CN102757542B - Block copolymer of polyolefine and phosphorus-containing alkene and preparation method thereof - Google Patents
Block copolymer of polyolefine and phosphorus-containing alkene and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of block copolymers and preparation method thereof of the phosphorous alkene of polyolefin-.The structural formula of the block copolymer is shown in Formulas I, wherein R is hydrogen or the alkyl of C1-C8；WhenWhen for Formula II, R1、R2For hydrogen or C1-C8 alkyl, R3、R4、R5It is hydrogen, C1-C8 alkyl, hydroxyl, carboxyl, nitro, amino or formula III, and at least one is formula III；Ra is alkyl, alkoxy or the azanyl of C1-C6 in formula III, and Rb, Rc are the alkyl of C1-C6 or the aryl of C6-C18；When
When for formula III, R1For hydrogen or C1-C8 alkyl, R2For the ester group of hydrogen, C1-C8 alkyl or C1-C8, Ra is alkyl, ester group, alkoxy or the azanyl of C1-C6, and Rb, Rc are the alkyl of C1-C8.The copolymer is to cause phosphorous olefinic polymerization with polyolefin macromole evocating agent to be made.The block copolymer of the gained phosphorous alkene of polyolefin-of the invention, improve polyolefin anti-flammability, in terms of be with a wide range of applications.
Description
Technical field
The present invention relates to segmented copolymer of a kind of polyolefine and phosphorous alkene and preparation method thereof.
Background technology
Polyolefine is due to abundant raw material, good mechanical performance, easy machine-shaping, features such as electric insulating quality is strong, stable chemical performance, density are little, quality is light and being widely used in daily life, household electrical appliances, weaving, automobile, building, agricultural and the field such as military.But, because polyolefine macromolecular chain is primarily of C, H two kinds of atomic buildings, for apolar chain, adding the crystalline feature of semicrystalline polyolefin makes its surface energy extremely low, thus itself and most polymers or mineral filler are difficult to reach effectively compatible, are difficult to the performance ensureing blend or matrix material.In addition, polyolefine belongs to hydrocarbon class material, have and hold incendive feature, the polyethylene that in polyolefine, consumption is maximum and polyacrylic oxygen index only have 17.0%-18.0%, and produce molten drop during polyolefine burning, so all require fire-retardant in many application scenarios, and traditional additive flame retardant also exists the shortcoming reducing polyolefin properties and easily separate out.So how to carry out modification to polyolefine, the basis keeping the performance of polyolefine own realizes its flame retardant properties becomes polyolefin modified important topic.
Polyolefin functional is on the basis keeping the original premium properties of polyolefine, polyolefine macromolecular chain introduces polar functional group, thus realizes the high performance of polyolefine material.Polyolefinic functionalization main path is as follows: (a) polyolefinic chemical modification; (b) alkene and the alpha-olefin copolymer containing functional group; C () carries out functionalization by reactive polyolefine intermediate.
Carrying out chemical modification to existing polyolefine is a kind of important polyolefin functional method.Because it does not relate to new polyreaction, these class methods more easily realize industrialization.Existing polyolefinic chemical modification method mainly contains chlorination, graft modification, surface modification etc.But chemical modification major part all utilizes free radical reaction to carry out, and often has crosslinked in the process of reaction, degraded side reaction of Denging occurs, so its range of application is restricted.
Olefinic monomer and the alpha-olefin copolymer containing functional group are the most direct polyolefin functional methods, technique are easy to realize.Currently reported comonomer has borine; the protected long-chain enol of the alpha-olefin of silane-functionalized or functional group etc.; but polar functional group can make the Ziegler-Natta catalyst of olefinic polymerization and metallocene catalyst activity reduce or even inactivation, so the catalyzer adopted mostly is the late transition metal catalyst of weak oxytropism.Therefore directly copolymerization also has certain limitation.
Carrying out functionalization by reactive polyolefine intermediate is by designing a kind of reactive monomer or chain-transfer agent altogether, this monomer or chain-transfer agent is altogether made to contain the reactive group to catalyst active center's toxicological harmless effect, then Ziegler-Natta catalyst and the excellent catalysis characteristics of metallocene catalyst is utilized, realize copolymerization or the chain transfer polymerization of olefinic monomer and the common monomer of this reactivity or chain-transfer agent with higher catalytic activity, obtain " the reactive polyolefine " containing reactive group.Utilize the chemical property that reactive group is active, optionally carry out various Functional Conversion reaction, prepare the macromole evocating agent based on polyolefinic active free radical polymerization, combine as atom transfer radical polymerization (ATRP) etc. has the polyreaction of living polymerization characteristic, realization has constructing of the functional polyolefin of block and Grafting Structure again.Such as, Dong etc. utilize metallocene catalyst rac-Me recently
2si [2-Me-4-Ph-Ind]
2zrCl
2catalyzing propone and p-divinyl benzene or 1; 2-bis-(4-ethenylphenyl) ethane copolymerization; prepare styrene end-capped isotatic polypropylene (iPP-t-St); hydrogenchloride addition reaction is then utilized end group vinylbenzene double bond to be changed into the benzyl chloride that can carry out ATRP reaction; obtain macromole evocating agent iPP-t-Cl; and adopt this macromole evocating agent to obtain PP-b-PMMA segmented copolymer (Huang, the H. of functionalization; Niu, H.; Dong, J.-Y.Journal ofPolymer Science PartA:Polymer Chemistry 2010,48,5783.).
Segmented copolymer, because the advantageous property of multiple polymers being combined, obtains the functional polymer material that Performance comparision is superior, thus of many uses.Polyolefin block copolymer by introducing functional groups in polyolefin chain, can achieve its functionalization, expanding its range of application especially.
The method preparing polyolefin block copolymer based on olefin coordination polymerization technology mainly contains four kinds: (a) living coordination polymerization is reacted; B () chain coordination transfer polymerization is reacted; C () utilizes coupling method synthesis of polyolefins segmented copolymer; (d) " reactive polyolefine intermediate " method.Wherein " reactive polyolefine intermediate " method is by the reactive polyolefine of the chain transfer reaction synthesis end of the chain in olefin coordination polymerization, again reactive polyolefine is converted into the macromole evocating agent of other living polymerization, for causing the polymerization of polar monomer, thus synthesis of polyolefins segmented copolymer.The method breaches some distinctive limitations of coordination poly-merization, for the polyolefin block copolymer preparing functionalization provides effective approach.The total class of polyolefin block copolymer kind is various, and more common is polyolefine and styrene block copolymer, polyolefine and methylmethacrylate copolymer etc.Polyolefinic performance can be improved by the segmented copolymer of synthesis of polyolefins, widen polyolefinic range of application.
Phosphorous polymer is of many uses, can be used in the aspects such as binding agent, coating, biomaterial, medicinal slow release agent, fire retardant.But the research of phosphorous block polymer is less, synthetic method is substantially all prepared by ATRP method.Matyjaszewski etc. cause phosphorous-containing monomers by polystyrene/polymethylmethacrylate ATRP macromole agent and are polymerized phosphorous segmented copolymer (Huang, the J. that have prepared vinylbenzene and methyl methacrylate; Matyjaszewski, K.Macromolecules 2005,38,3577.).Mullen etc. also adopt same method to obtain a kind of two blocks of phosphorous-containing monomers and the multipolymer of three blocks, and this polymkeric substance can apply to fuel cell aspect (Markova, D.; Kumar, A.; Klapper, M.; Mullen, K.Polymer 2009,50,3411.).
The segmented copolymer of polyolefine-phosphorous alkene is expected to cohesiveness and the flame retardant properties of improving polyolefine material, expands polyolefinic range of application.
Summary of the invention
The object of this invention is to provide the segmented copolymer of a kind of polyolefine-phosphorous alkene, and the preparation method of this functional polyolefin.
The segmented copolymer of polyolefine provided by the present invention-phosphorous alkene, its structural formula is such as formula shown in I:
Wherein, R is selected from the alkyl of hydrogen or C1-C8;
represent phosphorous group.
Work as phosphorus-containing groups
for its structure during aromatic group is such as formula shown in II:
Now, R in formula I
1and R
2represent hydrogen or C1-C8 alkyl, R
1and R
2can be the same or different.R in formula II
3, R
4, R
5all represent any one group following: hydrogen, C1-C8 alkyl, hydroxyl, carboxyl, nitro, the substituting group shown in amino and formula III, and R
3, R
4, R
5in have at least one to represent the substituting group shown in formula III.In formula III, Ra is the azanyl of the alkyl of C1-C6, the alkoxyl group of C1-C6 or C1-C6, and Rb, Rc are the alkyl of C1-C6 or the aryl of C6-C18.
Work as phosphorus-containing groups
for its structure during fat group is as shown in formula III.Now, R
1represent hydrogen or C1-C8 alkyl, R
2represent the ester group of hydrogen, C1-C8 alkyl or C1-C8, Ra is the azanyl of the alkyl of C1-C6, the ester group of C1-C6, the alkoxyl group of C1-C6 or C1-C6, and Rb, Rc are the alkyl of C1-C8.
Wherein n/m=0.001-100, further n/m=0.01-50.
The preparation method of the segmented copolymer of polyolefine of the present invention-phosphorous alkene, comprises the steps: that end group is can cause the polyolefine of controllable/active free radical polymerization as atom transfer radical polymerization (ATRP) to represent Cl or Br such as formula IV(X; Y and Z represents hydrogen or C1-C6 alkyl, Y and Z can identical also can be different; The definition cotype I of R, m) vacuumize drying after, add after organic solvent fully dissolves, add comonomer (such as formula V) successively, cuprous halide, multiple tooth containing n-donor ligand, under imposing a condition, carry out ATRP polymerization reaction after abundant deoxygenation, obtain the segmented copolymer of the polyolefine shown in described formula I-phosphorous alkene.
When polymerization single polymerization monomer is (a) in formula V, R
1and R
2represent hydrogen or C1-C8 alkyl, R
1and R
2can be the same or different; R
3, R
4, R
5all represent any one group following: hydrogen, C1-C8 alkyl, hydroxyl, carboxyl, nitro, the substituting group shown in amino and described formula III, and R
3, R
4, R
5in have at least one to represent the substituting group shown in described formula III.In formula III, Ra is the azanyl of the alkyl of C1-C6, the alkoxyl group of C1-C6 or C1-C6, and Rb, Rc are the alkyl of C1-C6 or the aryl of C6-C18.
When polymerization single polymerization monomer is (b) in formula V, R
1represent hydrogen or C1-C8 alkyl; R
2represent the ester group of hydrogen, C1-C8 alkyl or C1-C8; R6 is the substituting group shown in described formula III, and wherein Ra is the azanyl of the alkyl of C1-C6, the ester group of C1-C6, the alkoxyl group of C1-C6 or C1-C6, and Rb, Rc are the alkyl of C1-C8.
In preparation method, the mol ratio of the described polyolefine and comonomer that can cause ATRP polymerization is 1:0.1-1:50000; The mol ratio of the described polyolefine and cuprous halide that can cause ATRP polymerization is 1:0.01-1:100, is preferably 1:0.05-10; The mol ratio of described multiple tooth containing n-donor ligand and cuprous halide is 1:0.1-1:50.The volume ratio of reaction solvent and comonomer is 1:0.01-1:10.Described reaction is carried out under the protection of rare gas element (as nitrogen or argon gas).Temperature of reaction is 20-170 DEG C, is preferably 80-150 DEG C; Reaction times is 0.5-50 hour; Reaction solvent comprise in benzene, chlorine benzene,toluene,xylene, hexane or heptane, dimethyl formamide one or more; Stop by passing into air at the end of polyreaction, and with hexane or heptane precipitation polymers.Repetitive scrubbing polymkeric substance is precipitated to remove cupric ion in polymkeric substance with hexane or heptane again by adding the dissolving of the halohydrocarbon such as methylene dichloride or trichloromethane.
Cuprous halide described in the present invention comprises cuprous chloride, cuprous bromide or cuprous iodide; Described multiple tooth containing n-donor ligand comprises 2,2 '-dipyridyl, 4,4 '-diformyloxy-2,2 '-dipyridyl, 4,4 '-diheptyl-2,2 '-dipyridyl, pyridine imine, pentamethyl-diethylenetriamine, three (2-picolyl) amine, three-(2-dimethylaminoethyl) amine, three-(2-diethylaminoethyl) amine, 1, Isosorbide-5-Nitrae, 7,10,10-hexamethyl Triethylenetetramine (TETA).
The method preparing the segmented copolymer of polyolefine-phosphorous alkene provided by the present invention, raw material sources are extensive, and cost is lower, and partial monosomy is industrialized raw material, and reaction method is ripe.The segmented copolymer of the polyolefine utilizing the method to obtain-phosphorous alkene, polyolefine section and phosphorous alkene segment length accurate in scale controlled, the polyolefin copolymer of various phosphorous olefin(e) centent can be obtained, the segmented copolymer of this polyolefine-phosphorous alkene has excellent flame retardant properties on the basis ensureing former polyolefine premium properties, can be applied to need fire-retardant field as fire retardant polyolefin.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 prepares gained polyolefine-phosphorous olefin block copolymers
1h-NMR spectrogram.
Fig. 2 is that embodiment 2 prepares gained polyolefine-phosphorous olefin block copolymers
1h-NMR spectrogram.
Fig. 3 is that embodiment 3 prepares gained polyolefine-phosphorous olefin block copolymers
1h-NMR spectrogram.
Fig. 4 is that embodiment 4 prepares gained polyolefine-phosphorous olefin block copolymers
1h-NMR spectrogram.
Fig. 5 is that embodiment 1 prepares gained polyolefine-phosphorous olefin block copolymers infrared spectrogram.
Fig. 6 is that embodiment 2 prepares gained polyolefine-phosphorous olefin block copolymers infrared spectrogram.
Fig. 7 is that embodiment 1 prepares gained polyolefine-phosphorous olefin block copolymers thermogravimetic analysis (TGA) figure.
Fig. 8 is that embodiment 2 prepares gained polyolefine-phosphorous olefin block copolymers thermogravimetic analysis (TGA) figure.
Fig. 9 is that embodiment 4 prepares gained polyolefine-phosphorous olefin block copolymers thermogravimetic analysis (TGA) figure.
Figure 10 is that embodiment 12 prepares gained polyolefine-phosphorous olefin block copolymers thermogravimetic analysis (TGA) figure.
Figure 11 is the heat release rate figure (miniature calorimeter mensuration) that embodiment 1 prepares gained polyolefine-phosphorous olefin block copolymers.
Figure 12 is that embodiment 12 is prepared gained polyolefine-phosphorous olefin block copolymers and led to heat release rate figure (miniature calorimeter mensuration).
Embodiment
The segmented copolymer of polyolefine provided by the invention-phosphorous alkene has such as formula structure shown in I:
Wherein, R is selected from the alkyl of hydrogen or C1-C8;
represent phosphorous group.
Work as phosphorus-containing groups
for its structure during aromatic group is such as formula shown in II:
Now, R in formula I
1and R
2represent hydrogen or C1-C8 alkyl, R
1and R
2can be the same or different.R in formula II
3, R
4, R
5all represent any one group following: hydrogen, C1-C8 alkyl, hydroxyl, carboxyl, nitro, the substituting group shown in amino and formula III, and R
3, R
4, R
5in have at least one to represent the substituting group shown in formula III.In formula III, Ra is the azanyl of the alkyl of C1-C6, the alkoxyl group of C1-C6 or C1-C6, and Rb, Rc are the alkyl of C1-C6 or the aryl of C6-C18.
Work as phosphorus-containing groups
for its structure during fat group is as shown in formula III.Now, R
1represent hydrogen or C1-C8 alkyl, R
2represent the ester group of hydrogen, C1-C8 alkyl or C1-C8, in formula III, Ra is the azanyl of the alkyl of C1-C6, the ester group of C1-C6, the alkoxyl group of C1-C6 or C1-C6, and Rb, Rc are the alkyl of C1-C8.
Wherein n/m=0.001-100.
This polyolefine-phosphorous olefin block copolymers is obtained with the ATRP polymerization reaction causing the phosphorous olefinic monomer of formula V structure for macromole evocating agent such as formula the polyolefine of structure shown in IV:
When polymerization single polymerization monomer is (a) in formula V, R
1and R
2represent hydrogen or C1-C8 alkyl, R
1and R
2can be the same or different; R
3, R
4, R
5all represent any one group following: hydrogen, C1-C8 alkyl, hydroxyl, carboxyl, nitro, the substituting group shown in amino and described formula III, and R
3, R
4, R
5in have at least one to represent the substituting group shown in described formula III.In formula III, Ra is the azanyl of the alkyl of C1-C6, the alkoxyl group of C1-C6 or C1-C6, and Rb, Rc are the alkyl of C1-C6 or the aryl of C6-C18.
When polymerization single polymerization monomer is (b) in formula V, R
1represent hydrogen or C1-C8 alkyl; R
2represent the ester group of hydrogen, C1-C8 alkyl or C1-C8; R
6for the substituting group shown in described formula III, wherein Ra is the azanyl of the alkyl of C1-C6, the ester group of C1-C6, the alkoxyl group of C1-C6 or C1-C6, and Rb, Rc are the alkyl of C1-C8.
Its embodiment is as follows: to add quality be in the reactor the end group of 0.1-100kg is can the polyolefine of Atom Transfer Radical Polymerization (ATRP), vacuumize dry 1-10h under 0-100 DEG C of condition after, by causing that the polyolefine of ATRP and the mol ratio of comonomer are 1:0.1-1:50000, the mol ratio of the polyolefine causing ATRP polymerization and cuprous halide is 1:0.01-1:100, the mol ratio of multiple tooth containing n-donor ligand and cuprous halide is that 1:0.1-1:50 feeds in raw material.The volume ratio of reaction solvent and comonomer is 1:0.01-1:10.React 0.5-50 hour under nitrogen or argon shield condition after, pass into air termination reaction, and with hexane or heptane precipitation polymers.Dissolve by adding the halohydrocarbon such as methylene dichloride or trichloromethane, then precipitate with hexane or heptane, repetitive scrubbing polymkeric substance, removing unreacted monomer, filtration, drying, obtain polyolefine-phosphorous olefin block copolymers.
In following embodiment, the polypropylene macromole evocating agent synthetic method of benzyl chloride used or bromotoluene end-blocking is as follows: be equipped with after churned mechanically polymeric kettle vacuumizes 30min, a certain amount of hydrogen is passed at 30 DEG C, add toluene successively, the chain-transfer agent p-divinyl benzene (1 of predetermined mole number, 4-DVB) the methylaluminoxane of promotor drying, and metallocene catalyst rac-Me
2si [2-Me-4-Ph-Ind]
2zrCl
2toluene solution, pass into propylene again, and keep propylene to react at a predetermined pressure, reaction is to certain hour, and pressure release, by the ethanol termination reaction containing 10wt% hydrochloric acid, use tetrahydrofuran (THF) successively, water and washing with alcohol for several times, after putting into vacuum drying oven drying, obtain the isotatic polypropylene of vinylbenzene end-blocking.The isotatic polypropylene of this vinylbenzene end-blocking is dissolved in after in sym.-tetrachloroethane and continues to pass into dry HCl or HBr gas 8h under 60 DEG C of conditions.Stopped reaction, pours in ethanol and precipitates, and filters, namely obtain the polypropylene macromole evocating agent of this benzyl benzyl chloride or bromotoluene end-blocking after drying by distilled water, washing with alcohol.
In following embodiment, two kinds of phosphorous olefinic monomers used all synthesize by simple organic reaction, and the raw material of synthesis two kinds of monomers all can middlely from commercial channels obtain.Wherein monomer DEVBP reference literature (Dumitrascu, A.; Howell, B.A.Polymer Degradation and Stability 2011,96,342) synthesis; Monomer DEMMP is with reference to (Ebdon, J.R.; Hunt, B.J.; Joseph, P.; Konkel, C.S.; Price, D.; Pyrah, K.; Hull, T.R.; Milnes, G.J.; Hill, S.B.; Lindsay, C.I.; McCluskey, J.; Robinson, I.Polymer Degradation and Stability2000,70,425.) synthesis.
The structure warp of polyolefine-phosphorous olefin block copolymers
1h-NMR, examination of infrared spectrum analysis obtain confirmation, and the ratio of polyolefine section and phosphorous alkene segment length also can carry out analysis and characterization with nuclear-magnetism.The thermal characteristics of multipolymer characterizes through thermogravimetric analyzer (TGA) etc.And the length of phosphorous alkene section in polyolefine-phosphorous olefin block copolymers, by changing the add-on of phosphorous olefinic monomer, temperature of reaction can be changed, reaction times and change catalytic amount and regulate.
Shown in employing formula VI two kind of copolymerization monomer is specific embodiment, makes detailed explanation to the polyolefine-phosphorous olefin block copolymers invented and preparation thereof.But these embodiments do not limit the scope of the invention, also should not be construed as the condition, parameter or the numerical value that only have these embodiments to provide and could implement the present invention.
(formula VI)
Embodiment 1-8 is R=R in preparation formula I
1=R
2=H,
r for aromatic group shown in formula II and in formula II
3=R
4=H, R
5ra=CH for the substituting group shown in formula III and in formula III
2, Rb=Rc=CH
2cH
3multipolymer, just the value of n/m is different.
Embodiment 9-12 is R=R in preparation formula I
1=H, R
2=CH
3,
ra is C=OO, Rb=Rc=CH for the substituting group shown in formula III and in formula III
2cH
3multipolymer, just the value of n/m is different.
Embodiment 1,
In 100ml there-necked flask, add 0.300g (0.018mmol) Mn=1.7 × 10
4benzyl chloride end-blocking polypropylene after; vacuumize dry 4h under 60 DEG C of conditions after, add 20ml toluene stir the polypropylene of benzyl chloride end-blocking is fully dissolved after, add cuprous chloride 20.1mg (0.203mmol), 1 successively; 1; 4,7,10; 10-hexamethyl Triethylenetetramine (TETA) 45ul (0.17mmol); 5ml (24mmol) comonomer DEVBP, after abundant deoxygenation, under nitrogen protection in 90 DEG C of reaction 4h.Pass into air termination reaction, and with hexane or heptane precipitation polymers.Removing unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again by repeatedly adding the dissolving of the halohydrocarbon such as methylene dichloride or trichloromethane, obtaining this polyolefine/phosphorous olefin block copolymers.
1h-NMR characterizes and determines, the phosphorous alkene section molar content in this multipolymer is 1.51%(n/m=0.0153).
Fig. 7 is polyolefine-phosphorous olefin block copolymers thermogravimetic analysis (TGA) figure prepared by this embodiment.The introducing of phosphorous alkene can improve this polyolefinic thermal weight loss carbon left (when polyacrylic 650 DEG C, carbon left is almost nil) as known in the figure, thus can improve this polyolefinic flame retardant properties.
Figure 11 prepares the heat release rate figure of obtained polyolefine-phosphorous olefin block copolymers for this embodiment that miniature calorimeter measures.The introducing of phosphorous alkene can reduce this polyolefinic heat release rate (polyacrylic maximum heat rate of release is 1020W/g) as seen from the figure, thus can improve this polyolefinic flame retardant properties.
Embodiment 2
In 100ml there-necked flask, add 0.300g (0.018mmol) Mn=1.7 × 10
4benzyl chloride end-blocking polypropylene after; vacuumize dry 4h under 60 DEG C of conditions after, add 20ml toluene stir the polypropylene of benzyl chloride end-blocking is fully dissolved after, add cuprous chloride 20.1mg (0.20mmol), 1 successively; 1; 4,7,10; 10-hexamethyl Triethylenetetramine (TETA) 45ul (0.19mmol); 5ml (24mmol) comonomer DEVBP, after abundant deoxygenation, under nitrogen protection in 90 DEG C of reaction 12h.Pass into air termination reaction, and with hexane or heptane precipitation polymers.Removing unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again by repeatedly adding the dissolving of the halohydrocarbon such as methylene dichloride or trichloromethane, obtaining this polyolefine/phosphorous olefin block copolymers.
1h-NMR characterizes and determines, the phosphorous alkene section molar content in this multipolymer is 2.67%(n/m=0.0274).
Fig. 8 is polyolefine-phosphorous olefin block copolymers thermogravimetic analysis (TGA) figure prepared by this embodiment.As known in the figure along with the thermal weight loss carbon left of this multipolymer of increase of phosphorous alkene section improves, illustrate that the flame retardant resistance of this multipolymer improves with the increase of phosphorous alkene section.
Embodiment 3
In 100ml there-necked flask, add 0.300g (0.018mmol) Mn=1.7 × 10
4benzyl chloride end-blocking polypropylene after; vacuumize dry 4h under 60 DEG C of conditions after, add 20ml toluene stir the polypropylene of benzyl chloride end-blocking is fully dissolved after, add cuprous chloride 20.1mg (0.20mmol), 1 successively; 1; 4,7,10; 10-hexamethyl Triethylenetetramine (TETA) 45ul (0.19mmol); 5ml (24mmol) comonomer DEVBP, after abundant deoxygenation, under nitrogen protection in 90 DEG C of reaction 18h.Pass into air termination reaction, and with hexane or heptane precipitation polymers.Removing unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again by repeatedly adding the dissolving of the halohydrocarbon such as methylene dichloride or trichloromethane, obtaining this polyolefine/phosphorous olefin block copolymers.
1h-NMR characterizes and determines, the phosphorous alkene section molar content in this multipolymer is 4.07%(n/m=0.0424).
Fig. 9 is polyolefine-phosphorous olefin block copolymers thermogravimetic analysis (TGA) figure prepared by this embodiment.The identical result of embodiment 3 can be obtained by this figure.
Embodiment 4,
In 100ml there-necked flask, add 0.300g (0.018mmol) Mn=1.7 × 10
4benzyl chloride end-blocking polypropylene after; vacuumize dry 4h under 60 DEG C of conditions after, add 20ml toluene stir the polypropylene of benzyl chloride end-blocking is fully dissolved after, add cuprous chloride 20.1mg (0.20mmol), 1 successively; 1; 4,7,10; 10-hexamethyl Triethylenetetramine (TETA) 45ul (0.19mmol); 5ml (24mmol) comonomer DEVBP, after abundant deoxygenation, under nitrogen protection in 90 DEG C of reaction 10h.Pass into air termination reaction, and with hexane or heptane precipitation polymers.Removing unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again by repeatedly adding the dissolving of the halohydrocarbon such as methylene dichloride or trichloromethane, obtaining this polyolefine/phosphorous olefin block copolymers.
1h-NMR characterizes and determines, the phosphorous alkene section molar content in this multipolymer is 13.6%.（n/m=0.157）
Figure 10 is polyolefine-phosphorous olefin block copolymers thermogravimetic analysis (TGA) figure prepared by this embodiment.When phosphorous alkene section molar content is 13.6% as known in the figure, this polyolefinic thermal weight loss carbon left improves significantly, can well form layer of charcoal, thus can improve this polyolefinic flame retardant properties.
Embodiment 5,
In 100ml there-necked flask, add 0.300g (0.018mmol) Mn=1.7 × 10
4benzyl chloride end-blocking polypropylene after; vacuumize dry 4h under 60 DEG C of conditions after; add 20ml toluene stir the polypropylene of benzyl chloride end-blocking is fully dissolved after; add cuprous bromide 27.2mg (0.191mmol), pentamethyl-diethylenetriamine 35ul (0.19mmol) successively; 5ml (24mmol) comonomer DEVBP; after abundant deoxygenation, under nitrogen protection in 90 DEG C of reaction 4h.Pass into air termination reaction, and with hexane or heptane precipitation polymers.Removing unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again by repeatedly adding the dissolving of the halohydrocarbon such as methylene dichloride or trichloromethane, obtaining this polyolefine/phosphorous olefin block copolymers.
1h-NMR characterizes and determines, the phosphorous alkene section molar content in this multipolymer is 1.61%(n/m=0.0162).
Embodiment 6
In 100ml there-necked flask, add 0.300g (0.016mmol) M
n=1.9 × 10
4bromotoluene end-blocking polypropylene after; vacuumize dry 4h under 60 DEG C of conditions after; add 20ml toluene stir the polypropylene of benzyl chloride end-blocking is fully dissolved after; add cuprous bromide 27.2mg (0.19mmol), pentamethyl-diethylenetriamine 80ul (0.44mmol) successively; 7ml (34mmol) comonomer DEVBP; after abundant deoxygenation, under nitrogen protection in 90 DEG C of reaction 12h.Pass into air termination reaction, and with hexane or heptane precipitation polymers.Removing unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again by repeatedly adding the dissolving of the halohydrocarbon such as methylene dichloride or trichloromethane, obtaining this polyolefine/phosphorous olefin block copolymers.
1h-NMR characterizes and determines, the phosphorous alkene section molar content in this multipolymer is 2.66%(n/m=0.0284).
Embodiment 7
In 100ml there-necked flask, add 0.300g (0.012mmol) M
n=2.5 × 10
4bromotoluene end-blocking polypropylene after; vacuumize dry 4h under 60 DEG C of conditions after, add 40ml toluene stir the polypropylene of benzyl chloride end-blocking is fully dissolved after, add cuprous bromide 40.2mg (0.283mmol), 1 successively; 1; 4,7,10; 10-hexamethyl Triethylenetetramine (TETA) 70ul (0.30mmol); 9ml (42mmol) comonomer DEVBP, after abundant deoxygenation, under nitrogen protection in 80 DEG C of reaction 18h.Pass into air termination reaction, and with hexane or heptane precipitation polymers.Removing unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again by repeatedly adding the dissolving of the halohydrocarbon such as methylene dichloride or trichloromethane, obtaining this polyolefine/phosphorous olefin block copolymers,
1h-NMR characterizes and determines, the phosphorous alkene section molar content in this multipolymer is 4.23%(n/m=0.043).
Embodiment 8
In 100ml there-necked flask, add 0.300g (0.012mmol) M
n=2.5 × 10
4bromotoluene end-blocking polypropylene after; vacuumize dry 4h under 60 DEG C of conditions after, add 20ml toluene stir the polypropylene of benzyl chloride end-blocking is fully dissolved after, add cuprous bromide 42.3mg (0.298mol), 1 successively; 1; 4,7,10; 10-hexamethyl Triethylenetetramine (TETA) 100ul (0.43mmol); 10ml (46mmol) comonomer DEVBP, after abundant deoxygenation, under nitrogen protection in 90 DEG C of reaction 10h.Pass into air termination reaction, and with hexane or heptane precipitation polymers.Removing unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again by repeatedly adding the dissolving of the halohydrocarbon such as methylene dichloride or trichloromethane, obtaining this polyolefine/phosphorous olefin block copolymers.
1h-NMR characterizes and determines, the phosphorous alkene section molar content in this multipolymer is 14.70%(n/m=0.172).
Embodiment 9
In 100ml there-necked flask, add 0.300g (0.018mmol) Mn=1.7 × 10
4benzyl chloride end-blocking polypropylene after; vacuumize dry 4h under 60 DEG C of conditions after, add 20ml toluene stir the polypropylene of benzyl chloride end-blocking is fully dissolved after, add cuprous chloride 20.1mg (0.203mmol), 1 successively; 1; 4,7,10; 10-hexamethyl Triethylenetetramine (TETA) 45ul (0.19mmol); 5ml (24mmol) comonomer DEMMP, after abundant deoxygenation, under nitrogen protection in 90 DEG C of reaction 4h.Pass into air termination reaction, and with hexane or heptane precipitation polymers.Removing unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again by repeatedly adding the dissolving of the halohydrocarbon such as methylene dichloride or trichloromethane, obtaining this polyolefine/phosphorous olefin block copolymers.
1h-NMR characterizes and determines, the phosphorous alkene section molar content in this multipolymer is 1.10%(n/m=0.011).
Embodiment 10
In 100ml there-necked flask, add 0.300g (0.016mmol) M
n=1.9 × 10
4bromotoluene end-blocking polypropylene after; vacuumize dry 4h under 60 DEG C of conditions after, add 20ml toluene stir the polypropylene of benzyl chloride end-blocking is fully dissolved after, add cuprous bromide 27.2mg (0.19mmol), 1 successively; 1; 4,7,10; 10-hexamethyl Triethylenetetramine (TETA) 90ul (0.39mmol); 7ml (35mmol) comonomer DEMMP, after abundant deoxygenation, under nitrogen protection in 80 DEG C of reaction 12h.Pass into air termination reaction, and with hexane or heptane precipitation polymers.Removing unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again by repeatedly entering the dissolving of the halohydrocarbon such as methylene dichloride or trichloromethane, obtaining this polyolefine/phosphorous olefin block copolymers.
1h-NMR characterizes and determines, the phosphorous alkene section molar content in this multipolymer is 2.23%(n/m=0.0228).
Embodiment 11
In 100ml there-necked flask, add 0.300g (0.012mmol) M
n=2.5 × 10
4bromotoluene end-blocking polypropylene after; vacuumize dry 4h under 60 DEG C of conditions after; add 20ml toluene stir the polypropylene of benzyl chloride end-blocking is fully dissolved after; add cuprous bromide 42.3mg (0.298mol), pentamethyl-diethylenetriamine 70ul (0.38mmol) successively; 10ml (48.4mmol) comonomer DEMMP; after abundant deoxygenation, under nitrogen protection in 90 DEG C of reaction 18h.Pass into air termination reaction, and with hexane or heptane precipitation polymers.Removing unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again by repeatedly adding the dissolving of the halohydrocarbon such as methylene dichloride or trichloromethane, obtaining this polyolefine/phosphorous olefin block copolymers.
1h-NMR characterizes and determines, the phosphorous alkene section molar content in this multipolymer is 3.94%(n/m=0.0410).
Embodiment 12
In 100ml there-necked flask, add 0.300g (0.012mmol) M
n=2.5 × 10
4benzyl chloride end-blocking polypropylene after; vacuumize dry 4h under 60 DEG C of conditions after; add 20ml toluene stir the polypropylene of benzyl chloride end-blocking is fully dissolved after; add cuprous chloride 50.6mg (0.356mol), pentamethyl-diethylenetriamine 120ul (0.58mmol) successively; 10ml (48.4mmol) comonomer DEMMP; after abundant deoxygenation, under nitrogen protection in 90 DEG C of reaction 20h.Pass into air termination reaction, and with hexane or heptane precipitation polymers.Removing unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again by repeatedly adding the dissolving of the halohydrocarbon such as methylene dichloride or trichloromethane, obtaining this polyolefine/phosphorous olefin block copolymers.
1h-NMR characterizes and determines, the phosphorous alkene section molar content in this multipolymer is 10.01%(n/m=0.111).
Figure 12 prepares the heat release rate figure of obtained polyolefine-phosphorous olefin block copolymers for this embodiment that miniature calorimeter measures.The introducing of this phosphorous alkene can reduce this polyolefinic heat release rate (polyacrylic maximum heat rate of release is 1020W/g) equally as seen from the figure, thus can improve this polyolefinic flame retardant properties.
Embodiment 13
In 100ml there-necked flask, add 0.300g (0.018mmol) Mn=1.7 × 10
4bromotoluene end-blocking polypropylene after; vacuumize dry 4h under 60 DEG C of conditions after, add 20ml toluene stir the polypropylene of benzyl chloride end-blocking is fully dissolved after, add cuprous bromide 42.3mg (0.298mol), 1 successively; 1; 4,7,10; 10-hexamethyl Triethylenetetramine (TETA) 100ul (0.43mmol); 100ml (480mmol) comonomer DEVBP, after abundant deoxygenation, under nitrogen protection in 90 DEG C of reaction 24h.Pass into air termination reaction, and with hexane or heptane precipitation polymers.Removing unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again by repeatedly adding the dissolving of the halohydrocarbon such as methylene dichloride or trichloromethane, obtaining this polyolefine/phosphorous olefin block copolymers.
1h-NMR characterizes and determines, the phosphorous alkene section molar content in this multipolymer is 96.00%(n/m=24.00)
Embodiment 14
In 100ml there-necked flask, add 0.300g (0.018mmol) Mn=1.7 × 10
4bromotoluene end-blocking polypropylene after; vacuumize dry 4h under 60 DEG C of conditions after, add 20ml toluene stir the polypropylene of benzyl chloride end-blocking is fully dissolved after, add cuprous bromide 42.3mg (0.298mol), 1 successively; 1; 4,7,10; 10-hexamethyl Triethylenetetramine (TETA) 100ul (0.43mmol); 100ml (480mmol) comonomer DEVBP, after abundant deoxygenation, under nitrogen protection in 90 DEG C of reaction 78h.Pass into air termination reaction, and with hexane or heptane precipitation polymers.Removing unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again by repeatedly adding the dissolving of the halohydrocarbon such as methylene dichloride or trichloromethane, obtaining this polyolefine/phosphorous olefin block copolymers.
1h-NMR characterizes and determines, the phosphorous alkene section molar content in this multipolymer is 98.01%(n/m=49.01).
Claims (11)
1. polyolefine-phosphorous olefin block copolymers, its structural formula is such as formula shown in I:
In formula I, R is selected from the alkyl of hydrogen or C1-C8,
represent phosphorus-containing groups;
Described phosphorus-containing groups
structural formula such as formula shown in II:
In formula II, R
3, R
4, R
5all represent any one group following: hydrogen, C1-C8 alkyl, hydroxyl, carboxyl, nitro, the substituting group shown in amino and formula III, and R
3, R
4, R
5in have at least one to represent the substituting group shown in formula III; In formula III, Ra is the azanyl of the alkyl of C1-C6, the alkoxyl group of C1-C6 or C1-C6, and Rb, Rc are the alkyl of C1-C6 or the aryl of C6-C18;
In formula I, R
1and R
2identical or different, all represent hydrogen or C1-C8 alkyl;
n/m＝0.01-50。
2. polyolefine-phosphorous olefin block copolymers, its structural formula is such as formula shown in I:
In formula I, R is selected from the alkyl of hydrogen or C1-C8,
represent phosphorus-containing groups;
Described phosphorus-containing groups
structural formula as shown in formula III:
In formula III, Ra is the azanyl of the alkyl of C1-C6, the ester group of C1-C6, the alkoxyl group of C1-C6 or C1-C6, and Rb, Rc are the alkyl of C1-C8;
In formula I, R
1represent hydrogen or C1-C8 alkyl, R
2represent the ester group of hydrogen, C1-C8 alkyl or C1-C8;
n/m＝0.01-50。
3. prepare the method for the polyolefine-phosphorous olefin block copolymers shown in claim 1 Chinese style I, comprise the steps: with end group to be that the polyolefine of the group that can cause controllable/active free radical polymerization is for initiator, shown in initiation formula V (a), the polyreaction of monomer, obtains the polyolefine shown in claim 1 Chinese style I-phosphorous olefin block copolymers;
In formula V (a), R
1and R
2identical or different, all represent hydrogen or C1-C8 alkyl; R
3, R
4, R
5all represent any one group following: hydrogen, C1-C8 alkyl, hydroxyl, carboxyl, nitro, the substituting group shown in amino and formula III, and R
3, R
4, R
5in have at least one to represent the substituting group shown in formula III; In formula III, Ra is the azanyl of the alkyl of C1-C6, the alkoxyl group of C1-C6 or C1-C6, and Rb, Rc are the alkyl of C1-C6 or the aryl of C6-C18;
Described controllable/active free radical polymerization is atom transfer radical polymerization; Described initiator be specifically selected from following any one:
In formula IV, X represents Cl or Br; Y and Z is identical or different, all represents hydrogen or C1-C6 alkyl; The definition cotype I of R, m;
Described polyreaction is atom transition free radical polymerization reaction, and catalyzer used in described atom transition free radical polymerization reaction is cuprous halide.
4. prepare the method for the polyolefine-phosphorous olefin block copolymers shown in claim 2 Chinese style I, comprise the steps: with end group to be that the polyolefine of the group that can cause controllable/active free radical polymerization is for initiator, shown in initiation formula V (b), the polyreaction of monomer, obtains the polyolefine shown in claim 2 Chinese style I-phosphorous olefin block copolymers;
In formula V time (b), R
1represent hydrogen or C1-C8 alkyl; R
2represent the ester group of hydrogen, C1-C8 alkyl or C1-C8; R
6for the substituting group shown in formula III, wherein Ra is the azanyl of the alkyl of C1-C6, the ester group of C1-C6, the alkoxyl group of C1-C6 or C1-C6, and Rb, Rc are the alkyl of C1-C8;
Described controllable/active free radical polymerization is atom transfer radical polymerization; Described initiator be selected from following any one:
In formula IV, X represents Cl or Br; Y and Z is identical or different, all represents hydrogen or C1-C6 alkyl; The definition cotype I of R, m;
Described polyreaction is atom transition free radical polymerization reaction, and catalyzer used in described atom transition free radical polymerization reaction is cuprous halide.
5. the method according to claim 3 or 4, is characterized in that: catalyzer used in described atom transition free radical polymerization reaction comprises cuprous chloride, cuprous bromide or cuprous iodide; Ligand used in described atom transition free radical polymerization reaction comprises 2,2 '-dipyridyl, 4,4 '-diformyloxy-2,2 '-dipyridyl, 4,4 '-diheptyl-2,2 '-dipyridyl, pyridine imine, pentamethyl-Diethylenetriaminee (DETA), three (2-picolyl) amine, three-(2-dimethylaminoethyl) amine, three-(2-diethylaminoethyl) amine, 1, Isosorbide-5-Nitrae, 7,10,10-hexamethyl Triethylenetetramine (TETA).
6. the method according to claim 3 or 4, is characterized in that: the reaction solvent of described polyreaction is selected from following at least one: benzene, chlorine benzene,toluene,xylene, hexane, heptane and dimethyl formamide.
7. the method according to claim 3 or 4, is characterized in that: described end group is the polyolefine of the group that can cause controllable/active free radical polymerization and the mol ratio of described formula V (a) or the shown monomer of formula V (b) is 1:0.1-1:50000; Described end group is the polyolefine of the group that can cause controllable/active free radical polymerization and the mol ratio of described catalyzer is 1:0.01-1:100; The mol ratio of described ligand and described catalyzer is 1:0.1-1:50; The volume ratio of described reaction solvent and described formula V (a) or the shown monomer of formula V (b) is 1:0.01-1:10.
8. method according to claim 7, is characterized in that: described end group is the polyolefine of the group that can cause controllable/active free radical polymerization and the mol ratio of described catalyzer is 1:0.05-10.
9. the method according to claim 3 or 4, is characterized in that: the temperature of reaction of described polyreaction is 20-170 DEG C; Reaction times is 0.5-150 hour.
10. method according to claim 9, is characterized in that: the temperature of reaction of described polyreaction is 80-150 DEG C.
11. methods according to claim 3 or 4, is characterized in that: described polyreaction is carried out under anaerobic; The described polyreaction method passing into air stops.
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| Reactive modifications of some chain- and step-growth polymers with phosphorus- containing compounds: effects on flame retardance-a review;Paul Joseph et al.;《Polymers for Advanced Technologies》;20110127;第22卷(第4期);第395-406页 * |
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