Summary of the invention
Purpose of the present invention is exactly that the preparation method of the polyester-ether elastomer/carbon nanotube composite material that a kind of carbon nanotube dispersed is more even, electrical and thermal conductivity good, comprehensive mechanical property is good is provided for the defective that overcomes above-mentioned prior art existence.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of polyester-ether elastomer/carbon nanotube composite material is characterized in that, the method comprises the following steps:
(1) carbon nano tube surface is modified: take carbon nanotube and be placed in flask, add the mixed acid solution that was mixed with in 3: 1 by volume by the vitriol oil and concentrated nitric acid, controlling temperature of reaction is 80-160 ℃, magnetic agitation 0.5-6h, again through dilution, filter, washing, the dry carboxylic carbon nano-tube that gets, with carboxylic carbon nano-tube, thionyl chloride and N, dinethylformamide is placed in the flask that reflux condensing tube is housed, controlling temperature of reaction is 80-100 ℃ of magnetic agitation 24-48h, get the chloride carbon nanotube, adding concentration is that the polyoxyethylene glycol toluene solution of 40wt% and triethylamine are as catalyzer, controlling temperature of reaction is 90-140 ℃ of magnetic agitation 24-60h, get the carbon nanotube of polymerization materialization,
(2) transesterify: with dimethyl terephthalate (DMT), glycol and the first catalyst mix, the mixing solutions that obtains is placed in the reactor that band stirs, opens and stir, controlling temperature of reaction is 140-205 ℃, carries out transesterification reaction;
(3) polymerization: steam the methyl alcohol of theoretical value 92% until transesterify after, add the second catalyzer, thermo-stabilizer and photostabilizer in mixing solutions, then the carbon nanotube that adds wherein the polymerization materialization that step (1) obtains, the rising temperature is to 240-270 ℃, regulate vacuum tightness to carrying out polycondensation below 40Pa, reaction times is 4-6h, and controlling temperature after polycondensation finishes is that 80 ℃ of vacuum-drying 24-48h namely get product.
Carbon nanotube in described step (1) and the weight ratio of mixed acid solution are 1: (100-150), carboxylic carbon nano-tube, thionyl chloride and N in described step (1), the dinethylformamide weight ratio is 1: (100-300): (0.5-3), the chloride carbon nanotube in described step (1), concentration are that the polyoxyethylene glycol toluene solution of 40wt% and the weight ratio of triethylamine are 1: (40-200): (0.5-10).
Triethylamine in described step (1) can dewater through molecular sieve adsorption, and in described step (1), the polyoxyethylene glycol toluene solution can be through azeotropic water removing.
Glycol in described step (2) is that small molecules glycol and polyglycol are 1 by weight: alcohol mixture (0.25-1.5), described small molecules glycol is selected from 1,2-ethylene glycol, 1, ammediol or 1, one or more in the 4-butyleneglycol, described polyglycol is selected from one or more in polyoxyethylene glycol, polypropylene glycol or polytetrahydrofuran, the mol ratio of described dimethyl terephthalate (DMT) and glycol≤0.5.
the first catalyzer in described step (2) is selected from the acetate type compound, tin compound, the antimony compounds, one or more in titanium compound or germanium compounds, described acetate type compound comprises zinc acetate, described tin compound is selected from one or both in dibutyltin oxide or stannous octoate, described antimony compounds comprises antimonous oxide, described titanium compound is selected from one or both in titanium dioxide or tetra-n-butyl titanate, described germanium compounds comprises germanium dioxide, the add-on of the first catalyzer is 1 ‰ of dimethyl terephthalate (DMT)-10 ‰ (wt ‰).
The theoretical value that steams methyl alcohol in described step (3) is the twice of the dimethyl terephthalate (DMT) molar weight that adds.
the second catalyzer in described step (3) is selected from the acetate type compound, tin compound, the antimony compounds, one or more in titanium compound or germanium compounds, described acetate type compound comprises zinc acetate, described tin compound is selected from one or both in dibutyltin oxide or stannous octoate, described antimony compounds comprises antimonous oxide, described titanium compound is selected from one or both in titanium dioxide or tetra-n-butyl titanate, described germanium compounds comprises germanium dioxide, the add-on of the second catalyzer is 1 ‰ of dimethyl terephthalate (DMT)-10 ‰ (wt ‰).
photostabilizer in described step (3) is selected from photostabilizer 944 (poly--{ [6-[(1, 1, 3, 3,-tetramethyl butyl)-amido] 1, 3, 5,-triazine-2, 4-two bases] [(2, 2, 6, the 6-tetramethyl-piperidyl)-imido grpup]-1, 6-hexane two bases-[(2, 2, 6, the 6-tetramethyl-piperidyl)-imido grpup] }), photostabilizer 622 (poly-[1-(2 '-hydroxyethyl)-2, 2, 6, 6-tetramethyl--4-hydroxy piperidine succinic acid fat]), photostabilizer 770 (sebacic acid two 2, 2, 6, 6-tetramethyl piperidine alcohol ester) or photostabilizer 783 (poly-{ [6-[(1, 1, 3, the 3-tetramethyl butyl) amino]]-1, 3, 5-triazine-2, 4-two [(2, 2, 6, 6,-tetramethyl-4-piperidyl) imino-]-1, 6-oneself two the support [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-] } with poly-succinic (4-hydroxyl-2, 2, 6, 6-tetramethyl--1-piperidines ethanol) one or more the mixture of ester), the add-on of photostabilizer is 2 ‰-10 ‰ (wt ‰) of co-mixing system gross weight after transesterify.
thermo-stabilizer in described step (3) is selected from triphenyl phosphite, four (2, 4-two-tert.-butylbenzene) 4, 4 ' biphenylene-diphosphites, irgasfos 168 (tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester), antioxidant 264 (2, the 6-toluene di-tert-butyl phenol), oxidation inhibitor Topanol-A (2, 4-dimethyl-6-tert.-butyl phenol) or oxidation inhibitor IRGANOX 1330 (3, 3, 3, 5, 5, 5-six tertiary butyls-a, a, a-(1, 3, 5-Three methyl Benzene-2, 4, 6-three bases) one or more three-p-cresols), the add-on of thermo-stabilizer is 2 ‰-10 ‰ (wt ‰) of co-mixing system gross weight after transesterify.
The carbon nanotube of the polymerization materialization in described step (3) and the weight ratio of dimethyl terephthalate (DMT) are 1: (15-80).
Compared with prior art, the polyester-ether elastomer/carbon nanotube composite material of the present invention's preparation owing to the polyester-ether elastomerics, good similarity being arranged after surface modification of carbon nanotube, makes carbon nanotube disperse in matrix more even, electrical and thermal conductivity is better, and comprehensive mechanical property is better.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
A kind of preparation method of polyester-ether elastomer/carbon nanotube composite material, the method comprises the following steps:
(1) surface modification of carbon nanotube: take the 1g carbon nanotube and be placed in the single port flask, the mixed acid solution (vitriol oil and the concentrated nitric acid mixing solutions that add 100g, volume ratio is 3: 1), magnetic agitation 0.5h in 80 ℃ of oil baths, through dilution, filter washing, the dry carboxylic carbon nano-tube 0.98g that gets.0.98g carboxylic carbon nano-tube, thionyl chloride 110g and 0.5g DMF (dewatering through 4A molecular sieve and sodium Metal 99.5 backflow) are put into the flask bottle that reflux condensing tube is housed, and 80 ℃ of magnetic agitation 24h obtain 1g chloride carbon nanotube.Add the polyoxyethylene glycol toluene solution 45g of azeotropic water removing and triethylamine 0.5g that molecular sieve adsorption dewaters as catalyzer, 90 ℃ of magnetic agitation 24h obtain polyoxyethylene glycol grafting carbon nanotube 1.2g;
(2) with the 78g dimethyl terephthalate (DMT), 65g 1,3-PD, positive four butyl esters of 40g Macrogol 4000 and 0.4g metatitanic acid add churned mechanically 250ml three-necked flask are housed, and control temperature of reaction and are 190 ℃ and carry out transesterify;
(3) after the quantity of methyl alcohol that steams of transesterify reaches 31ml, add positive four butyl esters of 0.4g metatitanic acid and 0.15g zinc acetate, and add 0.4g photostabilizer 622 (poly-[1-(2 '-hydroxyethyl)-2,2,6,6-tetramethyl--4-hydroxy piperidine succinic acid fat]) and 0.4g thermo-stabilizer triphenyl phosphite.Add polyoxyethylene glycol grafting carbon nanotube 1g, controlling temperature is 255 ℃, polycondensation 4h under less than the pressure of 40Pa, and polycondensation namely gets product in 80 ℃ of vacuum-drying 24h after finishing.
Embodiment 2
A kind of preparation method of polyester-ether elastomer/carbon nanotube composite material, the method comprises the following steps:
(1) surface modification of carbon nanotube: take the 1g carbon nanotube and be placed in the single port flask, the mixed acid solution (vitriol oil and the concentrated nitric acid mixing solutions that add 150g, volume ratio is 3: 1), magnetic agitation 3h in 95 ℃ of oil baths, through dilution, filter washing, the dry carboxylic carbon nano-tube 0.97g that gets.With 0.97g carboxylic carbon nano-tube, thionyl chloride 300g and 1.5g N, dinethylformamide (dewatering through 4A molecular sieve and sodium Metal 99.5 backflow) is put into the flask bottle that reflux condensing tube is housed, 80 ℃ of magnetic agitation 36h obtain 1.1g chloride carbon nanotube.Add the polyoxyethylene glycol toluene solution 200g of azeotropic water removing and triethylamine 7.5g that molecular sieve adsorption dewaters as catalyzer, 100 ℃ of magnetic agitation 48h obtain polyoxyethylene glycol grafting carbon nanotube 1.0g;
(2) with the 78g dimethyl terephthalate (DMT), 70g 1,3-PD, positive four butyl esters of 40g Macrogol 4000 and 0.4g metatitanic acid add churned mechanically 250ml three-necked flask are housed, and control temperature of reaction and are 200 ℃ and carry out transesterify;
(3) after the quantity of methyl alcohol that steams of transesterify reaches 31.5ml, add positive four butyl esters of 0.4g metatitanic acid and 0.2g zinc acetate, and add 0.4g photostabilizer 770 (two 2,2,6, the 6-tetramethyl piperidine alcohol esters of sebacic acid) and 0.4g 2,6-toluene di-tert-butyl phenol.Add polyoxyethylene glycol grafting carbon nanotube 1g, controlling temperature is 260 ℃, polycondensation 4h under less than the pressure of 40Pa, and polycondensation namely gets product in 80 ℃ of vacuum-drying 24h after finishing.
Embodiment 3
A kind of preparation method of polyester-ether elastomer/carbon nanotube composite material, the method comprises the following steps:
(1) surface modification of carbon nanotube: take the 1g carbon nanotube and be placed in the single port flask, the mixed acid solution (vitriol oil and the concentrated nitric acid mixing solutions that add 120g, volume ratio is 3: 1), magnetic agitation 6h in 85 ℃ of oil baths, through dilution, filter washing, the dry carboxylic carbon nano-tube 0.96g that gets.0.96g carboxylic carbon nano-tube, thionyl chloride 200g and 10g DMF (dewatering through 4A molecular sieve and sodium Metal 99.5 backflow) are put into the flask that reflux condensing tube is housed, and 90 ℃ of magnetic agitation 48h obtain 0.99g chloride carbon nanotube.Add triethylamine 10g that polyoxyethylene glycol toluene solution 200g (Polyethylene glycol is 40%) through azeotropic water removing and molecular sieve adsorption dewater as catalyzer, 120 ℃ of magnetic agitation 48h obtain polyoxyethylene glycol grafting carbon nanotube 1.0g;
(2) with the 78g dimethyl terephthalate (DMT), 75g 1,3-PD, positive four butyl esters of 40g Macrogol 4000 and 0.5g metatitanic acid add churned mechanically 250ml three-necked flask are housed, and control temperature of reaction and are 205 ℃ and carry out transesterify;
(3) after the quantity of methyl alcohol that steams of transesterify reaches 32ml, add positive four butyl esters of 0.5g metatitanic acid and 0.5g zinc acetate, and add 0.5g photostabilizer 770 (two 2,2,6, the 6-tetramethyl piperidine alcohol esters of sebacic acid) and 0.5g thermo-stabilizer triphenyl phosphite.Add polyoxyethylene glycol grafting carbon nanotube 1g, controlling temperature is 265 ℃, polycondensation 4h under less than the pressure of 40Pa, and polycondensation namely gets product in 80 ℃ of vacuum-drying 24h after finishing.
Specific conductivity, thermal conductivity, elongation at break and the tensile strength data of the matrix material that table 1 obtains for embodiment 1-3.
Table 1
Embodiment |
25 ℃/Scm of specific conductivity
-1 |
150 ℃/w of thermal conductivity (mk)
-1 |
Elongation at break % |
Tensile strength MPa |
Embodiment 1 |
3.1×10
4 |
15 |
960 |
18.5 |
Embodiment 2 |
4.3×10
4 |
18.2 |
750 |
20 |
Embodiment 3 |
5.1×10
4 |
24.3 |
487 |
21.5 |
Embodiment 4
A kind of preparation method of polyester-ether elastomer/carbon nanotube composite material, the method comprises the following steps:
(1) surface modification of carbon nanotube: take the 1g carbon nanotube and be placed in the single port flask, the mixed acid solution (vitriol oil and the concentrated nitric acid mixing solutions that add 100g, volume ratio is 3: 1), magnetic agitation 0.5h in 80 ℃ of oil baths, through dilution, filter washing, the dry carboxylic carbon nano-tube 0.98g that gets.With 0.98g carboxylic carbon nano-tube, thionyl chloride 110g and 0.6gN, dinethylformamide (dewatering through 4A molecular sieve and sodium Metal 99.5 backflow) is put into the flask bottle that reflux condensing tube is housed, and 80 ℃ of magnetic agitation 24h obtain 1g chloride carbon nanotube.Add the polyoxyethylene glycol toluene solution 40g of azeotropic water removing and triethylamine 0.5g that molecular sieve adsorption dewaters as catalyzer, 90 ℃ of magnetic agitation 24h obtain polyoxyethylene glycol grafting carbon nanotube 1.2g;
(2) with the 78g dimethyl terephthalate (DMT), 72g BDO, positive four butyl esters of 40g Macrogol 4000 and 0.3g metatitanic acid add churned mechanically 250ml three-necked flask are housed, and control temperature of reaction and are 200 ℃ and carry out transesterify;
(3) after the quantity of methyl alcohol that steams of transesterify reaches 31ml, add positive four butyl esters of 0.3g metatitanic acid and 0.1g zinc acetate, and add 0.4g photostabilizer 770 (two 2,2,6, the 6-tetramethyl piperidine alcohol esters of sebacic acid) and 0.4g thermo-stabilizer triphenyl phosphite.Add polyoxyethylene glycol grafting carbon nanotube 1g, controlling temperature of reaction is 260 ℃, polycondensation 4h under less than the pressure of 40Pa, and polycondensation namely gets product in 80 ℃ of vacuum-drying 24h after finishing.
Embodiment 5
A kind of preparation method of polyester-ether elastomer/carbon nanotube composite material, the method comprises the following steps:
(1) surface modification of carbon nanotube: take the 1g carbon nanotube and be placed in the single port flask, the mixed acid solution (vitriol oil and the concentrated nitric acid mixing solutions that add 150g, volume ratio is 3: 1), magnetic agitation 3h in 80 ℃ of oil baths, through dilution, filter washing, the dry carboxylic carbon nano-tube 0.98g that gets.With 0.98g carboxylic carbon nano-tube, thionyl chloride 200g and 1.5g N, dinethylformamide (dewatering through 4A molecular sieve and sodium Metal 99.5 backflow) is put into the flask bottle that reflux condensing tube is housed, 80 ℃ of magnetic agitation 36h obtain 0.99g chloride carbon nanotube.Add the polyoxyethylene glycol toluene solution 180g of azeotropic water removing and triethylamine 7.5g that molecular sieve adsorption dewaters as catalyzer, 90 ℃ of magnetic agitation 48h obtain polyoxyethylene glycol grafting carbon nanotube 1.1g;
(2) with the 78g dimethyl terephthalate (DMT), 75g BDO, positive four butyl esters of 40g Macrogol 4000 and 0.35g metatitanic acid add churned mechanically 250ml three-necked flask are housed, and control temperature of reaction and are 200 ℃ and carry out transesterify;
(3) after the quantity of methyl alcohol that steams of transesterify reaches 31.5ml, add positive four butyl esters of 0.35g metatitanic acid and 0.15g zinc acetate, and add 0.4g photostabilizer 770 (two 2,2,6, the 6-tetramethyl piperidine alcohol esters of sebacic acid) and 0.4g thermo-stabilizer triphenyl phosphite.Add polyoxyethylene glycol grafting carbon nanotube 1.1g, controlling temperature of reaction is 260 ℃, polycondensation 4h under less than the pressure of 40Pa, and polycondensation namely gets product in 80 ℃ of vacuum-drying 24h after finishing.
Embodiment 6
A kind of preparation method of polyester-ether elastomer/carbon nanotube composite material, the method comprises the following steps:
(1) surface modification of carbon nanotube: take the 1g carbon nanotube and be placed in the single port flask, the mixed acid solution (vitriol oil and the concentrated nitric acid mixing solutions that add 150g, volume ratio is 3: 1), magnetic agitation 6h in 85 ℃ of oil baths, through dilution, filter washing, the dry carboxylic carbon nano-tube 0.97g that gets.With 0.9g carboxylic carbon nano-tube, thionyl chloride 200g and 2gN, dinethylformamide (dewatering through 4A molecular sieve and sodium Metal 99.5 backflow) is put into the flask that reflux condensing tube is housed, and 90 ℃ of magnetic agitation 48h obtain 1g chloride carbon nanotube.Add triethylamine 8g that polyoxyethylene glycol toluene solution 180g (Polyethylene glycol is 40%) through azeotropic water removing and molecular sieve adsorption dewater as catalyzer, 120 ℃ of magnetic agitation 48h obtain polyoxyethylene glycol grafting carbon nanotube 0.98g;
(2) with the 78g dimethyl terephthalate (DMT), 80g BDO, positive four butyl esters of 40g Macrogol 4000 and 0.4g metatitanic acid add churned mechanically 250ml three-necked flask are housed, and control temperature of reaction and are 200 ℃ and carry out transesterify.
(3) after the quantity of methyl alcohol that steams of transesterify reaches 32ml, add positive four butyl esters of 0.4g metatitanic acid and 0.2g zinc acetate, 0.4g photostabilizer 770 (two 2,2,6, the 6-tetramethyl piperidine alcohol esters of sebacic acid) and 0.4g 2,4 dimethyl 6 tert butyl phenol.The carbon nanotube 0.98g that adds front-surface polymerization materialization, controlling temperature of reaction is 260 ℃, polycondensation 4h under less than the pressure of 40Pa, polycondensation namely gets product in 80 ℃ of vacuum-drying 24h after finishing.
Specific conductivity, thermal conductivity, elongation at break and the tensile strength data of the matrix material that table 2 obtains for embodiment 4-6.
Table 2
Embodiment |
25 ℃/(Scm of specific conductivity
-1)
|
150 ℃/(w (mk) of thermal conductivity
-1)
|
Elongation at break % |
Tensile strength MPa |
Embodiment 4 |
3.2×10
4 |
14.6 |
960 |
17.5 |
Embodiment 5 |
4.5×10
4 |
17.1 |
820 |
19 |
Embodiment 6 |
5.2×10
4 |
23 |
450 |
20.5 |
The measuring method of specific conductivity: GB/T 6908-2005.
The measuring method of thermal conductivity: metal heat conductivity investigating instrument HLD-KT-III is at 150 ℃, the high batten that is respectively 6cm, 2cm, 1cm of static measurement length and width.
Mechanics performance determining method: DIN 53455 standards.
Embodiment 7
A kind of preparation method of polyester-ether elastomer/carbon nanotube composite material, the method comprises the following steps:
(1) carbon nano tube surface is modified: take carbon nanotube and be placed in flask, add the mixed acid solution that was mixed with in 3: 1 by volume by the vitriol oil and concentrated nitric acid, the weight ratio of carbon nanotube and mixed acid solution is 1: 100, controlling temperature of reaction is 80 ℃, magnetic agitation 0.5h, again through dilution, filter, washing, the dry carboxylic carbon nano-tube that gets, with carboxylic carbon nano-tube, thionyl chloride and N, dinethylformamide is placed in the flask that reflux condensing tube is housed, carboxylic carbon nano-tube wherein, thionyl chloride and N, the weight ratio of dinethylformamide is 1: 100: 0.5, controlling temperature of reaction is 80 ℃ of magnetic agitation 24h, get the chloride carbon nanotube, adding concentration is that the polyoxyethylene glycol toluene solution of 40wt% and triethylamine are as catalyzer, chloride carbon nanotube wherein, the weight ratio of polyoxyethylene glycol toluene solution and triethylamine is 1: 40: 0.5, controlling temperature of reaction is 90 ℃ of magnetic agitation 24h, get the carbon nanotube of polymerization materialization,
(2) transesterify: be 0.5 to add the first catalyst acetic acid zinc of dimethyl terephthalate (DMT) weight 1 ‰ after mixing in molar ratio with dimethyl terephthalate (DMT) and glycol, wherein glycol is 1,2-ethylene glycol and polyoxyethylene glycol are the alcohol mixture of 1: 0.25 by weight, the mixing solutions that obtains is placed in the reactor that band stirs, open and stir, controlling temperature of reaction is 140 ℃, carries out transesterification reaction;
(3) polymerization: steam the methyl alcohol of theoretical value (twice of dimethyl terephthalate (DMT) molar weight) 92% until transesterify after, the the second catalyst oxidation dibutyl tin that adds dimethyl terephthalate (DMT) weight 1 ‰ in the mixing solutions, the photostabilizer 944 of co-mixing system gross weight 2 ‰ after the thermo-stabilizer triphenyl phosphite of co-mixing system gross weight 2 ‰ and irgasfos 168 (weight ratio 1: 1) and transesterify after transesterify, then the carbon nanotube that adds wherein the polymerization materialization that step (1) obtains, wherein the weight ratio of the add-on of the carbon nanotube of polymerization materialization and dimethyl terephthalate (DMT) is 1: 15, rising temperature to 240 ℃, regulate vacuum tightness to carrying out polycondensation below 40Pa, reaction times is 4h, controlling temperature after polycondensation finishes is that 80 ℃ of vacuum-drying 24h namely get product.
Embodiment 8
A kind of preparation method of polyester-ether elastomer/carbon nanotube composite material, the method comprises the following steps:
(1) carbon nano tube surface is modified: take carbon nanotube and be placed in flask, add the mixed acid solution that was mixed with in 3: 1 by volume by the vitriol oil and concentrated nitric acid, the weight ratio of carbon nanotube and mixed acid solution is 1: 150, controlling temperature of reaction is 160 ℃, magnetic agitation 6h, again through dilution, filter, washing, the dry carboxylic carbon nano-tube that gets, with carboxylic carbon nano-tube, thionyl chloride and N, dinethylformamide is placed in the flask that reflux condensing tube is housed, carboxylic carbon nano-tube wherein, thionyl chloride and N, the weight ratio of dinethylformamide is 1: 300: 3, controlling temperature of reaction is 100 ℃ of magnetic agitation 48h, get the chloride carbon nanotube, adding concentration is that the polyoxyethylene glycol toluene solution of 40wt% and triethylamine are as catalyzer, chloride carbon nanotube wherein, the weight ratio of polyoxyethylene glycol toluene solution and triethylamine is 1: 200: 10, controlling temperature of reaction is 140 ℃ of magnetic agitation 60h, get the carbon nanotube of polymerization materialization,
(2) transesterify: be 0.1 to add the first catalyst oxidation dibutyl tin and the tetra-n-butyl titanate (weight ratio 1: 1) of dimethyl terephthalate (DMT) weight 10 ‰ after mixing in molar ratio with dimethyl terephthalate (DMT) and glycol, wherein glycol is 1, ammediol and polytetrahydrofuran are the alcohol mixture of 1: 1.5 by weight, the mixing solutions that obtains is placed in the reactor that band stirs, open and stir, controlling temperature of reaction is 205 ℃, carries out transesterification reaction;
(3) polymerization: steam the methyl alcohol of theoretical value (twice of dimethyl terephthalate (DMT) molar weight) 92% until transesterify after, the inferior tin of the second octoate catalyst and the antimonous oxide (weight ratio 2: 1) that add dimethyl terephthalate (DMT) weight 10wt ‰ in the mixing solutions, the thermo-stabilizer four (2 of co-mixing system gross weight 10 ‰ after transesterify, 4-two-tert.-butylbenzene) 4, the photostabilizer 622 of co-mixing system gross weight 10 ‰ after 4 ' biphenylene-diphosphites and antioxidant 264 (weight ratio 3: 1) and transesterify, then the carbon nanotube that adds wherein the polymerization materialization that step (1) obtains, wherein the weight ratio of the add-on of the carbon nanotube of polymerization materialization and dimethyl terephthalate (DMT) is 1: 80, rising temperature to 270 ℃, regulate vacuum tightness to carrying out polycondensation below 40Pa, reaction times is 6h, controlling temperature after polycondensation finishes is that 80 ℃ of vacuum-drying 48h namely get product.