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    • 专利摘要:
    ethylene-based polymer, composition, article and process for forming the ethylene-based polymer. the invention provides an ethylene-based polymer formed from the reaction of at least the following: ethylene and at least one asymmetric polyene, comprising an ''alpha, beta unsaturated end'' and a ''c-c double bond end' '' and the reaction takes place in the presence of at least one initiator via free radicals.
    公开号:BR112014032419B1
    申请号:R112014032419-0
    申请日:2013-03-08
    公开日:2021-06-22
    发明作者:John O. Osby
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    Invention history
    [001] Conventional low density polyethylene (LDPE) has good processability, however, when used in film application, it is still desired to increase its melt strength.
    [002] U.S. Publication No. 2008/0242809 discloses a process for the preparation of a copolymer of ethylene and a comonomer, and where the polymerization takes place in a tubular reactor, at a maximum temperature between 290°C and 350°C. The comonomer is a higher functional di(meth)acrylate or (meth)acrylate, and the comonomer is used in an amount between 0.008 mole percent and 0.200 mole percent relative to the amount of ethylene copolymer.
    [003] International publication No. WO 2007/110127 discloses an extrusion coating composition comprising an ethylene copolymer. The ethylene copolymer is obtained by a polymerization process in a tubular reactor, at a maximum temperature between 300°C and 350°C, and the comonomer is an α,w-alkadiene bifunctional.
    [004] US patent No. 5,539,075 discloses the polymerization of ethylene and at least one monomer, which is polymerizable with ethylene, and includes a polyunsaturated comonomer having a chain of at least eight carbon atoms and at least two doubles unconjugated bonds, of which at least one is terminal. Polymerization takes place at a pressure of about 100-300 MPa, and a temperature of about 80°C-300°C, under the action of a radical initiator. Preferably, the polyunsaturated comonomer is an α,w-alkadiene having 8 to 16 carbon atoms, and most preferably it is 1,9-decadiene. In addition to the polyunsaturated comonomer, the polymerization may also involve another unsaturated vinyl monomer preferably containing at least one functional group selected from hydroxyl groups, alkoxy groups, carbonyl groups and ester groups. The ethylene copolymers produced have an increased degree of unsaturation, which can be used to crosslink the ethylene copolymer or graft reactive groups.
    [005] International publication No. 97/45465 discloses an unsaturated ethylene copolymer, a method to produce it, and its use to produce crosslinked structures. The unsaturated ethylene copolymer comprises a polymer obtained by radical polymerization through a high pressure process of ethylene and at least one monomer that is copolymerizable with ethylene, and includes a bi-unsaturated comonomer of formula (I): H2C=CH -OR-CH=CH2 (I), in which R= -(CH2)mO-, -(CH2CH2)n-, or -CH2-C6H10-CH2-O-, m=2-10, and n=15. , the comonomer of formula (I) is 1,4-butanediol divinyl ether.
    [006] Tung, L.H., et al., "Preparation of Polystyrene with Long Chain Branches via Free Radical Polymerization", J. Polym. Sci., Polym. Chem. Ed. (1981), 19, 2027-39 discloses the use of small amounts of chain transfer monomers to copolymerize with styrene via free radicals. From the examined comonomers, vinyl benzyl thiol produced polystyrene with a branched structure. The branches are reported to occur primarily at the low molecular weight end of the distribution. Vinyl benzyl thiol has also been found to be an effective agent for broadening the molecular weight distribution.
    [007] Tung, L.H., "Branching Kinetics in Copolymerization of Styrene with a Chain-Transfer Monomer" ("Branching kinetics in copolymerization of styrene with a chain-transfer monomer"), J. Polym. Sci., Polym. Chem. Ed. (1981), 19, 3209-3217 discloses the use of polymerization kinetics to calculate theoretical molecular weight and degree of branching for polymerization with styrene with a chain transfer monomer (eg, vinyl benzyl thiol) .
    [008] Liu, J., et al., "Branched Polymer via Free Radical Polymerization of Chain Transfer Monomer: A Theoretical and Experimental Investigation". experimental”), J. Polym. Sci. Part A: Polym. Chem. (2007), 46, 1449-59, discloses a mathematical model for the free radical polymerization of chain transfer monomers, containing both polymerizable vinyl groups and telogen groups. The molecular architecture of the polymer is disclosed as being predicted according to the developed model, which was experimentally validated by the homopolymerization of 4-vinyl-benzylthiol (VBT), and its copolymerization with styrene.
    U.S. Patent No. 3,542,749 discloses ethylene copolymers containing polymerized ethylene and polymerized oleyl acrylate, erucil acrylate, N-oleyl-acrylamide, N-erucyl-acrylamide or any mixture thereof. Such copolymers and blending such copolymers with ethylene homopolymers are disclosed as exhibiting a low coefficient of friction and good non-stick properties when cast into films.
    [0010] U.S. Patent Publication No. 2009/0253878 discloses a polyolefin polymer comprising one or more terminal polymerizable methacryloyl groups, and a process for preparing the same. The polymer is prepared by a single reactor copolymerization reaction of an olefin, such as ethylene, and a hetero-bifunctional comonomer comprising a methacryloyl group, catalyzed by a delayed transition metal α-diimine catalyst, which is selectively not selective for methacryloyl groups. The terminal methacryloyl groups within the polymer are reactive in further polymerization reactions. U.S. Patent No. 5,763,629 discloses a process for preparing alkoxylated glycidyl (meth)acrylates. See also WO 2012/084787 for additional simulated reactions.
    [0011] However, as discussed, there remains a need for ethylene-based polymers, such as low density polyethylene (LDPE), with improved melt strength, especially for film and extrusion coating applications. These and other needs were met by the following invention. Invention Summary
    [0012] The invention provides an ethylene-based polymer formed from the reaction of at least the following: ethylene and at least one asymmetric polyene, comprising an "alpha, beta unsaturated end" and a "CC double bond end" and the reaction takes place in the presence of at least one initiator via free radicals. Detailed description of the invention
    [0013] As discussed above, the invention provides an ethylene-based polymer formed from the reaction of at least the following: ethylene and at least one asymmetric polyene, comprising an "alpha, beta unsaturated end" and an "end double bond CC” and the reaction takes place in the presence of at least one initiator via free radicals.
    [0014] In an embodiment the "alpha, beta unsaturated end" of the asymmetric polyene is selected from the group consisting of the following:
    in which R1 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3; B)
    in which R2 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3, R3 is selected from H, CH3, or CH2CH3, R4 is selected from H, CH3, or CH2CH3, and n is from 1 to 50, further from 1 to 20, and further from 1 to 10, and where, when R3 is CH3, or CH2CH3, then R4 is H, and when R4 is CH3, or CH2CH3, then R3 is H;
    in which R5 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3; and
    in which R'5 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3.
    [0015] In structures a) to d), the notation represents a break at the center of a covalent bond between the "alpha, beta unsaturated end" of the asymmetric polyene and the remainder of the chemical structure of the asymmetric polyene.
    [0016] In one embodiment, the "CC double bond end" of the asymmetric polyene is selected from the group consisting of the following: 1) in which R7 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl, and further CH3;
    in which R7 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3;
    in which R8 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3; 3)
    in which R9 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3;

    in which R10 is selected from H, or OH;

    in which R11 is selected from H, or OH;

    in which R12 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3, R13 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3, and R14 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl, and further CH3, or Ph; and 23)
    in which R15 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3, and R16 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3.
    [0017] In structures 1) to 23), the notation represents a break in the center of a covalent bond between the "end of double bond C-C" of the asymmetric polyene and the remainder of the chemical structure of the asymmetric polyene.
    [0018] In one embodiment, the "CC double bond end" of the asymmetric polyene is selected from the group consisting of the following: 1)
    in which R7 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3; two)
    in which R8 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3;
    in which R9 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3;

    in which R10 is selected from H, or OH;


    [0019] In one embodiment, the "CC double bond end" of the asymmetric polyene is selected from the group consisting of the following: 1), 2), 3), 4), 5), 6), 7), 8), 9 ), 10), 11) and 12 shown above.
    [0020] In one embodiment, the "C-C double bond end" of the asymmetric polyene is selected from the group consisting of the following: 1), 2), 3) and 12) shown above.
    [0021] In one embodiment, the "C-C double bond end" of the asymmetric polyene is selected from the group consisting of the following: 13),14), 15) and 16) shown above.
    [0022] In an embodiment, the "alpha, beta unsaturated end" of the asymmetric polyene is selected from the group consisting of the following: b)
    in which R2 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3, R3 is selected from H, CH3, or CH2CH3, R4 is selected from H, CH3, or CH2CH3, and n is from 1 to 50, further from 1 to 20, and further from 1 to 10, and where, when R3 is CH3, or CH2CH3, then R4 is H, and when R4 is CH3, or CH2CH3, then R3 is H; and
    in which R5 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3.
    [0023] In an embodiment, the "alpha, beta unsaturated end" of the asymmetric polyene is selected from the group consisting of the following: b)
    in which R2 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3, R3 is selected from H, CH3, or CH2CH3, R4 is selected from H, CH3, or CH2CH3, and n is from 1 to 50, further from 1 to 20, and further from 1 to 10, and where, when R3 is CH3, or CH2CH3, then R4 is H, and when R4 is CH3, or CH2CH3, then R3 is H.
    [0024] In an embodiment, the "alpha, beta unsaturated end" of the asymmetric polyene is selected from the group consisting of the following:
    in which R5 is selected from H, or C1-C6 alkyl, further C1-C3 alkyl and further CH3.
    [0025] In an embodiment the asymmetric polyene is present in an amount greater than or equal to 100 ppm, based on the total amount of ethylene in the reactor.
    [0026] In an embodiment, the asymmetric polyene is selected from the group consisting of the following: i)
    where n is from 1 to 50, still from 1 to 20 and still from 1 to 10, Ra is selected from H or methyl, Rb is selected from H or methyl, and when Ra is methyl, then Rb is hydrogen, and when Ra is hydrogen, then Rb will be methyl; ii)


    [0027] In one embodiment, the asymmetric polyene is selected from the group consisting of the following: I), II), III), IV) and V), shown above.
    [0028] In an embodiment, the asymmetric polyene is selected from the group consisting of the following: I) and V) shown above.
    [0029] In one embodiment, the asymmetric polyene is selected from the group consisting of the following: VI), VII), VIII), IX), shown above.
    [0030] In one embodiment, the asymmetric diene has 1H NMR signals of chemical shift from 3.0 to 6.5.
    [0031] In one embodiment, an inventive polymer is polymerized in the presence of at least two asymmetric polyenes, and further two asymmetric dienes, disclosed herein.
    [0032] An asymmetric polyene may comprise a combination of two or more embodiments described herein.
    [0033] In one embodiment, the ethylene-based polymer is a low density polyethylene (LDPE).
    [0034] In one embodiment, the ethylene-based polymer comprises at least one structure selected from the group consisting of the following structures A through D: A)
    in which n is from 1 to 50, R1 is selected from H or C1-C6 alkyl, Ra is selected from H or methyl, Rb is selected from H or methyl, and when Ra is methyl, then Rb will be hydrogen, and when Ra is hydrogen, then Rb will be methyl; B)
    in which R1 is selected from H or C1-C6 alkyl; Ç)
    in which R1 is selected from H or C1-C6 alkyl; and D)

    [0035] In one embodiment, polymer a comprises at least one structure structures A to C shown above.
    [0036] In an embodiment, polymer a comprises at least one structure structures A or B shown above.
    [0037] In one embodiment, the ethylene-based polymer comprises at least one structure selected from structure A shown above.
    [0038] In one embodiment, the ethylene-based polymer comprises at least one structure selected from structure B shown above.
    [0039] In one embodiment, the ethylene-based polymer comprises at least one structure selected from structure C shown above.
    [0040] In one embodiment, the ethylene-based polymer comprises at least one structure selected from structure D shown above. if π
    [0041] In structures A to D, the notation represents a break in the center of a carbon-carbon covalent bond in the hydrocarbon backbone of the ethylene-based polymer.
    [0042] In one embodiment, the ethylene-based polymer comprises, in reacted form, an amount greater than or equal to 0.075 moles of asymmetric polyene per 100 moles of the main chain carbons of the ethylene-based polymer, based on the weight of the polymer . In a further embodiment, the asymmetric polyene is an asymmetric diene.
    [0043] In one embodiment, the ethylene-based polymer comprises, in reacted form, an amount greater than or equal to 10 moles of asymmetric polyene per 1000 moles of the main chain carbons of the ethylene-based polymer, based on the weight of the polymer . In a further embodiment, the asymmetric polyene is an asymmetric diene.
    [0044] In one embodiment, the ethylene-based polymer comprises, in reacted form, an amount greater than or equal to 5 moles of asymmetric polyene per 1000 moles of the main chain carbons of the ethylene-based polymer, based on the weight of the polymer . In a further embodiment, the asymmetric polyene is an asymmetric diene.
    [0045] In one embodiment, the ethylene-based polymer comprises, in reacted form, at least 0.03 percent by weight of the asymmetric polyene, based on the weight of the polymer. In a further embodiment, the asymmetric polyene is an asymmetric diene.
    [0046] In one embodiment, the ethylene-based polymer has a melt index (I2) of 0.3 to 100 g/10 min, or 1 to 50 g/10 min, or 2 to 20 g/10 min .
    [0047] In an embodiment, the ethylene-based polymer has a density greater than or equal to 0.900 g/cm3, or greater than or equal to 0.905 g/cm3, or greater than or equal to 0.910 g/cm3.
    [0048] In an embodiment, the ethylene-based polymer has a density less than or equal to 0.950 g/cm3, or less than or equal to 0.945 g/cm3, or less than or equal to 0.940 g/cm3.
    [0049] In one embodiment, the ethylene-based polymer has a density of from 0.900 to 0.950 g/cm3, or from 0.905 to 0.945 g/cm3, or from 0.910 to 0.940 g/cm3.
    [0050] The invention also provides a composition comprising an inventive ethylene-based polymer described herein.
    [0051] In one embodiment, the composition further comprises an ethylene/α-olefin interpolymer with a density less than or equal to 0.94 g/cm3.
    [0052] In one embodiment, the composition further comprises another ethylene-based polymer that differs from the inventive ethylene-based polymer in one or more properties, for example, density, melt index (I2), Mw, Mn or Mw/Mn .
    [0053] The invention also provides an article comprising at least one component formed by an inventive composition.
    [0054] In an embodiment, the article is a film or coating.
    [0055] In an embodiment, the article is a film.
    [0056] An inventive ethylene-based polymer may comprise a combination of two or more embodiments described herein.
    [0057] An inventive composition may comprise a combination of two or more embodiments described herein.
    [0058] An inventive article may comprise a combination of two or more embodiments described herein.
    [0059] The invention also provides a process for forming an ethylene-based polymer as described herein, the process comprising polymerizing ethylene in the presence of asymmetric polyene comprising an "alpha, beta unsaturated end" and a "CC double bond end ”. In one embodiment, the asymmetric polyene is an asymmetric diene.
    [0060] In one embodiment, ethylene polymerizes in the presence of at least 50 molar ppm (based on the total amount of monomers in the reaction feed) of the asymmetric polyene. In a further embodiment, the asymmetric polyene is an asymmetric diene.
    [0061] In an embodiment, the process takes place in a reactor configuration comprising at least one tubular reactor.
    [0062] In an embodiment, the polymerization pressure is greater than or equal to 100 MPa. In a further embodiment, polymerization takes place at a pressure of 150 MPa to 350 MPa. In a further embodiment, the process takes place in a reactor configuration comprising at least one tubular reactor.
    [0063] In an embodiment, polymerization takes place in at least one tubular reactor or in at least one autoclave.
    [0064] In one embodiment, polymerization takes place in at least one autoclave.
    [0065] In an embodiment, polymerization takes place in at least one tubular reactor.
    [0066] In one embodiment, the asymmetric diene is added in the polymerization in an amount of 0.002 to 0.300 mole percent, further from 0.005 to 0.300 mole percent, based on the total moles of asymmetric ethylene and diene added in the polymerization. In a further embodiment, polymerization takes place in two reactors. In another embodiment, polymerization takes place in a reactor.
    [0067] The inventive process may comprise a combination of two or more embodiments described herein. Process
    [0068] To produce a highly branched ethylene-based polymer, a polymerization process initiated by free radicals is typically used. Two different types of high pressure free radical initiated polymerization processes are known. In the first type, an autoclave vessel having one or more reaction zones is used. The autoclave reactor typically has multiple injection points for initiator or monomer feeds, or both. In the second type, a jacketed tube is used as a reactor, which has one or more reaction zones. Suitable, but not limiting, reactor lengths can be 100 to 3000 m, or 1000 to 2000 m. Typically, the start of a reaction zone is defined, for either of the two types of reactors, by the injection side of the reaction initiator, ethylene, chain transfer agent (or telomer), comonomer(s), as well as any combination of them. A process can be carried out at high pressure in autoclaves or tubular reactors having one or more reaction zones, or in a combination of autoclaves and tubular reactors, each comprising one or more reaction zones.
    [0069] In an incorporation, an initiator is injected before the reaction zone where polymerization via free radicals will be induced.
    [0070] Often, a conventional chain transfer agent is used to control molecular weight. In a preferred embodiment, one or more chain transfer agents (CTAs) are added in the inventive polymerization process. Typical CTAs that can be used include, but are not limited to, propylene, isobutane, n-butane, 1-butene, methyl ethyl ketone, acetone, ethyl acetate, propionaldehyde, ISOPAR (ExxonMobil Chemical Company), and isopropanol. In one embodiment, the amount of CTA used in the process is from 0.03 to 10 percent by weight of the total reactant mixture.
    [0071] In one embodiment, the process includes a process recycling loop to improve conversion efficiency.
    [0072] In one embodiment, polymerization can take place in a tubular reactor described in international patent application PCT/US12/059469, filed October 10, 2012. This patent application describes a multizone reactor that describes alternating feed locations for new ethylene to control the ethylene to CTA ratio and therefore control polymer properties. New ethylene can be added simultaneously at multiple locations to achieve the desired ethylene to chain transfer ratio. In an addition mode similar to that of new CTA addition, points of addition can be carefully selected to control polymer properties as described in international patent application PCT/US12/064284 (filed November 9, 2012). Fresh CTA can be added simultaneously at multiple locations to achieve the desired CTA to ethylene ratio. Likewise, the addition points and amount of the novel branching agents described in this patent application can be controlled to control gel formation while maximizing the desired performance property and increased melt strength in target applications . One can simultaneously add branching agent at multiple locations to achieve the desired ratio of branching agent to ethylene. The use of a branching or coupling agent to broaden the molecular weight distribution and to increase the melt strength of the polymer will add additional demands on the distribution of CTA and branching agent throughout a reactor system in order to achieve change. desired in product properties without or minimizing potential negative impacts such as gel formation, reactor fouling, process instabilities, low branching agent efficiency, etc.
    [0073] In an embodiment, polymerization takes place in at least one tubular reactor. In the multiple reactor system, the autoclave comes before the tubular reactor. Addition points and amounts of new ethylene, new CTA, and new branching agent can be appropriately controlled to achieve the desired CTA to ethylene and branching agent to ethylene ratios in feeds to and/or in the reaction zones.
    [0074] In one embodiment, the asymmetric diene is added in the polymerization in an amount of 0.002 to 0.300 mole percent, further from 0.005 to 0.300 mole percent, based on the total moles of asymmetric ethylene and diene added in the polymerization. In a further embodiment, polymerization takes place in two reactors. In another embodiment, polymerization takes place in a reactor with multiple or at least two reaction zones.
    [0075] The ethylene used for the production of ethylene-based polymer can be purified ethylene, which is obtained by removing polar components from a continuous recycle stream, or using a reaction system configuration such that only new ethylene is used for preparing the inventive polymer. It is not typical that purified ethylene is required to prepare the ethylene-based polymer. In such cases, ethylene from the recycling loop can be used.
    [0076] In one embodiment, the ethylene-based polymer comprises ethylene and one or more comonomers, preferably a comonomer. Comonomers include, but are not limited to, α-olefins, acrylates, methacrylates and anhydrides, each typically having a number less than or equal to 20 carbon atoms. α-Olefin comonomers can have 3 to 10 carbon atoms, or alternatively, α-olefin comonomers can have 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl- 1-pentene.
    [0077] In one embodiment, the ethylene-based polymer comprises ethylene and at least one asymmetric polyene as the only monomeric units. Initiators
    [0078] Generally speaking, free radical initiators are used to produce inventive ethylene-based polymers. Exemplary organic peroxides include, but are not limited to, cyclic peroxides, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxycarbonates, peroxydicarbonates, peroxyesters, and peroxyketals. Preferred initiators are: t-butyl peroxy pivalate, di-t-butyl peroxide, t-butyl peroxy acetate and t-butyl peroxy-2-hexanoate, or mixtures thereof. In one embodiment, these organic peroxide initiators are used in an amount of 0.001 to 0.2 percent by weight, based on the weight of the polymerizable monomers.
    [0079] In an embodiment, an initiator is added in at least one polymerization reaction zone, and in which the initiator has a "half-life temperature in one second" greater than 255°C, preferably greater than 260°C . In a further embodiment, such initiators are used at a maximum polymerization temperature of 320°C to 350°C. In a further embodiment, the initiator comprises at least one peroxide group incorporated into a ring structure. Examples of such initiators include, but are not limited to, TRIGONOX 301 (3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane) and TRIGONOX 311 (3,3,5,7 ,7-pentamethyl-1,2,4-trioxopane), both obtainable from Akzo Nobel, and HMCH-4-AL (3,3,6,6,9,9-hexamethyl-1,2,4,5-tetroxonane ) obtainable from United Initiators. See also International Publication Nos. WO 02/14379 and WO 01/68723. Additions
    [0080] An inventive composition may comprise one or more additives. Additives include, but are not limited to, stabilizers, plasticizers, antistatic agents, pigments, dyes, nucleating agents, fillers, glidants, flame retardants, processing aids, smoke inhibitors, viscosity controlling agents, and non-stick agents. The polymer composition can, for example, comprise less than 10 percent of the combined weight of one or more additives, based on the weight of the inventive polymer.
    [0081] In one embodiment, the polymers of this invention are treated with one or more stabilizers, for example, antioxidants such as IRGANOX 1010, IRGANOX 1076 and IRGAFOS 168. In general, polymers are treated with one or more stabilizers prior to extrusion or of other processes under fusion.
    [0082] An inventive composition may further comprise at least one other polymer, in addition to an inventive ethylene-based polymer. Blends and compositions of the inventive polymer with other polymers can be prepared. Suitable polymers for blending with the inventive polymers include natural and synthetic polymers. Exemplary polymers for blending include propylene-based polymers (impact-modified polypropylene, isotactic polypropylene, atactic polypropylene, and random propylene/ethylene copolymers), various types of ethylene-based polymers, including LDPE via free radicals and high pressure, LLDPE heterogeneously branched (typically via Ziegler-Natta catalysis), substantially linear or linear homogeneously branched PE (typically via single site, including metallocene catalysis), including multi-reactor PE ("in-reactor" compositions of heterogeneously branched PE and homogeneously branched PE, such such as the products disclosed in US patents 6,545,088 (Kolthammer et al.), 6,538,070 (Cardwell, et al.), 6,566,446 (Parikh, et al.), 5,844,045 (Kolthammer et al. ), 5,869,575 (Kolthammer et al.), and 6,448,341 (Kolthammer et al.), ethylene/vinyl acetate (EVA) and ethylene/vinyl alcohol copolymers, polystyrene, impact-modified polystyrene , ABS, styrene/butadiene block copolymers and hydrogenated derivatives thereof (SBS and SEBS), and thermoplastic polyurethanes. Other ethylene-based polymers include homogeneous polymers such as plastomers and olefinic elastomers (eg polymers available under the tradenames AFFINITY plastomers and ENGAGE (The Dow Chemical Company) and EXACT (ExxonMobil Chemical Company) elastomers). Propylene-based copolymers (for example, polymers obtainable under the tradenames plastomers and elastomers VERSIFY (The Dow Chemical Company) and VISTAMAXX (ExxonMobil Chemical Company)) may also be useful as blended components comprising an inventive polymer. applications
    [0083] The polymers of this invention can be employed in a variety of thermoplastic manufacturing processes to produce useful articles, including single- and multi-layer films, molded articles, such as blow molded, injection molded, or rotational molded articles, coatings, fibers, and woven or non-woven cloths.
    [0084] An inventive polymer can be used in a variety of films including, but not limited to, clear shrink films, glue shrink films, cast stretch films, silage films, stretch wrap, sealants, and diaper liners disposables.
    [0085] Other suitable applications include, but are not limited to, wires and cables, gaskets and profiles, adhesives, footwear components, and automobile interior parts. Definitions
    [0086] Unless otherwise stated, implied by the context, or customary in the art, all parts and percentages are based on weight, and all methods are current as of the filing date of this disclosure.
    [0087] As used herein, the term "composition" refers to a mixture of materials, which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.
    [0088] When used, "blend" or "polymer blend" refers to a blend of two or more polymers. A mixture may or may not be miscible (not phased at the molecular level). A mixture may or may not be separated into phases. A mixture may or may not contain one or more domain configurations, determined from electronic transmission spectroscopy, light scattering, X-ray scattering, and other methods known in the art. Mixing can be achieved by physically mixing the two or more polymers at the macro level (eg combining or blending cast resins) or at the micro level (eg forming simultaneously within the same reactor).
    [0089] As used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing monomers, either of the same type or of different types. Thus, the term polymer includes the term homopolymer (used to refer to polymers prepared from a single type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymeric structure), and the term "interpolymer" defined below . Traces of impurities, such as catalyst residues, can be incorporated into the polymeric structure and/or within the polymeric mass.
    [0090] As used herein, the term "interpolymer" refers to polymers prepared by polymerizing at least two different types of monomers. Thus, the generic term interpolymer includes copolymers (used to refer to polymers made from two different types of monomers), and polymers made from more than two different types of monomers.
    [0091] As used herein, the term "ethylene-based polymer" refers to a polymer comprising at least a majority weight percentage of ethylene (based on polymer weight), and optionally may comprise one or more comonomers.
    [0092] As used herein, the term "ethylene-based interpolymer" refers to an interpolymer that comprises a major amount of polymerized ethylene, based on the weight of the interpolymer, and comprises at least one comonomer.
    [0093] As used herein, the term "ethylene-based copolymer" refers to a copolymer comprising a major amount of polymerized ethylene, based on the weight of the copolymer, and a comonomer, as the only types of monomers.
    [0094] As used herein, the term "propylene-based polymer" refers to a polymer comprising a major amount of propylene, based on the weight of the polymer, and optionally may comprise at least one comonomer.
    [0095] The terms "comprising", "including", "having" and its derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not it is specifically disclosed. On the other hand, the term “consisting essentially of” excludes from the scope of any subsequent mention any other component, step or procedure, except those that are not essential to operability. The term “consisting of” excludes any component, step or procedure not specifically described or listed. Density Test Methods
    To measure density, samples were prepared in accordance with ASTM D 1928. The samples were pressed at 190°C (374°F) and 30,000 psi for three minutes, and then at 21°C (70°F ) and 30,000 psi for one minute. Density measurements were carried out within one hour after pressing the sample, using method B of ASTN D792. fusion index
    The melt index (I2) was measured according to ASTM D-1238, Condition 190°C/2.16 kg, and the result was reported in grams eluted over 10 minutes. I10 was measured according to ASTM D-1238, Condition 190°C/10 kg, and the result was reported in grams eluted over 10 minutes. Cast strength
    Melt strength measurements were performed at 190°C using a Rheotens Gottfert 71.97 (Goettfert Inc., Rock Hill, SC). The molten sample (about 25 to 50 g) was fed into a Rheotester 2000 Gottfert capillary rheometer, equipped with a flat (180°) inlet angle, 30 mm in length and 2.0 mm in diameter. The sample was fed into the barrel (L = 300 mm, Diameter = 12 mm), compressed and allowed to melt for 10 minutes before being extruded at a constant plunger speed of 0.265 mm/s, which corresponds to a wall shear rate of 38.2 s-1 at the given die diameter. The extrudate passed through the Rheotens wheels, located 100 mm below the die outlet, and pulled down by the wheels, at an acceleration rate of 2.4 mm/s2. Traction force is recorded as a function of the tightening speed of the compression cylinders. The melt strength is recorded as the plateau force (cN) before the course breaks. Nuclear magnetic resonance (1H NMR)
    [0099] Each sample was prepared by adding approximately "0.1 g of ethylene-based polymer" into "2.7 g of tetrachloroethane-d2 containing 0.001M Cr(AcAc)3 (tris(acetyl acetonate) of chromium(III) ))” in a 10 mm NORELL 1001-7 NMR tube. Samples were purged by bubbling nitrogen (N2) through the solvent, via a pipette inserted into the tube, for approximately five minutes to prevent oxidation, and then samples were capped, sealed with TEFLON tape, and then saturated at room temperature in a day to day to facilitate sample dissolution. Samples were kept in an N2 purge box during storage, before and after preparation, to minimize exposure to oxygen. The samples were heated and vortexed to 115°C to ensure homogeneity. Each sample was visually inspected to ensure homogeneity.
    Data were collected using an AVANCE BRUKER 400 MHz spectrometer, equipped with a BRUKER Dual DUL high temperature cryogenic probe, and a sample temperature of 120°C. Each analysis was performed with a ZG pulse, 32 scans, 10,000 Hz SWH, AQ 1.64 s, D1 of 14 s. Acquisitions were repeated using D1 of 28 s to check quantification and results were similar. Experimental Inventive Ethylene-Based Polymers A-1, A-2 and A-3 (different amounts of asymmetric diene) and A-0 Control
    [00101] Synthesis of asymmetric diene of poly(propylene glycol) allyl ether methacrylate. All methacrylate monomers in this specification were prepared according to the method of example 1 of U.S. Patent No. 4,916,255. In this case, APPG-200 UCON, a polyglycol commercially obtainable from The Dow Chemical Company, was used to prepare the poly(propylene glycol) allyl ether methacrylate.
    [00102] Asymmetric Diene - Poly(propylene glycol) allyl ether methacrylate (PPGAEM) was charged to a 316 stainless steel supply vessel, and diluted with ethyl acetate to produce a final concentration of 7.8% by weight. This vessel was purged with nitrogen for three hours prior to use and kept under a nitrogen blanket at 70 psig during operation.
    [00103] Initiators - Tertiobutyl peroxyacetate peroxide initiator (TPA, 20% by weight solution in ISOPAR™ H), and di-tertiobutyl peroxide (DTBP, 20% by weight solution in ISOPAR™) initiator H) were combined with ISOPAR E, in a second 316 stainless steel supply vessel, to produce 1500 mass ppm TPA and 415 mass ppm DTBP (a ratio of moles TPA/mole DTBP of 4:1). The container was padded, requilted, five times with nitrogen at 70 psig prior to use, and kept under a nitrogen blanket during the operation.
    [00104] Control (A-0) - Ethylene was injected at 5440 g/h (194 mol/h) at a pressure of 1930 bar, in a stirred 300 mL (1600 rpm) high pressure CSTR reactor, with a jacket of heating set at 220°C. Propylene (chain transfer agent) was added into the ethylene stream at a pressure of 62 bar and at a rate of 177 g/h (4.2 mol/h) before the mixture was compressed to 1930 bar, and injected into the reactor. The peroxide initiator mixture was added directly into the reactor through the side wall of the CSTR reactor, and at a pressure of 1930 bar, and at a rate of 5 x 10-2 g/h (0.4 mmol/h) of TPA and 1.4 x 10-2 g/h (0.1 mmol/h) of DTBP. The conversion of ethylene to polymer was 11.2% by weight, based on the mass of ethylene entering the reactor, and the average reaction temperature was 224°C. An ethylene-based polymer having a melt index (I2) of 3.89 g/10 min was formed. Approximately 650 g of this ethylene-based polymer (A-0) was collected. Inventive Ethylene-Based Polymers A-1, A-2 and A-3
    [00105] Propylene (CTA) was added into the ethylene stream at a pressure of 62 bar, and at a rate of 163 g/h (3.9 mol/h), before compressing the mixture to 1930 bar, and injected in the reactor (see above). The PPGAEM solution in ethyl acetate was pumped at a pressure of 1930 bar and at a rate of 14.1 g/h (3.9 mmol/h) into the ethylene/propylene mixture, before injecting said mixture into the reactor. The peroxide initiator was added directly into the reactor, through the side wall, and at a pressure of 1930 bar, and at a rate of 5.5 x 10-2 g/h (0.42 mmol/h) of TPA and 1, 5 x 10-2 g/h (0.1 mmol/h) of DTBP. The conversion of ethylene to polymer was 9.2% by weight, based on the mass of ethylene entering the reactor, and the average reaction temperature was 228°C. An ethylene-based polymer having a melt index (I2) of 3.81 g/10 min was formed. Approximately 510 g of this ethylene-based polymer (A-1) were collected. The amount of PPGAEM was increased twice to form two more inventive polymers (A-2 and A-3). Reaction conditions are summarized in Table 1 below. Table 2 below shows the properties of the polymers. Table 1: Polymerization conditions
    *Determined by 1H NMR.
    [00106] Table 2 showed that the inventive polymers (A-1, A-2 and A-3) have significantly higher melt strength than the comparative control (A-0).
    [00107] An ethylene-based polymer formed from a symmetric diene, 1,4-butanediol dimethacrylate (BDDM-1) was compared with inventive examples A-2 and A-3. This comparative polymer was prepared under similar reaction conditions as used for A-2 and A-3. Table 3 below shows the polymer data. Table 3: Polymer Properties

    [00108] For each diene, one end is a methacrylate portion. For 1,4-butanediol dimethacrylate, the other end is a methacrylate. For PPGAEMA, the other end is an allyl ether. Unexpectedly, inventive examples A-2 and A-3 were found to have "melt strength increases" of approximately the same amount as the comparative ethylene-based polymer prepared using 1,4-butanediol dimethacrylate. These results are unexpected, since it is known from the published literature that the methacrylate portion is much more reactive towards ethylene than the allyl portion. For example, see Ehrlich and Mortimer in "Advances in Polymer Science", vol. 7, pp.432ff (1970), for reactivity ratios. Thus, it is unexpected that the melt strength improvement is practically the same for the two inventive polymers, on a molar basis, when compared to the comparative polymer. Inventive B-1, B-2 and B-3 Ethylene-Based Polymers and B-0 Control
    [00109] Asymmetric diene - Dicyclopentenyloxy-ethyl methacrylate (hereinafter DCPOEM, CAS [68586-196], The Dow Chemical Company) was charged into a 0.25 L glass supply vessel which was opened to the atmosphere . Sufficient ethyl acetate was added to produce a 14.2% by weight solution of DCPOEM in ethyl acetate.
    [00110] CTA - A 250 mL bottle of new propionaldehyde (97%) was used as the supply container, which was opened to the atmosphere.
    [00111] Initiator - The peroxide initiator, tertiarybutyl peroxyacetate (2.3 g of a 50% by weight solution in isododecane) was combined with 500 mL of n-heptane, and charged to a third supply container of glass. The solution was purged with nitrogen to minimize dissolved oxygen.
    [00112] Control (B-0) - Ethylene was injected at 1000 g/h (35.65 mol/h) at a pressure of 2000 bar, in a high pressure 54 mL CSTR reactor stirred (2000 rpm), with a external heating jacket set at 187°C. Then the propionaldehyde was degassed by an HPLC degasser, and then added into the ethylene stream at a pressure of 250 bar at a rate of 3.23 g/h (56 mmol/h) before the mixture was compressed to 2000 bar. The peroxide initiator was added to the ethylene/propionaldehyde mixture at a pressure of 2000 bar, and at a rate of 2.5 x 10-3 g/h (0.019 mmol/h), before the mixture entered the reactor. An ethylene-based polymer with a melt index (I2) of 1.7 g/10 min was obtained. Approximately 50 g of ethylene-based polymer was collected (Control B-0). Inventive ethylene-based polymers B-1, B-2 and B-3
    [00113] DCPOEM solution was pumped at a pressure of 250 bar, and at a rate of 2.0 g/h (1.1 mmol/h) through an HPLC degasser, and then into the propionaldehyde stream and mixed beforehand. of said mixture is added into the ethylene stream and compressed to 2000 bar. The peroxide initiator was added to the "ethylene/propionaldehyde/DCPOEM" mixture at a pressure of 2000 bar, and at a rate of 2.9 x 10-3 g/h (0.22 mmol/h), before the mixture entered. in the reactor. The conversion of ethylene to polymer was 12% by weight, based on the mass of ethylene entering the reactor, and the average reaction temperature was 222°C. An ethylene-based polymer with a melt index (I2) of 1.7 g/10 min was formed. Approximately 80 g of this ethylene-based polymer (B-1) was collected. The amount of asymmetric diene was increased twice to form two more inventive polymers (B-2 and B-3). Reaction conditions are summarized in Table 4 below. Table 5 below shows some properties of the polymers. Table 4: Polymerization conditions


    [00114] As shown in Table 5, the inventive polymers (B-1, B-2 and B-3) have significantly higher melt strength than the comparative control (B-0). Other asymmetric dienes
    [00115] Additional dienes shown in Table 6 were examined. Table 6: Other asymmetric dienes

    [00116] A procedure for the synthesis of the first three asymmetric dienes shown in Table 6, from the corresponding alcohols, is found in U.S. Patent No. 4,916,255. Asymmetric dicyclopentenyl methacrylate is commercially available from Sartomer Company. Asymmetric diene 3-(acryloyloxy)-2-hydroxypropyl methacrylate is commercially available from Aldrich Chemical Company.
    [00117] Asymmetric diene - An asymmetric diene was loaded into a 0.25 L glass supply vessel, which was opened to the atmosphere. Sufficient ethyl acetate was added to produce a "10 to 20% by weight" solution of the asymmetric diene in ethyl acetate, with the exception of oleyl methacrylate which was used undiluted.
    [00118] CTA - A “250 mL” bottle of new propionaldehyde (97%) was used as the supply container, which was opened to the atmosphere.
    [00119] Initiator - The peroxide initiator, tertiobutyl peroxyacetate (2.3 g of a 50% by weight solution in isododecane) was combined with 500 mL of n-heptane, and charged to a third supply container of glass. This solution was purged with nitrogen to minimize dissolved oxygen. Representative polymerization of an inventive ethylene-based polymer
    [00120] A solution of asymmetric diene, or oleyl methacrylate was pumped at a pressure of 250 bar, through an HPLC degasser, and then into the propionaldehyde stream, and mixed before said mixture was added into the ethylene stream, and compressed to 2000 bar. The asymmetric diene addition rate is given in Table 7 below. The peroxide initiator was added to the "asymmetric ethylene/propionaldehyde/diene" mixture, before the mixture entered the reactor at a pressure of 2000 bar, and at a rate sufficient to reach a reactor temperature of 200°C to 220°C. The conversion of ethylene to polymer was 9 to 12% by weight, based on the mass of ethylene entering the reactor. An ethylene-based polymer having a melt index (I2) of 1 to 5 g/10 min was obtained. In each case, approximately 50 to 100 g of ethylene-based polymer was collected.
    [00121] For each asymmetric diene, a control experiment without any diene was also performed. In each case, the polymer sample prepared with the asymmetric diene had a melt strength greater than the control, with each having approximately the same melt index. Table 7: Polymer Properties
    权利要求:
    Claims (14)
    [0001]
    1. Ethylene-based polymer, characterized in that it is formed from the reaction of at least the following: ethylene and at least one asymmetric polyene, comprising an "alpha, beta unsaturated end" and a "CC double bond end" , and the reaction taking place in the presence of at least one initiator via free radicals; wherein the ethylene-based polymer comprises ethylene and at least one asymmetric polyene as monomeric units only; whereby the "alpha, beta unsaturated end" of the asymmetric polyene is selected from the group consisting of the following: a)
    [0002]
    2. Ethylene-based polymer according to claim 1, characterized in that the "CC double bond end" of the asymmetric polyene is selected from the group consisting of the following:
    [0003]
    3. Ethylene-based polymer according to any one of claims 1 or 2, characterized in that the "alpha, beta unsaturated end" of the asymmetric polyene is selected from the group consisting of the following: b)
    [0004]
    4. Polymer based on ethylene, according to any one of claims 1 to 3, characterized in that in the reaction, the asymmetric polyene is present in an amount greater than or equal to 100 ppm, based on the total amount of ethylene.
    [0005]
    5. Ethylene-based polymer according to any one of claims 1 to 4, characterized in that the asymmetric polyene is selected from the group consisting of the following: i) i)
    [0006]
    6. Polymer based on ethylene, according to any one of claims 1 to 5, characterized in that it is a low density polyethylene (LDPE).
    [0007]
    7. Ethylene-based polymer according to any one of claims 1 to 6, characterized in that it comprises at least one structure selected from the group consisting of the following structures A to D: A)
    [0008]
    8. Ethylene-based polymer, according to claim 7, characterized in that it comprises at least one structure selected from structure A.
    [0009]
    9. Composition, characterized in that it comprises the ethylene-based polymer, as defined in any one of claims 1 to 8.
    [0010]
    10. Composition according to claim 9, characterized in that it further comprises at least one other polymer.
    [0011]
    11. Article, characterized in that it comprises at least one component formed by the composition, as defined in any one of claims 9 or 10.
    [0012]
    12. Process for forming the ethylene-based polymer, as defined by any one of claims 1-8, characterized in that it comprises polymerizing ethylene in the presence of asymmetric polyene.
    [0013]
    13. Process according to claim 12, characterized in that the polymerization takes place in a configuration of reactors comprising at least one tubular reactor.
    [0014]
    14. Ethylene-based polymer according to claim 1, characterized in that the ethylene-based polymer comprises, in the reacted form, less than or equal to 5 moles of asymmetric polyene per 1000 moles of main chain carbons of the ethylene-based polymer, based on the weight of the polymer.
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-11-12| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-01| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2021-04-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-22| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/03/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261664956P| true| 2012-06-27|2012-06-27|
    US61/664,956|2012-06-27|
    PCT/US2013/029881|WO2014003837A1|2012-06-27|2013-03-08|Ethylene-based polymers and processes for the same|
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