CN108329415B - Silicon functionalized polyolefin and preparation method thereof - Google Patents

Silicon functionalized polyolefin and preparation method thereof Download PDF

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CN108329415B
CN108329415B CN201810133888.4A CN201810133888A CN108329415B CN 108329415 B CN108329415 B CN 108329415B CN 201810133888 A CN201810133888 A CN 201810133888A CN 108329415 B CN108329415 B CN 108329415B
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陈昶乐
周世新
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University of Science and Technology of China USTC
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Abstract

The invention provides a preparation method of silicon functionalized polyolefin, which comprises the following stepsThe method comprises the following steps: ethylene and silicon-containing internal olefin are subjected to polymerization reaction under the catalytic action of an alpha-diimine nickel catalyst to obtain silicon-functionalized polyolefin; the alpha-diimine nickel has a structure shown in a formula III. According to the invention, alpha-nickel diimine is adopted to catalyze the polymerization reaction of silicon-containing endoolefin and ethylene, the reaction has high activity and moderate silicon-containing endoolefin insertion ratio, and the used alpha-nickel diimine catalyst has excellent stability, so that the silicon-functionalized copolymer with high molecular weight is prepared. The experimental results show that: the activity of the polymerization reaction can reach 3.4 multiplied by 10 to the maximum4g/(mol. Ni. h); the weight-average molecular weight of the copolymerization product is up to 8.6X 104g/mol, silicon-containing internal alkene insertion ratio of at most 2.9%.

Description

Silicon functionalized polyolefin and preparation method thereof
Technical Field
The invention relates to the technical field of compound preparation, in particular to silicon functionalized polyolefin and a preparation method thereof.
Background
Polyolefins are one of the indispensable materials in modern social life and production due to their excellent physical and mechanical properties and relatively low price. The continuous development of olefin polymerization catalysts leads to the rich variety and excellent performance of polyolefin products, and promotes the development of the whole polyolefin industry. At present, the demand for polyolefins is still quite enormous, and therefore research on polyolefins, especially functionalized polyolefins, is taking an important position.
It is well known that metal-catalyzed hydrosilylation of olefins is one of the largest scale homogeneous catalytic processes used. In industry, such catalytic processes are widely used to prepare materials for various purposes, such as surfactants, adhesives, etc. Generally, four different types of reactions will occur between a terminal olefin and a silane over a metal catalyst, respectively: markovinkov (Markovnikov) hydrosilylation, anti-Markovinkovinkovinkinig hydrosilylation, Maniconic dehydrosilylation, anti-Markovinkinig dehydrosilylation. Among them, the dehydrosilylation reaction was originally regarded as a type of side reaction in the course of the hydrosilylation reaction, but with the advent and emergence of non-noble metal highly selective catalytic systems for the dehydrosilylation reaction, the dehydrosilylation reaction has become more and more interesting due to the fact that the double bond in its reaction product can be further functionalized. For example, Chirik et al found that the compound of pyridine diimine cobalt methyl can effectively catalyze the dehydrogenation and silanization process under mild conditions, the applicability of substrates is wide, the selectivity of the catalyst is excellent, and allyl silane in the obtained productMuch greater than the amount of vinylsilane, and Chirik et al also found passage through MeLi, NaBEt3The reaction result can be successfully realized by using the pyridine diimine cobalt dichloride with reagents such as H and the like which are easier to prepare and more stable through in-situ activation. However, the above reaction inevitably produces a silicon-containing endoolefin compound as a by-product which is poor in activity and cannot be utilized, resulting in a great waste of resources.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a silicon-functionalized polyolefin and a preparation method thereof, wherein a silicon-containing internal olefin compound is used as a raw material, and is copolymerized with ethylene to prepare the silicon-functionalized polyolefin.
In order to solve the technical problems, the invention provides a preparation method of silicon functionalized polyolefin, which comprises the following steps:
ethylene and silicon-containing internal olefin are subjected to polymerization reaction under the catalytic action of an alpha-diimine nickel catalyst to obtain silicon-functionalized polyolefin;
the alpha-diimine nickel has a structure shown in formula III:
Figure BDA0001572334280000021
the silicon-containing internal olefin may be a silicon-containing internal olefin well known to those skilled in the art, and is preferably, but not limited to, 1-trimethoxysilyl-2-octene, 1-triethoxysilyl-2-octene or 1-bis (trimethylsiloxy) methylsilyl-2-octene.
The amount ratio of ethylene, silicon-containing internal alkene and alpha-diimine nickel is preferably one atmosphere of ethylene: 1mol/L silicon-containing internal alkene: 5. mu. mol of nickel alpha-diimine.
In the preferred embodiment of the present invention, the polymerization solvent is preferably toluene.
The polymerization reaction temperature is preferably 20-60 ℃, and the time is preferably more than 2 hours, and more preferably 2-6 hours.
Preferably, the polymerization reaction is carried out in an inert gas atmosphere. The inert gas is preferably, but not limited to, nitrogen.
The pressure of the polymerization reaction is preferably one atmosphere.
In the present invention, it is preferable that methylaluminoxane is added as a cocatalyst to the polymerization reaction system.
The prepared silicon functionalized polyolefin has a structure shown in a formula I or a formula II:
Figure BDA0001572334280000022
Figure BDA0001572334280000031
wherein R is1、R2、R3Independently preferably substituted or unsubstituted C1-C8A hydrocarbon group of1-C8Alkylene oxide of (C)1-C8An aryl group or an inert heterocyclic group.
The hydrocarbyl group refers to an alkyl group, an alkenyl group, or an alkynyl group.
The term "hydrocarbyloxide" refers to a hydrocarbyl group bonded to a Si atom through an O atom, and has the structure R-O, where R is a hydrocarbyl group, such as an alkoxy group.
The oxysilane group refers to a silane group bonded to the Si atom through an O atom, and has a structure such as R '-Si-O, wherein R' is an alkyl group.
The aryl group is preferably a phenyl group or a phenyl group having a halogen, nitro, hydroxyl, or C1-C5 alkyl substituent.
The inert heterocyclic group is preferably a thiophene group, a benzothiophene group, or a pyrrole group, etc.
l is preferably an integer of 1 to 5.
m is preferably 1 or 2.
n is the degree of polymerization and may be 1000< n < 2000.
C substituted as described above1-C8A hydrocarbon group of1-C8Alkylene oxide of (C)1-C8The substituent in the oxysilane group, aryl group or inert heterocyclic group of (A) is independently preferably C1-C8A hydrocarbon group of1-C8Alkylene oxide of (C)1-C8An aryl group or an inert heterocyclic group.
The number of said substituents may be 1,2 or 3.
In the above structural formula, a single bond "-" represents a connecting bond, and a slash "/" is used to divide different blocks.
In certain embodiments of the present invention, the silicon-functionalized polyolefin has, but is not limited to, any one of the structures 301-304:
Figure BDA0001572334280000032
Figure BDA0001572334280000041
the invention also provides silicon functionalized polyolefin with a structure shown as a formula I or a formula II, wherein R is1、R2、R3The ranges of l, m and n are the same as above, and are not described herein again.
Compared with the prior art, the invention provides a preparation method of silicon functionalized polyolefin, which comprises the following steps: ethylene and silicon-containing internal olefin are subjected to polymerization reaction under the catalytic action of an alpha-diimine nickel catalyst to obtain silicon-functionalized polyolefin; the alpha-diimine nickel has a structure shown in a formula III.
According to the invention, alpha-nickel diimine is adopted to catalyze the polymerization reaction of silicon-containing endoolefin and ethylene, the reaction has high activity and moderate silicon-containing endoolefin insertion ratio, and the used alpha-nickel diimine catalyst has excellent stability, so that the silicon-functionalized copolymer with high molecular weight is prepared. The experimental results show that: the activity of the polymerization reaction can reach 3.4 multiplied by 10 to the maximum4g/(mol. Ni. h); the weight-average molecular weight of the copolymerization product is up to 8.6X 104g/mol, silicon-containing internal alkene insertion ratio of at most 2.9%. Provides an alternative way for reasonably utilizing silicon-containing endoalkene which is abundant in industrial sources and low in price to participate in the polymerization process and the subsequent possible crosslinking process.
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FIG. 1 shows the results of copolymerization of 1-trimethoxysilyl-2-octene (1mol/L) and ethylene (one atmosphere of ethylene) in example 11NMR-H spectrum (deuterated reagent is 1,1,2, 2-tetrachloroethane, and temperature is 120 ℃);
FIG. 2 shows the results of copolymerization of 1-triethoxysilyl-2-octene (1mol/L) and ethylene (one atmosphere of ethylene) in example 21NMR-H spectrum (deuterated reagent is 1,1,2, 2-tetrachloroethane, and temperature is 120 ℃);
FIG. 3 shows the results of copolymerization of 1-triethoxysilyl-2-octene (1mol/L) and ethylene (one atmosphere of ethylene) in example 213NMR-C spectrum (deuterated reagent is 1,1,2, 2-tetrachloroethane, and temperature is 120 ℃);
FIG. 4 is a graph showing the results of copolymerization of 1-bis (trimethylsiloxy) methylsilyl-2-octene (1mol/L) and ethylene (one atmosphere of ethylene) in example 31NMR-H spectrum (deuterated reagent is 1,1,2, 2-tetrachloroethane, and temperature is 120 ℃);
FIG. 5 shows a copolymer obtained by copolymerizing 1-bis (trimethylsiloxy) methylsilyl-2-octene (1mol/L) and ethylene (ethylene is one atmosphere) in example 313NMR-C spectrum (deuterated reagent is 1,1,2, 2-tetrachloroethane, and temperature is 120 ℃).
Detailed Description
In order to further illustrate the present invention, the silicon-functionalized polyolefin and the preparation method thereof provided by the present invention are described in detail below with reference to examples.
In the following examples, the synthesis and polymerization of the complex was carried out in the absence of water and oxygen, all sensitive materials were stored in a glove box, all solvents were rigorously dried to remove water, and ethylene gas was purified by a water and oxygen removal column. All the raw materials were purchased and used without specific mention.
The silica gel column is prepared by 200-mesh 300-mesh silica gel, and the nuclear magnetism is realized by a Bruker 400MHz nuclear magnetism instrument. The elemental analysis was determined by the chemical and physical center of the university of science and technology in China. The molecular weight and the molecular weight distribution were determined by GPC (polystyrene type columns, HR2 and HR4, tank temperature 45 ℃ C., using Water 1515 and Water 2414 pumps, tetrahydrofuran as the mobile phase, flow rate 1.0 ml per minute, polydispersed polystyrene as standard).
Example 1: copolymerization of ethylene with 1-trimethoxysilyl-2-octene (formula 1-a)
In a glove box, 13mL of toluene was added under nitrogen atmosphere to a 350mL autoclave (with a magnetic stirring device, an oil bath heating device, and a thermometer), 4.6g (at this time the comonomer concentration was 1mol/L, noted as item 2) or 2.3g (at this time the comonomer concentration was 0.5mol/L, noted as item 1) of 1-trimethoxysilyl-2-octene was added, and 0.17g of methylaluminoxane was added. The vessel was connected to a line at atmospheric pressure and the line was evacuated. The vessel temperature was set at 40 ℃ and held for 15 minutes. The nickel complex (shown in formula III) (2.7mg) dissolved in 2ml of methylene chloride was injected into the polymerization system by means of a syringe. After the valve was closed and the ethylene pressure was adjusted to 1 atm, the reaction was carried out for 4 hours. Stopping the reaction, opening the reaction kettle, adding ethanol into the reaction kettle to precipitate solid, filtering the solid under reduced pressure, and drying the solid in a vacuum drying oven to obtain white solid.
The copolymerization results are shown in table 1:
Figure BDA0001572334280000061
TABLE 1 copolymerization results of ethylene and 1-trimethoxysilyl-2-octenea
Figure BDA0001572334280000062
aThe polymerization conditions comprise that the total volume of toluene and 1-trimethoxysilyl-2-octene is 18mL, the volume of dichloromethane is 2mL, the dosage of nickel complex is 5 mu mol, the molar ratio of methylaluminoxane to nickel complex is 500, the pressure of ethylene is 1 atmosphere, the polymerization time is 4 hours, and the polymerization temperature is 40 ℃.
bThe unit of activity is 104g·mol-1·h-1。
cMelting points were determined using differential scanning calorimetry.
d1-trimethoxysilyl-2-octene insertion ratio determined by nuclear magnetic hydrogenAnd (4) performing spectrum measurement.
eWeight average molecular weight of 104g mol-1The molecular weight was measured by GPC using polystyrene as a standard trichlorobenzene as a solvent at 150 ℃.
The NMR spectrum of the polymer is shown in FIG. 1.
Example 2: copolymerization of ethylene with 1-triethoxysilyl-2-octene (formula 2-a)
In a glove box, 12mL of toluene was added under nitrogen atmosphere to a 350mL autoclave (with a magnetic stirring device, an oil bath heating device, and a thermometer), 5.6g (at this time the comonomer concentration was 1mol/L, noted as item 2) or 2.8g (at this time the comonomer concentration was 0.5mol/L, noted as item 1) of 1-triethoxysilyl-2-octene was added, and 0.17g of methylaluminoxane was added. The vessel was connected to a line at atmospheric pressure and the line was evacuated. The vessel temperature was set at 40 ℃ and held for 15 minutes. The nickel complex (shown in formula III) (2.7mg) dissolved in 2ml of methylene chloride was injected into the polymerization system by means of a syringe. After the valve was closed and the ethylene pressure was adjusted to 1 atm, the reaction was carried out for 4 hours. Stopping the reaction, opening the reaction kettle, adding ethanol into the reaction kettle to precipitate solid, filtering the solid under reduced pressure, and drying the solid in a vacuum drying oven to obtain white solid.
The copolymerization results are shown in table 2:
Figure BDA0001572334280000071
TABLE 2 copolymerization results of ethylene and 1-trimethoxysilyl-2-octenea
Figure BDA0001572334280000072
aThe polymerization conditions comprise that the total volume of toluene and 1-trimethoxysilyl-2-octene is 18mL, the volume of dichloromethane is 2mL, the dosage of nickel complex is 5 mu mol, the molar ratio of methylaluminoxane to nickel complex is 500, the pressure of ethylene is 1 atmosphere, the polymerization time is 4 hours, and the polymerization temperature is 40 ℃.
bThe unit of activity is 104g·mol-1·h-1。
cMelting points were determined using differential scanning calorimetry.
dThe 1-trimethoxysilylene-2-octene insertion ratio is measured by nuclear magnetic hydrogen spectroscopy.
eWeight average molecular weight of 104g mol-1The molecular weight was measured by GPC using polystyrene as a standard trichlorobenzene as a solvent at 150 ℃.
fThe polymerization time was 12 hours
The NMR spectrum of the polymer is shown in FIG. 2.
The NMR spectrum of the polymer is shown in FIG. 3.
Example 3: copolymerization of ethylene with 1-bis (trimethylsiloxy) methylsilyl-2-octene (formula 3-a)
In a glove box, 11mL of toluene was added under nitrogen atmosphere to a 350mL autoclave (with a magnetic stirrer, an oil bath heater and a thermometer), 6.7g (at this time the comonomer concentration was 1mol/L, noted as item 2) or 3.3g (at this time the comonomer concentration was 0.5mol/L, noted as item 1) of 1-bis (trimethylsiloxy) methylsilyl-2-octene was added, and 0.17g of methylaluminoxane was added. The vessel was connected to a line at atmospheric pressure and the line was evacuated. The vessel temperature was set at 40 ℃ and held for 15 minutes. The nickel complex (shown in formula III) (2.7mg) dissolved in 2ml of methylene chloride was injected into the polymerization system by means of a syringe. After the valve was closed and the ethylene pressure was adjusted to 1 atm, the reaction was carried out for 4 hours. Stopping the reaction, opening the reaction kettle, adding ethanol into the reaction kettle to precipitate solid, filtering the solid under reduced pressure, and drying the solid in a vacuum drying oven to obtain white solid.
The copolymerization results are shown in table 3:
Figure BDA0001572334280000081
TABLE 3 copolymerization results of ethylene and 1-trimethoxysilyl-2-octenea
Figure BDA0001572334280000082
aThe polymerization conditions comprise that the total volume of toluene and 1-trimethoxysilyl-2-octene is 18mL, the volume of dichloromethane is 2mL, the dosage of nickel complex is 5 mu mol, the molar ratio of methylaluminoxane to nickel complex is 500, the pressure of ethylene is 1 atmosphere, the polymerization time is 4 hours, and the polymerization temperature is 40 ℃.
bThe unit of activity is 104g·mol-1·h-1。
cMelting points were determined using differential scanning calorimetry.
dThe 1-trimethoxysilylene-2-octene insertion ratio is measured by nuclear magnetic hydrogen spectroscopy.
eWeight average molecular weight of 104g mol-1The molecular weight was measured by GPC using polystyrene as a standard trichlorobenzene as a solvent at 150 ℃.
The NMR spectrum of the polymer is shown in FIG. 4.
The NMR spectrum of the polymer is shown in FIG. 5.
From the above examples, it is clear that the present invention provides a method for copolymerization of silicon-containing endoolefin and ethylene using nickel α -diimine as a catalyst, successfully producing silicon-functionalized polyolefin having a structure represented by formula (I) or (II). In the above method for preparing silicon-functionalized polyolefin, the alpha-nickel diimine catalyst for copolymerization of silicon-containing endoolefin and ethylene has high activity and moderate insertion ratio of silicon-containing endoolefin, and the used alpha-nickel diimine catalyst has excellent stability under the implemented catalytic conditions, resulting in a silicon-functionalized copolymer with high molecular weight.
The experimental results show that: the alpha-nickel diimine is used for catalyzing the copolymerization of silicon-containing allene and ethylene, and the activity can reach 3.4 multiplied by 10 to the maximum4g/(mol. Ni. h); the weight-average molecular weight of the copolymerization product is up to 8.6X 104g/mol, silicon-containing internal alkene insertion ratio of at most 2.9%.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (2)

1. A silicon-functionalized polyolefin having the structure of formula I or formula II:
Figure FDA0002532451220000011
wherein R is1、R2、R3Independently selected from C1-C8Alkyl of (C)1-C8Alkoxy or C1-C8An oxysilane group of (a);
the structure of the oxidized silane group is R '-Si-O, and R' is alkyl;
l is an integer of 1-5;
m is 1 or 2;
1000<n<2000；
the preparation method of the silicon functionalized polyolefin comprises the following steps:
ethylene and silicon-containing internal olefin are subjected to polymerization reaction under the catalytic action of an alpha-diimine nickel catalyst to obtain silicon-functionalized polyolefin;
the silicon-containing internal alkene is 1-triethoxysilyl-2-octene or 1-bis (trimethylsilyloxy) methylsilyl-2-octene;
the alpha-diimine nickel has a structure shown in formula III:
Figure FDA0002532451220000012
the dosage ratio of ethylene, silicon-containing internal alkene and alpha-diimine nickel is one atmosphere of ethylene: 1mol/L silicon-containing internal alkene: 5 μmol of alpha-diimine nickel;
the temperature of the polymerization reaction is 40 ℃, and the time is 4 hours;
the polymerization reaction is carried out in an inert gas atmosphere;
the pressure of the polymerization reaction is one atmosphere;
and methylaluminoxane is added into the polymerization reaction system.
2. The silicon-functionalized polyolefin of claim 1, having a structure of any one of formulas 301 to 304:
Figure FDA0002532451220000021
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