°C to 65°C, such as 45°C to 55°C. In addition, in at least any embodiment, the solid pure organic peroxide has a bulk density in the range of ^{0.4 g/cm 3} to 0.8 g/cm ^{3 , such as 0.5 g/cm 3} to 0.7 g/cm ³ . In at least any embodiment, the organic peroxide is in the form of solid particles, flakes, particles, powder, or other solid "granular" forms. It can be used in pure form or as a masterbatch with an inert polymer matrix or as a solution with an inert solvent. The size and shape of the organic peroxide can be customized by low-temperature methods, such as granulation or compaction, or other known means.

In at least any embodiment, the amount of organic peroxide combined with, contacted or "mixed" with the copolymer particles and/or pellets is 0.4% to 2% by weight based on the weight of the copolymer composition Within the range, such as 0.5% to 1.8% by weight, such as 0.6% to 1.6% by weight, such as 0.7% to 1.5% by weight, or 1% to 2% by weight.

Solid and liquid peroxydicarbonic acid can be used in the method according to the present disclosure. It is also possible to use a solution of peroxydicarbonate in an inert solvent such as isododecane, or in the form of frozen flakes. In at least any embodiment, the peroxydicarbonate is used as a solid peroxydicarbonate in the form of, for example, flakes, finely divided particles (powder), or as the case may be adsorbed or absorbed by a suitable carrier (such as silica or polycarbonate). Acrylic powder or pellets) liquid peroxydicarbonate is used. The use of solid peroxydicarbonate allows higher storage and processing temperatures. When using a (loss-in-weight) feeder to introduce peroxydicarbonate into the extruder, this higher temperature is beneficial.

-4-CH₂ 、C₂ H₅ CH(Cl)CH₂ 、4-CH₃ O-C₆ H₄ 、i-C₄ H₉ 、CH₃ SO₂ CH₂ CH₂ 、C₁₂ H₂₅ 、C₆ H₅ CH(Cl)CH₂ 、H₂ C=CHC(O)OCH₂ CH₂ 、4-NO₂ -C₆ H₄ 、C₄ H₉ 、C₁₀ H₂₁ 、C₄ H₉ CH(C₂ H₅ )CH₂ 、H₂ C=CHCH₂ 、2-Cl-c-C₆ H₁₀ 、H₂ C=C(CH₃ )CH₂ 、c-C₆ H₁₁ 、ClCH₂ CH₂ 、4-[C₆ H₅ -N=N]-C₆ H₄ CH₂ 、C₁₆ H₃₃ 、1-萘基、4-t-C₄ H₉ -C₆ H₁₀ 、2,4,5-三-Cl-C₆ H₂ 、Cl(CH₂ )₃ 、C₁₄ H₂₉ 、9-茀基、4-NO₂ -C₆ H₄ CH₂ 、2-i-C₃ H₇ -C₆ H₄ 、CH₃ OCH₂ CH₂ 、H₂ C=C(CH₃ )、3-CH₃ -C₆ H₄ 、BrCH₂ CH₂ 、3-CH₃ -5-i-C₃ H₇ -C₆ H₃ Br₃ CCH₂ 、C₂ H₅ OCH₂ CH₂ 、4-CH₃ OC(O)-C₆ H₄ 、H₂ C=CH、i-C₃ H₇ 、2-C₂ H₅ CH(CH₃ )-C₆ H₄ 、Cl₃ CCH₂ 、C₅ H₁₁ 、c-C₁₂ H₂₃ 、4-t-C₄ H₉ -C₆ H₄ 、C₆ H₁₃ 、C₃ H₇ 、CH₃ OCH₂ CH₂ 、C₆ H₁₃ CH(CH₃ )、CH₃ OC(CH₃ )₂ CH₂ CH₂ 、C₃ H₇ OCH₂ CH₂ 、CH₃ OCH₂ CH(CH₃ )、2-i-C₃ H₇ -5-CH₃ -c-C₆ H₉ 、C₄ H₉ OCH₂ CH₂ 、t-C₄ H₉ 、(CH3)₃ CCH₂ ，其中「i」為異，「t」為三級，而「Z」為順。於至少任一實施態樣中，過氧二碳酸酯為過氧二碳酸雙(4-三級丁基環己基)酯、過氧二碳酸雙十六酯、及/或過氧二碳酸肉豆蔻基酯，該等過氧化物於室溫下為固態；以及過氧二碳酸二異丙酯、過氧二碳酸二正丁酯及過氧二碳酸雙(2-乙基己基)酯，彼等於室溫下為液態，為純形式或呈於異十二烷中之溶液。視情況，可使用過氧二碳酸酯與其他過氧化物之組合以影響共聚物之熔體流率及/或增強共聚物之改質程度。待使用之過氧二碳酸酯的品質將取決於所希望的聚合物改質程度及取決於所使用之共聚物(例如，丙烯系彈性體)。Peroxydicarbonate can be represented by the formula R ¹ -OC(O)OOC(O)OR ² , wherein R ¹ and R ² are independently selected from CH ₃ , 2-iC ₃ H ₇ OC ₆ H ₄ , C ₂ H ₅ CH(CH ₃ ), 4-CH ₃ -C ₆ H ₄ , CI ₃ CC(CH ₃ ) ₂ , C ₇ H ₁₅ , C ₆ H ₁₁ CH ₂ , 3-tC ₄ H ₉ -C ₆ H ₅ , Cl ₃ Si(CH ₂ ) ₃ , C ₆ H ₅ , CH ₃ CH(OCH ₃ ) CH ₂ CH ₂ , C ₆ H ₅ OCH ₂ CH ₂ , C ₆ H ₅ CH ₂ , ZC ₈ H ₁₇ CH=CH( CH ₂ ) ₈ , 2-CH ₃ -C ₆ H ₄ , (CH ₃ ) ₂ CHCH ₂ CH(CH ₃ ), 3,4-bis-CH ₃ -C ₆ H ₃ , Cl ₃ C, CHCH(Cl) , ClCH ₂ , [C ₂ H ₅ OC(O)] ₂ CH(CH ₃ ), 3,5-bis-CH ₃ -C ₆ H ₃ , C ₈ H ₁₇ , C ₂ H ₅ , C ₁₈ H ₃₇ , 2-side oxy-1,3-di㗁

-4-CH ₂ , C ₂ H ₅ CH(Cl)CH ₂ , 4-CH ₃ OC ₆ H ₄ , iC ₄ H ₉ , CH ₃ SO ₂ CH ₂ CH ₂ , C ₁₂ H ₂₅ , C ₆ H ₅ CH (Cl)CH ₂ , H ₂ C=CHC(O)OCH ₂ CH ₂ , 4-NO ₂ -C ₆ H ₄ , C ₄ H ₉ , C ₁₀ H ₂₁ , C ₄ H ₉ CH(C ₂ H ₅ ) CH ₂ , H ₂ C=CHCH ₂ , 2-Cl-cC ₆ H ₁₀ , H ₂ C=C(CH ₃ )CH ₂ , cC ₆ H ₁₁ , ClCH ₂ CH ₂ , 4-[C ₆ H ₅ -N =N]-C ₆ H ₄ CH ₂ , C ₁₆ H ₃₃ , 1-naphthyl, 4-tC ₄ H ₉ -C ₆ H ₁₀ , 2,4,5-tri-Cl-C ₆ H ₂ , Cl( CH ₂ ) ₃ , C ₁₄ H ₂₉ , 9-茀基, 4-NO ₂ -C ₆ H ₄ CH ₂ , 2-iC ₃ H ₇ -C ₆ H ₄ , CH ₃ OCH ₂ CH ₂ , H ₂ C= C(CH ₃ ), 3-CH ₃ -C ₆ H ₄ , BrCH ₂ CH ₂ , 3-CH ₃ -5-iC ₃ H ₇ -C ₆ H ₃ Br ₃ CCH ₂ , C ₂ H ₅ OCH ₂ CH ₂ , 4-CH ₃ OC(O)-C ₆ H ₄ , H ₂ C=CH, iC ₃ H ₇ , 2-C ₂ H ₅ CH(CH ₃ )-C ₆ H ₄ , Cl ₃ CCH ₂ , C ₅ H ₁₁ , cC ₁₂ H ₂₃ , 4-tC ₄ H ₉ -C ₆ H ₄ , C ₆ H ₁₃ , C ₃ H ₇ , CH ₃ OCH ₂ CH ₂ , C ₆ H ₁₃ CH(CH ₃ ), CH ₃ OC (CH ₃ ) ₂ CH ₂ CH ₂ , C ₃ H ₇ OCH ₂ CH ₂ , CH ₃ OCH ₂ CH(CH ₃ ), 2-iC ₃ H ₇ -5-CH ₃ -cC ₆ H ₉ , C ₄ H ₉ OCH ₂ CH ₂ , tC ₄ H ₉ , (CH3) ₃ CCH ₂ , where "i" is different, "t" is three levels, and "Z" is cis. In at least any embodiment, the peroxydicarbonate is bis(4-tertiarybutylcyclohexyl) peroxydicarbonate, dihexadecyl peroxydicarbonate, and/or myristyl peroxydicarbonate These peroxides are solid at room temperature; and diisopropyl peroxydicarbonate, di-n-butyl peroxydicarbonate and bis(2-ethylhexyl) peroxydicarbonate, which are equal to It is liquid at room temperature, in pure form or as a solution in isododecane. Optionally, a combination of peroxydicarbonate and other peroxides can be used to affect the melt flow rate of the copolymer and/or enhance the degree of modification of the copolymer. The quality of the peroxydicarbonate to be used will depend on the desired degree of polymer modification and on the copolymer used (for example, propylene elastomer).

In at least any embodiment, the organic peroxide used to form the copolymer composition with enhanced melt strength and strain hardening performance is a low-temperature decomposition peroxide, such as dihexadecyl peroxydicarbonate. Dihexadecyl peroxydicarbonate can be mixed with copolymer particles and/or pellets at room temperature, for example, under an inert atmosphere such as nitrogen. Copolymer composition and foamed objects

The composition of the present disclosure can be used in foaming applications. In the extrusion foaming process, a metering unit is used to inject a foaming agent such as carbon dioxide, nitrogen, or a compound that decomposes to form carbon dioxide or nitrogen into the polymer melt. Then, the foaming agent is dissolved in the polymer in the extruder, and the pressure at all parts of the extruder is maintained. The rapid rate of pressure drop when leaving the extruder produces a foamed polymer with a uniform pore structure. The resulting foamed product can be lightweight, strong, and suitable for a wide range of industrial applications, such as packaging, automobiles, aerospace, transportation, electrical and electronic equipment, and manufacturing.

In at least any embodiment, a metering unit is used to inject physical blowing agents such as inert gases (for example, CO ₂ , N ₂ ) and/or hydrocarbons (for example, butanes, pentanes, etc.) into the polymer Melt. Chemical blowing agents that decompose to form gases such as CO ₂ and N ₂ , such as a blend of citric acid and sodium bicarbonate (Hydrocerol from Clariant) are physically added to the polymer pellets in the extruder. In some embodiments, physical and chemical foaming agents are used together. The chemical blowing agent can be added, for example, in a physical form such as a masterbatch or pellets instead of being metered in as a gas.

The pellets of the copolymer composition obtained by the method of the present disclosure have some characteristics. In at least any embodiment, the copolymer composition pellets have a melt strength (drawing force) of 1 cN to 15 cN, such as 1.02 cN to 12 cN, such as 1.04 cN to 11 cN, such as 1.06 cN to 10.5 cN .

The pellets of the copolymer composition formed from the copolymer particles mixed with the organic peroxide also exhibit strain hardening, as evidenced by the increase in viscosity when the melt is stretched in a rheometer, which is much higher than Copolymer composition pellets formed from copolymer pellets mixed with organic peroxides.

The copolymer composition pellets formed from the copolymer pellets mixed with the organic peroxide exhibit strain hardening, as evidenced by the increase in viscosity when the melt is stretched in a rheometer, as described below, the value varies with the organic peroxide The amount is increased to increase to a viscosity of 4,000 Pa or more, such as 20,000 Pa or more, such as 40,000 Pa or more, such as 45,000 Pa or more, and higher than in the range of ^{1 sec -1} to 10 sec ^-1 The rate of linear viscoelasticity (LVE) range. The extended viscosity range of pellets obtained under these conditions is 4,000 Pa∙s to 45,000 Pa∙s. In at least any embodiment, even when as little as 1% by weight, or 1.5% by weight, or 2% by weight of organic peroxide is mixed with the copolymer composition particles, the pellets can exhibit the above-mentioned strain hardening value.

Copolymer composition pellets formed from copolymer particles mixed with organic peroxides can exhibit greater strain hardening (compared to pellets), as evidenced by the increase in viscosity when the melt is stretched in a rheometer, as shown below As described herein, the value increases as the amount of organic peroxide increases to a viscosity of 5,000 Pa or more, such as 20,000 Pa or more, such as 40,000 Pa or more, such as 50,000 Pa or more, such as 100,000 Pa or more Larger, such as 150,000 Pa or more, such as 300,000 Pa or more, such as 400,000 Pa or more, such as 500,000 Pa or more, such as 600,000 Pa or more, higher than 1 sec ^-1 to 10 sec ^-1 The linear viscoelastic (LVE) range of the rate within the range. The extended viscosity range of pellets obtained under these conditions is 6,000 Pa∙s to 650,000 Pa∙s. In at least any embodiment, even when as little as 1% by weight, or 1.5% by weight, or 2% by weight of organic peroxide is mixed with the particles, the copolymer composition pellets exhibit this strain hardening value.

In addition, it has been found that as the ethylene content of the copolymer increases, the strain hardening of the copolymer composition particles increases. For example, at a draw ratio of 4, compared to a copolymer composition particle formed from a copolymer including an ethylene content of 11% by weight, a copolymer composition formed from a copolymer including an ethylene content of 4% by weight The strain hardening of the particles can be increased by 35%.

The mixing of the copolymer particles and the subsequent melt blending impart specific properties to the resulting copolymer composition and pellets. In at least any embodiment, the copolymer composition pellets formed from the copolymer particles have a branch index (g'vis) of 0.89 to 0.91, wherein the copolymer composition pellets formed from the copolymer pellets have greater than 0.95, such as G'vis value of 0.95 to 1. In addition, in at least any embodiment, the copolymer composition pellets formed from the copolymer pellets have a melt strength (drawing force) of 0.1 cN to 5 cN, such as 0.2 cN to 4.5 cN, such as 0.3 cN to 4 cN. ). In at least any embodiment, the copolymer composition pellets formed from the particles have a melt strength (drawing force) of 0.1 cN to 12 cN, such as 0.2 cN to 11 cN, such as 0.3 cN to 10.5 cN.

In at least any embodiment, the copolymer composition pellets formed from copolymer particles or pellets are 1 g/min to 10 g/10min, such as 1.2 g/10min to 9 g/10min, such as 1.5 g/10min to 8 Melt flow rate of g/10min (MFR, ASTM D1238, condition L, 230°C and 2.16 kg). In at least any embodiment, the copolymer composition pellets formed from the copolymer particles have a lower MFR (higher number and weight average molecular weight) than the copolymer composition pellets formed from the copolymer pellets because the pellets are Reactive extrusion product between particles and organic peroxides. When the amount of organic peroxide used in this method increases, the copolymer exhibiting MFR1 before reacting with the organic peroxide exhibits MFR2 lower than MFR1, when the copolymer is in granular form and when the copolymer has an ethylene content This is especially true when increasing, possibly due to the larger surface area used for the reaction to occur.

In at least any embodiment, the copolymer composition formed from the copolymer particles or pellets has a molecular weight distribution (Mw/ Mn). In at least any embodiment, the copolymer composition formed from the copolymer particles or pellets has 1 to 3, such as 1.2 to 2.8, such as 1.4 to 2.7 Mz _MALLS /Mw _MALLS .

In at least any embodiment, the copolymer is oxide-treated to provide a melt strength in the range of 1 cN to 11 cN, and a branch index (g' _vis ) of 0.978 or lower, as described herein Copolymer of the copolymer composition (in pellet form) with other characteristics mentioned above. In at least any one aspect, the copolymer after the oxide treatment can provide a composition (in pellet form) _{including a cross-linked copolymer, carbon dioxide, and a C 6} to C _{30 alcohol such as cetyl alcohol.} If alcohol is present, the level of alcohol can be 0.01% to 2% by weight based on the weight of the copolymer composition, such as 0.01% to 1% by weight, such as 0.01% to 0.5% by weight.

The copolymer composition (in pellet form) may have a range of 50,000 g/mol to 150,000 g/mol, such as 70,000 g/mol to 135,000 g/mol, such as 95,000 g/mol to The number average molecular weight (Mn) of 120,000 g/mole. In at least any embodiment, the copolymer composition has a range of 100,000 g/mole to 400,000 g/mole, such as 150,000 g/mole to 350,000 g/mole, such as 200,000 g/mole by MALLS analysis. /Mol to 300,000 g/mole weight average molecular weight (Mw _MALLS ) (in pellet form). In at least any one embodiment, the copolymer composition (in pellet form) has a range of 100,000 g/mole to 1,400,000 g/mole, such as 125,000 g/mole to 1,200,000 g/mole by MALLS analysis. , Such as 150,000 g/mole to 1,000,000 g/mole, such as 175,000 g/mole to 900,000 g/mole, such as 200,000 g/mole to 800,000 g/mole, such as 290,000 g/mole to 770,000 g/mole Mole's z average molecular weight (Mz _MALLS ).

As an indicator of high molecular weight component or "tail", the copolymer composition (in pellet form) may have 1 to 6, such as 1 to 5, such as 1 to 4, such as 1.2 to 3.5, such as 1.4 to 3 Mz _MALLS /Mw _MALLS value. _{In addition, the copolymer composition may have a Mz MALLS} /Mn _MALLS value in the range of 1 to 10, such as 1.5 to 8, such as 2 to 6. _{In at least any embodiment, the copolymer composition has a Mw MALLS} /Mn _MALLS (MWD _MALLS ) value in the range of 1 to 5, such as 1.2 to 4, such as 1.4 to 3, such as 1.6 to 2.5.

In at least any embodiment, the copolymer composition (in pellet form) has a strain rate of 0.01/sec (190°C) from 1×10 ³ Pa∙s to 1×10 ⁷ Pa∙s, such as 1× 10 ⁴ Pa∙s to 1×10 ⁶ Pa∙s peak extension viscosity.

The pellets of the copolymer composition thus manufactured can form useful objects. For example, the foamed article may be formed from copolymers and/or additives (eg, fillers, antioxidants, alkyl radical scavengers, etc.). Suitable blowing agents used in forming the foamed articles described herein may include generally gaseous, liquid, solid compounds or elements, or mixtures thereof. The characteristics of these foaming agents can be physical expansion or chemical decomposition. In the physical expansion foaming agent, the term "generally gaseous" is intended to mean that the expansion medium used is a gas at the temperature and pressure encountered during the preparation of the foamable compound, and the medium can be gaseous or gaseous for convenience. Liquid introduction. The foaming agent can be added to the copolymer composition by blending a dry polymer with a foaming agent and then melt-extrusion, or by blending the foaming agent in the polymer melt during extrusion. The blowing agent, especially the gaseous blowing agent, can be blended with the polymer melt when the polymer melt leaves the melt extruder or the mold used to form the foamed object (such as the copolymer composition pellet). The concentration of the blowing agent contained in the copolymer composition may be in the range of 100 ppm to 5000 ppm, such as 200 ppm to 4000 ppm, such as 300 ppm to 3000 ppm, such as 400 ppm to 2000 ppm, such as 500 ppm to 1000 ppm .

Included in the exemplary generally gaseous and liquid blowing agents are halogen derivatives of methane and ethane, such as fluoromethane, chloromethane, difluoromethane, dichloromethane, perfluoromethane, trichloromethane, and difluoromethane. Monochloromethane, dichlorofluoromethane, dichlorodifluoromethane, trifluorochloromethane, trichlorofluoromethane, fluoroethane, chloroethane, 2,2,2-trifluoro-1,1-two Chloroethane, 1,1,1-trichloroethane, difluoro-tetrachloroethane, 1,1-dichloro-1-fluoroethane, 1,1-difluoro-1-chloroethane, two Chlorine-tetrafluoroethane, chlorotrifluoroethane, trichlorotrifluoroethane, 1-chloro-1,2,2,2-tetrafluoroethane, 1,1-difluoroethane, 1,1, 1-trifluoroethane, 1,1,1,2-tetrafluoroethane, perfluoroethane, pentafluoroethane, 2,2-difluoropropane, 1,1,1-trifluoropropane, perfluoroethane Propane, dichloropropane, difluoropropane, chloroheptafluoropropane, dichlorohexafluoropropane, perfluorobutane, perfluorocyclobutane, sulfur hexafluoride, and mixtures thereof. The other generally gaseous and liquid blowing agents that can be used are hydrocarbons and other organic compounds, such as acetylene, ammonia, butadiene, butane, butene, isobutane, isobutene, dimethylamine, propane, dimethyl Propane, ethane, ethylamine, methane, methylamine, trimethylamine, pentane, cyclopentane, hexane, propane, propylene, alcohols, ethers, ketones, etc. Inert gases and compounds, such as nitrogen, argon, neon or helium, can also be used as blowing agents.

A solid chemical blowing agent that can be decomposed at high temperature to form a gas can be used to expand the copolymer composition. Generally, the decomposable blowing agent will have a decomposition temperature of 130°C to 350°C, such as 200°C to 300°C (resulting in the release of gaseous material). Exemplary chemical blowing agents include azodicarbamide, p,p'-oxybis(phenyl)sulfonyl hydrazine, p-toluenesulfonyl hydrazine, p-toluenesulfonyl semicarbazide, 5-phenyl tetrakis Azole, ethyl-5-phenyltetrazole, dinitrosopentyltetramine, and other azo, N-nitroso, carbonate and sulfonamide compounds, and various acids/carbonic acids that decompose when heated Hydrogen salt compound. Representative volatile liquid blowing agents include isobutane, difluoroethane, or a blend of the two. For the decomposable solid foaming agent, azodimethamide can be used, and for the inert gas, carbon dioxide can be used.

In addition, a method of manufacturing a foam structure from pellets of the copolymer composition can be used to form a foamed object. The foamed object (made from the pellets of the copolymer composition) of the present disclosure can take any physical structure, such as sheet, plate, other regular or irregular extruded profiles, and regular or irregular molded bulk materials. Examples of other usable forms of foamed or expandable objects include expandable or expandable particles, moldable foam particles, or beads, and formed by the expansion and/or consolidation and melting of such particles Objects. In at least any embodiment, the foamable object can be cross-linked before expansion, such as free radical-induced chemical cross-linking or ionizing radiation, or after expansion. If necessary, by exposing to a chemical crosslinking agent or radiation, or when using a silane graft polymer, exposing to moisture and optionally using a suitable silanolysis catalyst, crosslinking after expansion can be carried out.

The copolymer composition pellets disclosed herein can be used to produce foamed structures with any suitable density, for example, the density value can be in the range of 0.1 g/cm ³ to 0.6 g/cm ³ . For specific applications involving higher density, such as structural components or automotive components, the lower melt strength copolymers can be used alone or blended with higher melt strength copolymers to obtain a structure that can be formed at 0.4 g/cm A copolymer composition with a foam density in the range of ³ to 0.5 g/cm ^3. For lower foam density applications, such as food containers, the higher melt strength copolymer composition described herein can be used alone or can also be blended to adjust the foam density to, for example, 0.1 g/cm ³ The density of the foam to 0.3 g/cm ^3. Thus, for example, copolymer particles can be blended with copolymer composition pellets to produce any desired foam density for a particular end use.

Methods of combining various components of the foamable copolymer composition include but are not limited to melt blending, diffusion-limited swelling, liquid mixing, etc., as appropriate, pre-pulverization of any or all of the components or other particle size reduction. Melt blending can be done in batch or continuous methods, and can be performed under temperature control. In addition, many devices suitable for melt blending can be used, including those with single and multiple Archimedean-screw conveying barrels, high-shear "Banbury" type mixers, and others Internal mixer. The purpose of this blending or mixing is to provide a homogeneous mixture. One or more components can be introduced in a stepwise manner, later during an existing mixing operation, during a subsequent mixing operation, or in the case of an extruder, at one or more downstream locations of the barrel.

The pellets of expandable or foamable copolymer composition will incorporate a blowing agent, such as a chemical blowing agent that can be decomposed or physically expanded, to allow the composition to be exposed to heat and, as the case may be, appropriate conditions for sudden release of pressure , Swell in the mold. The copolymer composition can be used as a foaming object for many purposes, including as automotive components, insulation and other building components, food containers, sports equipment, and other household and commercial uses.

The pellets of the copolymer composition can also be thermoformed to make usable thermoformed articles. The copolymer composition described herein is desirably formed into a film or sheet suitable for thermoforming procedures. Thermoforming is a manufacturing method in which the copolymer composition is formed into a film and heated to a bendable forming temperature, formed into a special shape in a mold, and trimmed to produce a usable product. When referring to thinner specifications and specific material types, the film or "sheet" is heated in an oven to a temperature high enough to allow stretching into or on the mold, and then cooled to its final shape. Its simplified version is vacuum forming.

In at least any embodiment, a small tabletop or laboratory size machine is used to heat the small cut part of the copolymer composition sheet, and a vacuum is used to stretch it on the mold. This method is often used for samples or prototype parts. In complex and large-volume applications, a very large manufacturing machine can be used to heat and shape the copolymer composition sheet, and to trim the formed parts from the sheet in a continuous high-speed process. The copolymer composition described herein can be suitable for both types of thermoforming.

An ideal type of thermoforming is thin gauge thermoforming. Thin gauge thermoforming mainly manufactures disposable cups, containers, lids, plates, blister, clamshell and other products used in food, medical, and general retail industries. Thick gauge thermoforming includes various parts, such as carrier doors and dashboards, refrigerator linings, multi-function carrier beds, and plastic pallets. Heavy-gauge molding uses the same basic procedure as continuous thin-gauge sheet molding, thereby covering the mold with the heated copolymer composition. Many heavy gauge forming applications use only vacuum in the forming process, but some processes use two halves of the forming tool and include air pressure to aid forming.

In at least any embodiment, the sheet comprising the copolymer composition is fed from a roll or from an extruder to a set of indexing chains that transport the sheet through an oven for heating to the forming temperature. The heated sheet is then indexed to the forming station, where the matching mold and pressure box are closed on the sheet, and then a vacuum is applied to remove trapped air and the material is pulled into or on the mold with the pressurized air to make The copolymer composition forms the detailed shape of the mold. In the case of higher and deeper drawing forming parts, in addition to vacuum, a pressure-assisted plug can be used to provide the required material distribution and thickness in the final part. In any case, after a short period of time, when the forming tool is opened and the vacuum is broken, a sudden reverse air pressure can be initiated from the vacuum side of the mold, and the forming part can be separated or removed from the mold. The stripper plate can also be used on the mold when the mold is opened to discharge more detailed parts or has a negative draft or mold cavity area. The shaped parts formed from the copolymer composition film are then indexed to a finishing station, where the die system cuts the parts from the remaining webs, or indexed to an independent finishing press, where the shaped parts are finished. The web left after trimming the shaped parts can be wound to a take-up turntable or fed to a pelletizer on the production line for recycling.

The copolymer composition produced by the method disclosed herein can be used to produce many thermoformed objects, such as automobile components, construction components, electronic devices, medical equipment, sports equipment, food containers, appliances, and other household and commercial uses. Similarly, the copolymer composition can be used as a thermoformed article made from injection molding, blow molding, and rotational molding methods. Example

Melt flow rate . The total melt flow rate (MFR) is measured using ASTM D1238 at 230°C with a load of 2.16 kg. The measurement was performed using an ethylene-propylene copolymer with the following additives.

其中K_DRI 為藉由校正DRI所測定之常數，及(dn/dc)為系統之增量折射率。TCB於145℃且λ為690 nm下之折射率「n」為1.500。分子量之單位以kg/mol或g/mol表達，而固有黏度以dL/g表達。Branch index and molecular weight determination . The branch index and molecular weight are determined by using three production line detectors, differential refractive index detector ("DRI"), light scattering ("LS") detector, and viscosity It is measured by high temperature GPC (Agilent PL-220). Detector calibration is described in the paper by T. Sun, P. Brant, RR Chance, and WW Graessley in 34(19) MACROMOLECULES, 6812-6820 (2001) and references in it. Three Agilent PLgel 10 µm Mixed-B LS columns were used for the GPC test in this article. The nominal flow rate is 0.5 mL/min, and the nominal injection volume is 300 µL. Various transfer lines, tubing strings, viscometers and differential refractometers (DRI detectors) are contained in an oven maintained at 145°C. The solvent for this experiment was prepared by dissolving 6 grams of dibutyl hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4 trichlorobenzene (TCB). Then, the TCB mixture is filtered through a 0.1 µm polytetrafluoroethylene filter. Then the TCB system uses an on-line deaerator to degas before entering the GPC. The polymer solution was prepared by placing the dried polymer in a glass container, adding the required amount of TCB, and then heating the mixture at a temperature of 160° C. for 2 hours under continuous shaking. All quantities are measured gravimetrically. The density of TCB used to express polymer concentration in mass/volume units is 1.463 g/ml at 23°C and 1.284 g/ml at 145°C. The injection concentration is 0.5 mg/ml to 2.0 mg/ml, and the lower concentration is used for higher molecular weight samples. Before operating each sample, flush the DRI detector and viscometer. Then the flow rate in the column was increased to 0.5 ml/min, and the DRI was allowed to settle for 8 hours before injecting the first sample. Turn on the LS laser for at least 1 to 1.5 hours before handling the sample. The concentration c of each point in the chromatogram is calculated by _{subtracting the baseline DRI signal I DRI using the following equation:}

Where K _DRI is the constant determined by correcting DRI, and (dn/dc) is the incremental refractive index of the system. The refractive index "n" of TCB at 145°C and λ of 690 nm is 1.500. The unit of molecular weight is expressed in kg/mol or g/mol, and the intrinsic viscosity is expressed in dL/g.

。The LS detector is Wyatt Technology High Temperature Dawn Heleos. The molecular weight M at each point in the chromatogram was determined by analyzing the output of LS using the Zimm model of static light scattering (W. Burchard & W. Ritchering, "Dynamic Light Scattering from Polymer Solutions," in 80 PROGRESS IN COLLOID & POLYMER SCIENCE, 151-163 (Steinkopff, 1989)) and use the following equation to determine:

.

其中N_A 為亞佛加厥數(Avogadro's number)，而(dn/dc)為系統之增量折射率，其值與從DRI方法獲得之值相同，且「n」值如前文。測量分子量中的誤差提供± 5%之Mn、Mw及Mz值。Here, ΔR(θ) is the excessive Rayleigh scattering intensity measured at the scattering angle θ, “c” is the polymer concentration measured from DRI analysis, A ₂ is the second average work coefficient, P(θ ) Is the shape factor of the monodisperse random loop, and K _o is the optical constant of the system, as shown in the following equation:

Where N _A is the Avogadro's number, and (dn/dc) is the incremental refractive index of the system. Its value is the same as the value obtained from the DRI method, and the "n" value is the same as above. The error in measuring the molecular weight provides Mn, Mw and Mz values of ± 5%.

其中「c」為濃度且係從DRI輸出測定。樣本之平均固有黏度[η]_avg 係使用下示方程式計算：

其中在層析切片(chromatographic slice)(即，介於積分極限(integration limit)之間)上求和。就資料處理而言，使用之馬克-豪溫克常數(Mark-Houwink constant)為K=0.000579且a= 0.695。A high-temperature Viscotek Corporation viscometer with four capillaries arranged in a Wheatstone bridge structure and two pressure transducers was used to determine the specific viscosity and branching. One converter measures the total voltage drop across the detector, and another converter located between the two sides of the bridge measures the differential pressure. The specific viscosity (ηs) of the solution flowing through the viscometer is calculated from its output. The intrinsic viscosity [η] of each point in the chromatogram is calculated from the following equation:

Where "c" is the concentration and is measured from the DRI output. The average intrinsic viscosity [η] _avg of the sample is calculated using the following equation:

Among them, the sum is over the chromatographic slice (ie, between the integration limit). In terms of data processing, the Mark-Houwink constant used is K=0.000579 and a= 0.695.

。The branching index (g'vis or g'for short) is defined as the ratio of the inherent viscosity of the branched polymer to the inherent viscosity of the linear polymer of the same molecular weight and the same composition. The branch index g'coefficient is scientifically defined as:

.

The inherent viscosity of linear polymers of equal molecular weight and the same composition is calculated using the Mark-Houwink equation. For the purpose of the present disclosure and the scope of the patent application, the linear polyethylene homopolymer has α = 0.695 and k = 0.000579. Linear polyethylene homopolymers are used for g'calculations regardless of comonomer content. M _v is the viscosity-average molecular weight of the molecular weight determined by LS analysis.

SAOS and shear viscosity reduction The small angle oscillation spectroscopy (SAOS) method is used to measure the shear rheology and shear viscosity reduction of copolymer composition samples. The polymer sample was prepared using a hot press (Carver Pres or Wabash Press) to make a disc with a diameter of 25 mm and a thickness of 2.5 mm. In order to express the characteristics of shear viscosity reduction performance, a rheometer ARES-G2B (TA Instruments) was used to perform small-angle oscillating shear measurement at a temperature of 190°C and a fixed strain of 10% at an angular frequency of 0.01 to 500 rad/s. The data is then converted into a viscosity that changes with the shear rate. In order to ensure that the selected strain provides measurement results within the linear range, a strain sweep measurement (at an angular frequency of 100 Hz) has been performed. The data is processed using Trios software.

Extensional rheology and strain hardening . In order to express the characteristics of the strain hardening performance of polypropylene, use Anton-Paar MCR 501, use SER Universal Testing Platform (Xpansion Instruments, LLC), model SER2-P to test samples. MCR 501 is a rheometer with single-head stress controlled. The sample was prepared using the above-mentioned process (SAOS) and later cut into a rectangle with a size of approximately 18 mm long and 12.7 mm wide. The measurement was performed at a temperature of 190°C with Henky strain rates of ^{1, 5, and 10 s -1.} In addition to the extended test, the samples are also tested under transient stable shear conditions and matched with the extended data using a correlation factor of three. This provides linear viscoelastic range (LVE). The data is processed using Trios software.

Sample preparation . At room temperature and under an inert atmosphere, add 0% to 2% by weight of dihexadecyl peroxydicarbonate to contain the propylene-ethylene copolymer and other additives in the form of pure granules or pure pellets. Solvent-free container. The mixture is sent to a ZSK 30 mm twin screw extruder with underwater strand cutting.

Test temperature . The temperature for elongational viscosity study is set to 190°C for the copolymer composition test. As for the Hencky strain rate during extension, it operates ^{at 1.0 s -1} , 5.0 s ^-1 and 10.0 s ^-1.

Melt strength . The method used to measure melt strength using the Rheotester 1000 capillary rheometer in combination with Rheotens 71.97 (Göttfert) is described in the established test method RHE04-3.3 ("Melting Polymer Tensile Viscosity Measurement").

a) Test conditions: The conditions for using Rheotens 71.97 in combination with Rheotester 1000 to test the melt strength/extension viscosity are described in RHEO4-3.3: 1. Rheotester 1000: • Temperature: 190℃ • Die: 30/2 • Piston speed: 0.5 mm /s • Shear rate: 72 sec ^-1 2. Strand: • Length: 122 mm • Vo: 18 mm/s 3. Rheotens: • Gap: 0.7 mm • Guide wheel: grooved • Acceleration: 12.0 mm/ s ² b) Test: For each material, several measurements are performed. In fact, all the material in the barrel of Rheotester is extruded through the die and picked up by the drum of Rheotens. Once the strand is placed between the rollers, adjust the roller speed until the measured force is "zero". The initial speed "Vs" is the speed at which the strand passes through the clamping between the guide wheels at the beginning of the test.

Once the test is started, the speed of the drum is increased at an ^{acceleration of 12.0 mm/s 2} and the force at each given speed is measured. After each strand breaks or the strands slip between the rotors, stop the measurement and put the material back between the rollers for a new round of measurement. Record the new curve. Continue to measure until all the materials in the barrel are used. c) Data processing: After the test, save all the obtained curves. Disable inappropriate curves. The remaining curve is cut at the same point of fracture or slippage (maximum force measured) and used to calculate the average curve. Report the numerical data of the calculated average curve.

Figure 1 is a graph showing the melt flow rate (MFR) data of the composition. Table 1 shows the different copolymers used in the MFR study and the ethylene content of each copolymer. The initial MFR of the copolymer is about 8 g/10 min (2.16 kg, 230°C). In Figure 1, the sample labeled "G" has a base polymer in a granular form. The samples without "G" are in the form of pellets. At room temperature, make Vistamaxx ^TM 3588 acrylic elastomer ("V3588"), Vistamaxx ^TM 3980 acrylic elastomer ("V3980"), and Vistamaxx ^TM 3000 acrylic elastomer ("V3000") particles or pellets and 1% by weight, 1.5% by weight, and 2% by weight of dihexadecyl peroxydicarbonate were mixed. ^{The Vistamaxx TM} 3588, Vistamaxx ^TM 3980, and Vistamaxx ^TM 3000 propylene-based elastomers each in the form of granules and pellets maintain an initial MFR of 8 g/10 min before the reaction. After mixing with dihexadecyl peroxydicarbonate, an overall decrease in all MFR occurs. MFR decreases significantly depending on the following factors: a) the amount of dihexadecyl peroxydicarbonate added; b) if dihexadecyl peroxydicarbonate is added to the copolymer in pellet or granular form; c) if Vistamaxx ^TM propylene elastomer has a high ethylene content. Compared to the corresponding pellet form of the copolymer, the copolymer particles are indeed the most effective. This may be due to the larger surface area used to react with the peroxide. For example, when V3588 pellets are mixed with 1.5% by weight of dihexadecyl peroxydicarbonate, the MFR decreases from 8 g/10min to 6.5 g/10min. When V3588 particles ("G_V3588") are mixed under the same conditions, the MFR even drops to 3.5 g/10min. V3980 pellets mixed with 1.5% dihexadecyl peroxydicarbonate (MFR value 6.2 g/10min) and V3980 granules mixed with 1.5% dihexadecyl peroxydicarbonate ("G_V3980") (MFR value 3.1 g/10min) The same trend was observed. When V3000 particles ("G_V3000") with the highest ethylene content of 11% by weight are mixed with 1.5% by weight of dihexadecyl peroxydicarbonate, the lowest MFR value of 1.5 g/10min is obtained. The higher the ethylene content of the copolymer, the lower the MFR value. Without being bound by theory, in addition to the crosslinking of the copolymer with the existing free radicals during the reaction, it is generally believed that the MFR value is reduced due to the presence of ethylene in the copolymer backbone.

In addition to the decrease in MFR with higher ethylene content, an increase in the strain hardening performance and melt strength of the copolymer was also observed. These two characteristics are generally beneficial to foam applications.

Fig. 2 is a graph showing the extensional viscosity line graph of the drawing force (melt strength) of the composition as a function of the stretching ratio. (Please note: The melt strength measurement of V3588 at 190°C without any dihexadecyl peroxydicarbonate has not been obtained). Balanced melt strength copolymer particles, such as G_V3588, G_V3980, and G_V3000 mixed with 1.5% by weight of dihexadecyl peroxydicarbonate, have the highest melt strength and stretch ratio (an indication of elongation flow capacity), as shown in Figure 2 Shown. Experimental results also show that copolymer particles with higher ethylene content provide products with higher melt strength.

Figure 3 is a graph showing the elongational viscosity (Pa∙s) of a composition formed from small pellets of Vistamaxx ^TM 3588 and 0% by weight of dihexadecyl peroxydicarbonate at 190°C under three shear rates (Pa∙s) versus time (sec ) The graph of change.

Figure 4 is a graph showing the elongational viscosity (Pa∙s) of the composition formed from the pellets of Vistamaxx ^{TM 3588 and 1% by weight of dihexadecyl peroxydicarbonate at 190°C and three shear rates.} Graph of change over time (sec). The obtained pellets of the copolymer composition exhibited elongational viscosity values ranging from 4,000 Pa∙s to 45,000 Pa∙s.

Figure 5 is a graph showing the elongational viscosity (Pa∙s) of a composition formed from the pellets of Vistamaxx ^{TM 3588 and 2% by weight of dihexadecyl peroxydicarbonate at 190°C and three shear rates.} Graph of change over time (sec). The obtained pellets of the LCB copolymer composition exhibited an elongational viscosity value of 5,000 Pa∙s to 40,000 Pa∙s.

When the V3588 pellets are in their original state, they exhibit an extended viscosity value of 4,000 Pa∙s to 10,000 Pa∙s. According to the results obtained with V3588 in the form of pellets, an increase in the amount of organic peroxide triggers an increase in elongational viscosity (Figures 3 to 5).

Fig. 6 is a graph showing ^{the elongational viscosity (Pa∙s) of a composition formed from Vistamaxx TM} 3588 in granules and 1.5% by weight of dihexadecyl peroxydicarbonate at 190°C and three shear rates over time (sec ) The graph of change. The obtained pellets of the copolymer composition exhibit an elongational viscosity value of 6,000 Pa∙s to 100,000 Pa∙s.

Fig. 7 is a graph showing ^{the elongational viscosity (Pa∙s) of a composition formed from Vistamaxx TM} 3980 in granules and 1.5% by weight of dihexadecyl peroxydicarbonate at 190°C and three shear rates over time (sec ) The graph of change. The resulting pellets of the copolymer composition exhibited an elongation viscosity value ranging from 5,000 Pa∙s to 220,000 Pa∙s.

Figure 8 is a graph showing ^{the elongational viscosity (Pa∙s) of a composition formed from Vistamaxx TM} 3000 in granules and 1.5% by weight of dihexadecyl peroxydicarbonate at 190°C and three shear rates over time (sec ) The graph of change. The obtained pellets of the copolymer composition exhibited an elongation viscosity value ranging from 8,000 Pa∙s to 600,000 Pa∙s. This high level of strain hardening means that chain branching and crosslinking occur.

In addition, according to the results obtained in the form of particles of V3588, V3980, and V3000 with a fixed amount of dihexadecyl peroxydicarbonate (1.5% by weight) (Figures 6 to 8), the elongational viscosity value is increased to higher than linear viscoelasticity (LVE) curve.

Table 2 summarizes the operating conditions, instruments and polymer parameters of different compositions formed under the following conditions (conditions 1 to 5) (as an ethylene-propylene copolymer analysis with 96% by weight of comonomer): • Condition 1 (Composition 1): Vistamaxx ^TM 3588 (V3588) in pellets and 0 wt% dihexadecyl peroxydicarbonate. • Condition 2 (Composition 2): Vistamaxx ^TM 3588 (V3588) in pellets and 1.0% by weight dihexadecyl peroxydicarbonate. • Condition 3 (Composition 3): Vistamaxx ^TM 3588 (V3588) in pellets and 1.5% by weight dihexadecyl peroxydicarbonate. • Condition 4 (Composition 4): Vistamaxx ^TM 3588 (V3588) in pellets and 2.0% by weight of dihexadecyl peroxydicarbonate. • Condition 5 (Composition 5): Vistamaxx ^TM 3588 (G_V3588) in granules and 1.5% by weight dihexadecyl peroxydicarbonate.

Table 3 illustrates the comparison results obtained from the multi-angle light scattering (MALLS) 3D-GPC (DRI) intrinsic viscosity study of different compositions formed under the above-mentioned conditions (conditions 1 to 5).

Table 4 illustrates the formation from the above conditions (conditions 1 to 5) The comparison results obtained by the differential refractor [GPC(DRI)] of different compositions.

As shown in Tables 3 and 4, under condition 1, composition 1 (V3588 pellets) has Mw _MALLS of 203,146g/mol, PDI of 2.17, Mz _MALLS /Mw _MALLS of 1.46, and Mn _DRI of 103,508g/mol, Mz _MALLS /Mn _MALLS is 2.52, Mw _MALLS /Mn _MALLS (MWD _MALLS ) is 1.72, [η] is 1.269 dL/g, and g'vis is 1.00. The increased concentration of dihexadecyl peroxydicarbonate treatment and ^{the ethylene content of Vistamaxx TM} (especially in the form of granules) induce the molecular weight of the resulting copolymer composition pellets to increase and g'vis decrease, which is similar to that shown in Figure 10 to Figure 13 shows the same situation where there are higher branches. Treating V3588 pellets with 1.0% by weight dihexadecyl peroxydicarbonate (condition 2) provides a copolymer composition with the following properties: MW _MALLS is 229,704g/mol, PDI is 2.35, Mz _MALLS /Mw _MALLS is 1.79, Mn _DRI is 96,068 g/mol, Mz _MALLS /Mn _MALLS is 3.58, Mw _MALLS /Mn _MALLS (MWD _MALLS ) is 2.00, [η] is 1.331 dL/g, and g'vis is 0.978. Under condition 3, the V3588 pellets were treated with 1.5% by weight of dihexadecyl peroxydicarbonate to provide a copolymer composition with the following properties: Mw _MALLS was 220,832 g/mol, PDI was 2.08, and Mz _MALLS /Mw _MALLS was 1.65 , Mn _DRI is 108,177g/mol, Mz _MALLS /Mn _MALLS is 3.11, Mw _MALLS /Mn _MALLS (MWD _MALLS ) is 1.88, [η] is 1.285dL/g, and g'vis is 0.973. Treating V3588 pellets with 2.0% by weight dihexadecyl peroxydicarbonate (condition 4) provides a copolymer composition with the following properties: Mw _MALLS is 224,880g/mol, PDI is 2.09, Mz _MALLS /Mw _MALLS is 1.57, Mn _DRI is 116,596 g/mol, Mz _MALLS /Mn _MALLS is 2.87, Mw _MALLS /Mn _MALLS (MWD _MALLS ) is 1.83, [η] is 1.286 dL/g, and g'vis is 0.951. In addition, under condition 5, the V3588 particles "G_V3588" are treated with 1.5% by weight of dihexadecyl peroxydicarbonate to provide a copolymer composition with the following properties: Mw _MALLS is 292,712 g/mol, PDI is 2.36, and Mz _MALLS /Mw _MALLS is 2.61, Mn _DRI is 117,448 g/mol, Mz _MALLS /Mn _MALLS is 5.84, Mw _MALLS /Mn _MALLS (MWD _MALLS ) is 2.24, [η] is 1.401 dL/g, and g'vis is 0.894.

Table 5 illustrates the comparison results obtained from the normalized DRI, LS and viscometer chromatograms of different compositions formed under the above-mentioned conditions (conditions 1 to 5) as a function of the retention volume (ml).

FIG. 9A is a graph showing the recording curve of multi-angle light scattering (MALLS) 3D-GPC (DRI) inherent viscosity of a composition formed ^{from Vistamaxx Tm 3588 in the form of pellets and 0% by weight of dihexadecyl peroxydicarbonate.} FIG. 9B is a graph showing the normalized DRI, LS and viscometer chromatograms of the composition formed ^{from Vistamaxx TM 3588 in pellets and 0% by weight of dihexadecyl peroxydicarbonate as a function of retention volume (ml).} Figure 9C ^{is a diagram illustrating the gel permeation chromatography of the composition formed from Vistamaxx TM} 3588 in the form of pellets and 0% by weight of dihexadecyl peroxydicarbonate using a differential refractometer [GPC(DRI)] recording curve Figure.

FIG. 10A is a graph illustrating the MALLS 3D-GPC (DRI) inherent viscosity recording curve of a composition formed ^{from Vistamaxx TM} 3588 in the form of pellets and 1.0% by weight of dihexadecyl peroxydicarbonate. Figure 10B is a graph showing the normalized DRI, LS and viscometer chromatograms of the composition formed ^{from Vistamaxx TM 3588 in pellets and 1.0% by weight of dihexadecyl peroxydicarbonate as a function of retention volume (ml).} Figure 10C ^{is a diagram illustrating the gel permeation chromatography of the composition formed from Vistamaxx TM} 3588 in the form of pellets and 1.0% by weight of dihexadecyl peroxydicarbonate using a differential refractometer [GPC(DRI)] recording curve Figure.

FIG. 11 is a graph illustrating the MALLS 3D-GPC (DRI) inherent viscosity recording curve of a composition formed ^{from Vistamaxx TM} 3588 in the form of pellets and 1.5% by weight of dihexadecyl peroxydicarbonate.

FIG. 12 is a graph showing the MALLS 3D-GPC (DRI) inherent viscosity recording curve of a composition formed ^{from Vistamaxx TM} 3588 in the form of pellets and 2.0% by weight of dihexadecyl peroxydicarbonate.

FIG. 13 is a graph illustrating the MALLS 3D-GPC (DRI) inherent viscosity recording curve of a composition formed ^{from Vistamaxx TM} 3588 in the form of particles and 1.5% by weight of dihexadecyl peroxydicarbonate.

Fig. 14 is a graph comparing the complex viscosity (Pa∙s) of the composition and the composition formed ^{from Vistamaxx TM in the form of pellets or granules at various amounts of dihexadecyl peroxydicarbonate (190°C) with shaking shear} Graph of angular frequency change in rheological measurement. The viscosity curve obtained from the oscillating shear rheological test performed at 190°C is consistent with the MFR observation. ^{Vistamaxx TM} 3980 particles extruded at 190°C with 1.5% by weight of dihexadecyl peroxydicarbonate have the highest, steepest and longest complex viscosity curve, indicating the greatest shear viscosity reduction of the tested sample. According to the results obtained in this study, when the particles are mixed with the organic peroxide and when compared with the pellets, and when the ethylene content of the copolymer is higher than the comparative copolymer with a lower ethylene content, the shear viscosity reduction effect seems to be better. Strong. When longer chain branches appear, the angular frequency decreases and the shear viscosity reduction increases.

Overall, the polymer composition and method of the present disclosure provide a polymer composition with high melt strength and strain hardening suitable for forming commercially viable foamed objects.

As it is related to the method, the term "essentially composed of" means that there are no other method characteristics, solvents, temperature that change the claimed properties of polymers, polymer blends or objects made from them by more than 10, 15 or 20% Change, or mechanical operation, but may have other method characteristics that are not specified.

Based on the full jurisdiction of the application of the doctrine of "incorporated by reference", all test methods, patent applications, patents and references are incorporated in their entirety or in the form of citation in the relevant part of their citation.

Although this disclosure has described many implementation aspects and embodiments, under the benefit of this disclosure, those familiar with the art will understand other implementation aspects that do not violate the scope and spirit of this disclosure.

[ Fig. 1 ] is a graph showing melt flow rate (MFR) data of a composition according to any embodiment.

[ FIG. 2 ] is a graph illustrating the extension viscosity line graph of the drawing force (melt strength) of the composition according to any embodiment as a function of the draw ratio.

[ Figure 3 ] is a diagram showing a ^{composition formed from a pellet of Vistamaxx TM} 3588 propylene-based elastomer and 0 wt% dihexadecyl peroxydicarbonate at 190°C and at three shear rates according to any embodiment. Below is the graph of elongation viscosity (Pa∙s) versus time (sec).

[ Figure 4 ] is a diagram showing a ^{composition formed from Vistamaxx TM} 3588 propylene-based elastomer in pellets and 1% by weight of dihexadecyl peroxydicarbonate disclosed herein at 190°C, according to any embodiment. The graph of the extensional viscosity (Pa∙s) versus time (sec) under three shear rates.

[ Figure 5 ] is a diagram showing a ^{composition formed from Vistamaxx TM} 3588 propylene-based elastomer in pellets and 2% by weight of dihexadecyl peroxydicarbonate disclosed herein at 190°C, according to any embodiment. The graph of the extensional viscosity (Pa∙s) versus time (sec) under three shear rates.

[ Figure 6 ] is a graph showing a ^{composition formed from a granular Vistamaxx TM} 3588 propylene elastomer and 1.5% by weight dihexadecyl peroxydicarbonate at 190°C and at three shear rates according to any embodiment. Below is the graph of elongation viscosity (Pa∙s) versus time (sec).

[ Figure 7 ] It is a diagram showing ^{the composition formed from the granular Vistamaxx TM} 3980 propylene-based elastomer and 1.5% by weight dihexadecyl peroxydicarbonate at 190°C and at three shear rates according to any embodiment. Below is the graph of elongation viscosity (Pa∙s) versus time (sec).

[ Figure 8 ] is a diagram showing a ^{composition formed from a granular Vistamaxx TM} 3000 propylene-based elastomer and 1.5% by weight dihexadecyl peroxydicarbonate at 190°C and at three shear rates according to any embodiment. Below is the graph of elongation viscosity (Pa∙s) versus time (sec).

[ Figure 9A ] is a diagram showing the multi-angle light scattering (MALLS) 3D of a composition formed ^{from a pellet of Vistamaxx TM 3588 propylene elastomer and 0 wt% dihexadecyl peroxydicarbonate according to any embodiment} -GPC (DRI) Inherent Viscosity Recording Curve Graph.

[ Figure 9B ] shows the normalized DRI, LS and viscometer of a composition formed ^{from Vistamaxx TM} 3588 propylene elastomer in pellets and 0 wt% dihexadecyl peroxydicarbonate according to any embodiment The chromatogram changes with the retention volume (ml).

[FIG 9C] is a differential refractive illustrating use of the composition according to the aspect of the formed pellets from the Vistamaxx ^TM 3588 as a propylene-based elastomer, and 0% by weight of dicetyl peroxydicarbonate esters of any one of embodiments [GPC ( DRI)] a graph of gel permeation chromatography of the recording curve.

[ Figure 10A ] is a diagram showing the inherent MALLS 3D-GPC (DRI) of a composition formed ^{from a pellet of Vistamaxx TM 3588 propylene elastomer and 1.0 wt% dihexadecyl peroxydicarbonate according to any embodiment.} Graph of viscosity record curve.

[ Figure 10B ] shows the normalized DRI, LS and viscometer of a composition formed ^{from Vistamaxx TM} 3588 propylene elastomer in pellet form and 1.0 wt% dihexadecyl peroxydicarbonate according to any embodiment The chromatogram changes with the retention volume (ml).

[ Fig. 10C ] is a diagram showing the use of a differential refractor [GPC (DRI)] of a composition formed ^{from a pellet of Vistamaxx TM 3588 and 1.0% by weight of dihexadecyl peroxydicarbonate according to any embodiment.} Record the graph of gel permeation chromatography of the curve.

[ Fig. 11 ] It shows the inherent MALLS 3D-GPC (DRI) of a composition formed ^{from Vistamaxx TM} 3588 propylene elastomer in pellet form and 1.5% by weight dihexadecyl peroxydicarbonate according to any embodiment. Graph of viscosity record curve.

[ Fig. 12 ] It shows the inherent MALLS 3D-GPC (DRI) of a composition formed ^{from Vistamaxx TM} 3588 propylene elastomer in pellet form and 2.0 wt% dihexadecyl peroxydicarbonate according to any embodiment. Graph of viscosity record curve.

[ Figure 13 ] It shows the inherent MALLS 3D-GPC (DRI) of a composition formed ^{from a granular Vistamaxx TM} 3588 propylene elastomer and 1.5% by weight dihexadecyl peroxydicarbonate according to any embodiment. Graph of viscosity record curve.

[ Figure 14 ] is a diagram showing the comparison composition and the composition formed from the Vistamaxx ^TM propylene elastomer in the form of pellets or granules in various amounts of dihexadecyl peroxydicarbonate (190°C) according to any embodiment. The graph of the complex viscosity (Pa.s) of) changing with the angular frequency of the oscillating shear rheological measurement.

Claims (29)

A polypropylene copolymer composition comprising the following products: at least 50 mol% of propylene and at least 1% by weight of ethylene or C ₄ to C ₁₀ alpha olefin based on the total weight of the copolymer One of the copolymers, wherein the copolymer has an Mw of 50,000 g/mol to 400,000 g/mol by DRI analysis; and an Mn of 25,000 g/mol to 200,000 g/mol by DRI analysis; And by DRI analysis, it is 100,000 g/mol to 500,000 g/mol of Mz; and organic peroxide; wherein the composition has a Mw _MALLS /Mn _{MALLS of} 1 to 5. Such as the composition in claim 1, wherein the copolymer is a granule. As in the composition of claim 2, wherein the particles have a diameter of 100 micrometers to 2,000 micrometers. The composition according to any one of claims 1 to 3, wherein the composition is a pellet. Such as the composition in claim 4, wherein the pellets have a diameter greater than 1,000 microns. The composition according to any one of claims 1 to 3, wherein the copolymer contains 5 to 16% by weight of ethylene based on the total weight of the copolymer. The composition according to any one of claims 1 to 3, wherein the copolymer comprises 0.01% to 5% by weight based on the total weight of the copolymer, selected from the following C ₄ to C ₁₀ alpha olefins: Dicyclopentadiene, 1,3-cyclopentadiene, divinylbenzene, 1,4-hexadiene, 1,4-cyclohexadiene, 1,5-hexadiene, 5-methyl-1 ,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 3,7-dimethyl-1,6-octadiene, 1,9-decadiene, 1,13 -Tetradecadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, or a combination thereof. The composition of any one of claims 1 to 3, wherein the propylene of the copolymer has an isotactic triad part of 50% to 99% measured ^{by 13 C NMR.} The composition according to any one of claims 1 to 3, wherein the organic peroxide is selected from compounds represented by one or more structures selected from (a) and (b):

as well as

Wherein, each R group is independently selected from hydrogen, C ₁ or C ₅ to C ₂₄ or C ₃₀ linear alkyl, C ₁ or C ₅ to C ₂₄ or C ₃₀ secondary alkyl, C ₁ or C ₅ to C ₂₄ or C ₃₀ tertiary alkyl, C ₇ to C ₃₄ alkyl aryl, C ₇ to C ₃₄ aryl alkyl, and substituted modifications thereof. The composition of claim 9, wherein the organic peroxide is selected from di-secondary butyl peroxydicarbonate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and peroxydicarbonate Bis (4-tertiary butyl cyclohexyl) ester, dihexadecyl peroxydicarbonate, dibutyl peroxydicarbonate, peroxydicarbonate Di(2-ethylhexyl) oxydicarbonate, dilauryl peroxydicarbonate, diecosyl peroxydicarbonate, and tetracosyl peroxydicarbonate. The composition according to any one of claims 1 to 3, wherein the composition comprises a product of 0.01% to 3% by weight of organic peroxide based on the weight of the composition. The composition of claim 11, wherein the composition contains a product of 1% to 2% by weight of organic peroxide based on the weight of the composition. The composition of claim 12, wherein the composition comprises a product of 1% to 1.5% by weight of organic peroxide based on the weight of the composition. Such as the composition of any one of claims 1 to 3, wherein the composition has an Mn of 95,000 g/mol to 120,000 g/mol by DRI analysis, and 200,000 g/mol to MALLS analysis The Mw of 300,000 g/mole, and the Mz of 290,000 g/mole to 770,000 g/mole by MALLS analysis. Such as the composition of any one of claims 1 to 3, wherein the composition has a Mz _MALLS /Mw _{MALLS of} 1 to 4. Such as the composition of claim 15, wherein the composition has a Mz _MALLS /Mn _{MALLS of} 1 to 10. Such as the composition of claim 16, wherein the composition has a Mz _MALLS /Mn _{MALLS of} 1.6 to 2.5. Such as the composition of any one of claims 1 to 3, wherein the composition has a strain rate of 0.01/sec (190°C) of 1x10 ³ Pa. s to 1x10 ⁷ Pa. s is the peak extensional viscosity (Peak Extensional Viscosity). Such as the composition of claim 18, wherein the composition has a strain rate of 1×10 ⁴ Pa at a strain rate of 0.01/sec (190°C). s to 1x10 ⁶ Pa. The peak extension viscosity of s. Such as the composition of any one of claims 1 to 3, wherein the composition has a melt strength (pull-out force, pull- off-force). The composition of any one of claims 1 to 3, wherein the copolymer composition has a melting point in the range of 1g/min to 10g/min as measured by ASTM D1238 condition L (230°C/2.16kg) Body flow rate. The composition according to any one of claims 1 to 3, which further comprises an alkyl radical scavenger or a product thereof. The composition according to any one of claims 1 to 3, which further contains a foaming agent. A foaming object comprising the product of the foaming agent and the composition as in claim 23. A method for forming the polypropylene copolymer composition of claim 1, which comprises: mixing a copolymer with an organic peroxide, the copolymer containing at least 50 mole% based on the total weight of the copolymer At least one of propylene and at least 1% by weight of ethylene or C ₄ to C ₁₀ alpha olefin; and obtaining a composition comprising the copolymer and the product of the organic peroxide; wherein the composition has 1 to 5 Mw _MALLS /Mn _MALLS . The method of claim 25, wherein the mixing occurs in the presence of an inert gas. The method of claim 25 or 26, wherein the mixing occurs in a homogenizer at a rate of at least 50,000 pounds of polymer per hour. The method of claim 25 or 26, wherein the copolymer is a particle. The method of claim 28, wherein the particles have a diameter of 100 micrometers to 1,000 micrometers.

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