Patent Application
20200325262
The present disclosure relates to the technical field of olefin polymerization, and in particular, to a copolymer of an olefin and an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative.
Polyolefin products are inexpensive, have excellent performance, and have a wide range of applications. Under the condition that original excellent physical and chemical properties of polyolefin are retained, the introduction of polar groups into the molecular chain of polyolefin through a chemical synthesis method can improve chemical inertness, dyeing property, wettability, and compatibility with other materials thereof, giving new characteristics that raw materials do not have thereto.
The copolymerization method and the grafting method are main mature methods for preparing a copolymer having a polar group. High-pressure radical polymerization is mostly used in the copolymerization method to promote the copolymerization of an olefin and an olefin monomer having a polar group. Although polar monomers can be directly introduced into the polyolefin chain by using high-pressure radical copolymerization, this method requires high-temperature and high-pressure conditions, high energy consumption, and expensive equipment costs.
Coordination catalysis copolymerization, as a polymer preparation technology at room temperature and atmospheric pressure, has received widespread attention for its significant role in reducing energy consumption and improving reaction efficiency. The participation of the catalyst in the reaction process greatly reduces the activation energy of the copolymerization reaction of olefin monomers and polar monomers, which is conducive to obtaining functional polymers having a higher molecular weight at lower temperatures and pressures. Currently, only a small amount of literature reports the use of transition metal complexes to catalyze the copolymerization of the olefin and the unsaturated carboxylic acid. However, in the existing technologies, no matter which method is used for the polymerization reaction, obtained polymers are all thick sticky lumpy solids, which are easy to scale in the polymerization equipment, causing difficulties in polymer transportation, solvent removal, and granulation.
The present disclosure provides a copolymer of an olefin and an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative, and the copolymer includes a spherical and/or spherical-like polymer. The spherical and/or spherical-like polymer may be obtained by direct polymerization of an olefin and an unsaturated carboxylic acid or a derivative thereof, and subsequent processing such as granulation is not needed. The copolymer exhibits a good morphology and has good prospects in industrial use.
According to a first aspect of the present disclosure, a copolymer of olefin and unsaturated carboxylic acid or unsaturated carboxylic acid derivative is provided, which includes a spherical and/or spherical-like polymer.
According to a preferred embodiment of the present invention, in the copolymer, at least part of spherical and/or spherical-like polymers have a cavity therein.
According to a preferred embodiment of the present invention, the copolymer includes a structural unit derived from olefin and a structural unit of Formula I or a structural unit of a derivative of Formula I,
wherein in Formula I, L1-L3 each are independently selected from the group consisting of H and C1-C30 alkyl, and L4 is C1-C30 alkylene having a side group; the derivative of Formula I is a IIA, IIIA or IIB Group metal salt of Formula I; and the C1-C30 alkyl is optionally substituted by a substituent, and preferably the substituent is one or more selected from the group consisting of halogen, C1-C10 alkyl, C1-C10 alkoxy, C6-C10 aryl, cyano group and carboxyl.
According to a preferred embodiment of the present invention, the side group in L4 is one or more selected from the group consisting of halogen, C6-C20 aryl, C1-C20 alkyl and C1-C20 alkoxy. The C6-C20 aryl, C1-C20 alkyl, and C1-C20 alkoxy are optionally substituted by a substituent, and preferably the substituent is one or more selected from the group consisting of halogen, C1-C10 alkyl, C1-C10 alkoxy, C6-C10 aryl and carboxyl.
According to a preferred embodiment of the present invention, the side group in L4 is one or more selected from the group consisting of halogen, C6-C20 aryl, C1-C20 alkyl, C1-C20 alkyl substituted by carboxyl, and C1-C20 alkyl substituted by alkoxy. Preferably, the side group is one or more selected from the group consisting of halogen, C6-C20 aryl, C1-C20 alkyl, C1-C10 alkyl substituted by carboxyl, and C1-C10 alkyl substituted by alkoxy. More preferably, the side group is one or more selected from the group consisting of halogen, C6-C10 aryl, and C1-C10 alkyl. Further preferably, the side group is one or more selected from the group consisting of halogen, phenyl, and C1-C6 alkyl. Examples of the C1-C6 alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl and hexyl.
According to a preferred embodiment of the present invention, in Formula I, L1 and L2 are H, L3 being H or C1-C30 alkyl, L4 being C1-C30 alkylene having a side group. The C1-C30 alkyl is optionally substituted by a substituent, and preferably the substituent is one or more selected from the group consisting of halogen, C1-C10 alkyl, C1-C10 alkoxy, C6-C10 aryl, cyano group and carboxyl.
According to a preferred embodiment of the present invention, in Formula I, L1 and L2 are H, L3 is H, C1-C10 alkyl or C1-C10 alkyl substituted by halogen, preferably L3 is H or C1-C10 alkyl; and L4 is C1-C20 alkylene having a side group. For example, L4 is methylene having a side group, ethylidene having a side group, propylidene having a side group, butylidene having a side group, C5 alkylene having a side group, C6 alkylene having a side group, C7 alkylene having a side group, C8 alkylene having a side group, C9 alkylene having a side group, C10 alkylene having a side group, C12 alkylene having a side group, C14 alkylene having a side group, C18 alkylene having a side group, and C20 alkylene having a side group. Preferably L4 is C1-C10 alkylene having a side group.
According to a preferred embodiment of the present invention, in Formula I, L1 and L2 are H, L3 is H or C1-C10 alkyl; and L4 is C1-C10 alkylene having a side group.
According to a preferred embodiment of the present invention, in Formula I, L1 and L2 are H, L3 is H or C1-C6 alkyl (such as methyl, ethyl, propyl, butyl, pentyl and hexyl); and L4 is C1-C10 alkylene having a side group.
In the present invention, the carbon number n of Cn alkylene refers to the number of C on the linear chain, excluding the number of C on the side group. For example, isopropylidene (—CH2-CH(CH3)—) in the present invention is called C2 alkylene having a side group (methyl).
According to a preferred embodiment of the present invention, a density of the spherical and/or spherical-like polymer is in a range of 0.3000-0.8500 g/cm3. For example, the density may be 0.3000 g/cm3, 0.3500 g/cm3, 0.4000 g/cm3, 0.4500 g/cm3, 0.5000 g/cm3, 0.5500 g/cm3, 0.6000 g/cm3, 0.6500 g/cm3, 0.7000 g/cm3, 0.7500 g/cm3, 0.8000 g/cm3, 0.8500 g/cm3, or any value between them. Preferably, the density is in a range of 0.4000-0.7500 g/cm3. The density is measured by using a method in GB/T6463-2009.
According to a preferred embodiment of the present invention, an average particle size of the spherical and/or spherical-like polymer is in a range of 0.1-50.0 mm. For example, the particle size may be 0.1 mm, 0.5 mm, 1.0 mm, 2.0 mm, 3.0 mm, 5.0 mm, 8.0 mm, 10.0 mm, 15.0 mm, 20.0 mm, 25.0 mm, 30.0 mm, 35.0 mm, 40.0 mm, 45.0 mm, 50.0 mm, or any value between them. Preferably, the average particle size is in a range of 0.5-20.0 mm.
According to a preferred embodiment of the present invention, the volume of the cavity in the spherical and/or spherical-like polymer having a cavity therein is 5-99% of a volume of the spherical and/or spherical-like polymer. For example, the volume of the cavity may be 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, or any value between them, of the volume of the spherical and/or spherical-like polymer. Preferably, the volume of the cavity is 30-95% of the volume of the spherical and/or spherical-like polymer. More preferably, the volume of the cavity is 50-90% of the volume of the spherical and/or spherical-like polymer.
According to a preferred embodiment of the present invention, the spherical and/or spherical-like polymer having a cavity therein is a polymer of a core-shell structure. The cavity is the core, and a polymer layer wrapping the cavity is the shell. According to a preferred embodiment of the present invention, the cavity is spherical and/or spherical-like.
According to a preferred embodiment of the present invention, in the copolymer, a content of the structural unit of Formula I or the structural unit of the derivative of Formula I is in a range of 0.2-15.0 mol %. For example, the content may be 0.2 mol %, 0.4 mol %, 0.5 mol %, 0.7 mol %, 0.8 mol %, 1.0 mol %, 1.5 mol %, 2.0 mol %, 3.0 mol %, 4.0 mol %, 5.0 mol %, 8.0 mol %, 9.0 mol %, 10.0 mol %, 11.0 mol %, 12.0 mol %, 13.0 mol %, 14.0 mol %, 15.0 mol %, or any value between them. Preferably, the content is in a range of 0.4-10.0 mol % .
According to a preferred embodiment of the present invention, a number-average molecular weight of the copolymer is in a range of 5000-200000, preferably in a range of 15000-150000.
According to a preferred embodiment of the present invention, a melting point is in a range of 45-130° C. For example, the melting point is 45° C., 50° C., 60° C., 70° C., 80° C., 90° C., 100° C., 110° C., 120° C., 130 ° C., or any value between them.
According to a preferred embodiment of the present invention, the structural unit derived from the olefin includes a structural unit derived from C2-C16 olefin, and preferably is selected from a structural unit derived from C2-C16 α-olefin or from C3-C16 cycloolefin.
According to a preferred embodiment of the present invention, the α-olefin or the cycloolefin is monoolefine. For example, the structural unit derived from the olefin may be a structural unit derived from one or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene.
According to a preferred embodiment of the present invention, the IIA Group metal is Mg or Ca, preferably Mg; the IIIA Group metal is Al or Ga, preferably Al; and the IIB Group metal is Zn or Cd, preferably Zn.
According to another aspect of the present disclosure, a preparation method for the copolymer of olefin and unsaturated carboxylic acid or unsaturated carboxylic acid derivative is provided. The preparation method includes contacting an olefin and an unsaturated carboxylic acid shown in Formula II or a derivative of the unsaturated carboxylic acid shown in Formula II with a catalyst and optionally a chain transfer agent for reaction in the presence of an alkane solvent to obtain the copolymer;
wherein in Formula II, definitions of L1-L4 are the same as the definitions of L1-L4 in Formula I, and the derivative of the unsaturated carboxylic acid refers to a IIA, IIIA, or IIB Group metal salt of the unsaturated carboxylic acid; and
the catalyst includes a main catalyst and a co-catalyst, and the main catalyst is a metal complex shown in Formula III:
wherein in Formula III, R9 and R10 are identical to or different from each other, and each are independently selected from substituted or unsubstituted hydrocarbyl; R2 and R3 are identical to or different from each other, each are independently selected from the group consisting of H, halogen, and substituted or unsubstituted hydrocarbyl, and R2 and R3 optionally form a ring with each other; M is a Group VIII metal; X is one or more selected from the group consisting of halogen, hydrocarbyl and hydrocarbyloxy, and is preferably one or more selected from the group consisting of halogen and C1-C10 alkyl; and n is an integer that meets an M valence state.
According to a preferred embodiment of the present invention, R9 and R10 each are independently selected from the group consisting of substituted or unsubstituted aryl and substituted or unsubstituted aralkyl, and are preferably selected from the group consisting of substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C7-C30 aralkyl. Preferably, R9 and R10 each are independently selected from the group consisting of C6-C30 aryl substituted by C1-C10 hydrocarbyl and C6-C30 aryl substituted by C1-C10 hydrocarbyloxy, and are preferably selected from the group consisting of phenyl substituted by C1-C10 hydrocarbyl, and phenyl substituted by C1-C10 hydrocarbyloxy, for example, phenyl substituted by methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, tert-butyl, methoxyl, ethoxyl, isopropoxyl, n-propoxyl, isobutoxyl, n-butoxyl and/or tert-butoxyl.
According to a preferred embodiment of the present invention, the main catalyst is a metal complex shown in Formula IV:
wherein in Formula IV, R9, R10, M, X, and n have the same definitions as those in Formula III; and R5-R8 are identical to or different from each other, each are independently selected from the group consisting of H, halogen, and substituted or unsubstituted C1-C20 hydrocarbyl, and R5-R8 optionally form a ring with each other.
According to a preferred embodiment of the present invention, in Formula IV, R5-R8 are identical to or different from each other, each are independently selected from the group consisting of H and C1-C20 hydrocarbyl, and R5-R8 optionally form a ring with each other. Preferably, R5-R8 are identical to or different from each other, each are independently selected from the group consisting of H and C1-C6 alkyl, and preferably form a ring by bonding; and M is a VIII Group metal, and X is selected from halogen.
According to a preferred embodiment of the present invention, the main catalyst is a metal complex shown in Formula V:
wherein in Formula V, R1-R10 are identical to or different from each other, and each are independently selected from the group consisting of H, halogen, C1-C24 hydrocarbyl and C1-C24 hydrocarbyloxy, R1-R3, R9, and R10 optionally forming a ring to each other, R4-R6, R7, and R8 optionally forming a ring to each other; and M, X and n have the same definitions as those in Formula III and Formula IV.
According to a preferred embodiment of the present invention, in Formula III Formula IV and Formula V, the M is nickel.
According to a preferred embodiment of the present invention, the X is halogen, and is preferably Br or Cl.
According to a preferred embodiment of the present invention, in Formula V, R1-R10 are identical to or different from each other, each are independently selected from the group consisting of H and C1-C10 alkyl, and are preferably selected from the group consisting of H and C1-C6 alkyl. Preferably, R7-R10 are H, and R1-R6 are identical to or different from each other and each are independently selected from the group consisting of H and C1-C6 alkyl; and more preferably, R7-R10 are H, and R1-R6 are identical to or different from each other and each are independently selected from the group consisting of H and C1-C4 alkyl (including methyl, ethyl, n-propyl, isopropyl, butyl).
According to a preferred embodiment of the present invention, the main catalyst is one or more selected from the group consisting of the following complexes: Complex 1, in Formula V, R1-R6 are all methyl, and R7-R10 are H;
Complex 2, in Formula V, R1-R6 are all ethyl, and R7-R10 are H;
Complex 3, in Formula V, R1-R6 are all isopropyl, and R7-R10 are H;
Complex 4, in Formula V, R1-R6 are all n-propyl, and R7-R10 are H;
Complex 5, in Formula V, R1-R6 are all butyl, and R7-R10 are H;
Complex 6, in Formula V, R1, R3, R4, R6 are all methyl, and R2, R5, R7-R10 are H;
Complex 7, in Formula V, R1, R3, R4, R6 are all ethyl, and R2, R5, R7-R10 are H;
Complex 8, in Formula V, R1, R3, R4, R6 are all n-propyl, and R2, R5, R7-R10 are H;
Complex 9, in Formula V, R1, R3, R4, R6 are all isopropyl, and R2, R5, R7-R10 are H;
Complex 10, in Formula V, R1, R3, R4, R6 are all butyl, and R2, R5, R7-R10 are H.
According to a preferred embodiment of the present invention, the main catalyst is selected from at least one of a compound shown in Formula a, a compound shown in Formula b and a compound shown in Formula c:
in Formula a, Formula b and Formula c, X represents Br or Cl.
According to a preferred embodiment of the present invention, the main catalyst is selected from at least one of complex al, complex bl and complex cl.
According to a preferred embodiment of the present invention, a concentration of the main catalyst in the reaction system is in a range of 0.00001-100 mmol/L. For example, the concentration may be 0.00001 mmol/L, 0.00005 mmol/L, 0.0001 mmol/L, 0.0005 mmol/L, 0.0001 mmol/L, 0.005 mmol/L, 0.01 mmol/L, 0.05 mmol/L, 0.1 mmol/L, 0.3 mmol/L, 0.5 mmol/L, 0.8 mmol/L, 1 mmol/L, 5 mmol/L, 8 mmol/L, 10 mmol/L, 20 mmol/L, 30 mmol/L, 50 mmol/L, 70 mmol/L, 80 mmol/L, 100 mmol/L, or any value between them. Preferably, the concentration is in a range of 0.0001-1 mmol/L. More preferably, the concentration of the main catalyst in the reaction system is in a range of 0.001-0.5 mmol/L.
According to a preferred embodiment of the present invention, the co-catalyst is selected from the group consisting of an organic aluminum compound and an organic boron compound.
According to a preferred embodiment of the present invention, the organic aluminum compound is selected from the group consisting of an alkyl aluminoxane or an organic aluminum compound having a general formula AlRnX13-n (alkylaluminum or alkylaluminum halides). In the general formula AlRnX13-n, R is H, C1-C20 hydrocarbyl or C1-C20 hydrocarbyloxy, and is preferably C1-C20 alkyl, C1-C20 alkoxy, C7-C20 aralkyl, or C6-C20 aryl; and X1 is halogen, and is preferably chlorine or bromine; and 0<n≥3. Specific examples of the organic aluminum compound include, but are not limited to, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, methylaluminoxane (MAO) and modified methylaluminoxane (MMAO). Preferably, the organic aluminum compound is methylaluminoxane (MAO).
According to a preferred embodiment of the present disclosure, the organic boron compound is selected from aryl boron and/or borate. The aryl boron is preferably substituted or unsubstituted phenylboron, and is more preferably tris(pentafluorophenyl) boron. The borate is preferably N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and/or triphenylmethylium tetrakis (pentafluorophenyl) borate.
According to a preferred embodiment of the present invention, when the co-catalyst is the organic aluminum compound, a molar ratio of aluminum in the co-catalyst and M in the main catalyst is in range of (10-10000000):1. Preferably, the molar ratio is 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, 2000:1, 3000:1, 5000:1, 10000:1, 100000:1, 1000000:1, 10000000:1, or any value between them. Preferably, the molar ratio is in range of (10-100000):1. More preferably, the molar ratio is in range of (100-10000):1. When the co-catalyst is the organic boron compound, a molar ratio of boron in the co-catalyst and M in the main catalyst is in range of (0.1-1000):1. For example, the molar ratio is 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 5:1, 8:1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, or any value between them. Preferably, the molar ratio is in range of (0.1-500):1.
In some embodiments of the present disclosure, the olefin is C2-C16 olefin, and preferably the olefin is ethylene or α-olefin having 3-16 carbon atoms.
In other embodiments of the present disclosure, the olefin is C3-C16 cycloolefin, and is preferably a 5-membered or 6-membered cycloolefin.
According to a preferred embodiment of the present invention, specific examples of the unsaturated carboxylic acid shown in Formula II include, but are not limited to, 2-methyl-4-pentenoic acid, 2,3-dimethyl-4-pentenoic acid, 2,2-dimethyl-4-pentenoic acid, 2-ethyl-4-pentenoic acid, 2-isopropyl-4-pentenoic acid, 2,2,3-trimethyl-4-pentenoic acid, 2,3,3-trimethyl-4-pentenoic acid, 2-ethyl-3-methyl-4-pentenoic acid, 2-(2-methylpropyl)-4-pentenoic acid, 2,2-diethyl-4-pentenoic acid, 2-methyl-2-ethyl-4-pentenoic acid, 2,2,3,3-tetramethyl-4-pentenoic acid, 2-methyl-5-hexenoic acid, 2-ethyl-5-hexenoic acid, 2-propyl-5-hexenoic acid, 2,3-dimethyl-5-hexenoic acid, 2,2-dimethyl-5-hexenoic acid, 2-isopropyl-5-hexenoic acid, 2-methyl-2-ethyl-5-hexenoic acid, 2-(1-methylpropyl)-5-hexenoic acid, 2,2,3-trimethyl-5-hexenoic acid, 2,2-diethyl-5-hexenoic acid, 2-methyl-6-heptenoic acid, 2-ethyl-6-heptenoic acid, 2-propyl-6-heptenoic acid, 2,3-dimethyl-6-heptenoic acid, 2,4-dimethyl-6-heptenoic acid, 2,2-dimethyl-6-heptenoic acid, 2-isopropyl-5-methyl-6-heptenoic acid, 2-isopropyl-6-heptenoic acid, 2,3,4-trimethyl-6-heptenoic acid, 2-methyl-2-ethyl-6-heptenoic acid, 2-(1-methylpropyl)-6-heptenoic acid, 2,2,3-trimethyl-6-heptenoic acid, 2,2-diethyl-6-heptenoic acid, 2-methyl-7-octenoic acid, 2-ethyl-7-octenoic acid, 2-propyl-7-octenoic acid, 2,3-dimethyl-7-octenoic acid, 2,4-dimethyl-7-octenoic acid, 2,2-dimethyl-7-octenoic acid, 2-isopropyl-5-methyl-7-octenoic acid, 2-isopropyl-7-octenoic acid, 2,3,4-trimethyl-7-octenoic acid, 2-methyl-2-ethyl-7-octenoic acid, 2-(1-methylpropyl)-7-octenoic acid, 2,2,3-trimethyl-7-octenoic acid, 2,2-diethyl-7-octenoic acid, 2-methyl-8-nonenoic acid, 2-ethyl-8-nonenoic acid, 2-propyl-8-nonenoic acid, 2,3-dimethyl-8-nonenoic acid, 2,4-dimethyl-8-nonenoic acid, 2,2-dimethyl-8-nonenoic acid, 2,2-diethyl-8-nonenoic acid, 2-isopropyl-5-methyl-8-nonenoic acid, 2-methyl-9-decenoic acid, 2,3-dimethyl-9-decenoic acid, 2,4-dimethyl-9-decenoic acid, or 2-methyl-10-undecylenic acid.
According to a preferred embodiment of the present invention, a concentration of the unsaturated carboxylic acid in Formula II or the derivative of the unsaturated carboxylic acid shown in Formula II in the reaction system is in a range of 0.01-6000 mmol/L, preferably in a range of 0.1-1000 mmol/L, more preferably in a range of 1-500 mmol/L. For example, the concentration may be 1 mmol/L, 10 mmol/L, 20 mmol/L, 30 mmol/L, 50 mmol/L, 70 mmol/L, 90 mmol/L, 100 mmol/L, 200 mmol/L, 300 mmol/L, 400 mmol/L, 500 mmol/L, or any value between them.
According to a preferred embodiment of the present invention, the chain transfer agent is one or more selected from the group consisting of aluminum alkyl, magnesium alkyl and zinc alkyl.
According to a preferred embodiment of the present invention, the chain transfer agent is trialkylaluminum and/or dialkyl zinc, and is preferably one or more selected from the group consisting of trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, dimethylzinc and diethylzinc.
According to a preferred embodiment of the present invention, a molar ratio of the chain transfer agent and M in the main catalyst is in a range of (0.1-2000):1. For example, the molar ratio may be 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 5:1, 8:1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 600:1, 800:1, 1000:1, 2000:1, and any value between them. Preferably, the molar ratio is (10-600):1.
According to a preferred embodiment of the present invention, the alkane solvent is one or more selected from the group consisting of C3-C20 alkane. For example, the alkane solvent may be one or more selected from the group consisting of butane, isobutane, pentane, hexane, heptane, octane, and cyclohexane. Preferably, the alkane solvent is one or more selected from the group consisting of hexane, heptane, and cyclohexane. It is found by the inventor, through research, that the spherical and/or spherical-like polymer can only be formed by the olefin and the unsaturated carboxylic acid or the derivative of the unsaturated carboxylic acid having a structure defined in the present application, and at least part of spherical and/or spherical-like polymers have a hallow structure.
According to a preferred embodiment of the present invention, the unsaturated carboxylic acid is subjected to a pre-processing of removing active hydrogen in advance. Preferably, the co-catalyst or the chain transfer agent above is used to perform a pre-processing to the unsaturated carboxylic acid so as to remove the active hydrogen in the unsaturated carboxylic acid, thereby forming the unsaturated carboxylic acid derivative, i.e., a IIA, IIIA, or IIB Group metal salt. Preferably, in the pre-processing process, a molar ratio of the carboxyl in the unsaturated carboxylic acid and the co-catalyst or the chain transfer agent is 10:1-1:10.
According to a preferred embodiment of the present invention, the reaction is performed under a condition that water and oxygen are excluded.
According to a preferred embodiment of the present invention, reaction conditions include: a reaction temperature ranging from −50° C. to 50° C., preferably −20-50° C., more preferably 0-50° C., for example, 0° C., 10° C., 20° C., 30° C., 40° C., 50° C., or any value between them; and/or a reaction time length of 10-200 min, preferably 20-60 min. It is founded by the inventor of the present application, through research, that a temperature within the above temperature range is beneficial for the preparation of the spherical and/or spherical-like polymer.
In the present invention, there is no particular limitation to the reaction pressure, and a pressure is acceptable as long as a coordination copolymerization reaction of monomers can be performed. When the olefin is ethylene, in order to reduce cost and simplify the polymerization process, in a reactor, a pressure for ethylene is preferably 1-1000 atm, further preferably 1-200 atm, more preferably 1-50 atm.
In the present disclosure, the “reaction system” refers to the entirety formed by the solvent, the olefin, the monomer of the unsaturated carboxylic acid or of unsaturated carboxylic acid derivative, the catalyst, and optionally the chain transfer agent.
In the present disclosure, the particle size of the spherical and/or spherical-like polymer herein is regarded as being equivalent to a diameter of a sphere having the same volume as the particle.
In the present disclosure, “substitute” in the wording of “substituted or unsubstituted” refers to the group defined thereby. For example, C or H atoms in the olefin or the alkane are optionally substituted by a substituent. The substituent is selected from halogen, hydrocarbyl (such as C1-C10 alkyl), oxo(—O—-), and groups containing oxygen, nitrogen, boron, sulfur, phosphorus, silicon, germanium and tin atoms.
In the present disclosure, “hydrocarbyl” and “alkyl”, unless otherwise stated, include linear-chain, branched-chain or cyclic “hydrocarbyl” and “alkyl”. In the present disclosure, “hydrocarbyl”, unless otherwise stated, includes aliphatic hydrocarbyl or aromatic hydrocarbyl, and aliphatic hydrocarbyl includes alkyl, olefin, and alkynyl.
According to another aspect of the present disclosure, a use of the copolymer of an olefin and an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative as a foaming polyolefin material is provided.
In the present invention, by selecting unsaturated carboxylic acid monomers and catalysts for reaction and controlling a polymerization process, a spherical and/or spherical-like polymer having a good morphology is prepared. The obtained polymerization product is not easy to scale in the reactor and is convenient for transportation. At least part of the obtained spherical and/or spherical-like polymers have a hallow structure, can be used as a foaming material without undergoing a foaming process, and have good prospects in industrial use.
The accompanying drawings are provided for further understanding to the present disclosure, constitute one part of the description, are used for explaining the present disclosure together with embodiments of the present disclosure, and do not constitute limitation to the present disclosure. In the drawings:
The present disclosure is described in detail in conjunction with examples below, but the present disclosure is not limited by the following examples.
The results of the present invention were characterized by the following manners.
Before the measurement, the polymer was subject to a washing treatment with an acid solution, a content of metal in the polymer≥50 ppm.
A content of comonomers in the copolymer (the structural unit of the unsaturated carboxylic acid shown in Formula I or the structural unit of the derivative of the unsaturated carboxylic acid shown in Formula I) was measured by using 13C NMR spectrum, on a 400 MHz Bruker Avance 400 nuclear magnetic resonance spectrometer, with a 10 mm PASEX 13 probe, through dissolution of a polymer sample with deuterated tetrachloroethane at 130° C. and analysis and testing.
A molecular weight of the copolymer was measured by using PL-GPC220, with the trichlorobenzene as the solvent at 150° C. (standard sample: PS; flow velocity: 1.0 mL/min; and column: 3×Plgel 10 μm M1×ED-B 300×7.5 nm).
A melting point of the copolymer was tested by using the differential scanning calorimetry (DSC). A sample of 10 mg was placed in a crucible, and is measured at a Pekin Elmer DSC 8500 differential scanning calorimeter. Under a nitrogen atmosphere, the temperature was increased from 0° C. to 180° C. at an increasing rate of 10° C./min and maintained for 1 min, and decreased to 10° C. at a rate of 10° C./min and maintained for 3 min. After that, the temperature was increased to 180° C. at the increasing rate of 10° C./min, and scanning data during the second temperature increasing was recorded.
A density of the polymer was tested by using GB/T1033-1986 and GB/T6463-2009 respectively. When the testing was performed by using GB/T1033-1986, the test object was randomly selected from the copolymerization product. In the case that the testing was performed by using GB/T6463-2009, the test object was randomly selected from the spherical and/or spherical-like polymers when the copolymer contains spherical and/or spherical-like polymers, and the test object was randomly selected from the copolymerization product when the copolymer did not contain spherical and/or spherical-like polymers.
A particle size of the spherical and/or spherical-like polymers was tested by using ASTM D1921.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 15 mmol (2.55 g) of 2,2-dimethyl-7-octenoic acid, 15 mL of AlEt3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 60° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol/L of hexane solution), 0.25 mL diethylzinc (1 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol/L of hexane solution), 0.5 mL diethylzinc (1 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 80° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 50 mmol (8.51 g) of 2,2-dimethyl-7-octenoic acid, 50 mL of AlEt3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 100 mmol (17.02 g) of 2,2-dimethyl-7-octenoic acid, 100 mL of AlEt3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (4.69 g) of 2,2-dimethyl-7-heptenoic acid, 30 mL of AlEt3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (4.26 g) of 2-isopropyl-4-pentenoic acid, 30 mL of AlEt3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.5 mg) of complex bl, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 60 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.5 mg) of complex bl, 50 mmol (8.51 g) of 2,2-dimethyl-7-octenoic acid, 50 mL of AlEt3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 60 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.4 mg) of complex cl, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol/L of hexane solution) were added; and 2.5 mL of toluene solution containing N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (1 mmol/L toluene solution) was added, making Ni/B=1. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol/L of hexane solution), and 3 mL of AlEt2Cl (2 mmol/L hexane solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 5.0 μmol (3.2 mg) of complex al, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of toluene was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 1% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (5.53 g) of 10-undecylenic acid, 30 mL of AlEt3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.
It should be noted that the embodiments described above are only used to explain the present disclosure, and do not constitute any limitation to the present disclosure. The present disclosure has been described with reference to exemplary embodiments, but it should be understood that words used herein are descriptive and explanatory words, not limiting words. Modifications can be made to the present disclosure within the scope of the claims of the present disclosure according to provisions, and revisions can be made to the present disclosure without departing from the scope and spirit of the present disclosure. Although the present disclosure described relates to specific methods, materials, and embodiments, it does not mean that the present disclosure is limited to the specific examples disclosed herein, but rather the present disclosure can be extended to all other methods and applications having the same function.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201711008111.7 | Oct 2017 | CN | national |
This application is an U.S. national stage application of PCT International Application PCT/CN2018/111685, filed on Oct. 24, 2018, which claims the priority of Chinese patent application CN 201711008111.7, entitled “Polymer of olefin-unsaturated carboxylic acid” and filed on Oct. 24, 2017, the entirety of which is incorporated herein by reference.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2018/111685 | 10/24/2018 | WO | 00 |
