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CN120059012A - Catalyst system, ethylene/acrylic acid (ester) copolymer and preparation method thereof - Google Patents

Catalyst system, ethylene/acrylic acid (ester) copolymer and preparation method thereof Download PDF

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Publication number
CN120059012A
CN120059012A CN202311616738.6A CN202311616738A CN120059012A CN 120059012 A CN120059012 A CN 120059012A CN 202311616738 A CN202311616738 A CN 202311616738A CN 120059012 A CN120059012 A CN 120059012A
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substituted
unsubstituted
acrylic acid
ester
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宋文波
赵文青
方园园
吴子昂
韩书亮
吕静兰
王国栋
金钊
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Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene

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Abstract

本发明属于烯烃聚合领域，涉及一种催化剂体系、乙烯/丙烯酸(酯)共聚物及其制备方法。所述催化剂体系由以下组分组成：组分a，主催化剂，选自式(I)所示化合物中的至少一种，组分b，选自式(II)所示化合物和式(III)所示化合物中的至少一种。本发明的催化剂体系，通过配合使用后过渡金属催化剂和苯酚类化合物，在无需助催化剂的条件下，显著提高了乙烯与极性单体配位聚合的反应活性，将其应用于乙烯/丙烯酸(酯)共聚物的制备，反应活性显著提高，在较低压力下即可制得高共聚单体含量的共聚物。The present invention belongs to the field of olefin polymerization, and relates to a catalyst system, an ethylene/acrylic acid (ester) copolymer and a preparation method thereof. The catalyst system is composed of the following components: component a, a main catalyst, selected from at least one of the compounds shown in formula (I), and component b, selected from at least one of the compounds shown in formula (II) and the compounds shown in formula (III). The catalyst system of the present invention significantly improves the reaction activity of coordination polymerization of ethylene and polar monomers without the need for a co-catalyst by using a late transition metal catalyst and a phenol compound in combination. The catalyst system is applied to the preparation of ethylene/acrylic acid (ester) copolymers, and the reaction activity is significantly improved, so that copolymers with a high comonomer content can be prepared under relatively low pressure.

Description

Catalyst system, ethylene/acrylic acid (ester) copolymer and preparation method thereof
Technical Field
The invention belongs to the field of olefin polymerization, and in particular relates to a catalyst system for ethylene/polar monomer copolymerization, a preparation method of an ethylene/acrylic acid (ester) copolymer, and the ethylene/acrylic acid (ester) copolymer prepared by the method.
Background
The polyolefin has low price, excellent performance, high industrialization and maturity, and the proportion of the polyolefin in the world high polymer material is about half. The polyolefin material has high cost performance, only has the simplest hydrocarbon unit in a molecular structure, lacks polar groups, and is unfavorable for printing and dyeing, bonding, blending and other applications. Therefore, polar groups need to be introduced to realize polyolefin functionalization.
The introduction of polar groups into the polymer molecular chain is an important method for modifying the polymer. The introduction of polar groups can effectively improve the hardness, viscoelasticity, interfacial properties, surface properties, solvent adaptability, blending performance with other polymers, rheological properties and the like of the polymer, and has great influence on various properties of the polymer. Therefore, the application range of the polyolefin can be greatly expanded by combining the inherent material property of the polyolefin and the new property of the functional monomer, namely the functional polyolefin, so that the polymer has high added value and the commercial application range can be widened.
Disclosure of Invention
The object of the present invention is to provide a catalyst system for ethylene/polar monomer copolymerization and further to provide an ethylene/acrylic acid (ester) copolymer and a process for preparing the same based thereon.
In a first aspect the present invention provides a catalyst system for ethylene/polar monomer copolymerization, said catalyst system consisting of:
a component a, a main catalyst, which is at least one selected from compounds shown in a formula (I),
In formula (I), R 1、R2、R3, which are the same or different, are each independently a hydrogen atom, a substituted or unsubstituted C 1-C20 hydrocarbyl group, a substituted or unsubstituted C 1-C20 alkoxy group, or a substituted or unsubstituted C 6-C20 aryloxy group, which groups are linear, branched or cyclic and are optionally further substituted with a halogen atom, a C 1-C10 alkyl group, a C 1-C10 alkoxy group, a C 6-C10 aryl group, or a C 6-C10 aryloxy group, L is a ligand;
A component b selected from at least one of a compound represented by formula (II) and a compound represented by formula (III):
In formula (II), R 4 is selected from a hydrogen atom, a substituted or unsubstituted C 1-C20 hydrocarbyl group, a substituted or unsubstituted C 1-C20 alkoxy group, or a substituted or unsubstituted C 6-C20 aryloxy group, which groups are linear, branched or cyclic and are optionally further substituted with a halogen atom, a C 1-C10 alkyl group, a C 1-C10 alkoxy group, a C 1-C6 carbonyl group, a C 6-C10 aryl group, or a C 6-C10 aryloxy group;
In formula (III), R 5 is selected from a hydrogen atom, a substituted or unsubstituted C 1-C20 hydrocarbyl group, a substituted or unsubstituted C 1-C20 alkoxy group, or a substituted or unsubstituted C 6-C20 aryloxy group, which groups are linear, branched, or cyclic and are optionally further substituted with a halogen atom, a C 1-C10 alkyl group, a C 1-C10 alkoxy group, a C 1-C6 carbonyl group, a C 6-C10 aryl group, or a C 6-C10 aryloxy group.
In a second aspect the present invention provides the use of the above catalyst system in ethylene/polar monomer copolymerization.
In a third aspect, the invention provides a method for preparing an ethylene/acrylic acid (ester) copolymer, comprising the steps of carrying out polymerization reaction on ethylene and acrylic acid (ester) monomers in an inert solvent in the presence of a catalyst system to obtain the ethylene/acrylic acid (ester) copolymer;
The catalyst system is the catalyst system;
the acrylic acid (ester) monomer is at least one of the compounds shown in the formula (A),
In the formula (A), R a is a hydrogen atom, a linear or branched C 1-C4 alkyl group, and R b is a hydrogen atom, a linear or branched C 1-C10 alkyl group.
In a fourth aspect, the present invention provides an ethylene/acrylic acid (ester) copolymer prepared by the above-described preparation method.
The catalyst system of the invention, through the cooperation of the post-transition metal catalyst and the phenol compound, obviously improves the reactivity of the coordination polymerization of ethylene and polar monomers under the condition of no need of a cocatalyst, and is applied to the preparation of ethylene/acrylic acid (ester) copolymer, the reactivity is obviously improved, the copolymer with high comonomer content can be prepared under lower pressure, and the prepared ethylene/acrylic acid (ester) copolymer has higher comonomer insertion rate, so that the polarity of the polyethylene material is obviously improved, the interface performance, the adhesiveness, the compatibility with other materials and the like of the polyethylene material are improved, and the comprehensive performance of polyolefin is further improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The invention provides a catalyst system for ethylene/polar monomer copolymerization, which consists of the following components:
a component a, a main catalyst, which is at least one selected from compounds shown in a formula (I),
In formula (I), R 1、R2、R3 are identical or different and are each independently a hydrogen atom, a substituted or unsubstituted C 1-C20 hydrocarbon radical, a substituted or unsubstituted C 1-C20 alkoxy radical or a substituted or unsubstituted C 6-C20 aryloxy radical, these radicals being linear, Branched or cyclic and optionally further substituted by halogen atoms, C 1-C10 alkyl groups, C 1-C10 alkoxy groups, C 6-C10 aryl groups or C 6-C10 aryloxy groups, L being a ligand, preferably in formula (I), R 1、R2、R3 are identical or different and are each independently a hydrogen atom, Substituted or unsubstituted C 1-C10 hydrocarbon radical, substituted or unsubstituted C 1-C10 alkoxy radical or substituted or unsubstituted C 6-C10 aryloxy radical, which are linear, branched or cyclic and are optionally substituted by halogen atoms, C 1-C6 alkyl radicals, C 1-C6 alkoxy radical, C 6-C8 aryl or C 6-C8 aryloxy is further substituted, L is Me 2 SO, more preferably R 1、R2、R3 are the same or different and are each independently a hydrogen atom, Substituted or unsubstituted C 1-C6 alkyl, substituted or unsubstituted C 1-C6 alkoxy or substituted or unsubstituted C 6-C8 aryloxy which are linear, branched or cyclic and are optionally substituted by halogen atoms, C 1-C6 alkyl, Further substituted with C 1-C6 alkoxy, C 6-C8 aryl or C 6-C8 aryloxy;
A component b selected from at least one of a compound represented by formula (II) and a compound represented by formula (III):
In the formula (II), R 4 is selected from a hydrogen atom, a substituted or unsubstituted C 1-C20 alkyl group, a substituted or unsubstituted C 1-C20 alkoxy group or a substituted or unsubstituted C 6-C20 aryloxy group, and the groups are linear, Branched or cyclic and optionally further substituted by halogen atoms, C 1-C10 alkyl groups, C 1-C10 alkoxy groups, C 1-C6 carbonyl groups, C 6-C10 aryl groups or C 6-C10 aryloxy groups, preferably in formula (II), R 4 is selected from hydrogen atoms, Substituted or unsubstituted C 1-C10 alkyl, substituted or unsubstituted C 8-C16 conjugated cycloalkyl, substituted or unsubstituted C 1-C10 alkoxy or substituted or unsubstituted C 6-C10 aryloxy, which groups are linear, Branched or cyclic and optionally further substituted with a halogen atom, a C 1-C6 alkyl group, a C 1-C6 alkoxy group, a C 1-C3 carbonyl group, a C 6-C8 aryl group, or a C 6-C8 aryloxy group;
In formula (III), R 5 is selected from a hydrogen atom, a substituted or unsubstituted C 1-C20 hydrocarbon group, a substituted or unsubstituted C 1-C20 alkoxy group or a substituted or unsubstituted C 6-C20 aryloxy group, which groups are linear, Branched or cyclic and optionally further substituted by halogen atoms, C 1-C10 alkyl groups, C 1-C10 alkoxy groups, C 1-C6 carbonyl groups, C 6-C10 aryl groups or C 6-C10 aryloxy groups, preferably in formula (III), R 5 is selected from hydrogen atoms, Substituted or unsubstituted C 1-C10 alkyl, substituted or unsubstituted C 8-C16 conjugated cycloalkyl, substituted or unsubstituted C 1-C10 alkoxy or substituted or unsubstituted C 6-C10 aryloxy, which groups are linear, Branched or cyclic and optionally further substituted with a halogen atom, a C 1-C6 alkyl group, a C 1-C6 alkoxy group, a C 1-C3 carbonyl group, a C 6-C8 aryl group, or a C 6-C8 aryloxy group.
According to some embodiments of the invention, the component a is at least one of palladium 2- (bis (2-methoxyphenyl) phosphino) benzenesulfonate, palladium 2- (bis (2-phenoxyphenyl) phosphino) benzenesulfonate, and palladium 2- (bis (2-methoxyphenyl) phosphino) -4-methylbenzenesulfonate.
According to some embodiments of the invention, the component b is at least one of 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butylphenol, 2,4, 6-tri-tert-butylphenol and 2, 6-di-tert-butyl- α - (3, 5-di-tert-butyl-4-oxo-2, 5-cyclohexadienylidene) -p-tolyloxy radical.
According to the present invention, the molar ratio of the component a to the component b calculated on the Pd atom is preferably 1:1 to 1:200, preferably 1:3 to 1:100, more preferably 1:4 to 1:50, and even more preferably 1:5 to 1:30.
The catalyst system is only formed by the component a and the component b, does not need conventional cocatalysts (such as alkyl aluminum, alkyl aluminoxane, organoboron compound and the like) in the field of olefin polymerization, is suitable for ethylene/polar monomer copolymerization, can improve the reactivity and the content of the comonomer, and can also obviously improve the insertion rate of the comonomer.
In the present invention, the concept of "polar monomer" is well known to those skilled in the art and refers to an olefin-based monomer containing one or more polar groups, and according to one embodiment of the present invention, the polar monomer is an acrylic monomer.
The invention provides a preparation method of an ethylene/acrylic acid (ester) copolymer, which comprises the following steps of carrying out polymerization reaction on ethylene and acrylic acid (ester) monomers in an inert solvent in the presence of a catalyst system to obtain the ethylene/acrylic acid (ester) copolymer;
The catalyst system is the catalyst system;
the acrylic acid (ester) monomer is at least one of the compounds shown in the formula (A),
In the formula (A), R a is a hydrogen atom, a linear or branched C 1-C4 alkyl group, and R b is a hydrogen atom, a linear or branched C 1-C10 alkyl group.
The method is applicable to acrylic acid (ester) monomers, the general formula of which is shown in a formula (A), preferably R a is hydrogen atom or methyl, R b is hydrogen atom, linear or branched C 1-C8 alkyl, and the C 1-C8 alkyl comprises but is not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and 2-ethylhexyl.
Particularly preferably, the acrylic monomer is at least one of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate and 2-ethylhexyl methacrylate.
The inert solvent used in the preparation method of the present invention may be various inert solvents commonly used in the field of olefin polymerization, including aliphatic hydrocarbon solvents and/or aromatic hydrocarbon solvents, preferably the inert solvent is a linear, branched or cyclic C 6-C12 alkane and/or C 6-C10 monocyclic aromatic hydrocarbon, wherein the C 6-C12 alkane is preferably at least one of n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane and cyclohexane, the C 6-C10 monocyclic aromatic hydrocarbon is preferably toluene and/or xylene, more preferably the inert solvent is at least one of n-hexane, isohexane, cyclohexane and toluene, and most preferably toluene.
According to a preferred embodiment of the present invention, the acrylic monomer is premixed with the component b of the catalyst system to obtain a premix, and then mixed with other components of the polymerization system, so that the reactivity can be further improved. Specifically, the time for the preliminary mixing is preferably 1 to 30 minutes, more preferably 2 to 15 minutes, and still more preferably 3 to 10 minutes.
The method of the present invention can improve the insertion rate of the comonomer into the main chain, and thus, the copolymer can have a high comonomer content without excessively high comonomer addition, and specifically, the concentration of the acrylic monomer in the polymerization reaction system can be 5mol/L or less, preferably 2mol/L or less, and more preferably 1mol/L or less.
According to the present invention, preferably, the molar ratio of the acrylic monomer to the component b in the catalyst system is 50:1 to 800:1, preferably 100:1 to 350:1, more preferably 150:1 to 300:1.
The polymerization according to the invention may be carried out continuously or semi-continuously or batchwise.
The polymerization can adopt milder process conditions, specifically, the temperature of the polymerization reaction can be 20-150 ℃, preferably 40-120 ℃, more preferably 60-100 ℃, and the pressure of the polymerization reaction can be below 10MPa, preferably 0.01-5 MPa, more preferably 0.1-2 MPa.
For ethylene/acrylic acid (ester) copolymers, high pressure free radical reactions are generally required to achieve higher comonomer content, and the present invention employs coordination polymerization as described above to achieve high comonomer content ethylene/acrylic acid (ester) copolymers at lower pressures.
The preparation process of the present invention further comprises separating the resulting copolymer from the solvent and unreacted monomers, and various separation methods commonly used in the field of olefin polymerization, such as evaporation, may be employed. The preparation method further comprises drying the copolymer after separating and removing the solvent and unreacted monomers.
The invention also provides the ethylene/acrylic acid (ester) copolymer prepared by the preparation method.
The copolymer may contain 75 to 99mol% of structural units derived from ethylene and 1 to 25mol% of structural units derived from an acrylic monomer, and the proportion of acrylic acid (ester) inserted into the copolymer main chain may be 70mol% or more, preferably 80mol% or more, further preferably 85mol% or more, and still more preferably 90mol% or more.
According to the invention, the ratio of the insertion of acrylic acid (ester) into the copolymer backbone (comonomer insertion) refers to the ratio of the molar amount of structural units derived from acrylic acid (ester) on the polymer backbone to the total molar amount of structural units derived from acrylic acid (ester) in the copolymer.
The present invention will be further described with reference to examples, but the scope of the present invention is not limited to these examples.
The comonomer content in the product was determined by nuclear magnetic resonance hydrogen spectrometry at room temperature using deuterated chloroform as solvent, taking chemical shifts of 3.59ppm and 3.66ppm as MA units on the polymer chain, respectively, and calculating the MA content in the product and the proportion of MA inserted into the copolymer backbone by comparing peak areas.
The number average molecular weight was measured by a method of using a PL-GPC 220 type gel permeation chromatograph of Polymer Laboratory company by high temperature GPC, dissolving the sample in 1,2, 4-trichlorobenzene, and the concentration was 1.0mg/ml. The test temperature was 150℃and the solution flow rate was 1.0ml/min. A standard curve is established by taking the molecular weight of polystyrene as an internal reference, and the molecular weight of the sample is calculated according to the outflow time.
The ratio of the acrylic acid (ester) inserted into the main chain of the copolymer is determined and calculated by nuclear magnetic resonance hydrogen spectrum determination at room temperature by taking deuterated chloroform as a solvent, taking chemical shift of 3.59ppm and 1.25ppm as signals of MA units and polyethylene units on a polymer chain respectively, and calculating the ratio of the acrylic acid (ester) inserted into the main chain of the copolymer by comparing peak areas.
The catalyst PSPd-1 is prepared by the following method:
Preparation of An 2 P (OMe)
A solution of An 2PNEt2 (103 g,325 mmol) in methanol (200 mL) was heated to 65deg.C and stirred for 4 hours, cooled to room temperature, and the solution concentrated in vacuo to give An 2 P (OMe) (88.5 g, yield) as a white solid 99％).1H NMR(CD2Cl2):δ＝3.68(d,3H,POCH3),3.82(s,6H,2OCH3),6.9-7.4(m,8H,arom);31PNMR(CD2Cl2):δ＝101.7ppm.
Preparation of phosphine sulfonic acid ligand 1a
To a solution of 60mL benzenesulfonic acid (5.2 g,32.9 mmol) in tetrahydrofuran was added dropwise lithium hexyl (25 mL,62mmol,2.5M hexane solution) at 0 ℃. After warming to room temperature and stirring for 20 hours, a solution of 20mL of bis [2- ((oxo) diphenylphosphino) phenyl ] ether (9.1 g,32.9 mmol) in tetrahydrofuran was added dropwise and stirring was continued for 16 hours. Ammonium chloride (3.4 g,62 mmol) was then added thereto, concentrated under reduced pressure and 100mL of water was added to the crude product. The mixture was washed twice with 80mL of methyl tert-butyl ether and acidified with concentrated hydrochloric acid to ph=2. The aqueous phase was extracted twice with 120mL of dichloromethane, the organic phases were combined and dried over anhydrous magnesium sulfate, filtered, and the filtrate was cooled to-35 ℃ until white crystals precipitated. The solid was collected and dried to give the phosphine sulfonic ligand 1a (3.72 g, yield 28％).1H NMR(C2D2Cl4,400MHz,-25℃)δ＝9.25(d,1JPH＝607Hz,PH),6.7-8.2(m,12H,arom),3.79(s,6H,2OCH3).
Preparation of PdCl 2 (TMEDA)
50ML of palladium dichloride (1.76 g,10 mmol) in methanol was heated to reflux and dissolved, after cooling to 20℃2mL of tetramethyl ethylenediamine (TMEDA) was added to it, a yellow solid was precipitated, the yellow solid was collected, washed with diethyl ether and then dried under vacuum to give the product (2.5 g, 90% yield).
PdMe 2 (TMEDA) preparation
PdCl 2 (TMEDA) (2.37 g,8 mmol) was dispersed in 30mL of diethyl ether and cooled to-30℃and a solution of methyllithium in diethyl ether (12 mL, 1.44M) was added dropwise thereto. During stirring, the temperature was gradually raised to 0 ℃ and maintained for 1 hour, and an off-white suspension was gradually formed. To this mixture was slowly added 10mL of cold water and stirred until the ether phase was clear and the aqueous phase was black. The organic phase was separated, dried over anhydrous sodium sulfate and concentrated in vacuo to give colorless crystals PdMe 2 (TMEDA) (1.2 g, yield 60％).1H NMR(200MHz,CD3COCD3)303K,0.34(s,3H,PdMe),2.40(s,6H,NMe2),2.57(s,2H,CH2);183K,-0.36(s,PdMe),2.20(dd,J(H,H)＝10Hz,CHH-CHH),2.33(s,NMeAfe),2.34(s,NMeAfe),2.96(dd,J(H,H)＝10Hz,CHH-CHH).
1A-PdTMEDA preparation
Phosphine sulfonic ligand 1a (1 g,2.49 mmol) and PdMe 2 (TMEDA) (0.63 g,2.49 mmol) were dissolved in dioxane at room temperature, and the product precipitated out of solution rapidly with bubble generation. After the mixture was stirred for 60 minutes, it was filtered, and the solid phase was washed with diethyl ether and dried under reduced pressure to give 1a-PdTMEDA (1.4 g, yield) 98％)1H NMR(400MHz,DMSO-d6)δ＝7.7-6.8(m,20H),6.35(m,4H),3.49(s,12H,OCH3),2.30(s,4H,NCH2),2.13(s,12H,NCH3),0.10(6H,Pd-CH3).
PSPd-1 preparation
1A-PdTMEDA (115 mg,0.20 mmol) was suspended in 50mL of dimethyl sulfoxide at room temperature and stirred, then concentrated in vacuo to remove the solvent. This procedure was repeated until the solid was completely dissolved in DMSO. Concentrating under reduced pressure, adding diethyl ether to the rest solid, and filtering to obtain solid (90.1 mg, yield 76％)1HNMR(600MHz,CD2Cl2,25℃):δ8.06(ddd,3JHH＝8.0Hz,4JPH＝4.9,4JHH＝1.0,1H,6-H),7.55(vt,J＝7.6,2H,10-H),7.48(vt,J＝7.5,2H,12-H),7.45(br,1H,5-H),7.31(vt,J＝7.6,1H,4-H),7.25(ddd,3JHH＝11.3.
Other catalysts are prepared by changing the structure of the phosphine sulfonic ligand according to the preparation method.
Examples 1 to 4
This example is intended to illustrate the ethylene/acrylic acid (ester) copolymer of the present invention and its preparation method. The preparation was carried out in a 1.8L reactor equipped with mechanical stirring and a jacket, to which an ethylene line was connected, the reaction temperature being regulated by the temperature of the oil bath in the jacket.
The preparation method comprises the following steps:
(1) Methyl Acrylate (MA) was premixed with 2, 6-di-t-butyl-4-methylphenol (component b) in the amounts shown in Table 1 for 5 minutes to give a premix.
(2) 1000ML of toluene, 140. Mu. Mol of palladium 2- (bis (2-methoxyphenyl) phosphino) -4-methylbenzenesulfonate (calculated as Pd atoms) and the premix were added to the reactor. The temperature in the reactor was set at 80℃and ethylene was continuously fed into the reactor at a reactor pressure of 10bar. After half an hour the ethylene addition was stopped and the reaction was stopped by injecting acidified ethanol. After depressurization, the reaction solution was poured into a flask, the solvent and unreacted monomers were removed by evaporation, and placed in a vacuum oven and dried at 70 ℃ for 24 hours. The polymerization results and characterization data are shown in Table 1, with the activity of the unadditized component b as comparison data.
TABLE 1
Examples 5 to 8
This example is intended to illustrate the ethylene/acrylic acid (ester) copolymer of the present invention and its preparation method. The preparation was carried out in a 1.8L reactor equipped with mechanical stirring and a jacket, to which an ethylene line was connected, the reaction temperature being regulated by the temperature of the oil bath in the jacket.
The preparation method comprises the following steps:
(1) n-Butyl Acrylate (BA) was premixed with 2, 6-di-t-butyl-4-methylphenol (component b) in the amounts shown in Table 2 for 5 minutes to give a premix.
(2) 1000ML of toluene, 140. Mu. Mol of palladium 2- (bis (2-methoxyphenyl) phosphino) -4-methylbenzenesulfonate (calculated as Pd atoms) and the premix were added to the reactor. The temperature in the reactor was set at 80℃and ethylene was continuously fed into the reactor at a reactor pressure of 10bar. After half an hour the ethylene addition was stopped and the reaction was stopped by injecting acidified ethanol. After depressurization, the reaction solution was poured into a flask, the solvent and unreacted monomers were removed by evaporation, and placed in a vacuum oven and dried at 70 ℃ for 24 hours. The polymerization results and characterization data are shown in Table 2, with the activity of the unadditized component b as comparison data.
TABLE 2
Examples 9 to 12
This example is intended to illustrate the effect of the addition of different components b on the polymerization of the ethylene/acrylic acid (ester) copolymer of the present invention and its preparation. The preparation was carried out in a 1.8L reactor equipped with mechanical stirring and a jacket, to which an ethylene line was connected, the reaction temperature being regulated by the temperature of the oil bath in the jacket.
The preparation method comprises the following steps:
(1) Methyl Acrylate (MA) was premixed with 2, 6-di-t-butyl-4-methylphenol (component b) in the amounts shown in Table 3 for 2.5 minutes to give a premix.
(2) 1000ML of toluene, 140. Mu. Mol of palladium 2- (bis (2-methoxyphenyl) phosphino) -4-methylbenzenesulfonate (calculated as Pd atoms) and the premix were added to the reactor. The temperature in the reactor was set at 80℃and ethylene was continuously fed into the reactor at a reactor pressure of 10bar. After half an hour the ethylene addition was stopped and the reaction was stopped by injecting acidified ethanol. After depressurization, the reaction solution was poured into a flask, the solvent and unreacted monomers were removed by evaporation, and placed in a vacuum oven and dried at 70 ℃ for 24 hours. The polymerization results and characterization data are shown in Table 3.
TABLE 3 Table 3
Example 16
Copolymers were prepared according to the method of example 1 except that the comonomer was an equimolar amount of acrylic acid. The polymerization results and characterization data are shown in Table 4, with the activity of the unadditized component b as comparison data.
Example 17
A copolymer was prepared according to the procedure of example 1, except that the comonomer was an equimolar amount of methyl methacrylate. The polymerization results and characterization data are shown in Table 4, with the activity of the unadditized component b as comparison data.
Example 18
A copolymer was prepared according to the procedure of example 1, except that the comonomer was an equimolar amount of 2-ethylhexyl methacrylate. The polymerization results and characterization data are shown in Table 4, with the activity of the unadditized component b as comparison data.
Examples 19 to 21
Copolymers were prepared according to the procedure of examples 1-3 except that component b used was 2, 6-di-tert-butyl- α - (3, 5-di-tert-butyl-4-oxo-2, 5-cyclohexadienylidene) -p-tolyloxy radical. The polymerization results and characterization data are shown in Table 4, with the activity of the unadditized component b as comparison data.
Examples 22 to 23
Copolymers were prepared according to the method of examples 1-2 except that the comonomer was not premixed with component b, but the components were added directly to the reactor for mixing. The polymerization results and characterization data are shown in Table 4, with the activity of the unadditized component b as comparison data.
Examples 24 to 25
Copolymers were prepared according to examples 5-6 except that the comonomer was not pre-mixed with component b, but rather the components were added directly to the reactor for mixing. The polymerization results and characterization data are shown in Table 4, with the activity of the unadditized component b as comparison data.
Example 26
A copolymer was prepared according to the procedure of example 2, except that the polymerization temperature was 100℃and the pressure was 1.2MPa.
Example 27
A copolymer was prepared according to the procedure of example 2, except that the polymerization temperature was 60℃and the pressure was 0.8MPa.
Example 28
A copolymer was prepared according to the procedure of example 2, except that component a used was palladium 2- (bis (2-methoxyphenyl) phosphino) benzenesulfonate (PSPd-1). The polymerization results and characterization data are shown in Table 4, with the activity of the unadditized component b as comparison data.
Example 29
A copolymer was prepared according to the procedure of example 2, except that component a used was palladium 2- (bis (2-phenoxyphenyl) phosphino) benzenesulfonate. The polymerization results and characterization data are shown in Table 4, with the activity of the unadditized component b as comparison data.
Example 30
A copolymer was prepared according to the procedure of example 2, except that component b was 2, 6-di-tert-butylphenol. The polymerization results and characterization data are shown in Table 4, with the activity of the unadditized component b as comparison data.
Example 31
A copolymer was prepared according to the procedure of example 2, except that component b was 2,4, 6-tri-tert-butylphenol. The polymerization results and characterization data are shown in Table 4, with the activity of the unadditized component b as comparison data.
TABLE 4 Table 4
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.

Claims (16)

1.一种用于乙烯/极性单体共聚的催化剂体系，其特征在于，所述催化剂体系由以下组分组成：1. A catalyst system for ethylene/polar monomer copolymerization, characterized in that the catalyst system consists of the following components: 组分a，主催化剂，选自式(I)所示化合物中的至少一种，Component a, the main catalyst, is selected from at least one of the compounds represented by formula (I), 式(I)中，R1、R2、R3相同或不同，各自独立地为氢原子、取代或未取代的C1-C20烃基、取代或未取代的C1-C20烷氧基或者取代或未取代的C6-C20芳氧基，这些基团为线性、分支或环状的并任选地被卤原子、C1-C10烷基、C1-C10烷氧基、C6-C10芳基或C6-C10芳氧基进一步取代，L为配体；In formula (I), R 1 , R 2 , and R 3 are the same or different and are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 20 hydrocarbon group, a substituted or unsubstituted C 1 -C 20 alkoxy group, or a substituted or unsubstituted C 6 -C 20 aryloxy group, which groups are linear, branched or cyclic and are optionally further substituted by a halogen atom, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 6 -C 10 aryl group, or a C 6 -C 10 aryloxy group, and L is a ligand; 组分b，选自式(II)所示化合物和式(III)所示化合物中的至少一种：Component b is at least one selected from the group consisting of the compound represented by formula (II) and the compound represented by formula (III): 式(II)中，R4选自氢原子、取代或未取代的C1-C20烃基、取代或未取代的C1-C20烷氧基或者取代或未取代的C6-C20芳氧基，这些基团为线性、分支或环状的并任选地被卤原子、C1-C10烷基、C1-C10烷氧基、C1-C6羰基、C6-C10芳基或C6-C10芳氧基进一步取代；In formula (II), R4 is selected from a hydrogen atom, a substituted or unsubstituted C1 - C20 hydrocarbon group, a substituted or unsubstituted C1 - C20 alkoxy group, or a substituted or unsubstituted C6 - C20 aryloxy group, which groups are linear, branched or cyclic and are optionally further substituted by a halogen atom, a C1 - C10 alkyl group, a C1 - C10 alkoxy group, a C1 - C6 carbonyl group, a C6 - C10 aryl group or a C6 - C10 aryloxy group; 式(III)中，R5选自氢原子、取代或未取代的C1-C20烃基、取代或未取代的C1-C20烷氧基或者取代或未取代的C6-C20芳氧基，这些基团为线性、分支或环状的并任选地被卤原子、C1-C10烷基、C1-C10烷氧基、C1-C6羰基、C6-C10芳基或C6-C10芳氧基进一步取代。In formula (III), R5 is selected from a hydrogen atom, a substituted or unsubstituted C1 - C20 hydrocarbon group, a substituted or unsubstituted C1 - C20 alkoxy group, or a substituted or unsubstituted C6 - C20 aryloxy group, which groups are linear, branched or cyclic and are optionally further substituted by a halogen atom, a C1 - C10 alkyl group, a C1 - C10 alkoxy group, a C1 - C6 carbonyl group, a C6 - C10 aryl group, or a C6 - C10 aryloxy group. 2.根据权利要求1所述的催化剂体系，其中，式(I)中，R1、R2、R3相同或不同，各自独立地为氢原子、取代或未取代的C1-C10烃基、取代或未取代的C1-C10烷氧基或者取代或未取代的C6-C10芳氧基，这些基团为线性、分支或环状的并任选地被卤原子、C1-C6烷基、C1-C6烷氧基、C6-C8芳基或C6-C8芳氧基进一步取代，L为Me2SO；优选地，R1、R2、R3相同或不同，各自独立地为氢原子、取代或未取代的C1-C6烷基、取代或未取代的C1-C6烷氧基或者取代或未取代的C6-C8芳氧基，这些基团为线性、分支或环状的并任选地被卤原子、C1-C6烷基、C1-C6烷氧基、C6-C8芳基或C6-C8芳氧基进一步取代。2. The catalyst system according to claim 1, wherein in formula (I), R 1 , R 2 , and R 3 are the same or different, and are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 10 hydrocarbon group, a substituted or unsubstituted C 1 -C 10 alkoxy group, or a substituted or unsubstituted C 6 -C 10 aryloxy group, which are linear, branched or cyclic and are optionally further substituted by halogen atoms, C 1 -C 6 alkyl groups, C 1 -C 6 alkoxy groups, C 6 -C 8 aryl groups, or C 6 -C 8 aryloxy groups, and L is Me 2 SO; preferably, R 1 , R 2 , and R 3 are the same or different, and are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 6 alkyl group, a substituted or unsubstituted C 1 -C 6 alkoxy group, or a substituted or unsubstituted C 6 -C 8 aryloxy group, which are linear, branched or cyclic and are optionally further substituted by halogen atoms, C 1 -C 6 alkyl groups, C 1 -C 6 alkoxy groups, C 6 -C 8 aryl groups, or C 6 -C 8 aryloxy groups. The group may be further substituted with a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxy group, a C 6 -C 8 aryl group or a C 6 -C 8 aryloxy group. 3.根据权利要求2所述的催化剂体系，其中，所述组分a为2-(双(2-甲氧基苯基)膦基)苯磺酸钯、2-(双(2-苯氧基苯基)膦基)苯磺酸钯和2-(双(2-甲氧基苯基)膦基)-4-甲基苯磺酸钯中的至少一种。3. The catalyst system according to claim 2, wherein the component a is at least one of 2-(bis(2-methoxyphenyl)phosphino)benzenesulfonate palladium, 2-(bis(2-phenoxyphenyl)phosphino)benzenesulfonate palladium and 2-(bis(2-methoxyphenyl)phosphino)-4-methylbenzenesulfonate palladium. 4.根据权利要求1所述的催化剂体系，其中，式(II)中，R4选自氢原子、取代或未取代的C1-C10烷基、取代或未取代的C8-C16共轭环烃基、取代或未取代的C1-C10烷氧基或者取代或未取代的C6-C10芳氧基，并任选地被卤原子、C1-C6烷基、C1-C6烷氧基、C1-C3羰基、C6-C8芳基或C6-C8芳氧基进一步取代；4. The catalyst system according to claim 1, wherein in formula (II), R4 is selected from a hydrogen atom, a substituted or unsubstituted C1 - C10 alkyl group, a substituted or unsubstituted C8 - C16 conjugated cyclic hydrocarbon group, a substituted or unsubstituted C1 - C10 alkoxy group, or a substituted or unsubstituted C6 - C10 aryloxy group, and is optionally further substituted by a halogen atom, a C1 - C6 alkyl group, a C1 - C6 alkoxy group, a C1 - C3 carbonyl group, a C6 -C8 aryl group, or a C6 - C8 aryloxy group; 式(III)中，R5选自氢原子、取代或未取代的C1-C10烷基、取代或未取代的C8-C16共轭环烃基、取代或未取代的C1-C10烷氧基或者取代或未取代的C6-C10芳氧基，并任选地被卤原子、C1-C6烷基、C1-C6烷氧基、C1-C3羰基、C6-C8芳基或C6-C8芳氧基进一步取代。In formula (III), R5 is selected from a hydrogen atom, a substituted or unsubstituted C1 - C10 alkyl group, a substituted or unsubstituted C8 - C16 conjugated cyclic hydrocarbon group, a substituted or unsubstituted C1 - C10 alkoxy group, or a substituted or unsubstituted C6 - C10 aryloxy group, and is optionally further substituted by a halogen atom, a C1 - C6 alkyl group, a C1 - C6 alkoxy group, a C1 - C3 carbonyl group, a C6 - C8 aryl group, or a C6 - C8 aryloxy group. 5.根据权利要求4所述的催化剂体系，其中，所述组分b为2,6-二叔丁基-4-甲基苯酚、2,6-二叔丁基苯酚、2,4,6-三叔丁基苯酚和2,6-二叔丁基-α-(3,5-二叔丁基-4-氧-2,5-环己二烯亚基)-对甲苯氧基自由基中的至少一种。5. The catalyst system according to claim 4, wherein the component b is at least one of 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol and 2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxy-2,5-cyclohexadienyl)-p-tolyloxy free radical. 6.根据权利要求1-5中任意一项所述的催化剂体系，其中，以Pd原子计的所述组分a与所述组分b的摩尔比为1:1～1:200，优选为1:3～1:100，更优选为1:4～1:50，进一步优选为1:5～1:30。6. The catalyst system according to any one of claims 1 to 5, wherein the molar ratio of the component a to the component b, calculated as Pd atoms, is 1:1 to 1:200, preferably 1:3 to 1:100, more preferably 1:4 to 1:50, and further preferably 1:5 to 1:30. 7.权利要求1-6中任意一项所述的催化剂体系在乙烯/极性单体共聚反应的中应用。7. Use of the catalyst system described in any one of claims 1 to 6 in ethylene/polar monomer copolymerization. 8.一种乙烯/丙烯酸(酯)共聚物的制备方法，其特征在于，所述制备方法包括：在催化剂体系存在下，使乙烯与丙烯酸(酯)类单体在惰性溶剂中进行聚合反应，得到乙烯/丙烯酸(酯)共聚物；8. A method for preparing an ethylene/acrylic acid (ester) copolymer, characterized in that the preparation method comprises: in the presence of a catalyst system, polymerizing ethylene and acrylic acid (ester) monomers in an inert solvent to obtain the ethylene/acrylic acid (ester) copolymer; 所述催化剂体系为权利要求1-6中任意一项所述的催化剂体系；The catalyst system is the catalyst system according to any one of claims 1 to 6; 所述丙烯酸(酯)类单体为式(A)所示化合物中的至少一种，The acrylic acid (ester) monomer is at least one of the compounds represented by formula (A), 式(A)中，Ra为氢原子、直链或支链的C1-C4烷基，Rb为氢原子、直链或支链的C1-C10烷基。In formula (A), Ra is a hydrogen atom, a linear or branched C1 - C4 alkyl group, and Rb is a hydrogen atom, a linear or branched C1- C10 alkyl group. 9.根据权利要求8所述的制备方法，其中，式(A)中，Ra为氢原子或甲基，Rb为氢原子、直链或支链的C1-C8烷基；9. The preparation method according to claim 8, wherein, in formula (A), Ra is a hydrogen atom or a methyl group, and Rb is a hydrogen atom, a linear or branched C1 - C8 alkyl group; 优选地，所述丙烯酸(酯)类单体为丙烯酸、甲基丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸正丁酯、丙烯酸叔丁酯、丙烯酸2-乙基己酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯和甲基丙烯酸2-乙基己酯中的至少一种。Preferably, the acrylic acid (ester) monomer is at least one of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate and 2-ethylhexyl methacrylate. 10.根据权利要求8所述的制备方法，其中，所述惰性溶剂为脂肪族烃类溶剂和/或芳香族烃类溶剂；优选为直链、支链或环状的C6-C12烷烃和/或C6-C10单环芳香烃；所述C6-C12烷烃优选为正己烷、异己烷、正庚烷、异庚烷、正辛烷、异辛烷和环己烷中的至少一种；所述C6-C10单环芳香烃优选为甲苯和/或二甲苯；优选地，所述惰性溶剂为正己烷、异己烷、环己烷和甲苯中的至少一种。10. The preparation method according to claim 8, wherein the inert solvent is an aliphatic hydrocarbon solvent and/or an aromatic hydrocarbon solvent; preferably a linear, branched or cyclic C6 - C12 alkane and/or a C6 - C10 monocyclic aromatic hydrocarbon; the C6 - C12 alkane is preferably at least one of n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane and cyclohexane; the C6 - C10 monocyclic aromatic hydrocarbon is preferably toluene and/or xylene; preferably, the inert solvent is at least one of n-hexane, isohexane, cyclohexane and toluene. 11.根据权利要求8所述的制备方法，其中，聚合反应体系中，所述丙烯酸(酯)类单体的浓度为5mol/L以下，优选为2mol/L以下，更优选为1mol/L以下。11. The preparation method according to claim 8, wherein in the polymerization reaction system, the concentration of the acrylic acid (ester) monomer is 5 mol/L or less, preferably 2 mol/L or less, and more preferably 1 mol/L or less. 12.根据权利要求8所述的制备方法，其中，所述丙烯酸(酯)类单体与催化剂体系中的所述组分b预先混合，预先混合的时间优选为1～30分钟，更优选为2～15分钟，进一步优选为3～10分钟。12. The preparation method according to claim 8, wherein the acrylic acid (ester) monomer is premixed with the component b in the catalyst system, and the premixing time is preferably 1 to 30 minutes, more preferably 2 to 15 minutes, and further preferably 3 to 10 minutes. 13.根据权利要求8所述的制备方法，其中，所述丙烯酸(酯)类单体与催化剂体系中的所述组分b的摩尔比为50:1～800:1，优选100:1～350:1，更优选150:1～300:1。13. The preparation method according to claim 8, wherein the molar ratio of the acrylic acid (ester) monomer to the component b in the catalyst system is 50:1 to 800:1, preferably 100:1 to 350:1, and more preferably 150:1 to 300:1. 14.根据权利要求8-13中任意一项所述的制备方法，其中，所述聚合反应的温度为20～150℃，优选为40～120℃，更优选为60～100℃；所述聚合反应的压力为10MPa以下，优选为0.01～5MPa，更优选为0.1～2MPa。14. The preparation method according to any one of claims 8 to 13, wherein the polymerization reaction temperature is 20 to 150°C, preferably 40 to 120°C, and more preferably 60 to 100°C; the polymerization reaction pressure is below 10 MPa, preferably 0.01 to 5 MPa, and more preferably 0.1 to 2 MPa. 15.由权利要求8-14中任意一项所述的制备方法制备得到的乙烯/丙烯酸(酯)共聚物。15. Ethylene/acrylic acid (ester) copolymer prepared by the preparation method described in any one of claims 8 to 14. 16.根据权利要求15所述的乙烯/丙烯酸(酯)共聚物，其中，所述共聚物包含75～99mol％衍生自乙烯的结构单元和1～25mol％衍生自丙烯酸(酯)类单体的结构单元；丙烯酸(酯)插入共聚物主链的比例在70mol％以上，优选在80mol％以上，进一步优选在85mol％以上，更优选在90mol％以上。16. The ethylene/acrylic acid (ester) copolymer according to claim 15, wherein the copolymer comprises 75 to 99 mol % of structural units derived from ethylene and 1 to 25 mol % of structural units derived from acrylic acid (ester) monomers; the proportion of acrylic acid (ester) inserted into the main chain of the copolymer is above 70 mol %, preferably above 80 mol %, further preferably above 85 mol %, and more preferably above 90 mol %.
CN202311616738.6A 2023-11-29 2023-11-29 Catalyst system, ethylene/acrylic acid (ester) copolymer and preparation method thereof Pending CN120059012A (en)

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