CN102757542A - 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 block copolymer of polyolefine and phosphorus-containing alkene and a preparation method thereof. The block copolymer has the structural formula (I), wherein R is H or C1-C8 alkyl; when the phosphorus-containing group has the formula (II), R1 and R2 are H or C1-C8 alkyl, and R3, R4 and R5 are all H, C1-C8 alkyl, hydroxyl, carboxyl, nitryl, amino or substitutional groups in the formula (III), and at least one of R3, R4 and R5 is the substitutional group in the formula (III); in the formula (III), Ra is C1-C6 alkyl, alkoxyl or azanyl, Rb and Rc are both C1-C6 alkyl or C6-C18 aryl; and when the phosphorus-containing group has the formula (III), R1 is H or C1-C8 alkyl, R2 is H, C1-C8 alkyl or a C1-C8 ester group, Ra is C1-C6 alkyl, an ester group, alkoxyl or azanyl, and Rb and Rc are both C1-C8 alkyl. The copolymer is obtained by polymerization of phosphorus-containing alkene using polyolefine which acts as a polymer initiator. The block polymer of polyolefine and phosphorus-containing alkene has broad application prospects in the aspect of improving flame retardancy and adhesion property of polyolefine.
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 because abundant raw material; Mechanical property is good; Easily machine-shaping, characteristics such as electric insulating quality is strong, stable chemical performance, density are little, light weight and being widely used in fields such as daily life, household electrical appliances, weaving, automobile, building, agricultural and military affairs.But; Because the polyolefine macromolecular chain is mainly by C, two kinds of atomic buildings of H; Be apolar chain; Add the crystalline characteristics of semicrystalline polyolefin and make its surface energy extremely low, thereby itself and most polymers or mineral filler be difficult to reach effectively compatible, be difficult to guarantee blend or performance of composites.In addition; Polyolefine belongs to hydrocarbon type of material; Have easy incendiary characteristics, maximum Vilaterm and the polyacrylic oxygen index of consumption only has 17.0%-18.0% in the polyolefine, and produces molten drop during the polyolefine burning; So all require fire-retardantly in many application scenarios, and traditional additive flame retardant exists the shortcoming that reduces polyolefin properties and be prone to separate out.So how polyolefine is carried out modification, on the basis that keeps the performance of polyolefine own, realizes that its flame retardant properties becomes polyolefin modified important topic.
Polyolefin functional is on the basis that keeps the original premium properties of polyolefine, on the polyolefine macromolecular chain, introduces the polar functionalities group, thereby realizes the high performance of polyolefine material.The Functionalization of Polyolefins main path is following: (a) polyolefinic chemical modification; (b) alkene and the alpha-olefin copolymer that contains functional group; (c) carry out functionalization through reactive polyolefine midbody.
It is a kind of important polyolefin functional method that existing polyolefine is carried out chemical modification.Because of it does not relate to new polyreaction, these class methods are easy realization of industrialization more.Existing polyolefinic chemical modification method mainly contains chlorination, graft modification, surface-treated etc.But the chemical modification major part all utilizes free radical reaction to carry out, and often has crosslinkedly in the process of reaction, and side reactions such as degraded take place, so its range of application is restricted.
Olefinic monomer is the most direct polyolefin functional method with the alpha-olefin copolymer that contains functional group, on technology, is easy to realize.The comonomer of existing report has borine at present; The protected long-chain enol of the terminal olefin of silane-functionalized or functional group etc.; Reduce or even inactivation but polar functional group can make the Ziegler-Natta catalyst of olefinic polymerization and metallocene catalyst is active, so mostly the catalyzer that adopts is the late transition metal catalyst of weak oxytropism.Therefore directly copolymerization also has certain limitation.
Carrying out functionalization through reactive polyolefine midbody is through designing a kind of reactivity monomer or chain-transfer agent altogether; Make this monomer altogether or chain-transfer agent contain reactive group to catalyst active center's toxicological harmless effect; Utilize the good catalysis characteristics of Ziegler-Natta catalyst and metallocene catalyst then; Realize that with advantages of high catalytic activity olefinic monomer and this reactivity are total to the copolymerization or the chain transfer polymerization of monomer or chain-transfer agent, obtain containing " the reactive polyolefine " of reactive group.Utilize the active chemical property of reactive group; Optionally carry out various functional conversion reactions; Preparation is based on the macromole evocating agent of polyolefinic active free radical polymerization; Combine again as ATRP (ATRP) etc. has the polyreaction of living polymerization characteristic, and realization has the constructing of functional polyolefin of block and Grafting Structure.For example, Dong etc. utilizes metallocene catalyst rac-Me recently
2Si [2-Me-4-Ph-Ind]
2ZrCl
2Catalyzing propone with to Vinylstyrene or 1; 2-two (4-ethenylphenyl) ethane copolymerization; Prepare styrene end-capped isotatic polypropylene (iPP-t-St), then utilized the hydrogenchloride addition reaction to change the two keys of end group vinylbenzene into can carry out the ATRP reaction benzyl chloride, obtained macromole evocating agent iPP-t-Cl; And adopt this macromole evocating agent to make PP-b-PMMA segmented copolymer (Huang, the H. of functionalization; Niu, H.; Dong, J.-Y.Journal ofPolymer Science Part A:Polymer Chemistry 2010,48,5783.).
Segmented copolymer obtains relatively graceful function polymer materials of performance because of the advantageous property of multiple polymers being combined, thereby of many uses.Polyolefin block copolymer can have been realized its functionalization through in polyolefin chain, introducing functional groups especially, has enlarged its range of application.
The method for preparing polyolefin block copolymer based on the olefin coordination polymerization technology mainly contains four kinds: (a) living coordination polymerization reaction; (b) chain coordination transfer polymerization reaction; (c) utilize coupling method synthesis of polyolefins segmented copolymer; (d) " reactive polyolefine midbody " method.Wherein " reactive polyolefine midbody " method is through the reactive polyolefine of the synthetic end of the chain of the chain transfer reaction in the olefin coordination polymerization; Again reactive polyolefine is converted into the macromole evocating agent of other living polymerization; Be used to cause the polymerization of polar monomer, thus the synthesis of polyolefins segmented copolymer.This method has broken through some distinctive limitations of polycoordination reaction, for the polyolefin block copolymer for preparing functionalization provides valid approach.Total type of polyolefin block copolymer kind is various, and more common is polyolefine and styrene block copolymer, polyolefine and methylmethacrylate copolymer etc.Segmented copolymer through synthesis of polyolefins can improve polyolefinic performance, widens polyolefinic range of application.
Phosphorous polymer is of many uses, can be used in aspects such as sticker, coating, biomaterial, medicinal slow release agent, fire retardant.But the research of phosphorous block polymer is less, and compound method basically all is to prepare through the ATRP method.Matyjaszewski etc. cause phosphorous segmented copolymer (Huang, the J. that the phosphorous-containing monomers polymerization has prepared vinylbenzene and TEB 3K through PS/polymethylmethacrylate ATRP macromole agent; Matyjaszewski, K.Macromolecules 2005,38, and 3577.).Mullen etc. also adopt with quadrat method and have made 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, and 3411.).
The segmented copolymer of polyolefine-phosphorous alkene is expected to improve the cohesiveness and the flame retardant properties of polyolefine material, expands polyolefinic range of application.
Summary of the invention
The segmented copolymer that the purpose of this invention is to provide 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 suc as formula shown in the I:
Wherein, R is selected from the alkyl of hydrogen or C1-C8;
represents the phosphorated group.
When phosphorus-containing groups
when being aromatic group its structure suc as formula shown in the II:
At this moment, R among the formula I
1And R
2Represent hydrogen or C1-C8 alkyl, R
1And R
2Can be the same or different.R among the formula II
3, R
4, R
5All represent following any one group: the substituting group shown in hydrogen, C1-C8 alkyl, hydroxyl, carboxyl, nitro, amino and the formula III, and R
3, R
4, R
5In have at least one to represent the substituting group shown in the formula III.Ra is the alkyl of C1-C6, the alkoxyl group of C1-C6 or the azanyl of C1-C6 in the formula III, and Rb, Rc are the alkyl of C1-C6 or the aryl of C6-C18.
When phosphorus-containing groups
when being fat group its structure shown in formula III.At this moment, R
1Represent hydrogen or C1-C8 alkyl, R
2Represent the ester group of hydrogen, C1-C8 alkyl or C1-C8, Ra is the alkyl of C1-C6, the ester group of C1-C6, the alkoxyl group of C1-C6 or the azanyl of 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 controlled/active free radical polymerization such as ATRP (ATRP) (X represents Cl or Br suc as formula IV; Y and Z represent hydrogen or C1-C6 alkyl, Y and Z can be identical also can be different; The definition cotype I of R, m) vacuumize drying after; After the adding organic solvent fully dissolves; Add comonomer (suc as formula V) successively; Cuprous halide, multiple tooth containing n-donor ligand fully carry out the ATRP polyreaction after the deoxygenation under imposing a condition, obtain the segmented copolymer of the polyolefine shown in the said formula I-phosphorous alkene.
When polymerization single polymerization monomer is among the formula V when (a), 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 following any one group: the substituting group shown in hydrogen, C1-C8 alkyl, hydroxyl, carboxyl, nitro, amino and the said formula III, and R
3, R
4, R
5In have the substituting group of a representative shown in the said formula III at least.Ra is the alkyl of C1-C6, the alkoxyl group of C1-C6 or the azanyl of C1-C6 in the formula III, and Rb, Rc are the alkyl of C1-C6 or the aryl of C6-C18.
When polymerization single polymerization monomer is among the formula V when (b), 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 the said formula III, and wherein Ra is the alkyl of C1-C6, the ester group of C1-C6, the alkoxyl group of C1-C6 or the azanyl of C1-C6, and Rb, Rc are the alkyl of C1-C8.
In the preparation method, saidly can cause ATRP polymeric polyolefine and the monomeric mol ratio of copolymerization is 1:0.1-1:50000; The said mol ratio that can cause ATRP polymeric polyolefine and cuprous halide is 1:0.01-1:100, is preferably 1:0.05-10; The mol ratio of said multiple tooth containing n-donor ligand and cuprous halide is 1:0.1-1:50.The monomeric volume ratio of reaction solvent and copolymerization is 1:0.01-1:10.Carry out under the said protection that is reflected at rare gas element (like nitrogen or argon gas).Temperature of reaction is 20-170 ℃, is preferably 80-150 ℃; Reaction times is 0.5-50 hour; Reaction solvent comprises one or more in benzene, chlorobenzene, toluene, YLENE, hexane or heptane, the N; When finishing, polyreaction stops through bubbling air, and with hexane or heptane precipitation polymers.Precipitate the repetitive scrubbing polymkeric substance to remove cupric ion in the polymkeric substance with hexane or heptane again through adding halohydrocarbon dissolvings such as methylene dichloride or trichloromethane.
Cuprous halide described in the present invention comprises cuprous chloride, cuprous bromide or cuprous iodide; Said multiple tooth containing n-donor ligand comprises 2,2 '-dipyridyl, 4,4 '-two methanoyies-2; 2 '-dipyridyl, 4,4 '-diheptyl-2,2 '-dipyridyl, pyridine imine, pentamethyl-diethylenetriamine, three (2-picolyl) amine, three-(2-diformazan aminoethyl) amine, three-(2-diethylaminoethyl) amine, 1; 1,4,7; 10,10-hexamethyl Triethylenetetramine (TETA).
The method of the segmented copolymer of preparation polyolefine provided by the present invention-phosphorous alkene, raw material sources are extensive, and cost is lower, and partial monosomy is industrialized raw material, and reaction method is ripe.Utilize the segmented copolymer of polyolefine-phosphorous alkene that this method obtains; Polyolefine section and phosphorous alkene segment length accurate in scale controlled; Can make the polyolefin copolymer of various phosphorous olefin(e) centents; The segmented copolymer of this polyolefine-phosphorous alkene has good flame retardant property on the basis that guarantees former polyolefine premium properties, can be used as fire retardant polyolefin and be applied to the fire-retardant field of needs.
Description of drawings
Fig. 1 is embodiment 1 preparation gained polyolefine-phosphorous olefin block copolymers
1The H-NMR spectrogram.
Fig. 2 is embodiment 2 preparation gained polyolefine-phosphorous olefin block copolymers
1The H-NMR spectrogram.
Fig. 3 is embodiment 3 preparation gained polyolefine-phosphorous olefin block copolymers
1The H-NMR spectrogram.
Fig. 4 is embodiment 4 preparation gained polyolefine-phosphorous olefin block copolymers
1The H-NMR spectrogram.
Fig. 5 is embodiment 1 preparation gained polyolefine-phosphorous olefin block copolymers infrared spectrogram.
Fig. 6 is embodiment 2 preparation gained polyolefine-phosphorous olefin block copolymers infrared spectrograms.
Fig. 7 is embodiment 1 preparation gained polyolefine-phosphorous olefin block copolymers thermogravimetic analysis (TGA) figure.
Fig. 8 is embodiment 2 preparation gained polyolefine-phosphorous olefin block copolymers thermogravimetic analysis (TGA) figure.
Fig. 9 is embodiment 4 preparation gained polyolefine-phosphorous olefin block copolymers thermogravimetic analysis (TGA) figure.
Figure 10 is embodiment 12 preparation gained polyolefine-phosphorous olefin block copolymers thermogravimetic analysis (TGA) figure.
Figure 11 is the HRR figure (miniature calorimeter mensuration) of embodiment 1 preparation gained polyolefine-phosphorous olefin block copolymers.
Figure 12 is embodiment 12 preparation gained polyolefine-logical HRR figure (miniature calorimeter mensuration) of phosphorous olefin block copolymers.
Embodiment
The segmented copolymer of polyolefine provided by the invention-phosphorous alkene has suc as formula structure shown in the I:
Wherein, R is selected from the alkyl of hydrogen or C1-C8;
represents the phosphorated group.
When phosphorus-containing groups
when being aromatic group its structure suc as formula shown in the II:
At this moment, R among the formula I
1And R
2Represent hydrogen or C1-C8 alkyl, R
1And R
2Can be the same or different.R among the formula II
3, R
4, R
5All represent following any one group: the substituting group shown in hydrogen, C1-C8 alkyl, hydroxyl, carboxyl, nitro, amino and the formula III, and R
3, R
4, R
5In have at least one to represent the substituting group shown in the formula III.Ra is the alkyl of C1-C6, the alkoxyl group of C1-C6 or the azanyl of C1-C6 in the formula III, and Rb, Rc are the alkyl of C1-C6 or the aryl of C6-C18.
When phosphorus-containing groups
when being fat group its structure shown in formula III.At this moment, R
1Represent hydrogen or C1-C8 alkyl, R
2Represent the ester group of hydrogen, C1-C8 alkyl or C1-C8, Ra is the alkyl of C1-C6, the ester group of C1-C6, the alkoxyl group of C1-C6 or the azanyl of C1-C6 in the formula III, and Rb, Rc are the alkyl of C1-C8.
N/m=0.001-100 wherein.
This polyolefine-phosphorous olefin block copolymers is to be that the ATRP polyreaction that macromole evocating agent causes the phosphorous olefinic monomer of formula V structure makes with the polyolefine suc as formula structure shown in the IV:
When polymerization single polymerization monomer is among the formula V when (a), 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 following any one group: the substituting group shown in hydrogen, C1-C8 alkyl, hydroxyl, carboxyl, nitro, amino and the said formula III, and R
3, R
4, R
5In have the substituting group of a representative shown in the said formula III at least.Ra is the alkyl of C1-C6, the alkoxyl group of C1-C6 or the azanyl of C1-C6 in the formula III, and Rb, Rc are the alkyl of C1-C6 or the aryl of C6-C18.
When polymerization single polymerization monomer is among the formula V when (b), R
1Represent hydrogen or C1-C8 alkyl; R
2Represent the ester group of hydrogen, C1-C8 alkyl or C1-C8; R
6Be the substituting group shown in the said formula III, wherein Ra is the alkyl of C1-C6, the ester group of C1-C6, the alkoxyl group of C1-C6 or the azanyl of C1-C6, and Rb, Rc are the alkyl of C1-C8.
Its embodiment is following: the adding quality is that the end group of 0.1-100kg is the polyolefine that can cause ATRP (ATRP) in reactor drum; After vacuumizing dry 1-10h under the 0-100 ℃ of condition, be that the mol ratio of 1:0.1-1:50000, initiation ATRP polymeric polyolefine and cuprous halide is that the mol ratio of 1:0.01-1:100, multiple tooth containing n-donor ligand and cuprous halide is that 1:0.1-1:50 feeds in raw material by polyolefine that causes ATRP and the monomeric mol ratio of copolymerization.The monomeric volume ratio of reaction solvent and copolymerization is 1:0.01-1:10.In reaction under nitrogen or the argon shield condition after 0.5-50 hour, the bubbling air cessation reaction, and with hexane or heptane precipitation polymers.Through adding halohydrocarbon dissolvings such as methylene dichloride or trichloromethane, with hexane or heptane deposition, the repetitive scrubbing polymkeric substance is removed unreacted monomer again, and filtration, drying obtain polyolefine-phosphorous olefin block copolymers.
The end capped Vestolen PP 7052 macromole evocating agent of used benzyl chloride or bromotoluene compound method is following among the following embodiment: after churned mechanically polymeric kettle is housed vacuumizes 30min; Feed a certain amount of hydrogen down at 30 ℃; Add toluene successively; The chain-transfer agent of predetermined mole number to Vinylstyrene (1,4-DVB) promotor exsiccant MAO and metallocene catalyst rac-Me
2Si [2-Me-4-Ph-Ind]
2ZrCl
2Toluene solution feeds propylene again, and keeps propylene under predetermined pressure, to react; React to certain hour, pressure release is with the ethanol termination reaction that contains 10wt% hydrochloric acid; Use THF successively; Water and washing with alcohol for several times, put into the vacuum drying oven drying after, obtain the end capped isotatic polypropylene of vinylbenzene.The end capped isotatic polypropylene of this vinylbenzene is dissolved in the back lasting exsiccant HCl of feeding or HBr gas 8h under 60 ℃ of conditions in the sym.-tetrachloroethane.Stopped reaction is poured in the ethanol and is precipitated, and filters with zero(ppm) water, washing with alcohol, promptly obtains the end capped Vestolen PP 7052 macromole evocating agent of this benzyl benzyl chloride or bromotoluene after the drying.
Used two kinds of phosphorous olefinic monomers all can be synthetic through simple organic reaction among the following embodiment, and synthetic two kinds of monomeric raw materials all can obtain from commercial sources.Monomer DEVBP reference literature (Dumitrascu, A. wherein; Howell, B.A.Polymer Degradation and Stability 2011,96,342) synthetic; 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 Stability 2000,70,425.) synthetic.
The structure warp of polyolefine-phosphorous olefin block copolymers
1H-NMR, examination of infrared spectrum analysis have obtained confirmation, and the ratio of polyolefine section and phosphorous alkene segment length also can be come analysis and characterization with nuclear-magnetism.The thermal property of multipolymer waits through thermogravimetric analyzer (TGA) and characterizes.And the length of phosphorous alkene section in polyolefine-phosphorous olefin block copolymers, can change temperature of reaction through changing the add-on of phosphorous olefinic monomer, the reaction times with change catalytic amount and regulate.
Two kinds of copolymerization monomers shown in the employing formula VI are specific embodiment, and detailed explanation is made in the polyolefine-phosphorous olefin block copolymers and the preparation thereof of invention.But these embodiment do not limit the scope of the invention, and also should not be construed as the condition, parameter or the numerical value that have only these embodiment to provide could embodiment of the present invention.
(formula VI)
Embodiment 1-8 is R=R among the preparation formula I
1=R
2=H,
Be R among aromatic group shown in the formula II and the formula II
3=R
4=H, R
5Be Ra=CH in substituting group shown in the formula III and the formula III
2, Rb=Rc=CH
2CH
3Multipolymer, just the value of n/m is different.
Embodiment 9-12 is R=R among the preparation formula I
1=H, R
2=CH
3,,
For Ra in substituting group shown in the formula III and the formula III is C=OO, Rb=Rc=CH
2CH
3Multipolymer, just the value of n/m is different.
In the 100ml there-necked flask, add 0.300g (0.018mmol) Mn=1.7 * 10
4The end capped Vestolen PP 7052 of benzyl chloride after, after vacuumizing dry 4h under 60 ℃ of conditions, add 20ml toluene stir the end capped Vestolen PP 7052 of benzyl chloride is fully dissolved after; Add cuprous chloride 20.1mg (0.203mmol), 1,1,4 successively; 7,10,10-hexamethyl Triethylenetetramine (TETA) 45ul (0.17mmol); 5ml (24mmol) comonomer DEVBP fully after the deoxygenation, reacts 4h in 90 ℃ under nitrogen protection.The bubbling air termination reaction, and with hexane or heptane precipitation polymers.Remove unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again through adding halohydrocarbon dissolvings such as methylene dichloride or trichloromethane repeatedly, obtain this polyolefine/phosphorous olefin block copolymers.
1H-NMR characterizes and confirms that the phosphorous alkene section molar content in this multipolymer is 1.51% (n/m=0.0153).
Fig. 7 is the polyolefine-phosphorous olefin block copolymers thermogravimetic analysis (TGA) figure of this embodiment preparation.Can know that by this figure the introducing of phosphorous alkene can improve this polyolefinic thermal weight loss carbon residue amount (polyacrylic 650 ℃ time carbon residue amount almost nil), thereby can improve this polyolefinic flame retardant properties.
This embodiment that Figure 11 measures for miniature calorimeter prepares the HRR figure of resulting polyolefine-phosphorous olefin block copolymers.Can know that by figure the introducing of phosphorous alkene can reduce this polyolefinic HRR (polyacrylic maximum heat rate of release is 1020W/g), thereby can improve this polyolefinic flame retardant properties.
Embodiment 2
In the 100ml there-necked flask, add 0.300g (0.018mmol) Mn=1.7 * 10
4The end capped Vestolen PP 7052 of benzyl chloride after, after vacuumizing dry 4h under 60 ℃ of conditions, add 20ml toluene stir the end capped Vestolen PP 7052 of benzyl chloride is fully dissolved after; Add cuprous chloride 20.1mg (0.20mmol), 1,1,4 successively; 7,10,10-hexamethyl Triethylenetetramine (TETA) 45ul (0.19mmol); 5ml (24mmol) comonomer DEVBP fully after the deoxygenation, reacts 12h in 90 ℃ under nitrogen protection.The bubbling air termination reaction, and with hexane or heptane precipitation polymers.Remove unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again through adding halohydrocarbon dissolvings such as methylene dichloride or trichloromethane repeatedly, obtain this polyolefine/phosphorous olefin block copolymers.
1H-NMR characterizes and confirms that the phosphorous alkene section molar content in this multipolymer is 2.67% (n/m=0.0274).
Fig. 8 is the polyolefine-phosphorous olefin block copolymers thermogravimetic analysis (TGA) figure of this embodiment preparation.Can know that by this figure the thermal weight loss carbon residue amount along with this multipolymer of increase of phosphorous alkene section improves, the flame retardant resistance that this multipolymer is described improves with the increase of phosphorous alkene section.
Embodiment 3
In the 100ml there-necked flask, add 0.300g (0.018mmol) Mn=1.7 * 10
4The end capped Vestolen PP 7052 of benzyl chloride after, after vacuumizing dry 4h under 60 ℃ of conditions, add 20ml toluene stir the end capped Vestolen PP 7052 of benzyl chloride is fully dissolved after; Add cuprous chloride 20.1mg (0.20mmol), 1,1,4 successively; 7,10,10-hexamethyl Triethylenetetramine (TETA) 45ul (0.19mmol); 5ml (24mmol) comonomer DEVBP fully after the deoxygenation, reacts 18h in 90 ℃ under nitrogen protection.The bubbling air termination reaction, and with hexane or heptane precipitation polymers.Remove unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again through adding halohydrocarbon dissolvings such as methylene dichloride or trichloromethane repeatedly, obtain this polyolefine/phosphorous olefin block copolymers.
1H-NMR characterizes and confirms that the phosphorous alkene section molar content in this multipolymer is 4.07% (n/m=0.0424).
Fig. 9 is the polyolefine-phosphorous olefin block copolymers thermogravimetic analysis (TGA) figure of this embodiment preparation.Can obtain the identical result of embodiment 3 by this figure.
Embodiment 4,
In the 100ml there-necked flask, add 0.300g (0.018mmol) Mn=1.7 * 10
4The end capped Vestolen PP 7052 of benzyl chloride after, after vacuumizing dry 4h under 60 ℃ of conditions, add 20ml toluene stir the end capped Vestolen PP 7052 of benzyl chloride is fully dissolved after; Add cuprous chloride 20.1mg (0.20mmol), 1,1,4 successively; 7,10,10-hexamethyl Triethylenetetramine (TETA) 45ul (0.19mmol); 5ml (24mmol) comonomer DEVBP fully after the deoxygenation, reacts 10h in 90 ℃ under nitrogen protection.The bubbling air termination reaction, and with hexane or heptane precipitation polymers.Remove unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again through adding halohydrocarbon dissolvings such as methylene dichloride or trichloromethane repeatedly, obtain this polyolefine/phosphorous olefin block copolymers.
1H-NMR characterizes and confirms that the phosphorous alkene section molar content in this multipolymer is 13.6%.（n/m=0.157）
Figure 10 is the polyolefine-phosphorous olefin block copolymers thermogravimetic analysis (TGA) figure of this embodiment preparation.Can know that by this figure phosphorous alkene section molar content is at 13.6% o'clock, this polyolefinic thermal weight loss carbon residue amount improves significantly, can well form the charcoal layer, thereby can improve this polyolefinic flame retardant properties.
Embodiment 5,
In the 100ml there-necked flask, add 0.300g (0.018mmol) Mn=1.7 * 10
4The end capped Vestolen PP 7052 of benzyl chloride after; After vacuumizing dry 4h under 60 ℃ of conditions; Adding 20ml toluene adds cuprous bromide 27.2mg (0.191mmol), pentamethyl-diethylenetriamine 35ul (0.19mmol), 5ml (24mmol) comonomer DEVBP after stirring the end capped Vestolen PP 7052 of benzyl chloride fully being dissolved successively; Fully after the deoxygenation, under nitrogen protection, react 4h in 90 ℃.The bubbling air termination reaction, and with hexane or heptane precipitation polymers.Remove unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again through adding halohydrocarbon dissolvings such as methylene dichloride or trichloromethane repeatedly, obtain this polyolefine/phosphorous olefin block copolymers.
1H-NMR characterizes and confirms that the phosphorous alkene section molar content in this multipolymer is 1.61% (n/m=0.0162).
Embodiment 6
In the 100ml there-necked flask, add 0.300g (0.016mmol) M
n=1.9 * 10
4The end capped Vestolen PP 7052 of bromotoluene after; After vacuumizing dry 4h under 60 ℃ of conditions; Adding 20ml toluene adds cuprous bromide 27.2mg (0.19mmol), pentamethyl-diethylenetriamine 80ul (0.44mmol), 7ml (34mmol) comonomer DEVBP after stirring the end capped Vestolen PP 7052 of benzyl chloride fully being dissolved successively; Fully after the deoxygenation, under nitrogen protection, react 12h in 90 ℃.The bubbling air termination reaction, and with hexane or heptane precipitation polymers.Remove unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again through adding halohydrocarbon dissolvings such as methylene dichloride or trichloromethane repeatedly, obtain this polyolefine/phosphorous olefin block copolymers.
1H-NMR characterizes and confirms that the phosphorous alkene section molar content in this multipolymer is 2.66% (n/m=0.0284).
Embodiment 7
In the 100ml there-necked flask, add 0.300g (0.012mmol) M
n=2.5 * 10
4The end capped Vestolen PP 7052 of bromotoluene after, after vacuumizing dry 4h under 60 ℃ of conditions, add 40ml toluene stir the end capped Vestolen PP 7052 of benzyl chloride is fully dissolved after; Add cuprous bromide 40.2mg (0.283mmol), 1,1,4 successively; 7,10,10-hexamethyl Triethylenetetramine (TETA) 70ul (0.30mmol); 9ml (42mmol) comonomer DEVBP fully after the deoxygenation, reacts 18h in 80 ℃ under nitrogen protection.The bubbling air termination reaction, and with hexane or heptane precipitation polymers.Remove unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again through adding halohydrocarbon dissolvings such as methylene dichloride or trichloromethane repeatedly, obtain this polyolefine/phosphorous olefin block copolymers,
1H-NMR characterizes and confirms that the phosphorous alkene section molar content in this multipolymer is 4.23% (n/m=0.043).
Embodiment 8
In the 100ml there-necked flask, add 0.300g (0.012mmol) M
n=2.5 * 10
4The end capped Vestolen PP 7052 of bromotoluene after, after vacuumizing dry 4h under 60 ℃ of conditions, add 20ml toluene stir the end capped Vestolen PP 7052 of benzyl chloride is fully dissolved after; Add cuprous bromide 42.3mg (0.298mol), 1,1,4 successively; 7,10,10-hexamethyl Triethylenetetramine (TETA) 100ul (0.43mmol); 10ml (46mmol) comonomer DEVBP fully after the deoxygenation, reacts 10h in 90 ℃ under nitrogen protection.The bubbling air termination reaction, and with hexane or heptane precipitation polymers.Remove unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again through adding halohydrocarbon dissolvings such as methylene dichloride or trichloromethane repeatedly, obtain this polyolefine/phosphorous olefin block copolymers.
1H-NMR characterizes and confirms that the phosphorous alkene section molar content in this multipolymer is 14.70% (n/m=0.172).
Embodiment 9
In the 100ml there-necked flask, add 0.300g (0.018mmol) Mn=1.7 * 10
4The end capped Vestolen PP 7052 of benzyl chloride after, after vacuumizing dry 4h under 60 ℃ of conditions, add 20ml toluene stir the end capped Vestolen PP 7052 of benzyl chloride is fully dissolved after; Add cuprous chloride 20.1mg (0.203mmol), 1,1,4 successively; 7,10,10-hexamethyl Triethylenetetramine (TETA) 45ul (0.19mmol); 5ml (24mmol) comonomer DEMMP fully after the deoxygenation, reacts 4h in 90 ℃ under nitrogen protection.The bubbling air termination reaction, and with hexane or heptane precipitation polymers.Remove unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again through adding halohydrocarbon dissolvings such as methylene dichloride or trichloromethane repeatedly, obtain this polyolefine/phosphorous olefin block copolymers.
1H-NMR characterizes and confirms that the phosphorous alkene section molar content in this multipolymer is 1.10% (n/m=0.011).
Embodiment 10
In the 100ml there-necked flask, add 0.300g (0.016mmol) M
n=1.9 * 10
4The end capped Vestolen PP 7052 of bromotoluene after, after vacuumizing dry 4h under 60 ℃ of conditions, add 20ml toluene stir the end capped Vestolen PP 7052 of benzyl chloride is fully dissolved after; Add cuprous bromide 27.2mg (0.19mmol), 1,1,4 successively; 7,10,10-hexamethyl Triethylenetetramine (TETA) 90ul (0.39mmol); 7ml (35mmol) comonomer DEMMP fully after the deoxygenation, reacts 12h in 80 ℃ under nitrogen protection.The bubbling air termination reaction, and with hexane or heptane precipitation polymers.Remove unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again through going into halohydrocarbon dissolvings such as methylene dichloride or trichloromethane repeatedly, obtain this polyolefine/phosphorous olefin block copolymers.
1H-NMR characterizes and confirms that the phosphorous alkene section molar content in this multipolymer is 2.23% (n/m=0.0228).
Embodiment 11
In the 100ml there-necked flask, add 0.300g (0.012mmol) M
n=2.5 * 10
4The end capped Vestolen PP 7052 of bromotoluene after; After vacuumizing dry 4h under 60 ℃ of conditions; Adding 20ml toluene adds cuprous bromide 42.3mg (0.298mol), pentamethyl-diethylenetriamine 70ul (0.38mmol), 10ml (48.4mmol) comonomer DEMMP after stirring the end capped Vestolen PP 7052 of benzyl chloride fully being dissolved successively; Fully after the deoxygenation, under nitrogen protection, react 18h in 90 ℃.The bubbling air termination reaction, and with hexane or heptane precipitation polymers.Remove unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again through adding halohydrocarbon dissolvings such as methylene dichloride or trichloromethane repeatedly, obtain this polyolefine/phosphorous olefin block copolymers.
1H-NMR characterizes and confirms that the phosphorous alkene section molar content in this multipolymer is 3.94% (n/m=0.0410).
Embodiment 12
In the 100ml there-necked flask, add 0.300g (0.012mmol) M
n=2.5 * 10
4The end capped Vestolen PP 7052 of benzyl chloride after; After vacuumizing dry 4h under 60 ℃ of conditions; Adding 20ml toluene adds cuprous chloride 50.6mg (0.356mol), pentamethyl-diethylenetriamine 120ul (0.58mmol), 10ml (48.4mmol) comonomer DEMMP after stirring the end capped Vestolen PP 7052 of benzyl chloride fully being dissolved successively; Fully after the deoxygenation, under nitrogen protection, react 20h in 90 ℃.The bubbling air termination reaction, and with hexane or heptane precipitation polymers.Remove unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again through adding halohydrocarbon dissolvings such as methylene dichloride or trichloromethane repeatedly, obtain this polyolefine/phosphorous olefin block copolymers.
1H-NMR characterizes and confirms that the phosphorous alkene section molar content in this multipolymer is 10.01% (n/m=0.111).
This embodiment that Figure 12 measures for miniature calorimeter prepares the HRR figure of resulting polyolefine-phosphorous olefin block copolymers.Can know that by figure the introducing of this phosphorous alkene can reduce this polyolefinic HRR (polyacrylic maximum heat rate of release is 1020W/g) equally, thereby can improve this polyolefinic flame retardant properties.
Embodiment 13
In the 100ml there-necked flask, add 0.300g (0.018mmol) Mn=1.7 * 10
4The end capped Vestolen PP 7052 of bromotoluene after, after vacuumizing dry 4h under 60 ℃ of conditions, add 20ml toluene stir the end capped Vestolen PP 7052 of benzyl chloride is fully dissolved after; Add cuprous bromide 42.3mg (0.298mol), 1,1,4 successively; 7,10,10-hexamethyl Triethylenetetramine (TETA) 100ul (0.43mmol); 100ml (480mmol) comonomer DEVBP fully after the deoxygenation, reacts 24h in 90 ℃ under nitrogen protection.The bubbling air termination reaction, and with hexane or heptane precipitation polymers.Remove unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again through adding halohydrocarbon dissolvings such as methylene dichloride or trichloromethane repeatedly, obtain this polyolefine/phosphorous olefin block copolymers.
1H-NMR characterizes and confirms that the phosphorous alkene section molar content in this multipolymer is 96.00% (n/m=24.00)
Embodiment 14
In the 100ml there-necked flask, add 0.300g (0.018mmol) Mn=1.7 * 10
4The end capped Vestolen PP 7052 of bromotoluene after, after vacuumizing dry 4h under 60 ℃ of conditions, add 20ml toluene stir the end capped Vestolen PP 7052 of benzyl chloride is fully dissolved after; Add cuprous bromide 42.3mg (0.298mol), 1,1,4 successively; 7,10,10-hexamethyl Triethylenetetramine (TETA) 100ul (0.43mmol); 100ml (480mmol) comonomer DEVBP fully after the deoxygenation, reacts 78h in 90 ℃ under nitrogen protection.The bubbling air termination reaction, and with hexane or heptane precipitation polymers.Remove unreacted monomer, filtration, drying with hexane or heptane washing of precipitate polymkeric substance again through adding halohydrocarbon dissolvings such as methylene dichloride or trichloromethane repeatedly, obtain this polyolefine/phosphorous olefin block copolymers.
1H-NMR characterizes and confirms that the phosphorous alkene section molar content in this multipolymer is 98.01% (n/m=49.01).
Claims (10)
1. polyolefine-phosphorous olefin block copolymers, its structural formula is suc as formula shown in the I:
Among the formula I; R is selected from the alkyl of hydrogen or C1-C8, and
represents phosphorus-containing groups;
The structural formula of said phosphorus-containing groups
is suc as formula shown in the II:
Among the formula II, R
3, R
4, R
5All represent following any one group: the substituting group shown in hydrogen, C1-C8 alkyl, hydroxyl, carboxyl, nitro, amino and the formula III, and R
3, R
4, R
5In have at least one to represent the substituting group shown in the formula III; Ra is the alkyl of C1-C6, the alkoxyl group of C1-C6 or the azanyl of C1-C6 in the formula III, and Rb, Rc are the alkyl of C1-C6 or the aryl of C6-C18;
Among the formula I, R
1And R
2Identical or different, all represent hydrogen or C1-C8 alkyl;
n/m=0.001-100。
2. polyolefine-phosphorous olefin block copolymers, its structural formula is suc as formula shown in the I:
Among the formula I; R is selected from the alkyl of hydrogen or C1-C8, and
represents phosphorus-containing groups;
The structural formula of said phosphorus-containing groups
is shown in formula III:
Ra is the alkyl of C1-C6, the ester group of C1-C6, the alkoxyl group of C1-C6 or the azanyl of C1-C6 in the formula III, and Rb, Rc are the alkyl of C1-C8;
Among the formula I, R
1Represent hydrogen or C1-C8 alkyl, R
2Represent the ester group of hydrogen, C1-C8 alkyl or C1-C8;
n/m=0.001-100。
3. the method for preparing the polyolefine-phosphorous olefin block copolymers shown in the claim 1 Chinese style I; Comprise the steps: that be initiator with end group for the polyolefine of group that can cause controlled/active free radical polymerization; Monomeric polyreaction shown in the initiation formula V (a) obtains the polyolefine shown in the claim 1 Chinese style I-phosphorous olefin block copolymers;
Among the formula V (a), R
1And R
2Identical or different, all represent hydrogen or C1-C8 alkyl; R
3, R
4, R
5All represent following any one group: the substituting group shown in hydrogen, C1-C8 alkyl, hydroxyl, carboxyl, nitro, amino and the formula III, and R
3, R
4, R
5In have at least one to represent the substituting group shown in the formula III; Ra is the alkyl of C1-C6, the alkoxyl group of C1-C6 or the azanyl of C1-C6 in the formula III, and Rb, Rc are the alkyl of C1-C6 or the aryl of C6-C18.
4. the method for preparing the polyolefine-phosphorous olefin block copolymers shown in the claim 2 Chinese style I; Comprise the steps: that be initiator with end group for the polyolefine of group that can cause controlled/active free radical polymerization; Monomeric polyreaction shown in the initiation formula V (b) obtains the polyolefine shown in the claim 2 Chinese style I-phosphorous olefin block copolymers;
Among the formula V when (b), R
1Represent hydrogen or C1-C8 alkyl; R
2Represent the ester group of hydrogen, C1-C8 alkyl or C1-C8; R
6Be the substituting group shown in the formula III, wherein Ra is the alkyl of C1-C6, the ester group of C1-C6, the alkoxyl group of C1-C6 or the azanyl of C1-C6, and Rb, Rc are the alkyl of C1-C8.
5. according to claim 3 or 4 described methods, it is characterized in that: said controlled/active free radical polymerization is an ATRP; Said initiator specifically be selected from following any one:
Among the formula IV, X represents Cl or Br; Y and Z are identical or different, all represent hydrogen or C1-C6 alkyl; The definition cotype I of R, m.
6. according to each described method among the claim 3-5; It is characterized in that: said polyreaction is an atom transition free radical polymerization reaction; Catalyzer used in the said atom transition free radical polymerization reaction is a cuprous halide, comprises cuprous chloride, cuprous bromide or cuprous iodide; Ligand used in the said atom transition free radical polymerization reaction comprises 2,2 '-dipyridyl, 4,4 '-two methanoyies-2; 2 '-dipyridyl, 4,4 '-diheptyl-2,2 '-dipyridyl, pyridine imine, pentamethyl-Diethylenetriaminee (DETA), three (2-picolyl) amine, three-(2-diformazan aminoethyl) amine, three-(2-diethylaminoethyl) amine, 1; 1,4,7; 10,10-hexamethyl Triethylenetetramine (TETA).
7. according to each described method among the claim 3-6, it is characterized in that: the reaction solvent of said polyreaction is selected from following at least a: benzene, chlorobenzene, toluene, YLENE, hexane, heptane and N.
8. according to each described method among the claim 3-7, it is characterized in that: said end group is 1:0.1-1:50000 for monomeric mol ratio shown in polyolefine and the said formula V (a) or the formula V (b) of the group that can cause controlled/active free radical polymerization; Said end group is preferably 1:0.05-10 for polyolefine and the mol ratio of said catalyzer of the group that can cause controlled/active free radical polymerization are 1:0.01-1:100; The mol ratio of said ligand and said catalyzer is 1:0.1-1:50; Monomeric volume ratio is 1:0.01-1:10 shown in said reaction solvent and said formula V (a) or the formula V (b).
9. according to each described method among the claim 3-8, it is characterized in that: the temperature of reaction of said polyreaction is 20-170 ℃, preferred 80-150 ℃; Reaction times is 0.5-150 hour.
10. according to each described method among the claim 3-9, it is characterized in that: said polyreaction is carried out under oxygen free condition; Said polyreaction stops with the method for bubbling air.
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| CN109705247A (en) * | 2018-12-28 | 2019-05-03 | 中国科学技术大学 | The method that the compatibility of fire retardant polyolefin and preparation method thereof and improvement polyolefin and fire retardant enhances its anti-flammability simultaneously |
| CN113717302A (en) * | 2020-05-26 | 2021-11-30 | 中国科学院化学研究所 | Polyvinyl phosphorus antioxidant and preparation method and application thereof |
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| EP2138532A1 (en) * | 2008-06-25 | 2009-12-30 | Fujifilm Corporation | Barrier laminate, gas barrier film and device |
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| BALJINDER K. KANDOLA ET AL.: "Effect of different compatibilisers on nanoclay dispersion, thermal stability, and burning behavior of polypropylene–nanoclay blends", 《JOURNAL OF APPLIED POLYMER SCIENCE》, vol. 108, no. 2, 15 January 2008 (2008-01-15), pages 816 - 824 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109705247A (en) * | 2018-12-28 | 2019-05-03 | 中国科学技术大学 | The method that the compatibility of fire retardant polyolefin and preparation method thereof and improvement polyolefin and fire retardant enhances its anti-flammability simultaneously |
| CN109705247B (en) * | 2018-12-28 | 2020-05-12 | 中国科学技术大学 | Flame-retardant polyolefin and preparation method thereof, and method for improving compatibility of polyolefin and flame retardant and simultaneously enhancing flame retardance of polyolefin |
| CN113717302A (en) * | 2020-05-26 | 2021-11-30 | 中国科学院化学研究所 | Polyvinyl phosphorus antioxidant and preparation method and application thereof |
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