CN1293111C - Process for preparing polypropylene graft copolymer - Google Patents
Process for preparing polypropylene graft copolymer Download PDFInfo
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- CN1293111C CN1293111C CNB2004100626030A CN200410062603A CN1293111C CN 1293111 C CN1293111 C CN 1293111C CN B2004100626030 A CNB2004100626030 A CN B2004100626030A CN 200410062603 A CN200410062603 A CN 200410062603A CN 1293111 C CN1293111 C CN 1293111C
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Abstract
The present invention discloses a polypropylene 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 is used for copolymerization under the existence of a heterogeneous catalysis system containing a Ziegler-Natta catalyst and a co-catalyst, and the polypropylene graft copolymer is obtained by an addition reaction with simple conditions; the yield rate approaches to 100%. The grafting density and the grafting number of a functionalized functional group can be accurately regulated and controlled. The copolymer keeps the original favorable performance of polypropylene, such as a high melting point, high degree of crystallization, etc.
Description
Technical field
The present invention relates to a kind of polypropylene graft copolymer.
The invention still further relates to the preparation method of above-mentioned multipolymer.
Background technology
Polypropylene 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 polypropylene 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 polypropylene in dyeing, printing and field such as bonding.And the polypropylene of functionalization, be exactly on polypropylene chains, 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 polypropylene and other material, the printing and dyeing of Reinforced Polypropylene, wettability etc., the high performance of realization polyolefine material has been expanded polyacrylic 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, PartA: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 up to the present, the report for preparing the functional poly propylene graft copolymer by atom transfer radical polymerization (ATRP) technology seldom.The existing synthetic method that polyolefin copolymer is changed into atom transfer radical polymerization initiator is too complicated, severe reaction conditions, and yield is very low.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 propylene graft copolymer, have structure shown in the formula 1.This multipolymer keeps premium propertiess such as the original high-melting-point of polypropylene, high-crystallinity.And the grafting density of functionalization functional group, grafting quantity can be carried out accuracy controlling.
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 polypropylene copolymer that contains the styryl reaction member.Press every 100ml toluene in the reactor, heptane, hexane, the pentane equal solvent, the triethyl aluminum that adds 0.1-20ml, aluminum alkyls such as trimethyl aluminium or triisobutyl aluminium, 0.1-10g the olefinic monomer that contains styrene derivatives, 0.01-10g by magnesium halide is carrier, with the titanium tetrachloride is the loading type Ziegler-Natta catalyst (wherein Ti content is 1～6%) of catalyzer, keeping temperature of reaction is 0-100 ℃, be preferably 30-80 ℃, feed propylene, keeping reaction pressure is the 1-10 normal atmosphere, be preferably the 1-6 normal atmosphere, reacted 0.1～100 hour, with the polymkeric substance that makes by water, ethanol, the methyl alcohol thorough washing, filter, drying obtains containing the polypropylene copolymer of styrene derivatives.
The phenylbenzene dimethylsilane one that also can add 0-10g in this step reacts.
Styrene derivatives monomer in this step has structure shown in the formula 2
M=0-6 in the formula.
By
1H-NMR characterize to determine copolymer structure, and the content of styrene derivatives in the multipolymer.
(2) suspension that polypropylene copolymer 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 polypropylene copolymer aaerosol solution, feed hydrogen halide (hydrogenchloride, hydrogen bromide, hydrogen fluoride, hydrogen iodide etc.), reacted 0.5-20 hour, and obtained the polypropylene-base 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.
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 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 polypropylene graft copolymer of functionalization.
The grafting density of the functionalization functional group in this functional poly propylene base co-polymer 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 propylene base co-polymer keeps premium propertiess such as the original high-melting-point of polypropylene, high-crystallinity.The multipolymer of gained of the present invention can be with other polymkeric substance, preferably with entirely carry out blend with propene polymer, improves the consistency of polyolefine and other material.The example that carries out the polymkeric substance of blend with propene polymer in the presence of graft copolymer is polystyrene, polyethers, polyacrylic ester, as polymethacrylate.
The Ti content that the present invention uses as 1-6% the carrier of Ziegler-Natta catalyst be generally MgCl
2, MgBr
2, MgI
2, MgF
2Deng, also can be the reactant of magnesium halide and all kinds of alcohol, as with the reactant at 80-200 ℃ such as ethanol, propyl alcohol, butanols, amylalcohol.Also can add the carboxylicesters of 1-10% in this carrier, as diisobutyl phthalate, adjacent stupid dibutyl carboxylic acid, diethyl succinate etc. as internal electron donor.Relevant Ziegler-Natta catalyst discussed herein can adopt the commercial goods, is not emphasis of the present invention.
Description of drawings
Fig. 1 is the polypropylene copolymer that contains styrene units of embodiment 4 preparations
1The H-NMR spectrogram.
Fig. 2 is the polypropylene-base atom transfer radical polymerization initiator of embodiment 10 preparations
1The H-NMR spectrogram.
Embodiment
One, the preparation of Ziegler-Natta catalyst
Ziegler-Natta catalyst used in the present invention can be the commercial goods, also can be prepared by the method for following embodiment 1-3, and the preparation embodiment of the several catalytic agent that the present invention enumerates is just with helping describe technology contents of the present invention.
Embodiment 1
With 24 gram MgCl
2Add in the autoclave with 50ml ethanol, 390ml white vaseline oil, silicone oil 10ml, heated and stirred gets the logical nitrogen of homogeneous solution makes pressure rise to 1MPa, drives valve, make in the still mixture by 1.2mm, long 3.5 meters tubule sprays in the kerosene of 2.5L, hexane wash 5 times, drying at room temperature.Add 220mlTiCl4 then, and 3ml is a diisobutyl phthalate.Stir and heat up 200 ℃, handled 1.5 hours.Toluene wash obtains product 4 times.Ti content is 5.96%
Embodiment 2
With 24 gram MgCl
2Add in the autoclave with 50ml ethanol, 390ml white vaseline oil, silicone oil 10ml, heated and stirred gets the logical nitrogen of homogeneous solution makes pressure rise to 1MPa, drives valve, make in the still mixture by 1.2mm, long 3.5 meters tubule sprays in the kerosene of 2.5L, hexane wash 5 times, drying at room temperature.Add 160mlTiCl4 then, and the 1.4ml dibutyl phthalate.Stir and heat up 110 ℃, handled 1.5 hours.Hexane wash obtains product 4 times, and Ti content is 3.38%
Embodiment 3
With 24 gram MgBr
2Add in the autoclave with 50ml ethanol, 390ml white vaseline oil, silicone oil 10ml, heated and stirred gets the logical nitrogen of homogeneous solution makes pressure rise to 1MPa, drives valve, make in the still mixture by 1.2mm, long 3.5 meters tubule sprays in the kerosene of 2.5L, hexane wash 5 times, drying at room temperature.Add 30mlTiCl4 then, and the 0.4ml dibutyl phthalate.Stir and heat up 80 ℃, handled 1.5 hours.Heptane wash 4 times, hexane wash once obtains product then, and Ti content is 1.12%
Two, preparation contains the polypropylene copolymer of styrene derivatives
Embodiment 4
Get the 500ml reactor, add the 100ml hexane, add the n-heptane solution of 1ml triisobutyl aluminium, add phenylbenzene dimethylsilane (DDS) and the 0.1 gram Vinylstyrene of 5g, stirring adds 0.1g embodiment 2 catalyzer down.50 ℃ feed propylene 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 n-heptane solution of 20ml triethyl aluminum (TEA), add phenylbenzene dimethylsilane (DDS) and the 10 gram propenylbenzene ethene of 10g, stirring adds 0.1g embodiment 1 catalyzer down.0 ℃ feeds propylene gas, and reaction is 100 hours under 1 normal atmosphere, obtains polymkeric substance 18.7g.
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 n-heptane solution of 60ml trimethyl aluminium, add the 3 alkenyl benzene ethene of restraining oneself, stir and add 0.01g embodiment 2 catalyzer down.100 ℃ feed propylene gas, and reaction is 10 hours under 10 normal atmosphere, obtains polymkeric substance 10g.
1It is 10% that H-NMR characterizes the content of determining styrene derivatives in the multipolymer.
Embodiment 7
Get the 10L reactor, add the 1000ml heptane, add the n-heptane solution of 20ml triisobutyl aluminium, add phenylbenzene dimethylsilane (DDS) and the 5 gram octenyl vinylbenzene of 3g, stirring adds 10g embodiment 2 catalyzer down.50 ℃ feed propylene 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.
Three, preparation polypropylene-base atom transfer radical polymerization initiator
Embodiment 8
Get the 250ml there-necked flask, adding embodiment 4 gained contain the polypropylene copolymer 2.0g of styrene derivatives, add 100ml toluene, in the polypropylene copolymer aaerosol solution, feed hydrogen chloride gas, after 60 hours, use the above-mentioned prepared product of ethanol thorough washing, drying 0 ℃ of reaction, obtain polypropylene-base 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 polypropylene copolymer 2.0g of styrene derivatives, add the 100ml tetrahydrofuran (THF), in the polypropylene copolymer 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 polypropylene-base 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 polypropylene copolymer 2.0g of styrene derivatives, add the 100ml methyl-phenoxide, in the polypropylene copolymer aaerosol solution, feed hydrogen iodide gas, after 20 hours, use the above-mentioned prepared product of ethanol thorough washing, drying 100 ℃ of reactions, obtain polypropylene-base 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 polypropylene copolymer 2.0g of styrene derivatives, add the 100ml ethylene dichloride, in the polypropylene copolymer aaerosol solution, feed hydrogen chloride gas, after 10 hours, use the above-mentioned prepared product of ethanol thorough washing, drying 100 ℃ of reactions, obtain polypropylene-base atom transfer radical polymerization initiator 2.1g
1H-NMR characterizes and determines transformation efficiency 97%.
Four, prepare the graft polypropylene multipolymer with the polypropylene-base initiator
Embodiment 12
Get the 250ml there-necked flask, add embodiment 8 gained polypropylene-base 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 polypropylene grafted polystyrene copolymer 20.05g.
Embodiment 13
Get the 250ml there-necked flask, add embodiment 8 gained polypropylene-base 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 polypropylene grafted poly-p-methylstyrene multipolymer 25.0g.
Embodiment 14
Get the 250ml there-necked flask, add embodiment 8 gained polypropylene-base atom transfer radical polymerization initiator 10.0g, add the 100ml methyl-phenoxide, add cuprous chloride 0.05g, pentamethyl-two vinylidene triamine 0.1m1, add vinyl-acetic ester 40g, keeping temperature of reaction is 70 ℃, reacts after 1 hour, with ethanol thorough washing products therefrom, drying obtains polypropylene grafted polyvinyl acetate ester copolymer 35.0g.
Embodiment 15
Get the 250ml there-necked flask, add embodiment 8 gained polypropylene-base 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 polypropylene grafted polymethyl methacrylate copolymer 40.0g.
Embodiment 16
Get the 250ml there-necked flask, add embodiment 8 gained polypropylene-base 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 polypropylene grafted polyacrylonitrile multipolymer 32.5g.
Claims (9)
1. polypropylene graft copolymer has structure shown in the formula (1):
In the formula, z/y=0.1%～30%,, m is 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 polypropylene graft copolymer according to claim 1, key step is:
A) in the 100ml organic solvent, add the aluminum alkyls of 0.1-20ml, the olefinic monomer that contains styrene derivatives of 0.1-10g, the Ziegler-Natta catalyst of 0.01-10g respectively, feed propylene down in 0-100 ℃, keep-up pressure and be the 1-10 normal atmosphere, reacted 0.1-100 hour, and made the polypropylene copolymer 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 polypropylene-base 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 polypropylene 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 aluminum alkyls among the step a is triethyl aluminum, trimethyl aluminium or triisobutyl aluminium.
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, also adds the phenylbenzene dimethylsilane among the step a, and add-on is 0-10g.
8. the preparation method of claim 2 is characterized in that, the catalyzer among the step a is carrier with the magnesium halide, and titanium tetrachloride is an active ingredient, and wherein the weight of Ti is 1-6%.
9. the preparation method of claim 8 is characterized in that, is magnesium chloride, magnesium bromide, magnesium fluoride or magnesium iodide as the magnesium halide of carrier.
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| CNB2004100626030A CN1293111C (en) | 2004-06-30 | 2004-06-30 | Process for preparing polypropylene graft copolymer |
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| CNB2004100626030A CN1293111C (en) | 2004-06-30 | 2004-06-30 | Process for preparing polypropylene graft copolymer |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102268124A (en) * | 2010-06-07 | 2011-12-07 | 中国科学院化学研究所 | Long-chain branched polypropylene and preparation method thereof |
| CN106543369A (en) * | 2015-09-18 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of method of propylene polymer graft polar monomer |
| CN108586668B (en) * | 2018-04-11 | 2020-07-21 | 天津大学 | High-toughness polypropylene and polylactic acid ion graft copolymer and preparation method thereof |
| CN113563528A (en) * | 2020-04-29 | 2021-10-29 | 中国石油化工股份有限公司 | Application of aromatic olefin graft modified polypropylene as insulating material and insulating material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1364174A (en) * | 1999-07-26 | 2002-08-14 | 出光石油化学株式会社 | Branched olefinic macromonomer, olefin graft copolymer, and olefin resin composition |
| CN1495209A (en) * | 2002-08-30 | 2004-05-12 | ������ѧ��ʽ���� | Polyolefine macromonomer, graftmer obtained by utilizing polyolefine macromonomer and its application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1364174A (en) * | 1999-07-26 | 2002-08-14 | 出光石油化学株式会社 | Branched olefinic macromonomer, olefin graft copolymer, and olefin resin composition |
| CN1495209A (en) * | 2002-08-30 | 2004-05-12 | ������ѧ��ʽ���� | Polyolefine macromonomer, graftmer obtained by utilizing polyolefine macromonomer and its application |
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