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    • 专利摘要:
    ETHYLENE-BASED POLYMER, COMPOSITION AND ARTICLE The invention provides an ethylene-based polymer formed from at least one of the following: ethylene and a monometric chain transfer agent (CTA), containing a copolymerization terminal and a terminal chain transfer.
    公开号:BR112013010462B1
    申请号:R112013010462-7
    申请日:2011-10-05
    公开日:2020-10-27
    发明作者:John O. Osby；Mehmet Demirors
    申请人:Dow Global Technologies Llc.；
    IPC主号:
    专利说明:

    Background of the invention
    [0001] Conventional low density polyethylene (LDPE) has good processability, however, when used in application and film, increased resistance to melting is still desired.
    [0002] North American publication No. US 2008/0242809 describes a process for the preparation of an ethylene copolymer and a comonomer, and where the polymerization takes the form of a tubular reactor, at a peak temperature between 290 ° C and 350 ° C. The comonomer is a superior functional di- or (meth) acrylate, and the comonomer is used in an amount between 0.008 mol percent and 0.200 mol percent, relative to the amount of the ethylene copolymer.
    [0003] International publication No. WO 2007/110127 describes an extrusion coating composition comprising an ethylene copolymer. The ethylene copolymer is obtained by a polymerization process in a tubular reactor, at a peak temperature between 300 ° C and 350 ° C, and the comonomer is an oc, m-alkadiene.
    [0004] U.S. Patent No. US 5,539,075 describes the polymerization of ethylene and at least one monomer, which is copolymerizable with ethylene, and includes a polyunsaturated comonomer having a chain of at least eight carbon atoms and at least two double bonds not conjugated, of which at least one is terminal. Polymerization takes place at a pressure of about 100-300 Mpa, and a temperature of about 80 ° -300 ° C, under the action of a radical initiator. The polyunsaturated comonomer is preferably c, m-alkadiene having 8-16 carbon atoms and, more preferably, 1,9-decadeine. In addition to the polyunsaturated comonomer, the polymerization may also involve another vinyl-unsaturated monomer, preferably containing at least one functional group selected from hydroxyl groups, alkoxy groups, carbonyl groups, carboxyl groups and ester groups. The ethylene copolymers produced have an increased degree of implantation, which can be used to crosslink the ethylene copolymer or graft reactive groups.
    [0005] International publication No. WO 97/45465 describes an unsaturated ethylene copolymer, a method for producing it, and its use for producing cross-linked structures. The unsaturated ethylene copolymer comprises a polymer obtained by radical polymerization, through a high pressure process of ethylene and at least one monomer, which is copolymerizable with ethylene, and includes a di-unsaturated comonomer of formula (I): H2C = CH -OR-CH = CH2, where R = - (CH2) mO-, - (CH2CH2O) m-, or -CH2-C6H10-CH2-O-, m = 2-10, and n = 1-5. Preferably, the comonomer of formula (I) is 1,4-butanediol divinyl ether.
    [0006] 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, describes the use of small amounts of chain transfer monomers to copolymerize with radically free styrene. Of the comonomers examined, vinylbenzylthiol, polystyrene resulted in polystyrene with a branched structure. Branches are described as occurring mainly at low molecular weight distribution. Vinylbenzylthiol was also found to be an effective agent for the amplification of molecular weight distribution.
    [0007] Tung, L.H., "Branching Kinetics in Copolymerization of Styrene with a Chain-Transfer Monomer", J. Polym. Sci., Polym., Chem., Ed., (1981), 19, 329-3217, describes the use of polymerization kinetics to compute the theoretical molecular weight and the degree of branching for polymerization with styrene with a transfer monomer chain (e.g. vinylbenzylthiol).
    [0008] Liu, J., et al., "Branched Polymer via Free Radical Polymerization of Chain Transfer Monomer: A theoretical and Experimental Investigation", J. Polym. Sci., Part A: Polym. Chem. (2007), 46, 1449-59, describes a mathematical model for the polymerization of chain transfer monomers containing both polymerizable vinyl groups and telogen groups. The molecular architecture of the polymer is described as being predicted according to the model developed, which has been experimentally validated by homopolymerization of 4-vinyl benzyl thiol (VBT), and its copolymerization with styrene.
    [0009] However, as discussed, there remains a need for ethylene-based polymers, such as low density polyethylene (LDPE), with improved melt resistance, especially for film application. There is an additional need for said polymers with a low insoluble content. These needs and others were met by the invention defined below. Summary of the invention
    [0010] The invention provides an ethylene-based polymer formed from at least one of the following: ethylene and a monomeric chain transfer agent (monomeric CTA), comprising a copolymerization terminal and a chain transfer terminal.
    [0011] The invention also provides an ethylene-based polymer comprising at least one structural unit selected from the following:
    where R1 is selected from H or CH3. Brief description of the drawings
    [0012] Figure 1 represents the 1H NMR profile for the control A-0 polymer (lower profile) and the 1H NMR profile for the inventive A-3 polymer (upper profile);
    [0013] Figure 2 illustrates a graph of extensional viscosity versus time for the ethylene-based polymer of the invention B-3, at the Hencky stress rate of 10 s, l, 0s-1 and 0.1 s-1; and at 150 ° C. In this figure, "Eta" is the shear viscosity in Pa-s. Detailed description of the invention
    [0014] As discussed above, in a first aspect, the invention provides an ethylene-based polymer formed from at least one of the following: ethylene and a monomeric chain transfer agent (monomeric CTA), comprising a terminal copolymerization and a chain transfer terminal.
    [0015] The invention also provides, in a second aspect, an ethylene-based polymer comprising at least one structural unit selected from:
    Where R1 is selected from H or CH3. Here, the notation "IIIIIIIIII" represents a break in the center of a covalent bond between the observed portion of the structural unit and a portion of the remaining chemical structure of the polymer.
    [0016] The following embodiments apply to both the first and the second aspect of the invention, except where noted.
    [0017] In one embodiment, in the first aspect, the monomeric chain transfer agent is not an unconjugated di-unsaturated monomer.
    [0018] In one embodiment, the ethylene-based polymer comprises, in the reacted form, at least 0.075 moles of the monomeric CTA per 1000 moles of carbon in the main chain of the ethylene-based polymer, based on the weight of the polymer.
    [0019] In one embodiment, the ethylene-based polymer comprises, in the reacted form, less than, or equal to, 10 moles of monomeric CTA per 1000 moles of carbon in the main chain of the ethylene-based polymer, based on weight of the polymer.
    [0020] In one embodiment, the ethylene-based polymer comprises, in the reacted form, less than, or equal to, 5 moles of monomeric CTA per 1000 moles of carbon in the main chain of the ethylene-based polymer, based on weight of the polymer.
    [0021] In one embodiment, the ethylene-based polymer comprises, in the reacted form, at least 0.03% by weight of the monomeric CTA, based on the weight of the polymer.
    [0022] In one embodiment, the ethylene-based polymer has melt resistance [MS] (cN) and melt index 12 (g / 10 minutes), according to the following equation:

    [0023] In one embodiment, the ethylene-based polymer has a stress hardening factor (SHF) greater than 3, at Hencky stress rates from 10 s -1 to 1.0 s -1, and 150 ° C. SHF is the ratio of extensional viscosity to three times the shear viscosity in the same measure of time and at the same temperature. The measurement time is defined as the ratio of "three" to "the Hencky stress rate applied to the measured extensional viscosity". For example, the measurement time is 0.3 seconds for a stress rate of 10 s-1, 3.0 seconds for a stress rate of 1 s-1, and 30 seconds for a stress rate of 0.1 s-1.
    [0024] In one embodiment, the ethylene-based polymer has a melt index (12) from 0.01 to 1000, typically from 0.05 to 100, and more typically from 0.1 to 50 grams per 10 minutes (g / 10 minutes).
    [0025] In one embodiment, the ethylene-based polymer has a melt index (12) from 0.3 to 100 g / 10 minutes, or from 1 to 50 g / 10 minutes, or from 2 to 20 g / 10 minutes.
    [0026] In one embodiment, the ethylene-based polymer has a density greater than or equal to 0.091 or greater than or equal to 0.92 or greater than or equal to 0.93 grams per cubic centimeter (g / cc or g / cm3)
    [0027] In one embodiment, the ethylene-based polymer has a density less than, or equal to, 0, 96 or less than, or equal to 0, 95 or less than, or equal to, 0.94 grams per centimeters cubic (g / cc or g / cm3)
    [0028] In one embodiment, the ethylene-based polymer has a density of 0.91 to 0.96, or 0.91 to 0.95, or 0.91 to 0.94 g / cc.
    [0029] In one embodiment, the ethylene-based polymer has an insoluble material content of less than 10% by weight, preferably less than 8% by weight. The content of insoluble material is determined by high temperature gel permeation chromatography (HT GPC) as discussed here.
    [0030] In one embodiment, in the second aspect, [—S—} is selected from the following:

    [0031] For each “[-S-]” structure, the two free line ends of each structure represent the two connections connected to the remaining chemical structure of the polymer.
    [0032] In one embodiment, in the second aspect, [-S-] is selected from:

    [0033] In one embodiment, in the second aspect, at least one structural unit is as follows:

    [0035] Here, the remark "|" represents a break in the center of a covalent bond between the observed portion of the structural unit and a portion of the remaining chemical structure of the polymer.
    [0036] The invention also provides a composition comprising an ethylene-based polymer, as described herein.
    [0037] In one embodiment, the composition further comprises an ethylene / ocoolefin interpolymer with a density less than or equal to 0.94 g / cc.
    [0038] The invention also provides an article comprising at least one component formed from a composition of the invention.
    [0039] In one embodiment, the article is a film or coating
    [0040] In one embodiment, the article is a film.
    [0041] In one embodiment, the article is a coating.
    [0042] An ethylene-based polymer of the invention can comprise a combination of two or more embodiments as described herein.
    [0043] A composition of the invention can comprise a combination of two or more embodiments as described here.
    [0044] An article of the invention can comprise a combination of two or more embodiments as described here.
    [0045] The invention also provides a process for forming an ethylene-based polymer of the invention, as described herein, the process comprising the polymerization of ethylene in the presence of the monomeric chain transfer agent (monomeric CTA).
    [0046] In one embodiment, ethylene is polymerized in the presence of at least 50 moles-ppm (based on the amount of total monomers in the reaction feed) of the monomeric chain transfer agent (monomeric CTA).
    [0047] In one embodiment, the polymerization pressure is greater than, or equal to, 100 MPa.
    [0048] In one embodiment, polymerization occurs in at least one tubular reactor or at least one autoclave.
    [0049] In one embodiment, polymerization occurs in at least one autoclave.
    [0050] In one embodiment, polymerization occurs in at least one tubular reactor.
    [0051] In one embodiment, the monomeric chain transfer agent is added to the polymerization in an amount of 0.0050 to 0.3000 mole percent, based on the total moles of ethylene and the monomeric CTA added to the polymerization. In an additional embodiment, polymerization takes place in two reactors. In another embodiment, polymerization takes place in a reactor.
    [0052] A process of the invention can comprise a combination of two or more embodiments as described here.
    [0053] The ethylene-based polymers of the invention have been discovered, which are prepared from at least one of the following: ethylene and a monomeric chain transfer agent. The monomeric chain transfer agent preferably has a carbon-carbon double bond at one end of the molecule and a functional chemical group capable of reacting with the chain transfer agent at the other end. For example, the polymers of the invention were prepared by polymerizing ethylene in the presence of 2-propanoic acid, 2,2-dimethyl-3-oxopropyl ester, also known as isobutyl aldehyde acrylate (IBAA). The polymers of the invention have improved (superior) melt resistance when compared to conventional LDPE. It has also been found that the polymers of the invention can be mixed with other polymers, such as linear low density polyethylene (LLDPE), to make mixtures that have superior melt strength and rheology compared to conventional LDPE / LLDPE mixtures. The improved rheological characteristics make the polymers of the invention and their mixtures extremely suitable for extrusion coating or blow film applications. It has also been found that the polymers of the invention contain low amounts of insolubles. Process
    [0054] For the production of a highly branched ethylene-based polymer, a high pressure polymerization process, initiated in free radical, is typically used. Two different types of high pressure free radical initiation polymerization process are known. In the first type, a stirred autoclave container having one or more reaction zones is used. The autoclave reactor usually has several injection points for the initiator or the monomer feed, or both. In the second type, a coated tube is used as a reactor, which has one or more reaction zones. Appropriate, but not limiting, the reactor length can be from 100 to 3000 meters (m), or from 1000 to 2000 meters. The start of a reaction zone, for both types of reactor, is typically defined by a side injection of the same reaction initiator, ethylene, chain transfer agent (or telomer), comonomer (s), as well as any combination of the same. A high pressure process can be carried out in an autoclave or tubular reactors having one or more reaction zones, or in a combination of autoclave and tubular reactors, each comprising one or more reaction zones.
    [0055] In one embodiment, a primer is injected prior to the reaction zone where free radical polymerization is to be induced.
    [0056] Often, a conventional chain transfer agent is used to control molecular weight. In a preferred embodiment, one or more conventional chain transfer agents (CTAs) are added to a polymerization process of the invention. Topical CTA that can be used includes, but is not limited to, propylene, isobutane, n-butane, 1-butane, methyl ethyl ketone, acetone, ethyl acetate, propionaldehyde, ISOPAR (ExxonMobil Chemical Co.), and isopropanol. In one embodiment, the amount of CTA used in the process is 0.03 to 10 weight percent of the total reaction mixture.
    [0057] In one embodiment, the process may include a recycling cycle process to improve conversion efficiency.
    [0058] The ethylene used to produce the ethylene-based polymer can be purified ethylene, which is obtained by removing the polar components from the recycling cycle stream, or by using a reaction system configuration, so that only fresh ethylene is used to make the polymer of the invention. It is not typical that purified ethylene is required to make the polymer based on ethylene. In such cases, ethylene from the recycling cycle can be used.
    [0059] In one embodiment, the ethylene-based polymer comprises ethylene and one or more comonomers and, preferably, a comonomer. Comonomers include, but are not limited to, oc-olefins, acrylates, methacrylates, and anhydrides, each typically having no more than 20 carbon atoms. O-olefin comonomers can have 3 to 10 carbon atoms, or alternatively, oc-olefin comonomers can have 3 to 8 carbon atoms. Examples of comonomers of oc-olefins include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl- l-pentene.
    [0060] In one embodiment, the ethylene-based polymer comprises ethylene and at least one monomeric CTA as the monomeric units only. Monomeric chain transfer agents
    [0061] A monomeric CTA (mCTA) is a comonomer, where one end of the comonomer incorporates (or reacts) through copolymerization, and another portion of the comonomer incorporates (or reacts) through chain transfer.
    [0062] In one embodiment, the "copolymerization terminal" of the monomeric chain transfer agent is selected from the group consisting of the following:
    where RI is selected from H, CH3, CH2CH3, CN, or COCH3; (B)
    where R2 is selected from H, CH3, CH2CH3, CN, or COCH3; (ç)
    where R3 is selected from H, C1-C22 alkyl, C3-C8 cycloalkyl, or phenyl; (d)
    where R4 is selected from H, CH3, CH2CH3, CN or COCH3, and R5 is selected from H, C1-C22 alkyl, C3-C8 cycloalkyl, phenyl or COCH3; (and)
    where R6, R7, R8 are each independently selected from H, CH3, or CH2CH3; (f)
    where R9, RIO, R11 are each independently selected from H, CH3, or CH2CH3; (g)
    R> 2, where R12, R13 are each, independently, selected from H, CH3, CH2CH3 or phenyl; (H)
    where R14 is selected from H, CH3, CH2CH3, or CN; (i)
    where R15 is selected from H, C1-C22 alkyl, C3-C8 cycloalkyl, or phenyl; and (j) where R16 is selected from H, CH3, CN, or COCH3.

    [0063] In the structures, (a) to (j) above, the notation '/ vvv' represents a break in the center of a covalent bond between the "monomeric portion (copolymerization terminal)" of the monomeric chain transfer agent and the remaining chemical structure of the monomeric chain transfer agent.
    [0064] In one embodiment, the "copolymerization terminal" of the monomeric chain transfer agent is selected from the group consisting of structures (a) to (i) r as shown above.
    [0065] In one embodiment, the "copolymerization terminal" of the monomeric chain transfer agent is selected from the group consisting of structures (a) through (g) r as shown above.
    [0066] In one embodiment, "copolymerization terminal" of the monomeric chain transfer agent is selected from the group consisting of structures (a) through (d) r as shown above.
    [0067] In one embodiment, the "chain transfer terminal" of the monomeric chain transfer agent is selected from the group consisting of the following:
    where RI is selected from H, C1-C22 alkyl, C3-C8 cycloalkyl, CN, phenyl, COCH3, Cl, Br, or I;
    where R2, R3 are each independently selected from H, C1-C22 alkyl, C3-C8 cycloalkyl, CN, phenyl or COCH3; 3) on
    where n is 1 to 6;
    where R4 is selected from H, C1-C22 alkyl, C3-C8 cycloalkyl, phenyl, Cl, Br, or I; 5) where R5 is selected from C1-C22 alkyl, C3-C8 cycloalkyl, or phenyl;
    6) where R6 is selected from C1-C22 alkyl, C3-C8 cycloalkyl, or phenyl;
    7)
    where R7, R8, are each independent, selected from H, C1-C22 alkyl, C3-C8 cycloalkyl, phenyl, Cl, Br, or I; and X is selected from F, Cl, Br, or I; 8)
    where X is selected from Cl, Br, or 6; 9)
    where R9, RIO, are each independently from H, C1-C22 alkyl, C3 cycloalkyl or COCH3; and X is selected from Cl, Br, or I; 10)
    where X is selected from Cl, Br, or 6; 11)
    where R11, R12 are each, independently from H, C1-C22 alkyl, C3 cycloalkyl or COCH3; 12)
    where n is 1 to 6; 13)
    where R13 is selected from H, C1-C22 alkyl, C3-C8 cycloalkyl, or phenyl; R14 is selected from H, C1-C22 alkyl, or C3-C8 cycloalkyl; and Z is selected from N or P; 14)
    where R15 is selected from H, C1-C22 alkyl, C3-C8 cycloalkyl, or phenyl; R16 is selected from H, C22 alkyl, or C3 — C8 cycloalkyl; Z is selected from N or P; and n is 1 to 6; 15)
    where R17 is selected from C1-22 alkyl, C3 C8 cycloalkyl, or phenyl; z is selected from N orP; enédelaó; 16)
    where RI 8, RI 9, R2 0, R21, p. they are each independently selected from H, k'J- ~ C22 alkyl, or C3-C8 cycloalkyl; Z is selected from N or P; en - e selected from 1 to 6; and 17)
    where R23 is selected from H, C1-C22 alkyl, C3-C8 cycloalkyl, or phenyl; and R24 is selected from H, Cl-C22 alkyl, C3-C8 cycloalkyl, CN, phenyl, COCH3, Cl, Br or I.
    [0068] In structures 1 to 17 above, observation n li
    [0069]
    represents a break in the center of a covalent bond between the "chain transfer terminal" of the monomeric chain transfer agent and the remaining chemical structure of the monomeric chain transfer agent.
    [0070] In one embodiment, the "chain transfer terminal" of the monomeric chain transfer agent is selected from the group consisting of structures 1 to 16, as shown above.
    [0071] In one embodiment, the "chain transfer terminal" of the monomeric chain transfer agent is selected from the group consisting of structures 1 to 10, as shown above.
    [0072] In one embodiment, the "chain transfer terminal" of the monomeric chain transfer agent is selected from the group consisting of structures 1 to 4, as shown above.
    [0073] A monomeric chain transfer agent can comprise a combination of two or more embodiments as described here.
    [0074] In one embodiment, the monomeric chain transfer agent (monomeric CTA) is selected from the group consisting of those defined below:
    (A) where R1, R2, R3 are each independently selected from H, C1-C6 alkyl, C3-C8 cycloalkyl, or phenyl; and X is selected from CN, F, Cl, Br or I; (B)
    where R4 is selected from H, C1-C6 alkyl, C3-C8 cycloalkyl, or phenyl; R5 is selected from H, C1-C8 alkyl, C1-C18 carboxy ester, C7 aromatic ester, C3-C8 cycloalkyl, phenyl or benzyl; and X is selected from CN, F, Cl, Br or I; (Ç)
    where R6, R7, are each independently selected from H, C1-C6 alkyl, C3-C8 cycloalkyl, or phenyl; (D)
    where R8 is selected from H, C1-C6 alkyl, C3-C8 cycloalkyl, or phenyl; R9, R10, R11, R12 are each, independently selected from H or CH3; (AND)
    where R13, R14, R15 are each independently selected from H or CH3; (F)
    where R16, R17, R18, are each independently selected from H or CH3; (G)
    where RI9 is selected from H or CH3; (H)
    where R20 is selected from H or CH3; (D
    where R21 is selected from H or CH3; (J)
    where R22 is selected from H or CH3; R23, R24 are each independently selected from H, C1-C6 alkyl, C3-C8 cycloalkyl, or phenyl; (K)
    where R25 is selected from H or CH3; R26, R27 are each independently selected from H, C1-C6 alkyl, C3-C8 cycloalkyl, or phenyl; R28 is selected from H, C1-C22 alkyl, C3-C8 cycloalkyl, or phenyl;
    where R29 is selected from H or CH3; R30 is selected from H, C1-C6 alkyl, C3-C8 cycloalkyl, or phenyl; (M)
    where R31 is selected from H or CH3, R32 is selected from H, C1-C22 alkyl, C3-C8 cycloalkyl, or phenyl; R33 is selected from H, C1-22 alkyl, or C3-C8 cycloalkyl; Z is selected from N or P; enédelal7; (N)
    where R34 is selected from H or CH3; R35, R36, R37, R38, R39, are each independently selected from H, C1-C22 alkyl, or C3-C8 cycloalkyl, Z is selected from N or P; (0)
    where R40, R41 are each independently selected from H, C1-C6 alkyl, C3-C8 cycloalkyl, or phenyl; and X is selected from CN, F, Cl, Br or I; and (P)
    where R42, R43, R44, R45 are each independently selected from H, C1-C6 alkyl, C3-C8 cycloalkyl, or phenyl; and X is selected from Cn, F, Cl, Br, or I.
    [0075] In one embodiment, the monomeric chain transfer agent is selected from the group consisting of structures (A) through (0), as shown above.
    [0076] In one embodiment, the monomeric chain transfer agent is selected from the group consisting of structures (A) through (J), as shown above.
    [0077] In one embodiment, the monomeric chain transfer agent is selected from the group consisting of structures (A) through (F), as shown above.
    [0078] In one embodiment, the monomeric chain transfer agent is selected from the group consisting of structures (D) through (J) r as shown above.
    [0079] In one embodiment, the monomeric chain transfer agent is selected from the group consisting of those defined below:

    [0080] In one embodiment, the monomeric CTA is selected from the group consisting of (i) through (vii) and (x), as shown above.
    [0081] In one embodiment, the monomeric CTA is selected from the group consisting of (i) through (iv) r (vi) r (viii) r (ix) and (x), as shown above.
    [0082] In one embodiment, the monomeric CTA is selected from the group consisting of (i) through (iv), (vi) and (x), as shown above.
    [0083] In one embodiment, the monomeric chain transfer agent is an acrylate or a methacrylate.
    [0084] In one embodiment, the monomeric chain transfer agent is selected from the group consisting of those defined below: allyl thiol glycolate, aldehyde isobutyl acrylate, allyl acetoacetate, and allyl cyanoacetate.
    [0085] In one embodiment, the monomeric chain transfer agent is selected from the group consisting of those defined below: 2-propanoic acid, 2,2-dimethyl-3-oxopropyl ester, 2- (methacryloyloxy) acetoacetate ethyl; 2-methyl-3-oxopropyl methacrylate, 4-oxobutyl methacrylate; 2- (2-cyano-N-methylacetamido) ethyl methacrylate; 2- (2-cyanoacetoxy) ethyl methacrylate; 5-oxopentyl acrylate; and 3- (2-cyanoacetoxy) -2-hydroxyproyl methacrylate. In a further embodiment, the monomeric chain transfer agent is selected from 2-propenoic acid, 2,2-dimethyl-3-oxopropyl ester, 2- (methacryloyloxy) ethyl acetoacetate; 2-methyl-3-oxopropyl methacrylate; 4-oxobutyl methacrylate; 2- (2-cyano-N-methylacetamido) ethyl methacrylate; or 2- (2-cyanoacetoxy) Oethyl methacrylate.
    [0086] In one embodiment, the monomeric chain transfer agent is selected from the group consisting of those defined below: IBAA (isobutyl aldehyde acrylate or 2-propanoic acid; 2,2-dimethyl-2-oxopropyl ester) ; AAEM (2- (methacryloyloxy) ethyl acetoacetate); 4-oxobutyl methacrylate; 2-methyl-3-oxopropyl methacrylate; 5-oxopentyl acrylate; and 3- (2-cyanoacetoxy) -2-hydroxypropyl methacrylate. In a further embodiment, the monomeric chain transfer agent is selected from IBAA or AAEM.
    [0087] In a preferred embodiment, the monomeric CTA is not diene. Some examples of dienes include 1,5-hexadiene; 1,7-octadiene; 1,9-decadiene; ethylene glycol dimethacrylate, allyl methacrylate; diallyl phthalate, and divinyl tetramethyl 1,3-disyloxane.
    [0088] In one embodiment, the monomeric CTA has 1H NMR signals from 3.0 to 5.0 ppm of the chemical exchange.
    [0089] In one embodiment, a polymer of the invention is polymerized in the presence of at least two monomeric chain transfer agents as described herein.
    [0090] A monomeric CTA can comprise a combination of two or more embodiments as described here. Initiators
    [0091] Free radical initiators are generally used to produce the ethylene-based polymers of the present invention. Examples of organic peroxides include, but are not limited to, cyclic peroxides, diacyl peroxides, dialkyl peroxide, hydroperoxides, peroxycarbonates, peroxydicarbonates, peroxyesters, and peroxicetal. Preferred initiators are t-butyl peroxy pivalate, di-t-butyl peroxide, t-butyl peroxy acetate, and 1-butyl peroxy-2-hexanoate, or mixtures thereof. In one embodiment, these organic peroxy initiators are used in an amount of 0.001 to 0.2 weight percent, based on the weight of the polymerizable monomers. Additions
    [0092] A composition of the present invention can comprise one or more additives. Additives include, but are not limited to, stabilizers, plasticizers, anti-aesthetic agents, dyes, nucleating agents, fillers, glidants, flame retardants, processing aids, smoke inhibitors, viscosity control agents, and agents anti-blocking. The polymeric composition can, for example, comprise less than 10 percent of the combined weight of one or more additives, based on the weight of the polymer of the invention.
    [0093] 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 IRGANOX 168 (Ciba Specialty Chemicals; Glattbrugg, Switzerland). In general, polymers are treated with one or more stabilizers before extrusion or other melting processes.
    [0094] The combinations and mixtures of the polymers of the present invention with other polymers can be performed. Polymers suitable for combination with the polymer of the present invention include natural and synthetic polymers. Examples of combination polymers include polypropylene, (both impact modifying polypropylenes, isotactic polypropylene, atactic polypropylene, and random ethylene / propylene copolymers), various types of polyethylene, including high pressure free radical LDPE, LLDPE Ziegler-Natta, Catalyzed single site PE, including multiple reactor PE ("reactor" combination of PE Ziegler-Natta and "single site catalyzed" PE, such as the products described in U.S. Patent No. 6,545,088 (Kolthammer et al.); US 6,538,070 (Cardwell, et al); US 6,566,446 (Parikh, et al.); US 5,844,045 (Kolthammer et al.); US 5,869,575 (Kolthammer et al.); And US 6,448,341 (Kolthammer et al.)), Acetate ethylene-vinyl (EVA), alcohol / ethylene vinyl copolymers, polystyrene, impact modifier polystyrene, ABS, styrene / butadiene block copolymers, and hydrogenated derivatives thereof (SBS and SEES), and thermoplastic polyurethanes. applications
    [0095] The polymers of this invention can be employed in a variety of conventional thermoplastic fabrication processes to produce useful articles, including monolayer and multilayer films; molded articles, such as blow molded, injection molded, or rotational molded articles, coatings; fibers; and woven or non-woven fabrics.
    [0096] A polymer of the present invention can be used in a variety of films, including, but not limited to, bonding shrink films, fused stretch films, silage films, stretch cover, sealants, and diaper back .
    [0097] Other appropriate applications include, but are not limited to, wires and cables, gaskets and profiles, adhesives, shoe components, and automobile interior parts. Definitions
    [0098] The term "unconjugated di-unsaturated monomer" as used here, refers to a molecule that has two unconjugated carbon-carbon bonds anywhere in its structure and, preferably, at the terminal ends of the molecule.
    [0099] The term "composition", as used here, includes a mixture of materials comprising the composition, as well as products for reaction and decomposition of products formed from materials of the composition.
    [0100] The terms "combination" or "combined polymers", as used, refer to a mixture of two or more polymers. A mixture may or may not be miscible (no phase separated at the molecular level). A combination may or may not be in a separate phase. A combination may or may not contain one or more domain configurations, as determined from the transmission of electron spectroscopy, light scattering, X-ray scattering, and other methods known in the art. The mixing can be carried out by physically mixing two or more polymers at the macro level (for example, mixing resins by melting or composting) or at the micro level (for example, simultaneous formation within the same reactor).
    [0101] The term "polymer" refers to a compound prepared by the polymerization monomers, whether of the same or a different type. The generic term polymer thus encompasses the term homopolymer (which refers to polymers prepared from only one type of monomers with the understanding that traces of quantities of impurities can be incorporated within the polymer structure), and the term "interpolymer" as defined below.
    [0102] The term "interpolymer" refers to polymers prepared by the polymerization of at least two different types of monomers. The generic term interpolymer includes copolymers (which refer to polymers prepared from two different monomers), and polymers prepared from more than two different types of monomers.
    [0103] The term "ethylene-based polymer" refers to a polymer that comprises the majority of the amount of polymerized ethylene, based on the weight of the polymer and, optionally, can comprise at least one comonomer.
    [0104] The term "ethylene-based interpolymer" refers to an interpolymer that comprises the majority of the amount of ethylene polymerized based on the weight of the interpolymer, and comprises at least one comonomer.
    [0105] The terms "comprising", "including", "having", and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same specifically described. In order to avoid any doubt, all compositions claimed through the use of the term "comprising" may include any additive, adjuvant, or compound, additional, whether polymeric or otherwise, unless otherwise stated. In contrast, the term "essentially consisting of" excludes from the scope of any successive citation of any other component, step, or procedure, with the exception of those that are not essential for operability. The term "consisting of" excludes any component, step, or procedure not specifically outlined or listed. Testing methods Density:
    [0106] The samples that were measured for density were prepared according to ASTM D 1928. The samples were pressed at 374 ° F (190 ° C) and 30,000 psi for three minutes, and then at 70 ° F (21 ° C) and 30,000 psi for one minute. The density measurement was made within one hour of pressing the sample, using ASTM D792, Method B. melting index:
    [0107] The melting index, or 12, was measured according to ASTM D 1238, condition 190 ° C / 2.16 kg, reported in grams eluted for 10 minutes. The 110 was measured according to ASTM D 1238, Condition 190 ° C / 10 kg, and was reported in grams eluted for 10 minutes. Melting resistance:
    [0108] Melt strength was measured at 190 ° C using a Gõettfert Rheotens 71.97 (Gõettfert Inc .; Rock Hill, SC). The fused sample (about 25 to 50 grams) was fed with a capillary rheometer Gõettfert Rheotester, equipped with a straight entry angle (180 degrees) of length 0 mm and diameter 2 mm. 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 piston speed of 0.265 mm / s, which corresponds to a shear rate of the wall of 38.2 s-1 in a given diameter of the mold. The extrudate passed through the Rheotens' rounds, located 100 mm below the mold outlet, and was pulled by the wheels below, at an acceleration rate of 2.4 mm / s2. The force (in cN) exerted on the wheels was recorded as a function of the speed of the wheels (in mm / s). The samples were repeated at least twice, until two force curves (in cN) as a function of the tension speed (in mm / s) overlap, so the curves that have the highest speed in breaking the tension were reported. The resistance to the function was reported as the stopping force (cN) before the voltage broke. Extensional viscosity:
    [0109] Extensional viscosity was measured using a fixed instrument (EVF) from TA Instruments (New Castle, DE), connected to an ARES rheometer model from TA Instruments. Extensional viscosity at 150 ° C, and at Hencky stress rates of 10s-1, ls-1 and 0, ls-1, was measured. The sample plate was prepared on a programmable Tetrahedron MTP8 bench top press. The program retained 3.8 grams of melting at 180 ° C for five minutes, at a pressure of 1 x 107 Pa, to make a plate "75 mm x 50 mm" with a thickness of 0.7 mm to 1, 1 mm. The TEFLON-coated engraving containing the plate was then removed to the top of the bench for cooling. The test specimens were then cut into the mole from the plate using a drill press and a portable mold with dimensions of "10x8 mm (width x length)". The specimen thickness was in the range of about 0.7 mm to about 1.1 mm.
    [0110] The rheometer oven that covered the fixed EVF was represented at the test temperature of 150 ° C, and the fixation of the test that contacts the sample plate was balanced at that temperature for at least 60 minutes. The test fixture was then "zeroed" using the test software, to induce the fixture to move in contact with one another. Then the test fixtures were moved out of a fixed 0.5 mm range. The width and thickness of each plate was measured at three different locations on the plate with a micrometer, and the average values for thickness and width were entered into the test software (TA Orchestrator, version 7.2). The density of the sample measurement at room temperature was entered into the test software. For each sample, a value of "0.782 g / cc" was entered for the density at 150 ° C. These values were entered into the test software to allow calculation of the current plate dimensions at the test temperature. The sample plate was attached, using a pin, over each of the two drums of the fixture. The oven was then closed, and the temperature was allowed to equilibrate at 150 ° C + 0.5 ° C. As soon as the temperature entered this range, a timer was started manually, and after 60 seconds, the automated test was started by clicking on the "Start test" software button.
    [0111] The test was divided into three automated steps. The first stage was a "pre-expansion stage" which expanded the board at a very low tension rate of 0.005 s-1 for 11 seconds. The purpose of this step was to reduce the warping of the plate, introduced when it was heated above room temperature. This step was followed by a "relaxation step" of 60 seconds, to minimize the tension introduced in the pre-expansion step. The third step was the "measurement step", where the plate was expanded at Hencky's preset tension rate. The data collected in the third stage was stored, and then exported to Microsoft Excel, where the raw data were processed into values of the Tension Hardening Factor (SHF) reported here. Shear viscosity:
    [0112] Preparation of the sample to measure the shear viscosity.
    [0113] Specimens for measuring shear viscosity were prepared on a programmable Tetrahedron model MTP8 bench top press. The program left 2.5 grams of the melt at 180 ° C, for five minutes, in a cylindrical mold, at a pressure of 1 x 10 Pa, to make a cylindrical part with a diameter of 30 mm and a thickness of 3.5 mm. The engraving was then removed to the top bench to cool to room temperature. The round test specimens were then cut into molds from the plate using a drill press and a portable mold with a diameter of 25 mm. The specimens were about 3.5 mm thick. The measure of shear viscosity:
    [0114] Shear viscosity (Eta *) was obtained from the initial measurement of the stable shear that was performed with the TA Instruments ARES model rheometer, at 150 ° C, using "25 mm parallel plates" in an interval 2.0 mm, and under nitrogen purification. In the initial stable shear measurement, a constant shear rate of 0.005 s-1 was applied to the sample for 100 seconds. Viscosities were collected as a function of time on the logarithmic scale. A total of 200 data points were collected within the measurement period. The stress hardening factor (SHF) is the ratio of the extensional viscosity to three times the shear viscosity, at the same measurement time and at the same temperature. Determination of the weight fraction of insoluble materials:
    [0115] The weight fraction of the insoluble materials in each experimental polymer was determined as follows. Each polymer sample (0.1 g) was dissolved in 1,2,4-trichlorobenzene (TCB, 50 mL) at 155 ° C for four hours to make a "2.0 mg / mL solution ". This solution was filtered hot through a Mott filter (Watters) or through a layer of Perlite. The filtrate was collected, and characterized on high temperature gel permeation chromatography (HT GPC, Waters - Model 150C), equipped with an infrared concentration detector (IR-4, PolymerChar Inc.). The HT GPC had an injection fixed on the loop with a fixed injection volume (200 microliters). The HT GPC concentration detector was calibrated with NBS (National Bureau of Standards) 1475a, which was standardized with the polyethylene reference, at a concentration and 2.0 mg / mL. An instrument parameter, the constant mass, was determined as follows:
    Where Areí- is the response area of the NBS 1475a detector; Cref is the concentration of NBS 1475 a in TCB (units - mg / mL).
    [0116] The detected concentration of the filtrate in the polymer sample was then obtained using the following equation:
    Where a is the response area of the polymer sample filtrate detector, and Kmassa is the instrument constant (units = area * mL / mg).
    [0117] The recovery of the soluble mass (SMR) in the percentage of the polymer sample was calculated as follows:
    Here the number "2.0" represents the initial concentration "2.0 mg / ml" of the polymer sample.
    [0118] The percentage by weight (%) of the insoluble materials in the polymer sample was determined from the following equation:
    Nuclear magnetic resonance (1H NMR):
    [0119] Each NMR sample was prepared by adding approximately "0.10 g of ethylene-based polymer" to "2.7 g of tetrachloroethane-d2 (TCE), containing 0.001 M Cr (AcAc) 3 (tris / acetylacetonate) ) -chromium (III)) "in a" NORELL 1001-7, 10 mm NMR tube ". The samples were purified by nitrogen bubbles through the solvent via a pipette, inserted into the tube for approximately five minutes, to prevent oxidation, and then they were capped, sealed with TEFLON tape, and then rinsed at room temperature overnight. to facilitate the dissolution of the sample. The samples were kept in a nitrogen purification box during storage, before and after preparation to minimize exposure to oxygen. The samples were heated and mixed with a vortex mixer at 115 ° C to ensure homogeneity. Each sample was visually inspected to ensure homogeneity.
    [0120] The data were collected using a BRUKER AVANCE 400 HRz NMR spectrometer, equipped with a high temperature CRUOPROBE BRUKER DUAL DUL, at a sample temperature of 120 ° C. Each analysis was run with a ZG pulse, 32 mappings, SWH 10,000 Hz, AQ 1.64 s, and Dl 14 s. The acquisitions were repeated using a 28 second Dl to check the quantification and the results were equivalent. EXPERIMENTAL
    [0121] The ethylene-based polymers of the invention, A-1, A-2 and A-3 and Control A-O:
    [0122] CTA monomer - undiluted 2-propenoic acid, 2,2-dimethyl-3-oxopropyl ester (hereinafter IBAA; CAS [69288-03-5); see also US patent 4,191,838) was loaded into a stainless steel supply vessel, and diluted with ethyl acetate, to produce a final concentration of 21.5% by weight. This container was purified with nitrogen.
    [0123] Initiator initiator tert-butyl peroxyacetate peroxide (125 gm of 20% by weight of a solution in ISOP AR ™ H) was combined with 4400 gm of ISOPAR E, and loaded into a second stainless steel supply vessel . This container was purified with nitrogen.
    [0124] Control (A-0) - ethylene was injected at 5440 gm / well (194 moles / hours), at a pressure of 1931 bar, in a stirring reactor under high pressure 300 mL (1600 rpm), with a jacket external heating set at 250 ° C. Propylene (CTA) was added to the ethylene stream at a pressure of 62 bars at a rate of 100 gm / hour (2.38 moles / hour), before the mixture was compressed to 1931 bar; and injected into the reactor. The peroxide initiator was added directly to the reactor through the side wall of the CSTR reactor, at a pressure of 1931 bar, and at a rate of 1.85 x 10-1 gm / hour (1.4 millimoles / hour). The conversion of ethylene to polymer was 9.5% by weight based on the mass of ethylene entering the reactor, and the average reaction temperature was 247 ° C. An ethylene-based polymer with a melt index (12) of 1.13 g / 1 minutes was formed. Approximately 490 grams of this ethylene-based polymer (A-0) were collected.
    [0125] Ethylene-based polymers of the invention A-1, A-2 and A-3.
    [0126] Propylene (CTA) was added to the ethylene stream at a pressure of 62 bar, and at a rate of 69.9 gm / hour (1.66 mole / hour), before the mixture was compressed to 1931 bar; and injected into the 9ver reactor above). The IBAA solution in ethyl acetate was pumped at a pressure of 1931 bar, and at a rate of 28.19 gm / hour (38.8 millimoles / hour) into the ethylene-propylene mixture, before said mixture was injected into the reactor. The peroxide initiator was added directly to the reactor, through the side wall, at a pressure of 1931 bar, and at a rate of 2.26 x 10-1 gm / hour (1.7 millimoles / hour). The conversion of ethylene to polymer was 10.9% by weight, based on the mass of ethylene entering the reactor, and the average reaction temperature was 250 ° C. An ethylene-based polymer with a melt index (12) of 1.0 g / 10 minutes was formed. Approximately 870 grams of this ethylene-based polymer (Al) were harvested. The amount of IBAA (mCTA) was increased twice to form two more polymers of the invention (A-2 and A-3). The reaction conditions of the polymerization are summarized below in Table 1. The properties of the polymer are shown in Table 2 Below.

    Calculation of incorporated mole of IBAA per 1000 moles of carbon in the main chain:
    [0127] Each ethylene-based polymer of the invention and the control was analyzed by 1H NMR. The virgin homopolymer of ethylene made through the radical high pressure process had> 99% of its 1H NMR signal area in the region of 3 to -1 ppm (chemical structure), and <0.1% of its 1H NMR signal area in the region from 3 to 12 ppm (chemical exchange). The 1H NMR signal area in the region of 2 to -1 ppm (chemical exchange) corresponds to the region of the hydrogen main chain of the 1H NMR spectrum of LDPE. Because each mole of the main carbon chain has two moles of main chain hydrogens attached to it, if the moles of the main chain hydrogens are measured, one can calculate the moles of the main chain carbons. In addition, when IBAA or AAEM is copolymerized with ethylene to make the respective ethylene-based polymer of the present invention, some chemical portions of these comonomers have 1H NMR signals in the region of 3 to 12 ppm (chemical exchange). It is common practice to express the moles of various structural characteristics of LDPE, for example, moles of comonomers of the IBAA or AAEM type, in terms of moles of the structural characteristic per 1000 moles of the main chain carbons (1000 C).
    [0128] To measure these molar ratios, the 1H NMR of the polymer of the invention is acquired, and the signal area from a chemical exchange of approximately 3 to -1.0 ppm is integrated, and fixed to 200 moles of protons using the 1H NMR software. This step normalizes the signal area of this region to "2000 moles of protons", which represents "1000 moles of main chain carbons", due to an average of each main chain carbon in LDPE is bound to 2 protons. The software's automatic 1H NMR ratio of all other proton signals to this "2000 mole proton main chain" value. If comonomers are present in the sample, they may have chemical portions that have 1H NMR signals in the region of 3 to 12 ppm (chemical exchange). In the case of IBAA, the hydrogens in the -O-CH2- portion have a signal with a chemical exchange in the range of 4.01 to 4.25 ppm. In addition, aldehyde hydrogen has a chemical exchange in the range of 9.51 to 9.68. The total moles of the IBAA incorporated per 1000 moles of carbon from the main chain (1000 C) are determined as from the normalized integration of the signal -O-CH2- from approximately 4.01 to 4.25 ppm. This procedure is valid because there is only one mole of the -O-CH2- portion in each mole of IBAA. The total moles of the protons of the IBAA aldehyde remain (not consumed by the reaction via the chain transfer) is determined directly from the integer of the aldehyde proton at approximately 9.51 to 9, 68 ppm, since it is only one mole aldehyde protons for each mole of IBAA. The calculated moles of IBAA branches per 1000 moles of main chain carbon (1000 C) is determined by subtracting the unreacted moles of aldehyde from the incorporated moles of IBAA pro 1000 C. See the sample calculations below. The NMR results are summarized in Table 3 below. Table 3: NMR results

    [0129] * Calculation example for A-3: Integration from approximately 3 to 1.0 ppm; adjustment for 2000 moles of hydrogen, which represents carbons (1000 C). Half the integration of -O-CH2- in approximately 4.01 to 4.25 ppm = 2.30 / 2 = 1.15 moles -O-CH2- portion and, therefore, 1.15 moles of IBAA per 1000 moles of main chain carbons (1000 C). Aldehyde proton integration at approximately 9.51 to 9.68 ppm = 1.01 branches per 1000 moles of main chain carbons 1.15 - 1.01 = 0.14 moles of IBAA branches per 1000 moles of chain carbons main (1000 C).
    [0130] For ethylene-based polymers Al, A-2, and A-3, the monomeric CTA "2-propenoic acid; 2,2-dimethyl-3-oxopropyl ester (IBAA)" copolymerized within each main chain of the polymer. Figure 1 represents the 1H NMR profile for the control polymer A-0 (lower profile) and the 1H NMR profile for the polymer A-3 of the invention (upper profile). In addition, all polymers of the invention with IBAA have higher melt strength values than the control polymer (A-0), which does not contain IBAA. The fusion resistance of the control without IBAA (A-0) was 16.6 cN with a fusion index (12) of 1.13. The melt strength of polymer Al was 19.3 cN at a melt index (12) of 1.10, the melt strength of polymer A-2 was 18.2 cN at a melt index (12) of 1.65, and the melt strength of polymer A-3 was 18.1 cN at a melt index (12) of 1.66. In addition, the extensional viscosity - stress hardening factor was higher at both 10s ”1 and Is” 1 stress rates for each polymer of the invention Al, A-2, and A-3, when compared to the control sample ( A — 0) that does not contain IBAA. At the same time, the insoluble content of all four ethylene-based polymers was less than 10% by weight: thus, the low insoluble content was maintained in the inventive polymers.
    [0131] Ethylene-based polymers of the invention B-1, B2 and B-3 and Control B-0.
    [0132] The undiluted 2- (methacryloyloxy) ethyl monomeric CTA - acetoacetate (hereafter AAEM; CAS [21282-97-3]; Eastman Chemical Company) was loaded into a 0.25 L glass container. , which was open to the atmosphere.
    [0133] CTA - A fresh 250 mL bottle of undiluted propionaldehyde (97%) was used as a supply vessel, which was opened to the atmosphere.
    [0134] Primer - The tert-butyl peroxyacetate peroxide initiator (2.3 grams of 50% by weight of an isododecane solution) was combined with 500 ml of n-heptane, and loaded into a third glass container for supply. This solution was purified with nitrogen to minimize dissolved oxygen.
    [0135] Control (B-0) - Ethylene was injected at 1000 gm / hour (35.65 moles / hour), at a pressure of 2000 bar, in a stirred high pressure CSTR reactor (2000 rpm) 54 mL, with an external heating jacket, adjusted to 187 ° C. Without the addition of the peroxide initiator, only 0.1% by weight of ethylene entered the polymerized reactor. Then, propionaldehyde was degassed by means of an HPLC degasser, and then it was added to the ethylene stream at a pressure of 250 bar, and at a rate of 3.23 gm / hour (56 millimoles / hour), before mixing 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 2.2 x 10-3 gm / hour (0.017 millimoles / hour), before the mixture entered the reactor. The conversion of ethylene to polymer was 10.5% by weight based on the mass of ethylene entering the reactor, and the average reaction temperature was 219 ° C. An ethylene-based polymer having a melt index (12) of 2.9 g / 10 minutes was obtained. Approximately 50 grams of ethylene-based polymer was collected (Control B-0). Ethylene-based polymers of the invention B-1, B-2 and B-3:
    [0136] Undiluted AAEM was pumped at a pressure of 250 bar, and at a rate of 1.65 gm / hour (7.7 millimoles / hour) through an HPLC degasser, and then into the propionaldehyde stream, and mixed before said mixture is added to the ethylene stream and compressed to 2000 bar. The peroxide initiator was added to the ethylene-propionaldehyde-AAEM mixture at a pressure of 2000 bar, and at a rate of 2.5 x 10-3 gm / hour (0.019 millimoles / hour), before the mixture entered the reactor. The conversion of ethylene to polymer was 10% by weight based on the mass of ethylene entering the reactor, and the average reaction temperature was 216 ° C. An ethylene-based polymer having a melt index (12) of 3.2 g / 10 minutes was obtained. Approximately 100 grams of ethylene-based polymer was collected (Bl). The amount of AAEM (mCTA was increased twice to form two more polymers of the invention (B-2 and B-3). The reaction polymerization conditions are summarized below table 4. Some properties of the polymer are shown in table 5 below .
    Table 5: Polymer Properties
    Calculation of built-in mol of AAEM per 1000 moles of carbon in the main chain:
    [0137] The same standardization procedure and 1H NMR acquisition spectrum was used for the polymers of the AAEM invention, which was used for the polymers of the IBAA invention above. For the AAEM polymers of the invention, the moles of the AAEM incorporated per 1000 moles of carbon in the main chain (1000 C) were determined as U of the integer of the - 0-CH2-CH2-O portion, from approximately 3.76 to 4.56 ppm (chemical exchange), because one mole of this portion is present in each mole of AAEM. See the sample calculation below. The NMR results are summarized in Table 6 below. Table 6: Results of 1H NMR
    * Example of calculation for B-3: Integration from approximately 3 to -1.0 ppm; adjust to 2000 moles of hydrogens, which represent 1000 moles of carbon in the main chain (1000 C). A quarter of the integration of -O-CH2-CH2-O in approximately 3.78 to 4.56 ppm = M (6.18) = 1.55 moles of this portion and, therefore, 1.55 moles of AAEM per 1000 moles of main chain carbons (1000 C). Aldehyde proton integration at approximately 9.51 to 9.68 ppm = 1.01 branches per 1000 moles of main chain carbons 1.15 - 1.01 = 0.14 moles of IBAA branches per 1000 moles of chain carbons main (1000 C).
    [0138] For the ethylene-based polymer B-1, B-2 and B-3, the monomeric CTA "2- (methacryloyloxy) ethyl acetoacetate (AAEM)" copolymerized in each main polymer chain. In addition, all polymers of the present invention with AAEM had higher melt strength values than the control polymer (B-0), which did not contain AAEM. The melt strength of the control without AAEM (B-0) was 7.2 cN at a melt index (12) of 2.9. The melt strength of polymer Bl was 8.4 cN at a melt index (12) of 3.2, the melt strength of polymer B-2 was 9.5 cN at a melt index (12) of 3.1, and a melt strength of polymer B-3 was 11.4 cN at a melt index (12) of 2.8. In addition, the extensional viscosity - Strain hardening factor was higher in both stress rates of 10 s-1 and ls-1 for each polymer of the invention Bl, B — 2 and B-3, when compared to the control sample (Bl ) that did not contain AAEM. See also figure 2, which is a representation of the extensional viscosity versus time for the ethylene-based polymer of the invention B-3, at Hencky stress rates of 10 ”1, 1.0s" 1 and 0.1s "1 , and at 150 ° C.
    [0139] Ethylene-based polymers of the C-1 invention and C-0 Control:
    [0140] CTA monomer - A mixture of 2-methyl-3-oxopropyl methacrylate, CAS [1215085-21-4], see patent 2011/0144267, (45 gm); 4-oxobutyl methacrylate, CAS [139288-31-6], see US patent 2001/0144267, (54 gm); and 974 gm n-heptane) was loaded into a 0.25 L glass supply vessel, which was opened to the atmosphere.
    [0141] CTA - A fresh 250 mL bottle of undiluted propionaldehyde (97%) was used as a supply container, which was opened to the atmosphere.
    [0142] Primer - The tert-butyl peroxyacetate peroxide initiator (2.3 grams of 50% by weight of an isododecane solution) was combined with 500 ml of n-heptane, and loaded into a third glass container for supply. This solution was purified with nitrogen to minimize dissolved oxygen.
    [0143] Control (C-0) - Ethylene was injected at 1000 gm / hour (35.65 moles / hour), at a pressure of 2000 bar, in a stirred CSTR high pressure reactor (2000 rpm) 54 mL, with an external heating jacket, adjusted to 187 ° C. Then, propionaldehyde was degassed by means of an HPLC degasser, and then added to the ethylene stream at a pressure of 250 bar, and at a rate of 3.6 gm / hour (62 millimoles / hour), before mixing 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 2.2 x 10 “3 gm / hour (0.019 millimoles / hour), before the mixture entered the reactor. The conversion of ethylene to polymer was 10.5% by weight based on the mass of ethylene entering the reactor, and the average reaction temperature was 205 ° C. An ethylene-based polymer having a melt index (12) of 1.5 g / 10 minutes was obtained. Approximately 90 grams of ethylene-based polymer was collected (Control C-0). Ethylene-based polymers of the invention C-1:
    [0144] The monomeric CTA solution was pumped at a pressure of 250 bar, and at a rate of 2.73 gm / hour (10 millimoles / hour of monomeric CTA) through an HPLC degasser, and then into the propionaldehyde stream , and mixed before said mixture is added to the ethylene stream and compressed to 2000 bar. The peroxide initiator was added to the mCTA-ethylene-propionaldehyde mixture at a pressure of 2000 bar, and at a rate of 4.0 x 10-3 gm / hour (0.030 millimoles / hour), before the mixture enters the reactor. The conversion of ethylene to polymer was 9% by weight based on the mass of ethylene entering the reactor, and the average reaction temperature was 201 ° C. An ethylene-based polymer having a melt index (12) of 1.8 g / 10 minutes was obtained. Approximately 50 grams of ethylene-based polymer was collected (Cl). The polymerization conditions of the reaction are summarized below table 7. Some properties of the polymer are shown in table 8 below. Table 7: Polymerization conditions
    Table 8: polymer properties

    [0145] Ethylene-based polymers of the D-1 invention and D-0 Control
    [0146] CTA monomer - a mixture of 2- (2-cyano-N-methylacetamido) ethyl methacrylate (80 gm: CAS [116928-90-6]; see also EP 376590 A2), and 2-propanol (80 gm ) was loaded into a 0.25 L glass supply container, which was opened to the atmosphere.
    [0147] CTA - A fresh 250 mL bottle of undiluted propionaldehyde (97%) was used as a supply vessel, which was opened to the atmosphere.
    [0148] Primer - The tert-butyl peroxyacetate peroxide initiator (2.3 grams of 50% of a solution by weight in isododecane) was combined with 500 ml of n-heptane, and loaded into a third glass container of supply. This solution was purified with nitrogen to minimize dissolved oxygen.
    [0149] Control (C-0) - Ethylene was injected at 1000 gm / hour (35, 65 moles / hour), at a pressure of 2000 bar, in a stirred high pressure CSTR reactor (2000 rpm) 54 mL, with an external heating jacket, adjusted to 187 ° C. Then, propionaldehyde was degassed by means of an HPLC degasser, and then added to the ethylene stream at a pressure of 250 bar, and at a rate of 3.7 gm / hour (64 millimoles / hour), before mixing 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 2.3 x 10 “3 gm / hour (0.017 millimoles / hour), before the mixture entered the reactor. The conversion of ethylene to polymer was 8% by weight based on the mass of ethylene entering the reactor, and the average reaction temperature was 204 ° C. An ethylene-based polymer having a melt index (12) of 3.3 g / 10 minutes was obtained. Approximately 60 grams of ethylene-based polymer was collected (Control D-0). Ethylene-based polymers of the invention D-l:
    [0150] The monomeric CTA solution was pumped at a pressure of 250 bar, and at a rate of 3.2 gm / hour (7.6 millimoles / hour of monomeric CTA) through an HPLC degasser, and then into the stream of propionaldehyde, and mixed before said mixture is added to the ethylene stream and compressed to 2000 bar. The peroxide initiator was added to the mCTA-ethylene-propionaldehyde mixture at a pressure of 2000 bar, and at a rate of 6.3 x 10-3 gm / hour (0.048 millimoles / hour), before the mixture entered the reactor. The conversion of ethylene to polymer was 11% by weight based on the mass of ethylene entering the reactor, and the average reaction temperature was 220 ° C. An ethylene-based polymer having a melt index (12) of 5 g / 10 minutes was obtained. Approximately 70 grams of ethylene-based polymer was collected (Dl). The reaction polymerization conditions are summarized below table 9. Some properties of the polymer are shown in table 10 below. Table 9: Polymerization conditions
    Table 10: polymer properties

    [0151] Ethylene-based polymers of the E-1 invention and D-0 Control:
    [0152] CTA monomer - a mixture of 2- (2-cyanoacetoxy) ethyl methacrylate (80 gm: CAS [21115-26-4]; see also US patent 3658878 A), and 2-propanol (80 gm) was loaded into a 0.25 L glass supply container, which has been opened to the atmosphere.
    [0153] CTA - A fresh 250 mL bottle of undiluted propionaldehyde (97%) was used as a supply vessel, which was opened to the atmosphere.
    [0154] Primer - The tert-butyl peroxyacetate peroxide initiator (2.3 grams of 50% of a solution by weight in isododecane) was combined with 500 mL of n-heptane, and loaded into a third glass container of supply. This solution was purified with nitrogen to minimize dissolved oxygen.
    [0155] Control - Sample D-0 was used as a control for the ethylene-based polymers of the invention E-1 and E-2, since the melting index of D-0 was similar to that of E-1 and E-2.
    [0156] The monomeric CTA solution was pumped at a pressure of 250 bar, and at a rate of 2.8 gm / hour (7.2 millimoles / hour of monomeric CTA) through an HPLC degasser, and then into the stream of propionaldehyde, and mixed before said mixture is added to the ethylene stream and compressed to 2000 bar. The peroxide initiator was added to the mCTA-ethylene-propionaldehyde mixture at a pressure of 2000 bar, and at a rate of 4.7 x 10-3 gm / hour (0.036 millimoles / hour), before the mixture enters the reactor. The conversion of ethylene to polymer was 11.7% by weight based on the mass of ethylene entering the reactor, and the average reaction temperature was 210 ° C. An ethylene-based polymer having a melt index (12) of 3.5 g / 10 minutes was obtained. Approximately 95 grams of ethylene-based polymer was collected (E-1). The polymerization conditions of the reaction are summarized below table 11. Some properties of the polymer are shown in table 12 below.
    [0157] Ethylene-based polymers of the invention E-2:
    [0158] The monomeric CTA solution was pumped at a pressure of 250 bar, and at a rate of 4.2 gm / hour (10.7 millimoles / hour of monomeric CTA) through an HPLC degasser, and then into the stream of propionaldehyde, and mixed before said mixture is added to the ethylene stream and compressed to 2000 bar. The peroxide initiator was added to the mCTA-ethylene-propionaldehyde mixture at a pressure of 2000 bar, and at a rate of 4.2 x 10 3 gm / hour (0.032 millimoles / hour), before the mixture entered the reactor . The conversion of ethylene to polymer was 11.8% by weight based on the mass of ethylene entering the reactor, and the average reaction temperature was 216 ° C. An ethylene-based polymer having a melt index (12) of 3.5 g / 10 minutes was obtained. Approximately 80 grams of ethylene-based polymer was collected (E-2). The polymerization conditions of the reaction are summarized below table 11. Some properties of the polymer are shown in table 12 below. Table 11: Polymerization conditions
    Table 12: Polymer properties
    权利要求:
    Claims (8)
    [0001]
    1. Ethylene-based polymer, characterized by the fact that it comprises a majority of polymerized ethylene, based on the weight of the polymer, formed from at least one of the following: ethylene and a monomeric chain transfer agent (CTA) , comprising a copolymerization terminal and a chain transfer terminal, the copolymerization terminal of the monomeric chain transfer agent being selected from the group consisting of those defined below: (a)
    [0002]
    2. Polymer according to claim 1, characterized in that the monomeric chain transfer agent is not an unconjugated di-unsaturated monomer.
    [0003]
    Polymer according to either of Claims 1 and 2, characterized in that the ethylene-based polymer comprises, in the reacted form, at least 0.075 mol of monomeric CTA per 1000 moles of ethylene-based main chain carbons , based on the weight of the polymer.
    [0004]
    4. Polymer according to any one of claims 1 to 3, characterized in that the monomeric CTA has 1H NMR signals from 3.0 to 5.0 ppm of chemical exchange.
    [0005]
    5. Polymer according to any one of claims 1 to 4, characterized in that the ethylene-based polymer has a melt resistance [MS] (cN), as measured at 190 ° C using a Goettfert Rheotens 71, 97, and a melting index 12 (g / 10 minutes), as measured according to ASTM D1238, condition at 190 ° C / 2.16 kg, according to the following equation:
    [0006]
    6. Polymer according to any one of claims 1 to 5, characterized by the fact that the polymer has a stress hardening factor (SHF) greater than 3, at Hencky stress rates of 10 s-1 al, 0s- 1, where SHF is the ratio of extensional viscosity to three times the shear viscosity in the same measure of time and at the same temperature, the measure of time being the ratio of three to the Hencky stress rate applied in the measurement of extensional viscosity.
    [0007]
    7. Composition, characterized by the fact that it comprises the ethylene-based polymer, as defined in any one of claims 1 to 6.
    [0008]
    8. Article, characterized by the fact that it comprises at least one component formed from the composition as defined in claim 7.
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    同族专利:
    公开号 | 公开日
    JP2013540877A|2013-11-07|
    CA2816287A1|2012-05-03|
    CA2816287C|2019-06-18|
    KR101844104B1|2018-03-30|
    SG190030A1|2013-06-28|
    BR112013010462A2|2016-08-02|
    EP2632961B1|2014-12-24|
    US20130237678A1|2013-09-12|
    KR20140000254A|2014-01-02|
    CN103282391B|2016-12-07|
    JP5980219B2|2016-08-31|
    ES2530861T3|2015-03-06|
    EP2632961A1|2013-09-04|
    AR083592A1|2013-03-06|
    US9150681B2|2015-10-06|
    CN103282391A|2013-09-04|
    WO2012057975A1|2012-05-03|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2019-12-10| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-04-14| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-10-27| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 05/10/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US40812410P| true| 2010-10-29|2010-10-29|
    US61/408,124|2010-10-29|
    PCT/US2011/054843|WO2012057975A1|2010-10-29|2011-10-05|Ethylene-based polymers and processes for the same|
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