CN1304443C - Polyethylene graft copolymer and its preparation method - Google Patents
Polyethylene graft copolymer and its preparation method Download PDFInfo
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- CN1304443C CN1304443C CNB2004100837972A CN200410083797A CN1304443C CN 1304443 C CN1304443 C CN 1304443C CN B2004100837972 A CNB2004100837972 A CN B2004100837972A CN 200410083797 A CN200410083797 A CN 200410083797A CN 1304443 C CN1304443 C CN 1304443C
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Abstract
The present invention discloses a polyethylene graft copolymer prepared by polymerization initiated by an atom transfer free radical polymerization initiating agent under a mild condition. The preparation method of the initiating agent comprises the steps that a homogeneous catalysis system containing a metallocene catalyst is used for copolymerization and then the initiating agent with the yield approaching to 100% is obtained through an addition reaction with simple conditions. The graft density and the graft number of functionalized functional groups can be accurately regulated and controlled. The copolymer keeps the favorable original performance of polyethylene, such as a high melting point, high degree of crystallization, etc.
Description
Technical field
The present invention relates to a kind of polyethylene graft copolymer.
The invention still further relates to the preparation method of above-mentioned multipolymer.
Background technology
Polyethylene is as large kind of general-purpose plastics, because its good mechanical performance, good processability, electric insulating quality are strong, stable chemical performance and advantage such as cheap and be widely used in fields such as daily life, packaging industry, automobile, building, agricultural and military affairs.Yet, because polyethylene belongs to nonpolar polymkeric substance, has low-down surface energy, cause it to be difficult to realize effectively bonding and compatible at interface with other most polymers or inorganic materials blend or compound tense, make blend or the performance of composites be difficult to be protected, limited the application of polyethylene in dyeing, printing and field such as bonding.And the polyethylene of functionalization, be exactly on Polyethylene Chain, to introduce the polar functionalities group, on the basis that keeps the original premium properties of polyolefine, increase polyolefinic polarity, improve consistency, the tackiness of polyethylene and other material, strengthen poly printing and dyeing, wettability etc., realize the high performance of polyolefine material, expanded poly Application Areas.
Atom transfer radical polymerization (ATRP) is the controlled activity polymerizating technology that new development is in recent years got up, and can make a series of polarity or nonpolar polymerization of vinyl monomer.Recently, increasing people introduces polyolefin backbone by atom transfer radical polymerization (ATRP) technology with polar group, the preparation functional polyolefin.(Macromolecules such as Sen, 2001,34 (5): 1529-1532) by the ethylene-styrene copolymer of bromination by metallocene catalysts, bromine is incorporated into the benzyl position of styrene units, thereby ethylene-styrene copolymer is changed into the macromole evocating agent of an atom transfer radical polymerization, synthesized multiple functional poly grafted ethylene copolymer.(Polymer such as Shimada, 2003,44 (25): 7661-7669) method by gamma-radiation irradiation produces the hydrogen peroxide group on the sub polyethylene subchain, be catalyzer with iron trichloride/PPH3 then, with the hydrogen peroxide on the macromolecular chain is initiator, has prepared polyethylene-polymethylmethacrylate graft copolymer.(J.Polym.Sci. such as Matyjaszewski, Part A:Polym.Chem., 2000,38 (13): 2440-2448) from commodity ethylene-methyl methacrylate glycidyl ester copolymer, also be translated into the macromole evocating agent of atom transfer radical polymerization by a series of conversion reactions, prepared the graft copolymer of polyethylene-polystyrene and polyethylene-polymethylmethacrylate with reagent such as Mono Chloro Acetic Acid and 2-isobutyl bromides.But the existing synthetic method that polyethylene and ethylene copolymers is changed into atom transfer radical polymerization initiator is too complicated, severe reaction conditions, and yield is very low; Perhaps gained multipolymer side chain is to be connected by the C-O key with main chain, so structure is stable inadequately.And the grafting density of functionalization functional group, grafting quantity are difficult to carry out accuracy controlling in the functional polyolefin graft copolymer.
Summary of the invention
Based on above background, the invention provides a kind of functional poly grafted ethylene copolymer, have structure shown in the formula 1.This multipolymer keeps premium propertiess such as the original high-melting-point of polyethylene, high-crystallinity.And the grafting density of functionalization functional group, grafting quantity can be carried out accuracy controlling.
(formula 1)
In the formula, z/y=0.1%～30%, m are the integer of 0-6, and M is vinylbenzene, vinyl-acetic ester, methacrylic ester, methyl methacrylate, vinyl cyanide of vinylbenzene, replacement etc., and n is the integer of 10-5000, and X is halogen groups such as F, Cl, Br, I.
This multipolymer is caused under mild conditions by a kind of novel atom transfer radical polymerization initiator by following method, divides the preparation of three steps:
(1) at first prepares the polyethylene and ethylene copolymers that contains the styryl reaction member.Press every 100ml toluene, heptane, hexane, pentane equal solvent in the reactor, the alkylaluminoxane that adds 0.001-100mmol, 0.1-10g the olefinic monomer that contains styrene derivatives, 0.01-10 μ mol metallocene catalyst, keeping temperature of reaction is 0-100 ℃, be preferably 30-80 ℃, feed ethene, keeping reaction pressure is the 1-10 normal atmosphere, be preferably the 1-6 normal atmosphere, reacted 0.1～100 hour, the polymkeric substance that makes by water, ethanol, methyl alcohol thorough washing, filtration, drying, is obtained containing the polyethylene and ethylene copolymers of styrene derivatives.
Styrene derivatives monomer in this step has structure shown in the formula 2
(formula 2)
M=0-6 in the formula.
Can be the linear aikyiaiurnirsoxan beta of following formula (4) as the aikyiaiurnirsoxan beta of promotor
In the formula, R
1Be selected from halogen, linearity or branching, saturated or undersaturated C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkylaryl and C
7-C
20Aromatic yl alkyl group, y are 0-40;
Or the ring aikyiaiurnirsoxan beta of following formula (5)
R in the formula
1Have implication described herein, y is the integer of 2-40.
Above aikyiaiurnirsoxan beta can be by various method preparation.According to known the whole bag of tricks in the prior art level, by making water and formula AlR
1 3Or from Al
2R
1 6Organo-aluminium compound react and can obtain above-mentioned various aikyiaiurnirsoxan beta, condition is at least one R
1It or not halogen.The mol ratio of Fan Ying Al/ water is 1 in this case: 1-100: between 1.For example, a kind of trialkylaluminium (for example trimethyl aluminium etc.) can be dissolved in (for example benzene, aliphatic hydrocrbon etc.) in the appropriate solvent, the solution that is obtained contacts with water again, just can be made into this aikyiaiurnirsoxan beta.
Used metallocene catalyst is the compound with following general formula:
Wherein, M is the transition metal of IVa family in the periodic table of chemical element, Va family and VIa family;
R
1It is the alkyl of 2 to 6 carbon atoms;
R
2Be aryl that can be replaced by halogen atom, the 6-16 carbon atom, hydrogen atom, the alkyl of 1-20 carbon atom or Organosilyl;
X
1And X
2Respectively be hydrogen atom, halogen atom, the alkyl of 1-20 carbon atom, the halo alkyl of 1-20 carbon atom, oxy radical or sulfur-containing group; With Y be the alkyl of the 1-20 carbon atom of divalence, the halo alkyl of the 1-20 carbon atom of divalence, the silicon-containing group of divalence, the germanic group of divalence ,-O-,-CO-,-S-,-SO-,-SO
2-,-NR
3-,-P (R
3)-,-P (O) (R
3)-,-BR
3-or-AlR
3-(R
3Be hydrogen atom, halogen atom, the halo alkyl of the alkyl of 1-20 carbon atom or 1-20 carbon atom).
By
1H-NMR characterize to determine copolymer structure, and the content of styrene derivatives in the multipolymer.
(2) suspension that polyethylene and ethylene copolymers and toluene, tetrahydrofuran (THF), methyl-phenoxide or the halogenated alkane equal solvent of step 1 preparation are made 1-100g/100ml.Keeping temperature of reaction is 0-100 ℃, in the polyethylene and ethylene copolymers aaerosol solution, feed hydrogen halide (hydrogenchloride, hydrogen bromide, hydrogen fluoride, hydrogen iodide etc.), reacted 0.5-20 hour, and obtained the polyvinyl atom transfer radical polymerization initiator by the simple addition reaction of condition, by
1H-NMR characterizes and determines copolymer structure, and the initiator yield.This initiator structure as shown in Equation 3, yield is near 100%.With the above-mentioned prepared product of ethanol thorough washing, drying.
(formula 3)
In the formula, z/y=0.01-30%, m are the integer of 0-6, and X is halogen groups such as F, Cl, Br, I.
(3) initiator that step 2 is obtained and toluene, chloroparaffin or methyl-phenoxide solvent are made 1.0-20.0g/100ml suspension, add the 0.01-0.1g cuprous chloride, 0.02-0.1ml pentamethyl-two vinylidene triamines are catalyzer, in 70-150 ℃, add vinylbenzene, p-methylstyrene, vinyl-acetic ester, methacrylic ester, methyl methacrylate or vinyl cyanide 20-40g, reacted 0.01-8 hour, and obtained the polyethylene graft copolymer of functionalization.
The grafting density of the functionalization functional group in this functional poly ethylenic copolymer can be by kind or the concentration that changes polymerization temperature in the initiator preparation process or catalyst component, the add-on that contains the olefinic monomer of styrene derivatives, and reaction conditionss such as the concentration that grafting quantity can be by the various function monomers of atom transfer radical polymerization, reaction times carry out accuracy controlling.Gained functional poly ethylenic copolymer keeps premium propertiess such as the original high-melting-point of polyethylene, high-crystallinity.The multipolymer of gained of the present invention can be with other polymkeric substance, preferably with entirely carry out blend with ethene polymers, improves the consistency of polyolefine and other material.The example that carries out the polymkeric substance of blend with ethene polymers in the presence of graft copolymer is polystyrene, polyethers, polyacrylic ester, as polymethacrylate.
Description of drawings
Fig. 1 is the polyethylene and ethylene copolymers that contains styrene units of embodiment 4 preparations
1The H-NMR spectrogram.
Fig. 2 is the polyvinyl atom transfer radical polymerization initiator of embodiment 10 preparations
1The H-NMR spectrogram.
Specific embodiment
One, preparation contains the polyethylene and ethylene copolymers of styrene derivatives
Get the 500ml reactor, add the 100ml hexane, add the toluene solution of 0.1mmol methylaluminoxane, add 0.1 gram Vinylstyrene, stirring adds 0.1 μ mol racemize-ethene-two (1-indenyl)-ZrCl down
2Catalyzer.50 ℃ feed ethylene gas, and reaction is 1 hour under 5 normal atmosphere, obtains polymkeric substance 19g.
1It is 0.1% that H-NMR characterizes the content of determining styrene units in the multipolymer,
1The H-NMR spectrogram is seen accompanying drawing 1.
Get the 500mL reactor, add the 100ml pentane, add the toluene solution of 0.01mmol ethyl aikyiaiurnirsoxan beta, add 10 gram vinylstyrenes, stirring adds 0.1 μ mol racemize-isopropylidene-two (1-indenyl)-ZrCl down
2Catalyzer.0 ℃ feeds ethylene gas, and reaction is 100 hours under 1 normal atmosphere, obtains polymkeric substance 16.7g.
1It is 30% that H-NMR characterizes the content of determining styrene derivatives in the multipolymer.
Embodiment 3
Get the 500mL reactor, add 100ml toluene, add the toluene solution of 0.001mmol methylaluminoxane, add the 3 alkenyl benzene ethene of restraining oneself, stir and add 0.01 μ mol racemize-dimetylsilyl-two (1-indenyl)-ZrCl down
2Catalyzer.100 ℃ feed ethylene gas, and reaction is 10 hours under 10 normal atmosphere, obtains polymkeric substance 8.8g.
1It is 10% that H-NMR characterizes the content of determining styrene derivatives in the multipolymer.
Embodiment 4
Get the 500ml reactor, add the 100ml hexane, add the toluene solution of 1mmol methylaluminoxane, add 0.1 gram Vinylstyrene, stirring adds 0.1 μ mol racemize-dimetylsilyl-two (2-methyl isophthalic acid-indenyl)-ZrCl down
2Catalyzer.50 ℃ feed ethylene gas, and reaction is 1 hour under 5 normal atmosphere, obtains polymkeric substance 20g.
1It is 0.1% that H-NMR characterizes the content of determining styrene units in the multipolymer,
1The H-NMR spectrogram is seen accompanying drawing 1.
Embodiment 5
Get the 10L reactor, add the 1000ml pentane, add the toluene solution of 10mmol methylaluminoxane, add 10 gram vinylstyrenes, stirring adds 1 μ mol racemize-dimetylsilyl-two (2-methyl-4-sec.-propyl-1-indenyl)-ZrCl down
2Catalyzer.0 ℃ feeds ethylene gas, and reaction is 100 hours under 1 normal atmosphere, obtains polymkeric substance 25.7g.
1It is 30% that H-NMR characterizes the content of determining styrene derivatives in the multipolymer.
Embodiment 6
Get the 1L reactor, add 300ml toluene, add the toluene solution of 1mmol methylaluminoxane, add the 3 alkenyl benzene ethene of restraining oneself, stir and add 0.03 μ mol racemize-dimetylsilyl-two (2-methyl-4-phenyl-1-indenyl)-ZrCl down
2Catalyzer.100 ℃ feed ethylene gas, and reaction is 10 hours under 10 normal atmosphere, obtains polymkeric substance 13.2g.
1It is 10% that H-NMR characterizes the content of determining styrene derivatives in the multipolymer.
Embodiment 7
Get the 500mL reactor, add the 100ml heptane, add the toluene solution of 100mmol methylaluminoxane, add 5 gram octenyl vinylbenzene, stirring adds 10 μ mol racemize-dimetylsilyl-two (2-methyl-4-phenyl-1-indenyl)-ZrCl down
2Catalyzer.50 ℃ feed ethylene gas, and reaction is 0.1 hour under 10 normal atmosphere, obtains polymkeric substance 40g.
1It is 4% that H-NMR characterizes the content of determining styrene derivatives in the multipolymer.
Two, preparation polyvinyl atom transfer radical polymerization initiator
Embodiment 8
Get the 250ml there-necked flask, adding embodiment 4 gained contain the polyethylene and ethylene copolymers 2.0g of styrene derivatives, add 100ml toluene, in the polyethylene and ethylene copolymers aaerosol solution, feed hydrogen chloride gas, after 60 hours, use the above-mentioned prepared product of ethanol thorough washing, drying 0 ℃ of reaction, obtain polyvinyl atom transfer radical polymerization initiator 2.1g
1H-NMR characterizes and determines transformation efficiency 88%.
Embodiment 9
Get the 250ml there-necked flask, adding embodiment 4 gained contain the polyethylene and ethylene copolymers 2.0g of styrene derivatives, add the 100ml tetrahydrofuran (THF), in the polyethylene and ethylene copolymers aaerosol solution, feed bromize hydrogen gas, after 0.5 hour, use the above-mentioned prepared product of ethanol thorough washing, drying 60 ℃ of reactions, obtain polyvinyl atom transfer radical polymerization initiator 2.0g
1H-NMR characterizes and determines transformation efficiency 98%.
Embodiment 10
Get the 250ml there-necked flask, adding embodiment 4 gained contain the polyethylene and ethylene copolymers 2.0g of styrene derivatives, add the 100ml methyl-phenoxide, in the polyethylene and ethylene copolymers aaerosol solution, feed hydrogen iodide gas, after 20 hours, use the above-mentioned prepared product of ethanol thorough washing, drying 100 ℃ of reactions, obtain polyvinyl atom transfer radical polymerization initiator 2.1g
1H-NMR characterizes and determines transformation efficiency 100%.
1The H-NMR spectrogram is seen accompanying drawing 2.
Embodiment 11
Get the 250ml there-necked flask, adding embodiment 4 gained contain the polyethylene and ethylene copolymers 2.0g of styrene derivatives, add the 100ml ethylene dichloride, in the polyethylene and ethylene copolymers aaerosol solution, feed hydrogen chloride gas, after 10 hours, use the above-mentioned prepared product of ethanol thorough washing, drying 100 ℃ of reactions, obtain polyvinyl atom transfer radical polymerization initiator 2.1g
1H-NMR characterizes and determines transformation efficiency 97%.
Three, prepare the grafted polyethylene multipolymer with the polyvinyl initiator
Embodiment 12
Get the 250ml there-necked flask, add embodiment 8 gained polyvinyl atom transfer radical polymerization initiator 20.0g, add the 100ml methyl-phenoxide, add cuprous chloride 0.03g, pentamethyl-two vinylidene triamine 0.05ml, add vinylbenzene 40g, keeping temperature of reaction is 150 ℃, reacts after 0.01 hour, with ethanol thorough washing products therefrom, drying obtains polycthylene grafted polystyrene copolymer 20.05g.
Embodiment 13
Get the 250ml there-necked flask, add embodiment 8 gained polyvinyl atom transfer radical polymerization initiator 1.0g, add the 100ml methyl-phenoxide, add cuprous chloride 0.01g, pentamethyl-two vinylidene triamine 0.02ml, add p-methylstyrene 20g, keeping temperature of reaction is 120 ℃, reacts after 0.5 hour, with ethanol thorough washing products therefrom, drying obtains polycthylene grafted poly-p-methylstyrene multipolymer 25.0g.
Embodiment 14
Get the 250ml there-necked flask, add embodiment 8 gained polyvinyl atom transfer radical polymerization initiator 10.0g, add the 100ml methyl-phenoxide, add cuprous chloride 0.05g, pentamethyl-two vinylidene triamine 0.1ml, add vinyl-acetic ester 40g, keeping temperature of reaction is 70 ℃, reacts after 1 hour, with ethanol thorough washing products therefrom, drying obtains polycthylene grafted polyvinyl acetate ester copolymer 35.0g.
Embodiment 15
Get the 250ml there-necked flask, add embodiment 8 gained polyvinyl atom transfer radical polymerization initiator 20.0g, add the 100ml methyl-phenoxide, add cuprous chloride 0.1g, pentamethyl-two vinylidene triamine 0.05ml, add methyl methacrylate 30g, keeping temperature of reaction is 100 ℃, reacts after 2 hours, with ethanol thorough washing products therefrom, drying obtains polycthylene grafted polymethyl methacrylate copolymer 40.0g.
Embodiment 16
Get the 250ml there-necked flask, add embodiment 8 gained polyvinyl atom transfer radical polymerization initiator 20.0g, add 100ml toluene, add cuprous chloride 0.03g, pentamethyl-two vinylidene triamine 0.05ml, add vinyl cyanide 40g, keeping temperature of reaction is 75 ℃, reacts after 8 hours, with ethanol thorough washing products therefrom, drying obtains polycthylene grafted polyacrylonitrile multipolymer 32.5g.
Claims (7)
1. polyethylene graft copolymer has structure shown in the formula (1):
In the formula, z/y=0.1%～30%, m are the integer of 0-6, and M is vinylbenzene, p-methylstyrene, vinyl-acetic ester, methacrylic ester, methyl methacrylate or vinyl cyanide, and n is the integer of 10-5000, and X is F, Cl, Br or I halogen group.
2. the preparation method of polyethylene graft copolymer according to claim 1, key step is:
A) in the 100ml organic solvent, add the alkylaluminoxane of 0.001-100mmol, the olefinic monomer that contains styrene derivatives of 0.1-10g, the metallocene catalyst of 0.01-10 μ mol respectively, feed ethene down in 0-100 ℃, keep-up pressure and be the 1-10 normal atmosphere, reacted 0.1-100 hour, and made the polyethylene and ethylene copolymers that contains styrene derivatives;
The olefinic monomer that wherein contains styrene derivatives has structure shown in the formula 2
M=0-6 in the formula;
B) product that step a is made and organic solvent are made the 1-100g/100ml aaerosol solution, in this aaerosol solution, feed hydrogen halide in 0-100 ℃, reacted 0.5-20 hour, and got the polyvinyl atom transfer radical polymerization initiator, this initiator structure as shown in Equation 3
In the formula, z/y=0.01%～30%, m are the integer of 0-6, and X is F, Cl, Br or I halogen group;
C) initiator that step b is obtained and toluene or methyl-phenoxide solvent are made 1.0-20.0g/100ml suspension, add the 0.01-0.1g cuprous chloride, 0.02-0.1ml pentamethyl-two vinylidene triamines are catalyzer, in 70-150 ℃, add vinylbenzene, p-methylstyrene, vinyl-acetic ester, methacrylic ester, methyl methacrylate or vinyl cyanide 20-40g, reacted 0.01-8 hour, and obtained the polyethylene graft copolymer of functionalization.
3. the preparation method of claim 2 is characterized in that, the organic solvent among the step a is toluene, pentane, hexane or heptane.
4. the preparation method of claim 2 is characterized in that, the aikyiaiurnirsoxan beta that is used as promotor among the step a can be the linear aikyiaiurnirsoxan beta of following formula (4)
In the formula, R
1Be selected from halogen, linearity or branching, saturated or undersaturated C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkylaryl and C
7-C
20Aromatic yl alkyl group, y are 0-40; Or the ring aikyiaiurnirsoxan beta of following formula (5)
R in the formula
1Have implication described herein, y is the integer of 2-40.
5. the preparation method of claim 2 is characterized in that, the organic solvent among the step b is toluene, tetrahydrofuran (THF), methyl-phenoxide or halogenated alkane.
6. the preparation method of claim 2 is characterized in that, the hydrogen halide among the step b is hydrogenchloride, hydrogen bromide, hydrogen fluoride or hydrogen iodide gas.
7. the preparation method of claim 2 is characterized in that, the metallocene catalyst among the step a is the compound with following general formula:
Wherein, M is the transition metal of IVa family in the periodic table of chemical element, Va family and VIa family;
R
1It is the alkyl of 2 to 6 carbon atoms;
R
2Be aryl that can be replaced by halogen atom, the 6-16 carbon atom, hydrogen atom, the alkyl of 1-20 carbon atom or Organosilyl;
X
1And X
2Respectively be hydrogen atom, halogen atom, the alkyl of 1-20 carbon atom, the halo alkyl of 1-20 carbon atom, oxy radical or sulfur-containing group; With Y be the alkyl of the 1-20 carbon atom of divalence, the halo alkyl of the 1-20 carbon atom of divalence, the silicon-containing group of divalence, the germanic group of divalence ,-O-,-CO-,-S-,-SO-,-SO
2-,-NR
3-,-P (R
3)-,-P (O) (R
3)-,-BR
3-or-AlR
3-; R
3Be the alkyl of hydrogen atom, halogen atom, 1-20 carbon atom or the halo alkyl of 1-20 carbon atom.
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