CN105017737A - Polypropylene-polyester-carbon nano tube ternary composite alloy and preparation method thereof - Google Patents
Polypropylene-polyester-carbon nano tube ternary composite alloy and preparation method thereof Download PDFInfo
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Abstract
The invention provides polypropylene-polyester-carbon nano tube ternary composite alloy and a preparation method thereof. The preparation method includes the steps that 1, an alkene monomer, dual-functional carbon nano tubes and a promoter are used for undergoing an in-situ coordination polymerization reaction, so that an intermediate product is obtained, wherein the alkene monomer comprises a propylene monomer and a mixture of the propylene monomer and ethylene and/or 1-butene; 2, the intermediate product is subjected to acid alcohol treatment, hydroxyl used for modifying a polyolefin catalyst is made to be recovered, in the existence of the catalyst system, the recovered hydroxyl is used as an initiator to trigger ring-opening polymerization of cyclic ester monomers, and accordingly the polypropylene-polyester-carbon nano tube ternary composite alloy is obtained. According to the polypropylene-polyester-carbon nano tube ternary composite alloy and the preparation method thereof, polypropylene and polycaprolactone are used for establishing strong interfacial force through the chemical attachment of the carbon nano tubes, and the polycaprolactone and the carbon nano tubes are stably dispersed in a polypropylene matrix at the same time. The polypropylene has a good mechanical property and a good thermal property, has good wettability, printing and dyeing properties and the compatibility with other polar polymers, and further has certain biocompatibility, and thus the polypropylene is turned into a high performance resin material with excellent overall performance.
Description
Technical field
The invention belongs to polymkeric substance and nano material interleaving techniques field, be specifically related to a kind of polypropylene-polyester-carbon nanometer pipe ternary composite alloy and preparation method thereof.
Background technology
Polypropylene is a kind of important resins for universal use, has the Hao ﹑ thermal characteristics Wen of ratio of performance to price Gao ﹑ mechanical property and Dings the features such as the good Jue Yuan ﹑ processing characteristics of ﹑ is excellent, is widely used in Gong Nong Ye ﹑ Yi and treats the every field such as the military and daily life of Wei Sheng ﹑.But polypropylene is non-polar polymer, in its chemical structure, lack polar functional group, in a lot of field, therefore limit its application.In order to overcome this shortcoming, it is a kind of important and efficient manner that the polar polymer introduced in polypropylene with functional group forms alloy material.Polyacrylic spinning property (Journal of Macromolecular Science can be improved as added polyethylene terephthalate (PET), Part B:Physics, 44:2, 203-216, Composites Part A:Applied Science and Manufacturing, 2008, 39 (2): 164-175), add ethylene/vinyl alcohol copolymer (EVOH), polyvinyl chloride (PVC), nylon (PA) etc. can improve polyacrylic barrier (Advances in Polymer Technology, 2001, 20 (3), 191-201.Journal ofsol-gel science and technology, 2003, 26 (1-3), 699-703.Packaging Technology and Science, 2003, 16 (4), 149-158.), add PA and PC and can improve (Polymer, 2001,42 (2) such as polyacrylic wetting property and water-absorbent, 713-725.Polymer Engineering & Science, 1997,37 (7), 1226-1237.).But polypropylene is completely incompatible with these polar polymeric thermodynamics, the alloy phase of preparation is separated serious, and cause two kinds of polymkeric substance effectively not mix, cause the mechanical property of material weak, the functional of polar polymer can not fully demonstrate.
Melt blending prepares the conventional method of polypropylene and polar polymer alloy.As Friedrich, K etc. report (Composites Science and Technology, 2005,65 (1), 107-116.Journal of MacromolecularScience, Part B:Physics, 44:2,203-216) and the patent No. be CN101665603A provide a kind of extrude PP/PET alloy by melt blending after, then drawn and thermal treatment obtain the polyacrylic method that PET in-situ micro-fibrilization strengthens.PET is distributed in polypropylene matrix with micron order threadiness, can obtain the polypropylene alloy of intensity and toughness raising.(Polymer, 2001 such as Tseng, F, 42 (2), 713-725.) and the patent No. be that (CN103275482A, CN102286200B, CN102329456A) etc. reports to utilize and extrude or the method for injection moulding PP/PA blend alloy.According to different compositions, obtain PA with the Granular composite of micron order yardstick at polypropylene matrix or the alloy material forming two-arch tunnel, its wetting property and water-absorbent are improved.Yeo, J. (Advances in PolymerTechnology is waited, 2001,20 (3), 191-201. and the patent No. are CN102660076A, CN101633761B) EVOH with excellent gas barrier property and organic solvent resistance is blended in a mouthful mould place with polypropylene fusion forms stratiform melt, then drawn superposes cooling and shaping formation alternate multiple matrix material, oil field tubing can be widely used in, can the container etc. of filling solvent based coating.Utilize polypropylene alloy prepared by the method for above melt blending, thermodynamic (al) incompatible owing to existing between nonpolar polypropylene and the polymkeric substance of polarity, cause the intermolecular forces of two-phase little, even if add the consistency between raising two-phase that certain compatilizer also can only be limited.Particularly in high temperature working processes, because phase morphology is unstable, phase-splitting is serious, finally causes the specified property of polar polymer to be effectively delivered in polypropylene matrix.
The research of Polypropylene/Carbon Nanotube Composites is in the ascendant in recent years.Carbon nanotube is as a kind of quasi-one-dimensional nanometer material, there is the features such as the low close degree ﹑ high length-diameter ratio of suction attached property energy ﹑ of the superpower power energy ﹑ excellence of peculiar electricity performance ﹑, since Ijima report finds carbon nanotube (CNTs), carbon nanotube just starts the preparation (Nature being applied to polymer matrix composite, 1991,354:56 ~ 61).
Aliphatic polyester (being mainly poly-epsilon-caprolactone) is the polar macromolecule material of a class uniqueness, there is hypertonicity, good biocompatibility, nontoxic and biodegradable, and can be well compatible with a lot of commercial polymerization thing, such as PET, PVC, PVCl, SAN etc.
So far, containing carbon nanotube, polycaprolactone, the preparation method of polyacrylic tri compound alloy is mainly obtained by melt blending.The object preparing this ternary blends is the electroconductibility of the excellence utilizing carbon nanotube, it can be used as conductive filler material to add in the system of inconsistent two polymer blendings and prepares conducing composite material.In the blend polymer of this two-phase, its electrical property depends on phase morphology and the distribution of carbon nanotube in system of blend microcosmic.If the patent No. is that CN103113732A provides a kind of method preparing conductive polymer composite.
, (MRS Proceedings, the Cambridge Univ Press:2008 such as P; Pp1143-KK05-14.MRSProceedings, Cambridge Univ Press:2012; Pp mrsf11-1410-dd05-04.Advances in Scienceand Technology, 2013,80,65-70) report in polypropylene/polycaprolactone/carbon nanometer pipe ternary blend, carbon nanotube is only distributed in polycaprolactone phase, because conductive filler material specific in incompatible two-phase polymer " two ooze threshold " is theoretical, can draw and add carbon nanotube relative in straight polymer, its percolation threshold is lower, thus can change conductive polymer composite under less filler content.Utilize the electroconductibility of this ternary alloy and carbon nanotube to the feature of outside stimulus sensitivity and then to the change detection of outside atmosphere, liquid sensing can be applied to, the fields such as temperature sensing.But this ternary blends is because between polymkeric substance and carbon nanotube and between polypropylene and polycaprolactone, interfacial energy is widely different in itself, incompatible on thermodynamics, cohesive force is very low each other, in the process of processing, carbon nanotube moves and assembles, two polymer phase flowings make the unstable phase domain of phase increase, destroy Percolation network structure, materials conductive performance is declined.In addition, the polypropylene/polycaprolactone/research of carbon nanometer pipe ternary blend to other performances have not been reported, and there is not yet the report chemically preparing polypropylene-polyester-carbon nanometer pipe ternary composite alloy.
Summary of the invention
The object of this invention is to provide a kind of polypropylene
-polyester
-the preparation method of carbon nanometer pipe ternary composite alloy.
The method preparing polypropylene-polyester-carbon nanometer pipe ternary composite alloy provided by the present invention, comprises the steps:
1) olefinic monomer, difunctional carbon nano tube, promotor are carried out in-situ coordination reaction, obtain intermediate product;
Wherein, described olefinic monomer is: 1) propylene monomer, 2) mixture of propylene monomer and ethene and/or 1-butylene; The mol ratio of described ethene and/or 1-butylene and propylene monomer is 1.0-70.0:30.0 ~ 99.0;
Described difunctional carbon nano tube prepares by the following method: the group first part of hydroxyl in hydroxylated carbon nanotube being converted into carbon-carbon double bonds, obtains double-bond functionalized carbon nanotube carrier; And then by polyolefin catalyst on remaining hydroxyl modified in described double-bond functionalized carbon nanotube carrier, obtain described difunctional carbon nano tube;
Described polyolefin catalyst comprises transistion metal compound and metallic compound; Wherein, described transistion metal compound is selected from least one in Ziegler-Natta catalyst and metallocene catalyst; Described metallic compound is selected from least one in magnesium-containing compound and aluminum contained compound;
2) by step 1) described intermediate product carries out acid alcohol process, the hydroxyl of polyolefin catalyst in described modification is restored, in the presence of a catalyst system, with the ring-opening polymerization of the hydroxyl restored for initiator initiation ring-type esters monomer, obtain described polypropylene-polyester-carbon nanometer pipe ternary composite alloy.
Wherein, aforesaid method step 1) in, described in-situ coordination reaction specifically can be slurry polymerization or bulk polymerization.
Described slurry polymerization carries out in organic solvent, and described organic solvent is selected from following at least one: the alkane of C5 ~ C10 or the aromatic hydrocarbon of C6-C8, be specially heptane, hexane or toluene.
The temperature of reaction of described slurry polymerization and bulk polymerization is 30 DEG C ~ 90 DEG C, preferably 40 DEG C ~ 80 DEG C, be more specifically 70 DEG C, the time is 0.05 ~ 10.0 hour, preferably 0.1 ~ 2.0 hour is more specifically 0.2 hour or 0.5 hour or 0.2-0.5 hour; Pressure is 0-4MPa (described pressure is not 0), and being specially 0.5-3.5MPa, is more specifically 0.5MPa or 1.0MPa or 0.5-1.0MPa.
When described in-situ coordination reaction is for slurry polymerization, step 1) also comprise the step adding acid alcohol solution termination reaction in the reaction system of described slurry polymerization.The volume ratio consisting of hydrochloric acid and ethanol of described acid alcohol solution is 1:10.
Aforesaid method step 1) in, the particle diameter of described hydroxylated carbon nanotube is 20-40nm, is specially 25nm, and length is 0.5-50 μm, and be specially 0.5 μm or 5 μm or 0.5-5 μm, length-to-diameter ratio is 25-1000, is specially 100 or 250 or 25-250.In described hydroxylated carbon nanotube, the adsorbed hydroxyl content is 3.06wt%.
Described double-bond functionalized carbon nanotube carrier prepares by the following method: by described hydroxylated carbon nanotube dispersed in reaction medium, add solid phosgene and carry out priming reaction after 4 ~ 24 hours in 30 ~ 50 DEG C, described reaction medium is removed, adds C
nh
2n-2o
2shown olefin(e) acid or C
nh
2nunreacted olefin(e) acid or enol, in 30 ~ 50 DEG C of reactions 4 ~ 24 hours, are removed, are used methanol wash product, obtain described double-bond functionalized carbon nanotube carrier by enol shown in O afterwards.
Wherein, described reaction medium is selected from following at least one: hexane, heptane, ether and butyl ether; The mass ratio of described carbon nanotube and reaction medium is 0.01 ~ 0.5:1; The mass ratio of described carbon nanotube and solid phosgene is 0.01 ~ 0.5:1; Described C
nh
2n-2o
2and C
nh
2nin O, n>=3, are specifically selected from the integer of 3-20; The mass ratio of described carbon nanotube and described olefin(e) acid or enol is 0.01 ~ 0.5:1; Generate carbon-carbon double bond consume that carbon nano tube surface hydroxyl accounts for the whole hydroxyl of carbon nanotube 20 ~ 70%.
Aforesaid method step 1) in, described Ziegler-Natta catalyst titanium tetrahalide used is TiCl
4, TiBr
4or TiI
4; Titan-alkoxide used is Ti (OEt) Cl
3, Ti (OEt)
2cl
2, Ti (OEt)
3cl, Ti (OEt)
4or Ti (OBu)
4;
The general structure of described metallocene catalyst is such as formula shown in I:
(Cp
I-B
e-Cp
II)MR
1 aR
2 b
(formula I)
In described formula I, M is selected from least one in Ti, Zr, Hf, V, Fe, Y, Sc and lanthanide series metal; Described Cp
iand Cp
iIrepresent cyclopentadienyl or contain substituent cyclopentadienyl, described containing in substituent cyclopentadienyl, substituting group is C
1~ C
6alkyl, C
3~ C
18cycloalkyl or C
6~ C
18aromatic base; Described R
1and R
2for aryl, C that H, halogen atom, the carbonatoms alkyl that is 1 ~ 8, the carbonatoms alkoxyl group that is 1 ~ 8, carbonatoms are 6 ~ 20
1~ C
15acyloxy, allyl group or C that the aryl that the carbonatoms that alkyl replaces is 6 ~ 20, carbonatoms are 1 ~ 8
1~ C
15silylation; Described B represents alkyl bridge or silylation bridge, preferably-C (R
3r
4)-or-Si (R
3r
4)-; R
3and R
4for H, carbonatoms be 1 ~ 4 alkyl or carbonatoms be the aryl of 6 ~ 10;
ebe 1,2 or 3;
abe 0,1 or 2 with b, wherein
a+ b=2;
Described metallocene catalyst is specially C
2h
4(Ind)
2zrCl
2, C
2h
4(H
4ind)
2zrCl
2, Me
2si (Ind)
2zrCl
2, Me
2si (2-Me-4-Ph-Ind)
2zrCl
2, Me
2si (Me
4cp)
2zrCl
2, Me
2si (Flu)
2zrCl
2, Me
2si (2-Me-4-Naph-Ind)
2zrCl
2or Ph
2si (Ind)
2zrCl
2, wherein, Me is methyl, and Ph is phenyl, and Cp is cyclopentadienyl, and Ind is indenyl, H
4ind is 4,5,6,7-tetrahydro-indenes, and Flu is fluorenyl, and Naph is naphthyl;
Described metallic compound is magnesium-containing compound and/or aluminum contained compound; Described magnesium-containing compound is molecular formula is MgX
2magnesium halide or general structure be the Grignard reagent of RMgX; Described MgX
2in, X is fluorine, chlorine, bromine or iodine element, and preferred X is chlorine; In described RMgX, the alkyl of R to be carbonatoms be 1-10, preferable methyl, ethyl, propyl group, sec.-propyl, butyl or isobutyl-, X is fluorine, chlorine, bromine or iodine; Described aluminum contained compound is Al (OR ')
nr
3-n, 0≤n≤3, R and R ' carbonatoms is the alkyl of 2 ~ 10, preferred trimethyl aluminium, triethyl aluminum, triisobutyl aluminium or methylaluminoxane.
Aforesaid method step 1) in, described polyolefin catalyst also can comprise auxiliary agent; Described auxiliary agent is internal electron donor compound, is selected from diether and/or carbonate, is specially diisobutyl phthalate, fluorenes diether, methyl benzoate or dibutyl phthalate.
The mass percentage of carbon nanotube carrier double-bond functionalized in described difunctional carbon nano tube is 70.0 ~ 99.0%, is specially 75.0-95.0%.
Summation shared mass percentage in described difunctional carbon nano tube of the transition metal in the metallic element in described metallic compound and described transistion metal compound is 1.0 ~ 30.0%, is specially 1.0-25.0%;
When described metallic compound is magnesium-containing compound, the mass percentage of the transition metal in described transistion metal compound in described difunctional carbon nano tube is 0.5 ~ 5.0%, is specially 0.5-4.0%;
When described metallic compound is aluminum contained compound, the mass percentage of the transition metal in described transistion metal compound in described difunctional carbon nano tube is 0.05 ~ 2.0%, is specially 0.1-2.0%;
Described metallic compound be magnesium-containing compound and aluminum contained compound time, the mass percentage of the transition metal in described transistion metal compound in described difunctional carbon nano tube is 0.55-7.0%, is specially 0.55-5.0%.
The mass percentage of described internal electron donor in described difunctional carbon nano tube is 2.50-15.0%.
Be that the preparation method of the polyolefin catalyst being carrier is prepared according to application number by the method for polyolefin catalyst on remaining hydroxyl modified in described double-bond functionalized carbon nanotube carrier in the present invention with nanotube in the Chinese patent of 201110095036.9.
Concrete grammar is as follows:
When described metallic compound is described magnesium-containing compound, the preparation method of described difunctional carbon nano tube, comprises the steps:
1) described double-bond functionalized carbon nanotube carrier and described magnesium-containing compound are reacted in organic solvent, obtain the magnesium mixture of double-bond functionalized carbon nanotube carrier;
2) by described titanium tetrahalide or titan-alkoxide and described step 1) isothermal reaction after 0.5 ~ 2.0 hour at-20 DEG C of the magnesium mixture of the double-bond functionalized carbon nanotube carrier of gained, be warming up to 120 DEG C of isothermal reactions 1.0 ~ 4.0 hours, obtain the difunctional carbon nano tube that described metallic compound is described magnesium-containing compound.
When described metallic compound is described aluminum contained compound, the preparation method of described difunctional carbon nano tube, comprises the steps:
1) described double-bond functionalized carbon nanotube carrier and described aluminum contained compound are reacted in varsol, obtain the double-bond functionalized carbon nanotube carrier activated;
2) described transistion metal compound and described aluminum contained compound are reacted in described varsol, obtain the catalyst solution activated;
3) by described step 2) catalyst solution of gained activation and described step 1) the double-bond functionalized carbon nanotube carrier that activates of gained reacts, and obtains the difunctional carbon nano tube that described metallic compound is described aluminum contained compound.
When described metallic compound be described magnesium-containing compound and described aluminum contained compound time, the preparation method of described difunctional carbon nano tube, comprises the steps:
1) described double-bond functionalized carbon nanotube carrier and described magnesium-containing compound are reacted in organic solvent, obtain the magnesium mixture of double-bond functionalized carbon nanotube carrier;
2) by described titanium tetrahalide or titan-alkoxide and described step 1) isothermal reaction after 0.5 ~ 2.0 hour at-20 DEG C of the magnesium mixture of the double-bond functionalized carbon nanotube carrier of gained, be warming up to 120 DEG C of isothermal reactions 1.0 ~ 4.0 hours, obtain the magnesium mixture supported titanium compound that described metallic compound is the double-bond functionalized carbon nanotube carrier of described magnesium-containing compound;
3) by step 2) metallic compound described in gained is that the magnesium mixture supported titanium compound of the double-bond functionalized carbon nanotube carrier of magnesium-containing compound and described aluminum contained compound react in varsol, obtains the magnesium mixture supported titanium compound of the double-bond functionalized carbon nanotube carrier activated;
4) described transistion metal compound and described aluminum contained compound are reacted in varsol, obtain the catalyst solution activated;
5) by described step 3) the magnesium mixture supported titanium compound of double-bond functionalized carbon nanotube carrier of gained activation and described step 4) catalyst solution that activates of gained reacts, and obtains the difunctional carbon nano tube that described metallic compound is described magnesium-containing compound and described aluminum contained compound.
Described promotor is selected from following at least one: the aluminum alkyls of C1-C4 and the alkoxy aluminum compound of C1-C4, be specially trimethyl aluminium, triethyl aluminum, triisobutyl aluminium or methylaluminoxane.
Aluminium in described promotor and the mol ratio between transition metal are 50-5000:1, are preferably 50-2000:1, specifically can be 120:1.More specifically described promotor is triethyl aluminum and methylaluminoxane, and the metal in described transistion metal compound is titanium and zirconium, and in the aluminium element in triethyl aluminum and catalyzer, between transition metal titanium, mol ratio is 50:1; In described catalyzer, in methylaluminoxane, in aluminium content and catalyzer, the mol ratio of transition metal zirconium is 2000:1.
The add-on of described difunctional carbon nano tube is the 0.1-5.0% of olefinic monomer quality, is specially 0.1-0.4%, is more specifically 0.34% or 1.21% or 0.22% or 0.34%-1.25% or 0.4%-1.25% or 0.34%-0.4%.
In above-mentioned ring-opening polymerization, described ring-type esters monomer is selected from following at least one: caprolactone, glycollide, rac-Lactide or to dioxy ring ethyl ketone, preferred caprolactone.
Described ring-opening polymerization catalyst system used is mainly metal catalyst system, and described metal catalyst system is selected from following at least one: stannous octoate [Sn (Oct)
2], triethyl aluminum [Al (Et)
3] and the derivative of titanium (Ti), zirconium (Zr), cadmium (Cd) and mercury (Hg), the sub-tin of preferably octanoic acid.
Described ring-opening polymerization is solution polymerization, described solution polymerization carries out in organic solvent, described organic solvent is selected from following at least one: aromatic hydrocarbons and halogenated alkane, wherein aromatic hydrocarbons is selected from benzene, toluene, ethylbenzene, dimethylbenzene or chlorobenzene, preferred toluene, dimethylbenzene or the mixture of the two; Halogenated alkane is selected from the C of halogen substiuted
5-C
10alkane.
The temperature of reaction of described ring-opening polymerization is 100 DEG C ~ 170 DEG C, and the reaction times is 1 ~ 48 hour, preferably 4 ~ 24 hours.
Described ring-type esters monomer volumetric molar concentration is in organic solvent 1-10mol/L, and the mass ratio of the intermediate product after described ring-type esters monomer and acid alcohol process is 5 ~ 250, preferably 5 ~ 100.Used catalyst is stannous octoate, described catalyzer and ring-type esters monomer mol ratio be 0.001 ~ 0.1, being preferably 0.003 ~ 0.05, is more specifically 0.01.
The preparation method of above-mentioned polypropylene-polyester-carbon nanometer pipe ternary composite alloy is also included in and carries out described step 1) in-situ coordination reaction before, in reaction system, add the step of electron donor, the general structure of described electron donor is R4-nSi (OR ') n.
Described R
4-nsi (OR ')
nin, n is the integer of 1-3, and R and R ' is all selected from following at least one: the aryl of the alkyl of C1-C8, the cycloalkyl of C5-C10 or C6-C10, is specially diphenyldimethyl silane, dicyclohexyl dimethylsilane or phenyl-trimethylsilicane.
In described electron donor and described promotor, the mol ratio of aluminium element is 0.01 ~ 1.0:1, is specially 0.1-1.0:1.
The preparation method of above-mentioned polypropylene-polyester-carbon nanometer pipe ternary composite alloy is included in further and carries out described step 1) in-situ coordination reaction before, in reaction system, pass into hydrogen; Wherein, the add-on of hydrogen is the 0.001%-0.5% of olefinic monomer quality, is specially 0.005-0.08%, is more specifically 0.067% or 0.08% or 0.067%-0.08%.
The polypropylene-polyester that aforesaid method prepares-carbon nanometer pipe ternary composite alloy also belongs to the scope that the present invention protects.
Described polypropylene-polyester-carbon nanometer pipe ternary composite alloy comprises PP matrix and carbon nanotube and polyester dispersion phase.
Described PP matrix is selected from the random copolymer resin of homo-polypropylene and propylene and ethene or 1-butylene.
Described homo-polypropylene is selected from following at least one: isotatic polypropylene, syndiotactic polypropylene and Atactic Polypropelene.
In the random copolymer resin of described propylene and ethene or 1-butylene, the proportioning of propylene and ethene and/or 1-butylene is 30.0 ~ 99.0:1.0 ~ 70.0.
Described polyester is aliphatic polyester, and described aliphatic polyester is selected from the homopolymer or multipolymer that are formed by following at least one monomer: caprolactone, glycollide, rac-Lactide and to dioxy ring ethyl ketone; Preferred polycaprolactone.
The particle diameter of described carbon nanotube is 20-40nm, is specially 25nm, and length is 0.5-50 μm, and be specially 0.5 μm or 5 μm or 0.5-5 μm, length-to-diameter ratio is 25-1000, is specially 100 or 250 or 25-250.
In described polypropylene-polyester-carbon nanometer pipe ternary composite alloy, the mass percentage of described PP matrix is 0.5-98%, preferred 8.0-90.0%, specifically can be 88.9% or 69.2% or 54.8% or 29.1% or 12.5% or 18.6% or 61.0% or 16.4% or 89.3% or 78.0% or 56.6% or 25.7% or 8.2%; The mass percentage of described aliphatic polyester is 0.5-98%, preferred 8.0-90.0%, specifically can be 9.5% or 27.5% or 43.2% or 66.7% or 86.2% or 80.1% or 37.5% or 80.2% or 8.5% or 20.8% or 42.2% or 72.3 or 89.2%; Described carbon nanotube mass percentage composition is 0.2-4.5%, preferred 1.2%-4.2%, specifically can be 1.6% or 2.0% or 4.2% or 1.3% or 1.5% or 3.4% or 1.2% or 2.6%.
Described carbon nanotube exists with the form of single dispersion in described polypropylene-polyester-carbon nanometer pipe ternary composite alloy.
The present invention prepares a kind of polypropylene-polyester-carbon nanometer pipe ternary composite alloy by chemical process, polypropylene and polycaprolactone are passed through the chemical connection establishment strong interface reactive force of carbon nanotube, and make polycaprolactone and carbon nanotube simultaneously and stable dispersion in polypropylene matrix, form novel tertiary composite alloy, by making polypropylene, there is excellent mechanical property, thermal characteristics and good wetting property, printing and dyeing property and the consistency with other polar polymer simultaneously, with certain biocompatibility, become the performance resins material of excellent combination property.
Accompanying drawing explanation
Fig. 1 is the nuclear magnetic spectrogram of the polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy in embodiment 3; In figure, a, b are CH in polycaprolactone
2o and CH
2the corresponding chemical shift of C=O methylene; C is the chemical shift with correspondence in the methylene radical in polycaprolactone in polypropylene; D, e are respectively chemical shift corresponding to methyne and methyl in polypropylene.
Fig. 2 is the infrared spectrum of the polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy of preparation in embodiment 3.
Fig. 3 is the thermogravimetric analysis spectrogram of the polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy of preparation in embodiment 3.
Fig. 4 is the DSC scanning curve (temperature rise rate 10 DEG C/min) of the polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy of preparation in embodiment 3.
Fig. 5 is the atomic force microscope figure of the polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy of preparation in embodiment 3; Wherein, figure a represents the atomic force microscope figure of the first step in-situ polymerization polypropylene/carbon nanotube binary composite, and figure b represents the atomic force microscope figure of the ternary alloy obtained after second step g-polycaprolactone.
Fig. 6 is the transmission electron microscope picture of the polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy of preparation in embodiment 3; Wherein, figure a represents the lens Electronic Speculum figure of the ternary-alloy material of preparation after xylene soluble after a film, figure b represents the transmission electron microscope picture observed after perosmic anhydride dyeing after ternary-alloy material drips film, and figure c represents the transmission electron microscope picture of ternary-alloy material sections observation after epoxy resin embedding.
Fig. 7 is the phase morphology of polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy and the ternary alloy phase morphology comparison diagram prepared by scorification with embodiment 1 same composition of preparation in embodiment 1,2,3.Figure a, b represent embodiment 1 and contrast sample respectively, and c, d represent embodiment 2 and embodiment 3 respectively.
Fig. 8 is the phase morphology contrast of face after tetrahydrofuran (THF) etching and after KOH hydrolysis absolutely of quenching of the polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy of preparation in embodiment 3; Figure a represents that ternary alloy etches the cross-section morphology after 24 hours in tetrahydrofuran (THF), and figure b represents that ternary alloy is at the cross-section morphology of highly basic hydrolysis after 24h hour.
Fig. 9 is the evolution process of polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy phase in 200 DEG C of heat treatment processes of preparation in embodiment 3.
Figure 10 is the polypropylene-crystal habit of polycaprolactone-carbon nanotube after secondary isothermal crystallization of preparation in embodiment 3.
Embodiment
Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto.
The experimental technique used in following embodiment if no special instructions, is ordinary method; Reagent used in following embodiment, biomaterial etc., if no special instructions, all can obtain from commercial channels.
In following embodiment, the content of titanium elements and zr element all records by ultraviolet spectrophotometry, and the content of magnesium elements and aluminium element all records by volumetry.
Hydroxylated carbon nanotube used in following embodiment is purchased from the organic institute in Chinese Academy of Sciences Chengdu, and its adsorbed hydroxyl content is 3.06wt%.
Double-bond functionalized carbon nanotube used prepares by the following method:
Be scattered in by hydroxylated carbon nanotube 5g in 150mL heptane (reaction medium), the mass ratio of described hydroxylated carbon nanotube and heptane is 0.05:1; Add solid phosgene in 30 DEG C of activation 24 hours, the mass ratio of described hydroxylated carbon nanotube and solid phosgene is 0.1:1, afterwards reaction medium vacuum pump is drained, add undecylenic acid 30 DEG C reaction 24 hours, the mass ratio of described hydroxylated carbon nanotube and undecylenic acid is 0.1:1, afterwards unreacted undecylenic acid vacuum pump is drained, methanol wash 5 times, obtain described double-bond functionalized carbon nanotube 4.5g.Wherein, generate carbon-carbon double bond consume the 23.2wt% that carbon nano tube surface hydroxyl accounts for whole hydroxyl.
Difunctional carbon nano tube used prepares according to the method comprised the steps:
1) by 2.0g Magnesium Chloride Anhydrous MgCl
2be scattered in 20ml decane with 6.0ml isooctyl alcohol, be heated to 110 DEG C, form clear solution, react 4.0 hours at 110 DEG C, obtain magnesium chloride alcohol adduct 1.9g.
Above-mentioned magnesium chloride alcohol adduct is added dropwise in the suspension of carbon nanotube double-bond functionalized described in 2.0g/100ml decane, isothermal reaction 12.0 hours at 90 DEG C, then filtering liquid, the solid decane leached washs 3 times, obtains the magnesium mixture 1.8g of double-bond functionalized carbon nanotube carrier after drying.
2) in the 100ml titanium tetrachloride solution of-20 DEG C, add the magnesium mixture of the above-mentioned double-bond functionalized carbon nanotube carrier of 10.0g, and isothermal reaction 1.0 hours at-20 DEG C.Slowly be warming up to 60 DEG C, add 2.0ml diisobutyl phthalate, then isothermal reaction 2.0 hours at 110 DEG C, has reacted rear filtering liquid, has again added 100ml titanium tetrachloride solution, isothermal reaction 2.0 hours at 120 DEG C.Finally, with hexanes wash 3 ~ 6 times, the magnesium mixture supported titanium compound 8.8g of double-bond functionalized carbon nanotube carrier after drying, is obtained.
3) the magnesium mixture supported titanium compound getting the above-mentioned double-bond functionalized carbon nanotube carrier of 5.0g is scattered in 50ml toluene, then the toluene solution 30ml containing 0.1mol methylaluminoxane is added, react 4.0 hours at 90 DEG C, then use toluene wash 5 times, after drying, obtain the magnesium mixture supported titanium compound of the double-bond functionalized carbon nanotube carrier activated.
4) by 0.10g transistion metal compound Et (Ind)
2zrCl
2be added in the toluene solution 40ml containing 0.10mol methylaluminoxane, react 4.0 hours at 20 DEG C, obtain the catalyst solution activated.
5) above-mentioned catalyst solution is added dropwise to containing step 3 described in 5.0g) prepare in the 50ml toluene suspension of the magnesium mixture supported titanium compound of the double-bond functionalized carbon nanotube carrier of gained activation, react 4.0 hours at 90 DEG C.After having reacted, by toluene wash 5 times, after drying, obtain described difunctional carbon nano tube 4.8g.
In above-mentioned difunctional carbon nano tube, titanium elements, magnesium elements, the content of zr element and aluminium element is respectively 1.81wt%, 3.34wt%, 0.135wt% and 8.55%, the mass percentage 9.55% of diisobutyl phthalate.
Embodiment 1
1) 300g propylene liquid is added in reactor, adds 0.019mol triethyl aluminum and 0.029mol methylaluminoxane at 30 DEG C successively as promotor and the difunctional carbon nano tube (MgCl of 1.0g
2/ BMMF/TiCl
4catalyst system) (in described promotor, in the aluminium element in triethyl aluminum and catalyzer, between transition metal titanium, mol ratio is 50:1; In described promotor, in methylaluminoxane, in aluminium content and catalyzer, the mol ratio of transition metal zirconium is 2000:1, aluminium in described promotor and the mol ratio between transition metal (titanium+zirconium) they are 120:1) and pass into hydrogen 0.2g, pressure is 3.0MPa, be warming up to 70 DEG C, react 0.5 hour, obtain intermediate product polymkeric substance 90.0g.Acid alcohol (20% hydrochloric acid) (the volume ratio 1:5 of hydrochloric acid and ethanol) is used by the intermediate product obtained (Polypropylene/Carbon Nanotube Composites) to process.Product uses ethanol and deionized water wash respectively, then vacuum-drying 24h at 60 DEG C, obtains the intermediate product 88.0g after acid alcohol process.
2) by above-mentioned steps 1) intermediate product 1g after the process of gained acid alcohol and 30ml toluene adds in the flask of the 100ml drying that magneton is housed, the dry 4h of pump drainage in the oil bath of 50 DEG C.Be warming up to 130 DEG C, after stirring 4h, add the stannous octoate of 0.1ml at 130 DEG C, the caprolactone monomer of 10ml starts reaction, continues stirring reaction 24h.Product is washed several times with excessive tetrahydrofuran (THF) and uses the tetrafluoroethylene membrane filtration of Φ 0.22 μm, until topple over ice methyl alcohol no longer occur precipitation in filtrate, then distilled water and washing with alcohol is used again successively, filter, 40 DEG C are dried to constant weight, finally obtain polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy 0.8g.
This polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy is made up of carbon nanotube, homo-polypropylene resin and homopolymerization polycaprolactone; Show that the mass ratio of carbon nanotube, polypropylene, polycaprolactone is 1.6:88.9:9.5 by thermogravimetric analysis.
Embodiment 2
Intermediate product 1g after the acid alcohol process obtained in embodiment 1 and 10ml toluene are added in the flask of the 100ml drying that magneton is housed, the dry 4h of pump drainage in the oil bath of 50 DEG C.Be warming up to 80 DEG C, at 80 DEG C, stir 4h.Be warming up to 130 DEG C, add the stannous octoate of 0.03ml, the caprolactone monomer of 30ml starts reaction, continues stirring reaction 24h.Product is washed 4 times with excessive tetrahydrofuran (THF) and uses the tetrafluoroethylene membrane filtration of Φ 0.22 μm, until topple over ice methyl alcohol no longer occur precipitation in filtrate, then distilled water and washing with alcohol is used again successively, filter, 40 DEG C are dried to constant weight, finally obtain polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy 1.2g.
Described polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy is made up of carbon nanotube, homo-polypropylene resin and homopolymerization polycaprolactone; Show that the mass ratio of carbon nanotube, polypropylene, polycaprolactone is 2.0:70.5:27.5 by thermogravimetric analysis.
Embodiment 3
Intermediate product 1g after the acid alcohol process obtained in embodiment 1 and 10ml toluene are added in the flask of the 250ml drying that magneton is housed, the dry 4h of pump drainage in the oil bath of 50 DEG C.Be warming up to 80 DEG C, at 80 DEG C, stir 4h.Be warming up to 130 DEG C, add the stannous octoate of 1.0ml, the caprolactone monomer of 100ml starts reaction, continues stirring reaction 24h.Product is washed 4 times with excessive tetrahydrofuran (THF) and uses the tetrafluoroethylene membrane filtration of Φ 0.22 μm, until topple over ice methyl alcohol no longer occur precipitation in filtrate, then distilled water and washing with alcohol is used again successively, filter, 40 DEG C are dried to constant weight, finally obtain polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy 1.3g.
Described polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy is made up of carbon nanotube, homo-polypropylene resin and homopolymerization polycaprolactone; Show that the mass ratio of carbon nanotube, polypropylene, polycaprolactone is 2.0:54.8:43.2 by thermogravimetric analysis.
The nuclear magnetic spectrogram of the polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy of Fig. 1 prepared by the present embodiment.
The infrared spectrum characterization of the polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy of Fig. 2 prepared by the present embodiment.
From Fig. 1 and Fig. 2, successfully prepare polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy by present method.
The thermogravimetric analysis spectrogram of the polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy of Fig. 3 prepared by the present embodiment.
As shown in Figure 3, there is the platform obviously can distinguishing two kinds of different polymeric constituents in Fig. 3, the composition of described ternary alloy can be drawn thus.
The DSC scanning curve (temperature rise rate 10 DEG C/min) of the polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy of Fig. 4 prepared by the present embodiment.
As shown in Figure 4, the analysis and observation of material thermal characteristics be correspond to respectively to the melt temperature of different polymeric constituent to two peaks.
The atomic force microscope figure of the polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy of Fig. 5 prepared by the present embodiment.
The transmission electron microscope picture of the polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy of Fig. 6 prepared by the present embodiment.
The form of heterophase polymerization nitride layer enveloped carbon nanometer tube can be observed and carbon nanotube is uniformly dispersed with single form in multiphase polymer matrix by Fig. 5 and Fig. 6.
Fig. 7 is the phase morphology of the polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy of preparation in embodiment 1,2,3 and the phase morphology comparison diagram of the ternary alloy (product prepared by comparative example) prepared by scorification that forms with embodiment 1 same polymer.
As shown in Figure 7, by the contrast experiment with same composition melt blending, can observe two kinds of inconsistent two kinds of polymkeric substance through in-situ polymerization is connected with carbon nanotube chemical key, and phase interface effect power is significantly improved, and disperse phase is dispersed with nanoscale.
The phase morphology contrast of face after tetrahydrofuran (THF) etching and after KOH hydrolysis absolutely of quenching of the polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy of Fig. 8 prepared by the present embodiment.
As shown in Figure 8, quench in liquid nitrogen after the multiphase polymer alloy molten hot pressing of preparation disconnected, more only observe swelling after tetrahydrofuran (THF) etching, illustrate that polycaprolactone and carbon nanotube establish strong bonding effect (Fig. 8 (a)); And after strong lye solution polycaprolactone, the hole stayed is former polycaprolactone disperse phase, can observe its size is 50 ~ 100nm, and dispersed (Fig. 8 (b)).
The evolution process of Fig. 9 polypropylene-polycaprolactone prepared by the present embodiment-carbon nanometer pipe ternary alloy phase in 200 DEG C of heat treatment processes.
As shown in Figure 9, the ternary alloy of preparation is heat-treated and observed its form (5min, 10min, 30min and 60min) over time by phase microscope, in whole observing time process, because significantly improving of phase interface interaction force makes phase morphology keep stable, do not appear at flowing and the fusion of the phase often caused because phase interface effect power is weak in heat treatment process.
Figure 10 polypropylene prepared by the present embodiment-crystal habit of polycaprolactone-carbon nanotube after secondary isothermal crystallization.
As shown in Figure 10, for prepared crystallization-crystallization multiphase polymer, through secondary isothermal crystallization, obtain polycaprolactone crystal grain homodisperse form on acrylic sphere Jingjing sheet.
Embodiment 4
The mixed solvent of the intermediate product 1g after the acid alcohol process obtained in embodiment 1 and 2ml toluene and 8ml dimethylbenzene is added in the flask of the 100ml drying that magneton is housed, the dry 4h of pump drainage in the oil bath of 50 DEG C.Be warming up to 80 DEG C, at 80 DEG C, stir 4h.Be warming up to 130 DEG C, add the stannous octoate of 0.3ml, the caprolactone monomer of 30ml starts reaction, continues stirring reaction 24h.Product is washed 4 times with excessive tetrahydrofuran (THF) and uses the tetrafluoroethylene membrane filtration of Φ 0.22 μm, until topple over ice methyl alcohol no longer occur precipitation in filtrate, then distilled water and washing with alcohol is used again successively, filter, 40 DEG C are dried to constant weight, finally obtain polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy 1.1g.
This polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy is made up of carbon nanotube, homo-polypropylene resin and homopolymerization polycaprolactone; Show that the mass ratio of carbon nanotube, polypropylene, polycaprolactone is 4.2:29.1:66.7 by thermogravimetric analysis.
Embodiment 5
Intermediate product 1g after the acid alcohol process obtained in embodiment 1 and 10ml dimethylbenzene are added in the flask of the 250ml drying that magneton is housed, the dry 4h of pump drainage in the oil bath of 50 DEG C.Be warming up to 80 DEG C, at 80 DEG C, stir 4h.Be warming up to 130 DEG C, add the stannous octoate of 1.0ml, the caprolactone monomer of 50ml starts reaction, continues stirring reaction 24h.Product is washed 4 times with excessive tetrahydrofuran (THF) and uses the tetrafluoroethylene membrane filtration of Φ 0.22 μm, until topple over ice methyl alcohol no longer occur precipitation in filtrate, then distilled water and washing with alcohol is used again successively, filter, 40 DEG C are dried to constant weight, finally obtain polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy 1.13g.
This polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy is made up of carbon nanotube, homo-polypropylene resin and homopolymerization polycaprolactone; Show that the mass ratio of carbon nanotube, polypropylene, polycaprolactone is 1.3:12.5:86.2 by thermogravimetric analysis.
Embodiment 6
Intermediate product 1g after the acid alcohol process obtained in embodiment 1 and 10ml toluene are added in the flask of the 100ml drying that magneton is housed, the dry 4h of pump drainage in the oil bath of 50 DEG C.Be warming up to 80 DEG C, at 80 DEG C, stir 4h.Be warming up to 140 DEG C, add the stannous octoate of 0.05ml, the lactide monomer of 5.0ml starts reaction, continues stirring reaction 24h.Product is washed 4 times with excessive tetrahydrofuran (THF) and uses the tetrafluoroethylene membrane filtration of Φ 0.22 μm, until topple over ice methyl alcohol no longer occur precipitation in filtrate, then distilled water and washing with alcohol is used again successively, filter, 40 DEG C are dried to constant weight, finally obtain polypropylene-polylactic acid-carbon nanometer pipe ternary alloy 1.02g.
This polypropylene-polycaprolactone-carbon nanometer pipe ternary alloy is made up of carbon nanotube, homo-polypropylene resin and homopolymerization poly(lactic acid); Show that the mass ratio of carbon nanotube, polypropylene, poly(lactic acid) is 1.2:8.8:90.0 by thermogravimetric analysis.
Embodiment 7
Intermediate product 1g after the acid alcohol process obtained in embodiment 1 and 10ml toluene are added in the flask of the 100ml drying that magneton is housed, the dry 4h of pump drainage in the oil bath of 50 DEG C.Be warming up to 80 DEG C, at 80 DEG C, stir 4h.Be warming up to 140 DEG C, add the stannous octoate of 0.1ml, the lactide monomer of 10.0ml starts reaction, continues stirring reaction 24h.Product is washed 4 times with excessive tetrahydrofuran (THF) and uses the tetrafluoroethylene membrane filtration of Φ 0.22 μm, until topple over ice methyl alcohol no longer occur precipitation in filtrate, then distilled water and washing with alcohol is used again successively, filter, 40 DEG C are dried to constant weight, finally obtain polypropylene-polylactic acid-carbon nanometer pipe ternary alloy 1.13g.
This polypropylene-polylactic acid-carbon nanometer pipe ternary alloy is made up of carbon nanotube, homo-polypropylene resin and homopolymerization poly(lactic acid); Show that the mass ratio of carbon nanotube, polypropylene, poly(lactic acid) is 1.3:18.6:80.1 by thermogravimetric analysis.
Embodiment 8
Intermediate product 1g after the acid alcohol process obtained in embodiment 1 and 10ml toluene are added in the flask of the 150ml drying that magneton is housed, the dry 4h of pump drainage in the oil bath of 50 DEG C.Be warming up to 80 DEG C, at 80 DEG C, stir 4h.Be warming up to 140 DEG C, add the stannous octoate of 0.5ml, the lactide monomer of 50.0ml starts reaction, continues stirring reaction 24h.Product is washed 4 times with excessive tetrahydrofuran (THF) and uses the tetrafluoroethylene membrane filtration of Φ 0.22 μm, until topple over ice methyl alcohol no longer occur precipitation in filtrate, then distilled water and washing with alcohol is used again successively, filter, 40 DEG C are dried to constant weight, finally obtain polypropylene-polylactic acid-carbon nanometer pipe ternary alloy 1.22g.
This polypropylene-polylactic acid-carbon nanometer pipe ternary alloy is made up of carbon nanotube, homo-polypropylene resin and homopolymerization poly(lactic acid); Show that the mass ratio of carbon nanotube, polypropylene, poly(lactic acid) is 1.5:61.0:37.5 by thermogravimetric analysis.
Embodiment 9
Intermediate product 1g after the acid alcohol process obtained in embodiment 1 and 2ml toluene and 8ml xylene mixture solvent are added in the flask of the 150ml drying that magneton is housed, the dry 4h of pump drainage in the oil bath of 50 DEG C.Be warming up to 80 DEG C, at 80 DEG C, stir 4h.Be warming up to 140 DEG C, add the stannous octoate of 0.5ml, the lactide monomer of 50.0ml starts reaction, continues stirring reaction 24h.Product is washed 4 times with excessive tetrahydrofuran (THF) and uses the tetrafluoroethylene membrane filtration of Φ 0.22 μm, until topple over ice methyl alcohol no longer occur precipitation in filtrate, then distilled water and washing with alcohol is used again successively, filter, 40 DEG C are dried to constant weight, finally obtain polypropylene-polylactic acid-carbon nanometer pipe ternary alloy 1.22g.
This polypropylene-polylactic acid-carbon nanometer pipe ternary alloy is made up of carbon nanotube, homo-polypropylene resin and homopolymerization poly(lactic acid); Show that the mass ratio of carbon nanotube, polypropylene, poly(lactic acid) is 2.2:37.3:60.5 by thermogravimetric analysis.
Embodiment 10
Intermediate product 1g after the acid alcohol process obtained in embodiment 1 and 10ml xylene mixture solvent are added in the flask of the 250ml drying that magneton is housed, the dry 4h of pump drainage in the oil bath of 50 DEG C.Be warming up to 80 DEG C, at 80 DEG C, stir 4h.Be warming up to 140 DEG C, add the stannous octoate of 1.0ml, the lactide monomer of 100.0ml starts reaction, continues stirring reaction 24h.Product is washed 4 times with excessive tetrahydrofuran (THF) and uses the tetrafluoroethylene membrane filtration of Φ 0.22 μm, until topple over ice methyl alcohol no longer occur precipitation in filtrate, then distilled water and washing with alcohol is used again successively, filter, 40 DEG C are dried to constant weight, finally obtain polypropylene-polylactic acid-carbon nanometer pipe ternary alloy 1.02g.
This polypropylene-polylactic acid-carbon nanometer pipe ternary alloy is made up of carbon nanotube, homo-polypropylene resin and homopolymerization poly(lactic acid); Show that the mass ratio of carbon nanotube, polypropylene, poly(lactic acid) is 3.4:16.4:80.2 by thermogravimetric analysis.
Embodiment 11
Intermediate product 1g after the acid alcohol process obtained in embodiment 1 and 10ml toluene Mixed Solvent are added in the flask of the 50ml drying that magneton is housed, the dry 4h of pump drainage in the oil bath of 50 DEG C.Be warming up to 80 DEG C, at 80 DEG C, stir 4h.Be warming up to 120 DEG C, add the stannous octoate of 0.05ml, the Lanthanum Isopropoxide monomer of 5.0ml starts reaction, continues stirring reaction 24h.Product is washed 4 times with excessive tetrahydrofuran (THF) and uses the tetrafluoroethylene membrane filtration of Φ 0.22 μm, until topple over ice methyl alcohol no longer occur precipitation in filtrate, then distilled water and washing with alcohol is used again successively, filter, 40 DEG C are dried to constant weight, finally obtain polypropylene-PPDO-carbon nanometer pipe ternary alloy 1.05g.
This polypropylene-PPDO-carbon nanometer pipe ternary alloy is made up of carbon nanotube, homo-polypropylene resin and homopolymerization PPDO; Show that the mass ratio of carbon nanotube, polypropylene, PPDO is 1.2:89.3:8.5 by thermogravimetric analysis.
Embodiment 12
Intermediate product 1g after the acid alcohol process obtained in embodiment 1 and 10ml toluene Mixed Solvent are added in the flask of the 50ml drying that magneton is housed, the dry 4h of pump drainage in the oil bath of 50 DEG C.Be warming up to 80 DEG C, at 80 DEG C, stir 4h.Be warming up to 120 DEG C, add the stannous octoate of 0.3ml, the Lanthanum Isopropoxide monomer of 30.0ml starts reaction, continues stirring reaction 24h.Product is washed 4 times with excessive tetrahydrofuran (THF) and uses the tetrafluoroethylene membrane filtration of Φ 0.22 μm, until topple over ice methyl alcohol no longer occur precipitation in filtrate, then distilled water and washing with alcohol is used again successively, filter, 40 DEG C are dried to constant weight, finally obtain polypropylene-PPDO-carbon nanometer pipe ternary alloy 1.11g.
This polypropylene-PPDO-carbon nanometer pipe ternary alloy is made up of carbon nanotube, homo-polypropylene resin and homopolymerization PPDO; Show that the mass ratio of carbon nanotube, polypropylene, PPDO is 1.2:78.0:20.8 by thermogravimetric analysis.
Embodiment 13
Intermediate product 1g after the acid alcohol process obtained in embodiment 1 and 10ml toluene Mixed Solvent are added in the flask of the 150ml drying that magneton is housed, the dry 4h of pump drainage in the oil bath of 50 DEG C.Be warming up to 80 DEG C, at 80 DEG C, stir 4h.Be warming up to 120 DEG C, add the stannous octoate of 0.8ml, the Lanthanum Isopropoxide monomer of 80.0ml starts reaction, continues stirring reaction 24h.Product is washed 5 times with excessive tetrahydrofuran (THF) and uses the tetrafluoroethylene membrane filtration of Φ 0.22 μm, until topple over ice methyl alcohol no longer occur precipitation in filtrate, then distilled water and washing with alcohol is used again successively, filter, 40 DEG C are dried to constant weight, finally obtain polypropylene-PPDO-carbon nanometer pipe ternary alloy 1.21g.
This polypropylene-PPDO-carbon nanometer pipe ternary alloy is made up of carbon nanotube, homo-polypropylene resin and homopolymerization PPDO; Show that the mass ratio of carbon nanotube, polypropylene, PPDO is 1.2:56.6:42.2 by thermogravimetric analysis.
Embodiment 14
Intermediate product 1g after the acid alcohol process obtained in embodiment 1 and 4ml toluene and 6ml xylene mixture solvent are added in the flask of the 100ml drying that magneton is housed, the dry 4h of pump drainage in the oil bath of 50 DEG C.Be warming up to 100 DEG C, at 80 DEG C, stir 4h.Be warming up to 120 DEG C, add the stannous octoate of 0.5ml, the Lanthanum Isopropoxide monomer of 50.0ml starts reaction, continues stirring reaction 24h.Product is washed 4 times with excessive tetrahydrofuran (THF) and uses the tetrafluoroethylene membrane filtration of Φ 0.22 μm, until topple over ice methyl alcohol no longer occur precipitation in filtrate, then distilled water and washing with alcohol is used again successively, filter, 40 DEG C are dried to constant weight, finally obtain polypropylene-PPDO-carbon nanometer pipe ternary alloy 1.08g.
This polypropylene-PPDO-carbon nanometer pipe ternary alloy is made up of carbon nanotube, homo-polypropylene resin and homopolymerization PPDO; Show that the mass ratio of carbon nanotube, polypropylene, PPDO is 2.0:25.7:72.3 by thermogravimetric analysis.
Embodiment 15
Intermediate product 1g after the acid alcohol process obtained in embodiment 1 and 10ml dimethylbenzene are added in the flask of the 250ml drying that magneton is housed, the dry 4h of pump drainage in the oil bath of 50 DEG C.Be warming up to 100 DEG C, at 100 DEG C, stir 4h.Be warming up to 120 DEG C, add the stannous octoate of 1.0ml, the Lanthanum Isopropoxide monomer of 100.0ml starts reaction, continues stirring reaction 24h.Product is washed 4 times with excessive tetrahydrofuran (THF) and uses the tetrafluoroethylene membrane filtration of Φ 0.22 μm, until topple over ice methyl alcohol no longer occur precipitation in filtrate, then distilled water and washing with alcohol is used again successively, filter, 40 DEG C are dried to constant weight, finally obtain polypropylene-PPDO-carbon nanometer pipe ternary alloy 0.89g.
This polypropylene-PPDO-carbon nanometer pipe ternary alloy is made up of carbon nanotube, homo-polypropylene resin and homopolymerization PPDO; Show that the mass ratio of carbon nanotube, polypropylene, PPDO is 2.6:8.2:89.2 by thermogravimetric analysis.
Comparative example
By the intermediate product 9.5g after the acid alcohol process that obtains in embodiment 1 and 3.0g polycaprolactone melt blending 15min at 200 DEG C, obtain with the tri compound alloy obtained by embodiment 1 with the ternary alloy prepared through scorification formed.
The present invention start using carbon nanotube as medium, connect the polycaprolactone of nonpolar polypropylene and polarity with strong chemical bond, prepare the tri compound alloy that consistency significantly improves.Relative to the product that melt blending obtains, tri compound alloy prepared by the present invention, the wherein dispersion of disperse phase and carbon nanotube stable and uniform in polypropylene matrix, therefore the characteristic performance of carbon nanotube and polycaprolactone can well be delivered in polypropylene matrix, therefore polyacrylic tensile property can be significantly improved, the mechanical properties such as the shock resistance of low temperature, the thermostability of material and wetting property improve, and significantly improve and certain biological degradability with the consistency of other polar polymers.As in embodiment 3 the initial decomposition temperature of ternary alloy polycaprolactone that obtains be 350 DEG C, compared to initial decomposition temperature 200 ° (the Polymer Degradation and Stability of pure polycaprolactone, 2002,76 (1), 53-59), the thermostability of illustrative material significantly improves.Material is in polar solvent tetrahydrofuran (THF), and as tetrahydrofuran (THF), polar solvent can immerse in material, and (Fig. 8 a), makes the wetting property of material in polar solvent improve by mutually swelling for polycaprolactone.Relative to polypropylene and the polycaprolactone material of melt blending, be immersed in by polycaprolactone phase decomposition in material at polar solvent, the wetting property of material in polar solvent disappears.In embodiment 5 when polycaprolactone content accounts for 86.2wt%, by material hot pressing press mold again at the Water Under solution polycaprolactone of highly basic, found that material is decomposed, illustrate because decomposable polycaprolactone accounts for major part mutually, polypropylene matrix is decomposed, again because polycaprolactone has biodegradability, therefore in the field of following degradable plastics, there is potential using value.
Claims (10)
1. prepare a method for polypropylene-polyester-carbon nanometer pipe ternary composite alloy, comprise the steps:
1) olefinic monomer, difunctional carbon nano tube, promotor are carried out in-situ coordination reaction, obtain intermediate product;
Wherein, described olefinic monomer is: 1) propylene monomer, 2) mixture of propylene monomer and ethene and/or 1-butylene, ethene and/or 1-butylene and propylene monomer mole are 30.0 ~ 99.0:1.0-70.0;
Described difunctional carbon nano tube prepares by the following method: the group first part of hydroxyl in hydroxylated carbon nanotube being converted into carbon-carbon double bonds, obtains double-bond functionalized carbon nanotube carrier; And then by polyolefin catalyst on remaining hydroxyl modified in described double-bond functionalized carbon nanotube carrier, obtain described difunctional carbon nano tube;
Described polyolefin catalyst comprises transistion metal compound and metallic compound; Wherein, described transistion metal compound is selected from least one of Ziegler-Natta catalyst and metallocene catalyst; Described metallic compound is selected from least one in magnesium-containing compound and aluminum contained compound;
2) by step 1) described intermediate product carries out acid alcohol process, the hydroxyl of polyolefin catalyst in described modification is restored, in the presence of a catalyst system, with the ring-opening polymerization of the hydroxyl restored for initiator initiation ring-type esters monomer, obtain described polypropylene-polyester-carbon nanometer pipe ternary composite alloy.
2., according to the method described in claim 1, it is characterized in that: step 1) in, described in-situ coordination reaction is slurry polymerization or bulk polymerization;
Described slurry polymerization carries out in organic solvent, and described organic solvent is selected from following at least one: the alkane of C5 ~ C10 or the aromatic hydrocarbon of C6-C8, be specially heptane, hexane or toluene;
The temperature of reaction of described slurry polymerization and bulk polymerization is 30 DEG C ~ 90 DEG C, and preferably 40 DEG C ~ 80 DEG C, the time is 0.05 ~ 10.0 hour, preferably 0.1 ~ 2.0 hour; Pressure is 0-4MP
aand be not 0, be preferably 0.5-3.5MPa;
When described in-situ coordination reaction is for slurry polymerization, step 1) also comprise the step adding acid alcohol solution termination reaction in the reaction system of described slurry polymerization; In described acid alcohol solution, the volume ratio of hydrochloric acid and ethanol is 1:10.
3. according to the method described in claim 1 or 2, it is characterized in that: aforesaid method step 1) in, the particle diameter of described hydroxylated carbon nanotube is 20-40nm, and length is 0.5-50 μm, and length-to-diameter ratio is 25-250; The adsorbed hydroxyl content of described hydroxylated carbon nanotube is 3.06wt%.
4. the method according to any one of claim 1-3, it is characterized in that: described promotor is selected from following at least one: the aluminum alkyls of C1-C4 and the alkoxy aluminum compound of C1-C4, be specially trimethyl aluminium, triethyl aluminum, triisobutyl aluminium or methylaluminoxane;
Aluminium in described promotor and the mol ratio between transition metal are 50-5000:1, are preferably 50-2000:1;
The add-on of described difunctional carbon nano tube is the 0.1-5.0% of olefinic monomer quality, preferred 0.1-0.4%.
5. the method according to any one of claim 1-4, is characterized in that: described Ziegler-Natta catalyst titanium tetrahalide used is TiCl
4, TiBr
4or TiI
4; Titan-alkoxide used is Ti (OEt) Cl
3, Ti (OEt)
2cl
2, Ti (OEt)
3cl, Ti (OEt)
4or Ti (OBu)
4;
The general structure of described metallocene catalyst is such as formula shown in I:
(Cp
I-B
e-Cp
II)MR
1 aR
2 b
(formula I)
In described formula I, M is selected from least one in Ti, Zr, Hf, V, Fe, Y, Sc and lanthanide series metal; Described Cp
iand Cp
iIrepresent cyclopentadienyl or contain substituent cyclopentadienyl, described containing in substituent cyclopentadienyl, substituting group is C
1~ C
6alkyl, C
3~ C
18cycloalkyl or C
6~ C
18aromatic base; Described R
1and R
2for aryl, C that H, halogen atom, the carbonatoms alkyl that is 1 ~ 8, the carbonatoms alkoxyl group that is 1 ~ 8, carbonatoms are 6 ~ 20
1~ C
15acyloxy, allyl group or C that the aryl that the carbonatoms that alkyl replaces is 6 ~ 20, carbonatoms are 1 ~ 8
1~ C
15silylation; Described B represents alkyl bridge or silylation bridge, preferably-C (R
3r
4)-or-Si (R
3r
4)-; R
3and R
4for H, carbonatoms be 1 ~ 4 alkyl or carbonatoms be the aryl of 6 ~ 10; E is 1,2 or 3;
abe 0,1 or 2 with b, wherein
a+ b=2;
Described metallocene catalyst is specially C
2h
4(Ind)
2zrCl
2, C
2h
4(H
4ind)
2zrCl
2, Me
2si (Ind)
2zrCl
2, Me
2si (2-Me-4-Ph-Ind)
2zrCl
2, Me
2si (Me
4cp)
2zrCl
2, Me
2si (Flu)
2zrCl
2, Me
2si (2-Me-4-Naph-Ind)
2zrCl
2or Ph
2si (Ind)
2zrCl
2, wherein, Me is methyl, and Ph is phenyl, and Cp is cyclopentadienyl, and Ind is indenyl, H
4ind is 4,5,6,7-tetrahydro-indenes, and Flu is fluorenyl, and Naph is naphthyl;
Described metallic compound is magnesium-containing compound and/or aluminum contained compound; Described magnesium-containing compound is molecular formula is MgX
2magnesium halide or general structure be the Grignard reagent of RMgX; Described MgX
2in, X is fluorine, chlorine, bromine or iodine element, and preferred X is chlorine; In described RMgX, the alkyl of R to be carbonatoms be 1-10, preferable methyl, ethyl, propyl group, sec.-propyl, butyl or isobutyl-, X is fluorine, chlorine, bromine or iodine; Described aluminum contained compound is Al (OR ')
nr
3-n, 0≤n≤3, R and R ' carbonatoms is the alkyl of 2 ~ 10, preferred trimethyl aluminium, triethyl aluminum, triisobutyl aluminium or methylaluminoxane;
Step 1) in, described polyolefin catalyst also comprises auxiliary agent; Described auxiliary agent is internal electron donor compound, is selected from diether and/or carbonate, is specially diisobutyl phthalate, fluorenes diether, methyl benzoate or dibutyl phthalate;
The mass percentage of carbon nanotube carrier double-bond functionalized in described difunctional carbon nano tube is 70.0 ~ 99.0%, preferred 75.0-95.0%;
Summation shared mass percentage in described difunctional carbon nano tube of the transition metal in the metallic element in described metallic compound and described transistion metal compound is 1.0 ~ 30.0%, preferred 1.0-25.0%;
When described metallic compound is magnesium-containing compound, the mass percentage of the transition metal in described transistion metal compound in described difunctional carbon nano tube is 0.5 ~ 5.0%, preferred 0.5-4.0%;
When described metallic compound is aluminum contained compound, the mass percentage of the transition metal in described transistion metal compound in described difunctional carbon nano tube is 0.05 ~ 2.0%, preferred 0.1-2.0%;
Described metallic compound be magnesium-containing compound and aluminum contained compound time, the mass percentage of the transition metal in described transistion metal compound in described difunctional carbon nano tube is 0.55-7.0%, preferred 0.55-5.0%.
The mass percentage of described internal electron donor in described difunctional carbon nano tube is 2.50-15.0%.
6. the method according to any one of claim 1-5, is characterized in that: in ring-opening polymerization, and described ring-type esters monomer is selected from following at least one: caprolactone, glycollide, rac-Lactide or to dioxy ring ethyl ketone, preferred caprolactone;
Described ring-opening polymerization catalyst system used is metal catalyst system, and described metal catalyst system is selected from following at least one: the derivative of stannous octoate, triethyl aluminum and titanium, zirconium, cadmium and mercury, the sub-tin of preferably octanoic acid;
Described ring-opening polymerization is solution polymerization, described solution polymerization carries out in organic solvent, described organic solvent is selected from following at least one: aromatic hydrocarbons and halogenated alkane, wherein aromatic hydrocarbons is selected from benzene, toluene, ethylbenzene, dimethylbenzene or chlorobenzene, preferred toluene, dimethylbenzene or the mixture of the two; Halogenated alkane is selected from the C of halogen substiuted
5-C
10alkane;
The temperature of reaction of described ring-opening polymerization is 100 DEG C ~ 170 DEG C, and the reaction times is 1 ~ 48 hour, preferably 4 ~ 24 hours;
Described ring-type esters monomer volumetric molar concentration is in organic solvent 1-10mol/L, and the mass ratio of the intermediate product after described ring-type esters monomer and acid alcohol process is 5 ~ 250, preferably 5 ~ 100; Used catalyst is stannous octoate, described catalyzer and ring-type esters monomer mol ratio be 0.001 ~ 0.1, preferably 0.003 ~ 0.05.
7. the method according to any one of claim 1-6, it is characterized in that: the preparation method of described polypropylene-polyester-carbon nanometer pipe ternary composite alloy is also included in carry out step 1) in-situ coordination reaction before, in reaction system, add the step of electron donor;
The general structure of described electron donor is R
4-nsi (OR ')
n, described R
4-nsi (OR ')
nin, n is the integer of 1-3, and R and R ' is all selected from following at least one: the aryl of the alkyl of C1-C8, the cycloalkyl of C5-C10 or C6-C10, preferred diphenyldimethyl silane, dicyclohexyl dimethylsilane or phenyl-trimethylsilicane;
In described electron donor and described promotor, the mol ratio of aluminium element is 0.01 ~ 1.0:1, preferred 0.1-1.0:1.
8. the method according to any one of claim 1-7, it is characterized in that: the preparation method of described polypropylene-polyester-carbon nanometer pipe ternary composite alloy is included in further carry out step 1) in-situ coordination reaction before, in reaction system, pass into hydrogen;
Wherein, the add-on of hydrogen is the 0.001%-0.5% of olefinic monomer quality, preferred 0.005-0.08%.
9. the polypropylene-polyester that the method according to any one of claim 1-8 prepares-carbon nanometer pipe ternary composite alloy.
10., according to the polypropylene-polyester described in claim 9-carbon nanometer pipe ternary composite alloy, it is characterized in that:
Described polypropylene-polyester-carbon nanometer pipe ternary composite alloy is by PP matrix and carbon nanotube and polyester dispersion phase composite;
Described PP matrix is selected from the random copolymer resin of homo-polypropylene and propylene and ethene or 1-butylene;
In the random copolymer resin of described propylene and ethene or 1-butylene, the proportioning of propylene and ethene and/or 1-butylene is 30.0 ~ 99.0:1.0 ~ 70.0;
Described polyester is aliphatic polyester, and described aliphatic polyester is selected from the homopolymer or multipolymer that are formed by following at least one monomer: caprolactone, glycollide, rac-Lactide and to dioxy ring ethyl ketone; Preferred polycaprolactone;
The particle diameter of described carbon nanotube is 20-40nm, preferred 25nm, and length is 0.5-50 μm, and length-to-diameter ratio is 50-1000;
In described polypropylene-polyester-carbon nanometer pipe ternary composite alloy, the mass percentage of described PP matrix is 0.5-95.0%, preferred 10.0-90.0%;
In described polypropylene-polyester-carbon nanometer pipe ternary composite alloy, the mass percentage of described PP matrix is 0.5-98%, preferred 8.0-90.0%; The mass percentage of described aliphatic polyester is 0.5-98%, preferred 8.0-90.0%; Described carbon nanotube mass percentage composition is 0.2-4.5%, preferred 1.2%-4.2%.
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| CN113444290A (en) * | 2021-07-22 | 2021-09-28 | 浙江师范大学 | Vinyl modified nano filler interface compatilizer and preparation method of compatibilized blending polymer thereof |
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| US7855001B2 (en) * | 2008-07-28 | 2010-12-21 | Ovation Polymer Technology And Engineered Materials, Inc. | Thermoplastic polymer for electrically conductive thermoforming applications |
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| CN1530404A (en) * | 2003-02-26 | 2004-09-22 | ���ǵ�����ʽ���� | Preparations of carbon nano tube layout film or composite material from polymerisable semgental surface modified carbon nano tubes |
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