CN103881336A - Adipic acid-terephthalic acid-butanediol ternary copolyester/graphene oxide composite material and preparation method thereof - Google Patents
Adipic acid-terephthalic acid-butanediol ternary copolyester/graphene oxide composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an adipic acid-terephthalic acid-butanediol ternary copolyester/graphene oxide composite material which comprises adipic acid-terephthalic acid-butanediol ternary copolyester and graphene oxide, wherein the weight percent of the graphene oxide in the composite material is 0.01-1%, and the thickness of the graphene oxide is 0.8-10nm. The graphene oxide can be uniformly dispersed in the polymeric matrix, so that the barrier property of the composite material is greatly enhanced. The invention also discloses a preparation method of the adipic acid-terephthalic acid-butanediol ternary copolyester/graphene oxide composite material. The method has the advantages of simple technique and strong operability, and can easily implement industrial production.
Description
Technical field
The present invention relates to polymeric material field.More specifically, relate to a kind of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material and preparation method thereof.
Background technology
Along with being widely used of plastics, the non-degradable plastics that abandon in environment have caused serious pollution to environment.Hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester is a kind of novel bio-degradable plastics.Have poly adipate succinic acid ester and mutual-phenenyl two acid bromide two alcohol ester's characteristic concurrently, existing good ductility and elongation at break, also have good thermotolerance and impact property.It has good processing characteristics, can carry out the forming process such as injection moulding, injection moulding, blown film, foaming.Because it has good biodegradable performance and good film forming properties at agricultural mulching, the fields such as food and medicine packing film have very potential using value.The barrier property of general Plastic Packaging Materials is difficult to meet actual requirement, easily causes the putrid and deteriorated of food and medicine.Therefore, the barrier property of raising wrapping material has extremely important.Graphene oxide is that graphite is peeled off the two-dimensional nano laminated structure material obtaining through peroxidation, and its surface has abundant structure of functional groups, and because it has huge specific surface area, excellent mechanical property, is the ideal filler of preparing polymer composites.The subject matter existing is at present that graphene oxide is easily reunited, and is difficult to disperse.How to be to prepare the subject matter that polymkeric substance/graphene oxide composite material faces by being distributed in polymeric matrix of graphene oxide homogeneous.Therefore, research and develop new preparation method extremely important.
Chinese patent CN102115566A used a kind of can simultaneous oxidation Graphene and the solvent of polymkeric substance prepare laminated film, but can be both the can selective solvent very limited of dissolved oxygen Graphene and polymkeric substance, there is very strong limitation in the method therefore.In addition, exist solvent by the method casting film-forming and be difficult to the shortcomings such as volatilization.
Chinese patent CN102827315A discloses a kind of preparation method of graphene oxide/polystyrene, and the method is only applicable to carry out the monomer of radical polymerization, and the inapplicable polymkeric substance obtaining with polycondensation, is of limited application, and is not suitable for polyester.
Chinese patent CN102199303A discloses a kind of graphene oxide/polymer composite film of liquid-vapo(u)r interface self-assembly, and the shortcoming of the method is to produce in a large number, unstable product quality, the shortcoming such as film morphology is uncontrollable.
And hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material and preparation method thereof has no report.
Summary of the invention
First technical problem that the present invention will solve is to provide a kind of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide high-barrier composite material.
Second technical problem that the present invention will solve is to provide the preparation method of a kind of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide high-barrier composite material, and this preparation method is simple, is applicable to scale operation.
For solving above-mentioned first technical problem, the present invention adopts following technical proposals:
A kind of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material, described matrix material comprises hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester and graphene oxide, and described graphene oxide is scattered in hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester;
Described hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester number-average molecular weight is 10000-150000;
The weight fraction of described graphene oxide is 0.01-1%; The thickness of described graphene oxide is 0.8-10nm.
For solving above-mentioned second technical problem, the present invention adopts following technical proposals:
A preparation method for hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material, comprises the following steps:
(1) graphene oxide is dispersed in polar solvent, obtains the bright graphene oxide dispersion liquid of brown color;
(2) hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester is dissolved in good solvent A, obtains the solution of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester; Described good solvent refers to that solubleness is greater than 2mg/mL under the condition of 25 DEG C.
(3) when stirring, graphene oxide dispersion liquid is joined in the solution of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester and obtains mixed solution;
(4) mixed solution is poured into the throw out that obtains hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material in the poor solvent B of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester; Described poor solvent refers to that solubleness is less than 0.2mg/mL under the condition of 25 DEG C.
(5) throw out step (4) being obtained filters, dry, obtains hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material.
Preferably, the dry hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material obtaining can be made to film.More preferably, described in to make film be by blowing, curtain coating, the method for compacting is made film.
Preferably, the described dispersion of step (1) comprises the ultrasonic dispersion of employing or stirring; Described jitter time is 1-4 hour.
Preferably, the described polar solvent of step (1) is selected from DMF, tetrahydrofuran (THF), N-Methyl pyrrolidone, N-ethyl pyrrolidone, ethylene glycol or water; Described graphene oxide dispersion liquid concentration is 0.001-2mg/mL.
Preferably, step (2) described hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester is made by polycondensation by hexanodioic acid, terephthalic acid and butyleneglycol; Described hexanodioic acid is 1.5-4:1 with the molfraction ratio of terephthalic acid.
Preferably, the described good solvent A of step (2) is trichloromethane.
Preferably, described in step (3), adding is that graphene oxide dispersant liquid drop is added in hexanodioic acid-terephthalic acid-butyleneglycol terpolymer ester solution.
Preferably, the described poor solvent B of step (4) is selected from water, ether, anhydrous methanol, or dehydrated alcohol.
Preferably, described dry two steps that comprise of step (5): 1. first carry out more than 6 hours predrying under the condition of 20-40 DEG C, 2. put into vacuum drying oven and be dried, temperature rise rate is 1～20 DEG C/min.More preferably, in process of vacuum drying described above vacuum tightness between 0.9～0.01Mpa; Vacuum drying temperature is 130-140 DEG C.
Beneficial effect of the present invention is as follows:
1. compared with polymkeric substance/graphene oxide in prior art, graphene oxide can be dispersed in polymeric matrix uniformly, and the barrier property of matrix material is increased substantially.
2. preparation method's technique of hexanodioic acid-terephthalic acid of the present invention-butyleneglycol three-element copolymerized ester/graphene oxide composite material is simple, workable, is easy to suitability for industrialized production.
3. the required graphene oxide content of high-isolation film of the present invention is very low.
Brief description of the drawings
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 a, b illustrate the atomic force microscope after ultrasonic peeling off (AFM) figure in DMF solvent of the graphene oxide before mixing in the embodiment of the present invention 1;
Fig. 2 illustrates transmission electron microscope (TEM) picture of graphene oxide in hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester in the embodiment of the present invention 1.
Embodiment
In order to be illustrated more clearly in the present invention, below in conjunction with preferred embodiments and drawings, the present invention is described further.Parts similar in accompanying drawing represent with identical Reference numeral.It will be appreciated by those skilled in the art that specifically described content is illustrative and nonrestrictive below, should not limit the scope of the invention with this.
Embodiment 1
The preparation method of a kind of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material
(1) take the graphene oxide that 300mg is dry and be dissolved in the DMF of 150mL, ultrasonic dispersion 4 hours, obtaining concentration is the graphene oxide dispersion liquid of 2mg/mL;
(2) take hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester (hexanodioic acid: terephthalic acid=7:3 of 30g, mol/mol), in the air dry oven of 60 DEG C, be dried 24 hours, then be dissolved in the trichloromethane of 150mL, obtain the chloroform soln of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester;
(3) the graphene oxide dispersion liquid solution obtaining is slowly joined in the chloroform soln of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester while stirring, obtain the mixing solutions of the two;
(4) when mixing solutions stirring, pour in the dehydrated alcohol of 300mL, separate out hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material;
(5) by the matrix material of separating out first in the air atmosphere of 40 DEG C predrying 6 hours, transferring in vacuum drying oven, under the condition that is 0.1Mpa in vacuum tightness, be warmed up to 140 DEG C with the temperature rise rate of 5 DEG C/min of per minute, maintain 1 hour, cooling, obtain hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material, graphene oxide massfraction 1%;
(6) by the hexanodioic acid-terephthalic acid obtaining-butyleneglycol three-element copolymerized ester/graphene oxide composite material at 120 DEG C, it is the film of 107 microns that the condition of 20Mpa depresses to thickness, from Fig. 1 a, Fig. 1 b and Fig. 2, can go to find out that graphene oxide has obtained peeling off completely before mixing, and there is not agglomeration after mixing, be uniformly dispersed, dispersion effect is good.
(1) graphene oxide that takes 150mg is dissolved in the DMF of 150mL, ultrasonic dispersion 2 hours, and obtaining concentration is the graphene oxide dispersion liquid of 1mg/mL;
(2) take hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester (hexanodioic acid: terephthalic acid=8:2 of 30g, mol/mol), in the air dry oven of 60 DEG C, be dried 24 hours, then be dissolved in the trichloromethane of 150mL, obtain the chloroform soln of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester;
(3) the graphene oxide solution limit stirring obtaining is slowed down and joined slowly in the chloroform soln of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester, obtain the mixing solutions of the two;
(4) mixing solutions is poured in the dehydrated alcohol of 300mL while stirring, separated out hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material;
(5) by the mixture of separating out first in the air atmosphere of 20 DEG C predrying 6 hours, transferring in vacuum drying oven, under the condition that is 0.1Mpa in vacuum tightness, be warmed up to 140 DEG C with the temperature rise rate of 5 DEG C/min of per minute, maintain 1 hour, cooling, obtain hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material, graphene oxide massfraction 0.5%;
(6) by the hexanodioic acid-terephthalic acid obtaining-butyleneglycol three-element copolymerized ester/graphene oxide composite material at 120 DEG C, it is the film of 160 microns that the condition of 20Mpa depresses to thickness.
(1) graphene oxide that takes 30mg is dissolved in the tetrahydrofuran (THF) of 150mL, ultrasonic dispersion 2 hours, and obtaining concentration is the graphene oxide dispersion liquid of 0.2mg/mL;
(2) take hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester (hexanodioic acid: terephthalic acid=7:3 of 30g, mol/mol), in the air dry oven of 40 DEG C, be dried 24 hours, then be dissolved in the trichloromethane of 150mL, to the chloroform soln of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester;
(3) the graphene oxide solution limit stirring obtaining is slowed down and joined slowly in the chloroform soln of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester, obtain the mixing solutions of the two;
(4) mixing solutions is poured in the dehydrated alcohol of 300mL while stirring, separated out hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material;
(5) by the hexanodioic acid-terephthalic acid of separating out-butyleneglycol three-element copolymerized ester/graphene oxide mixture first in the air atmosphere of 20 DEG C predrying 8 hours, transferring in vacuum drying oven, under the condition that is 0.1Mpa in vacuum tightness, be warmed up to 130 DEG C with the temperature rise rate of 5 DEG C/min of per minute, maintain 1 hour, cooling, obtain hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material, graphene oxide massfraction 0.1%;
(6) by the hexanodioic acid-terephthalic acid obtaining-butyleneglycol three-element copolymerized ester/graphene oxide composite material at 120 DEG C, it is the film of 142 microns that the condition of 20Mpa depresses to thickness.
(1) graphene oxide that takes 15mg is dissolved in the DMF of 150mL, ultrasonic dispersion 1 hour, and obtaining concentration is the graphene oxide dispersion liquid of 0.1mg/mL;
(2) take hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester (hexanodioic acid: terephthalic acid=6:4 of 30g, mol/mol), in the air dry oven of 40 DEG C, be dried 24 hours, then be dissolved in the trichloromethane of 150mL, to the chloroform soln of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester;
(3) the graphene oxide solution limit stirring obtaining is slowed down and joined slowly in the chloroform soln of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester, obtain the mixing solutions of the two;
(4) mixing solutions is poured in the dehydrated alcohol of 300mL while stirring, separated out hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material;
(5) by the mixture of separating out first in the air atmosphere of 40 DEG C predrying 6 hours, transferring in vacuum drying oven, under the condition that is 0.1Mpa in vacuum tightness, be warmed up to 130 DEG C with the temperature rise rate of 5 DEG C/min of per minute, maintain 1 hour, cooling, obtain hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material, graphene oxide massfraction 0.05%;
(6) by the hexanodioic acid-terephthalic acid obtaining-butyleneglycol three-element copolymerized ester/graphene oxide composite material at 120 DEG C, it is the film of 152 microns that the condition of 20Mpa depresses to thickness.
Comparative example
Comparative example does not add graphene oxide, be by hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester (hexanodioic acid: terephthalic acid=7:3, mol/mol) at 120 DEG C, it is the film of 161 microns that the condition of 20Mpa depresses to thickness.
Comparative example and embodiment 1-4 see the following form 1 according to GB/T1038-2000 test result
Table 1
As seen from Table 1, hexanodioic acid-terephthalic acid of the present invention-butyleneglycol three-element copolymerized ester/graphene oxide composite material film has very excellent oxygen barrier property.
Embodiment 5,6
With embodiment 1, its difference is only, making film described in step (6) is respectively to make by blowing or curtain coating.
Embodiment 7
With embodiment 1, its difference is only, step (4) poor solvent B changes anhydrous methanol into, and the described temperature rise rate of step (5) is 20 DEG C/min.
Embodiment 8-11
With embodiment 1, its difference is only, the described polar solvent DMF of step (1) is used respectively N-Methyl pyrrolidone, N-ethyl pyrrolidone, and ethylene glycol or water replace, and experimental results is similar to embodiment 1.
Embodiment 12
With embodiment 1, its difference is only, dry described in step is first under the condition of 30 DEG C, to carry out 24 hours predrying, then puts into vacuum drying oven under the condition that vacuum tightness is 0.5Mpa dry, and temperature rise rate is 20 DEG C/min.
Embodiment 13
With embodiment 1, its difference is only, dry described in step is first under the condition of 30 DEG C, to carry out 16 hours predrying, then puts into vacuum drying oven under the condition that vacuum tightness is 0.9Mpa dry, and temperature rise rate is 1 DEG C/min.
Embodiment 14,15
With embodiment 1, its difference is only, step (4) poor solvent B changes respectively ether or acetone into.
Embodiment 16
With embodiment 1, its difference is only, step (3) is that the graphene oxide dispersion liquid solution obtaining is added drop-wise in the chloroform soln of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester, obtains the mixing solutions of the two.
Embodiment 17-19
With embodiment 1, its difference is only, hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester number-average molecular weight of the 30g that step (2) takes is respectively 10000,80000 or 150000.
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give all embodiments exhaustively, everyly belong to apparent variation or the still row in protection scope of the present invention of variation that technical scheme of the present invention extends out.
Claims (10)
1. hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material, it is characterized in that, described matrix material comprises hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester and graphene oxide, and described graphene oxide is scattered in hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester;
Described hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester number-average molecular weight is 10000-150000;
The weight fraction of described graphene oxide is 0.01-1%; The thickness of described graphene oxide is 0.8-10nm.
2. the preparation method of hexanodioic acid-terephthalic acid according to claim 1-butyleneglycol three-element copolymerized ester/graphene oxide composite material, is characterized in that, comprises the following steps:
(1) graphene oxide is dispersed in polar solvent, obtains graphene oxide dispersion liquid;
(2) hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester is dissolved in good solvent A, obtains the solution of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester;
(3) when stirring, graphene oxide dispersion liquid is joined in the solution of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester and obtains mixed solution;
(4) mixed solution is poured into the throw out that obtains hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material in the poor solvent B of hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester;
(5) throw out step (4) being obtained filters, dry, obtains hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material;
Preferably, the dry hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester/graphene oxide composite material obtaining can be made to film.
3. the preparation method of hexanodioic acid-terephthalic acid according to claim 2-butyleneglycol three-element copolymerized ester/graphene oxide composite material, is characterized in that: the described dispersion of step (1) comprises the ultrasonic dispersion of employing or stirring; Described jitter time is 1-4 hour.
4. the preparation method of hexanodioic acid-terephthalic acid according to claim 2-butyleneglycol three-element copolymerized ester/graphene oxide composite material, it is characterized in that: the described polar solvent of step (1) is selected from N, dinethylformamide, tetrahydrofuran (THF), N-Methyl pyrrolidone, N-ethyl pyrrolidone, ethylene glycol or water; Described graphene oxide dispersion liquid concentration is 0.001-2mg/mL.
5. the preparation method of hexanodioic acid-terephthalic acid according to claim 2-butyleneglycol three-element copolymerized ester/graphene oxide composite material, is characterized in that: step (2) described hexanodioic acid-terephthalic acid-butyleneglycol three-element copolymerized ester is made by polycondensation by hexanodioic acid, terephthalic acid and butyleneglycol; Described hexanodioic acid is 1.5:1-4:1 with the molfraction ratio of terephthalic acid; Described good solvent A is trichloromethane.
6. the preparation method of hexanodioic acid-terephthalic acid according to claim 2-butyleneglycol three-element copolymerized ester/graphene oxide composite material, is characterized in that: described in step (3), adding is that graphene oxide dispersant liquid drop is added in hexanodioic acid-terephthalic acid-butyleneglycol terpolymer ester solution.
7. the preparation method of hexanodioic acid-terephthalic acid according to claim 2-butyleneglycol three-element copolymerized ester/graphene oxide composite material, it is characterized in that: the described poor solvent B of step (4) is selected from water, ether, acetone, tetrahydrofuran (THF), anhydrous methanol or dehydrated alcohol.
8. the preparation method of hexanodioic acid-terephthalic acid according to claim 2-butyleneglycol three-element copolymerized ester/graphene oxide composite material, it is characterized in that: described dry two steps that comprise of step (5): 1. first under the condition of 20-40 DEG C, carry out 6～24 hours predrying, 2. put into vacuum drying oven dry, temperature rise rate is 1～20 DEG C/min.
9. the preparation method of hexanodioic acid-terephthalic acid according to claim 8-butyleneglycol three-element copolymerized ester/graphene oxide composite material, is characterized in that: in described process of vacuum drying, vacuum tightness is 0.9～0.1Mpa; Vacuum drying temperature is 130-140 DEG C.
10. the preparation method of hexanodioic acid-terephthalic acid according to claim 2-butyleneglycol three-element copolymerized ester/graphene oxide composite material, is characterized in that: described in step (5), making film is by blowing, curtain coating, and the method for compacting is made film.
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