Background technology
Esters polymer such as polybutylene terephthalate (PBT) and polyethylene terephthalate (PET) are applied to packing, automobile component etc. now just day by day increasedly, its annual volumetric usage about 11% of whole engineering plastics that account for basically.Especially PBT, because it has high toughness, intensity, dimensional stability is good, and is water-fast, and resistance to chemical attack and excellent properties such as non-conductive have purposes widely, especially at aspects such as automobile, building and structured materials aspect engineering.
Terephthalic acid cyclobutanediol ester (CBT) is to be raw material with mutual-phenenyl two acid bromide two alcohol ester (PBT), in solution, PBT is cracked into the oligopolymer of short chain with catalyzer, and is closed into ring-type.CBT is the mixture of different lower molecular weight cyclic oligomers.Its feature be exactly the heating situation under, can become as water, viscosity is very low.As if the adding catalyzer and under suitable temperature, CBT assembles the PBT resin of synthetic macromolecule amount.
It is not high enough that but the shortcoming of PBT is exactly its Tc, and this point has also limited its some ranges of application, and therefore, the Tc that improves PBT will have very important use value.
Summary of the invention
The object of the invention is exactly for the deficiency that overcomes above-mentioned prior art existence a kind of PBT/ Nanometer Composite Material Of Montmorillonite And Its Preparation Method with high crystallization temperature to be provided.
The object of the invention can be realized through following technical scheme:
A kind of PBT/ Nano composite material of montmorillonite with high crystallization temperature is characterized in that, prescription below this composite material by adopting is feedstock production:
Terephthalic acid cyclobutanediol ester (CBT) 50-99.99 weight part,
Nano imvite 0.01-50 weight part.
A kind of preparation method with PBT/ Nano composite material of montmorillonite of high crystallization temperature; It is characterized in that it is the lower molecular weight cyclic oligomer by a kind of type material PBT---terephthalic acid cyclobutanediol ester (CBT) carries out in-situ polymerization with nano imvite and prepares.
This method comprises following technology:
A. with CBT in the fusion of 70-180 ℃ of scope internal heating, when its viscosity number is 10~50MPa.s, polynite is added, carry out thermostatic ultrasonic and disperse or continue to stir 1-50 hour;
B. scattered CBT/ nano imvite mixture is warming up to 180-250 ℃ and carries out in-situ polymerization.
This method can also comprise following technology:
A. nano imvite is dissolved in and carries out ultra-sonic dispersion in the solvent or continue stirring 1-30 hour;
B. CBT is dissolved in the homogeneous solvent;
C. CBT solution is poured in the described finely dispersed polynite solution of step a, continued ultra-sonic dispersion or continue to stir 1-30 hour;
D. solvent evaporates is fallen;
E. be warming up to 180-250 ℃ of scope, make scattered CBT, nano imvite mixture carry out in-situ polymerization.
The CBT that is adopted is the CBT of various models such as CBT100 or CBT160.
Used CBT structural formula is:
N=2-10 wherein.
Used nano imvite is meant the original soil of non-modified.
Used solvent is one or more in acetone, methylene dichloride, trichloromethane, the trifluoroacetic acid.
Compared with prior art, the present invention adopts CBT and nano imvite to carry out home polymerization mode to have prepared the PBT/MMT nano composite material, significantly improved the Tc of PBT.In addition, because can forming nano level in polymkeric substance, disperses montmorillonite layer, so the adding of polynite also all is significantly improved intensity, modulus, barrier property and the thermotolerance etc. of matrix material.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1
CBT98 part is heated to 150 ℃ of fusions, when CBT melt viscosity value is 10MPa.s, adds 2 parts of nano imvites, fully stir 20h, logical N
2, nano imvite is uniformly dispersed in the CBT melt.Be warming up to 190 ℃ then, make CBT carry out in-situ polymerization, preparation PBT/ Nano composite material of montmorillonite.Gained sample Tc is as shown in table 1.
Embodiment 2
CBT98 part is heated to 150 ℃ of fusions, when CBT melt viscosity value is 20MPa.s, adds 2 parts of nano imvites, ultra-sonic dispersion 20h, N
2Protection is uniformly dispersed nano imvite in the CBT melt.Be warming up to 190 ℃ then, make CBT carry out in-situ polymerization, preparation PBT/ Nano composite material of montmorillonite.Gained sample Tc is as shown in table 1.
Embodiment 3
CBT90 part is heated to 150 ℃ of fusions, when CBT melt viscosity value is 30MPa.s, adds 10 parts of nano imvites, fully stir 20h, logical N
2, nano imvite is uniformly dispersed in the CBT melt.Be warming up to 190 ℃ then, make CBT carry out in-situ polymerization, preparation PBT/ Nano composite material of montmorillonite.Gained sample Tc is as shown in table 1.
Embodiment 4
CBT90 part is heated to 150 ℃ of fusions, when CBT melt viscosity value is 50MPa.s, adds 10 parts of nano imvites, ultra-sonic dispersion 20h, N
2Protection is uniformly dispersed nano imvite in the CBT melt.Be warming up to 190 ℃ then, make CBT carry out in-situ polymerization, preparation PBT/ Nano composite material of montmorillonite.Gained sample Tc is as shown in table 1.
Embodiment 5
2 parts of nano imvites are dissolved in the acetone, continue about 80 ℃ to stir 20h, it is slowly dissolved.Then 98 parts of CBT are dissolved in the acetone, continue about 80 ℃ to stir, make its dissolving.This CBT solution is poured in the scattered polynite solution, continued to continue to stir 20h.Vapor away solvent, 80 ℃ of vacuum-dryings.To be warming up to 190 ℃ through CBT, the nano imvite mixture that drying is crossed at last, and make CBT carry out in-situ polymerization and prepare the PBT/ Nano composite material of montmorillonite.Gained sample Tc is as shown in table 1.
Embodiment 6
2 parts of nano imvites are dissolved in the acetone, and 80 ℃ of left and right sides ultra-sonic dispersion 20h slowly dissolve it.Then 98 parts of CBT are dissolved in the acetone, 80 ℃ of left and right sides ultra-sonic dispersion make its dissolving.This CBT solution is poured in the scattered polynite solution, continued ultra-sonic dispersion 20h.Vapor away solvent, 80 ℃ of vacuum-dryings.To be warming up to 190 ℃ through CBT, the nano imvite mixture that drying is crossed at last, and make CBT carry out in-situ polymerization and prepare the PBT/ Nano composite material of montmorillonite.Gained sample Tc is as shown in table 1.
Embodiment 7
10 parts of nano imvites are dissolved in the acetone, continue about 80 ℃ to stir 20h, it is slowly dissolved.Then 90 parts of CBT are dissolved in the acetone, continue about 80 ℃ to stir, make its dissolving.This CBT solution is poured in the scattered polynite solution, continued to continue to stir 20h.Vapor away solvent, 80 ℃ of vacuum-dryings.To be warming up to 190 ℃ through CBT, the nano imvite mixture that drying is crossed at last, and make CBT carry out in-situ polymerization and prepare the PBT/ Nano composite material of montmorillonite.Gained sample Tc is as shown in table 1.
Embodiment 8
10 parts of nano imvites are dissolved in the acetone, and 80 ℃ of left and right sides ultra-sonic dispersion 20h slowly dissolve it.Then 90 parts of CBT are dissolved in the acetone, 80 ℃ of left and right sides ultra-sonic dispersion make its dissolving.This CBT solution is poured in the scattered polynite solution, continued ultra-sonic dispersion 20h.Vapor away solvent, 80 ℃ of vacuum-dryings.To be warming up to 190 ℃ through CBT, the nano imvite mixture that drying is crossed at last, and make CBT carry out in-situ polymerization and prepare the PBT/ Nano composite material of montmorillonite.Gained sample Tc is as shown in table 1.
Each embodiment sample Tc of table 1.
Embodiment |
Tc (℃) |
1 |
198 |
2 |
198 |
3 |
206 |
4 |
206 |
5 |
198 |
6 |
198 |
7 |
206 |
8 |
206 |
Pure PBT |
190 |
Embodiment 9
CBT65 part is heated to 100 ℃ of fusions, when CBT melt viscosity value is 15MPa.s, adds 35 parts of nano imvites, fully stir 35h, logical N
2, nano imvite is uniformly dispersed in the CBT melt.Be warming up to 210 ℃ then, make CBT carry out in-situ polymerization, preparation PBT/ Nano composite material of montmorillonite.
Embodiment 10
CBT85 part is heated to 165 ℃ of fusions, when CBT melt viscosity value is 42MPa.s, adds 15 parts of nano imvites, ultra-sonic dispersion 45h, N
2Protection is uniformly dispersed nano imvite in the CBT melt.Be warming up to 235 ℃ then, make CBT carry out in-situ polymerization, preparation PBT/ Nano composite material of montmorillonite.
Embodiment 11
50 parts of nano imvites are dissolved in the methylene dichloride, continue about 80 ℃ to stir 30h, it is slowly dissolved.Then 50 parts of CBT are dissolved in the methylene dichloride, continue about 80 ℃ to stir, make its dissolving.This CBT solution is poured in the scattered polynite solution, continued to continue to stir 30h.Vapor away solvent, 80 ℃ of vacuum-dryings.To be warming up to 250 ℃ through CBT, the nano imvite mixture that drying is crossed at last, and make CBT carry out in-situ polymerization and prepare the PBT/ Nano composite material of montmorillonite.
Embodiment 12
0.01 part of nano imvite is dissolved in the trifluoroacetic acid, and 80 ℃ of left and right sides ultra-sonic dispersion 1h slowly dissolve it.Then 99.99 parts of CBT are dissolved in the trifluoroacetic acid, 80 ℃ of left and right sides ultra-sonic dispersion make its dissolving.This CBT solution is poured in the scattered polynite solution, continued ultra-sonic dispersion 1h.Vapor away solvent, 80 ℃ of vacuum-dryings.To be warming up to 180 ℃ through CBT, the nano imvite mixture that drying is crossed at last, and make CBT carry out in-situ polymerization and prepare the PBT/ Nano composite material of montmorillonite.