CN102532817A - Polyester/carbon nano tube-nucleating agent composite material and preparation method thereof - Google Patents
Polyester/carbon nano tube-nucleating agent composite material and preparation method thereof Download PDFInfo
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- CN102532817A CN102532817A CN2010105767308A CN201010576730A CN102532817A CN 102532817 A CN102532817 A CN 102532817A CN 2010105767308 A CN2010105767308 A CN 2010105767308A CN 201010576730 A CN201010576730 A CN 201010576730A CN 102532817 A CN102532817 A CN 102532817A
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Abstract
The invention belongs to the technical field of high polymer material preparation, and in particular relates to a polyester/carbon nano tube-nucleating agent composite material and a preparation method thereof. The composite material provided by the invention comprises the following components in parts by weight: 78 parts of dimethyl terephthalate, 61-100 parts of 1,3-propylene glycol, 0.0078-0.78 part of ester exchange catalyst, 0.0078-0.78 part of polymerization catalyst, 0.05-5 parts of carbon nano tube and 0.02-2 parts of nucleating agent. The invention also provides the preparation method of the polyester/carbon nano tube-nucleating agent composite material. The preparation method comprises two steps, namely ester exchange and polymerization. For the composite material provided by the invention, the addition of the nucleating agent enhances the heterogeneous nucleation crystallization capability, improves the crystallization speed, reduces the sphaerocrystal size of dimethyl terephthalate and improves mechanical property; at the moment, the strength-increasing and toughening capabilities are mainly exerted by the addition of the carbon nano tube so that the great improvement of the property of the composite material can be realized only by less filling, thus the application field of the composite material is greatly expanded.
Description
Technical field
The invention belongs to field of polymer material preparing technology, be specifically related to a kind of Pdyester/carbon nano tube-nucleator matrix material and preparation method thereof.
Background technology
PTT (PTT) is by DMT. Dimethyl p-benzenedicarboxylate or terephthalic acid and 1, the ammediol polymerization and polyester.PTT is a kind of new polyester macromolecular material that has development prospect of new research and development after polyethylene terephthalate the 1950's (PET) and the polybutylene terephthalate seventies (PBT), is chosen as one of six big petrochemical industry product innovations by the U.S. in 1998.PTT is a kind of hemicrystalline superpolymer with higher melt temperature and second-order transition temperature, and he has good wear resistance, thermotolerance and chemical proofing, is widely used in fields such as synthon, film and engineering plastics.But, be restricted in the engineering plastics Application for Field because the rigidity of PTT makes its crystallization rate slower.Therefore for many years, improve the crystallization rate of PTT, improve its processing characteristics is one of main direction of PTT modification always.And the research of this respect mainly is the research that concentrates on the PTT crystallization nucleating agent, through adding nucleator, improves the crystallization rate of PTT, promotes the one-tenth crystalline nucleation of PTT, reduces its injection molding temperature, makes it reach the application requiring of engineering plastics.
High molecular crystallization nucleating agent of a great variety can be divided into mineral-type, organic type and polymer three major types substantially.The mineral-type nucleator mainly comprises MOX, inorganic salt and clay class etc.; Organic type of nucleator generally includes salt such as monacid sodium, potassium, like Sodium Benzoate (potassium), and aromatic hydroxyl sulphonate etc.; And high score subclass nucleator comprises an alkali metal salt, ionic polymer of polyester oligomer etc.And up to the present; Research about improving the PTT crystallization rate mainly concentrates on some mineral fillers; If you would take off soil (Cho HW; Lee JS, Prabu AA, Kim KJ.Physical properties of poly (trimethylene terephthalate)/organoclay nanocomposites obtained via melt compounding and in situ polymerization.Polym Compos 2008; 29 (12); 1328-36.), permanent white (Yao CG, Yang GS.Synthesis, thermal, and rheological properties of poly (trimethylene terephthalate)/BaSO
4Nanocomposites.Polym Adv Technol 2009; 20 (10): 768-74.); Silicon-dioxide (Yao CG; Yang GS.Poly (trimethylene terephthalate)/silica nanocomposites prepared by dual in situ polymerization:synthesis; Morphology, crystallization behavior and mechanical properties.Polym Int 2010; 59 (4): 492-500.) etc., thereby obviously merely from improve mechanical property that angle that crystallization rate reduces spherulite size removes to improve PTT especially shock resistance be extremely limited.
Carbon nanotube since 1991 by Japanese expert's Iijima (Iijima) since unexpected the discovery; Because its remarkable physicals; For example high modulus, intensity, good heat-conductivity conducting ability; Make it since finding, just receive the extensive concern of academia and industrial community deeply, macromolecule/carbon nano-tube composite material becomes history the most active research field of recent two decades always, and carbon nanotube has constituted the most active branch in macromolecule/carbon nano-tube composite material field for the influence of hypocrystalline macromolecular material crystal property; A large amount of research shows carbon nanotube makes it also can be as the high molecular heterogeneous nucleation agent of hypocrystalline owing to have higher specific surface area; The PTT/ carbon nano tube compound material also has report (Xu Y, Jia HB, Piao JN; Ye SR, Huang J.Crystallization behavior of poly (trimethylene terephthalate)/multi-walled carbon nanotube composites.J Mater Sci 2008; 43 (1): 417-21.); Yet; It promotes crystalline nucleation ability to weaken along with the enhancing of carbon nanotube and polymer reactive force; That is to say that carbon nanotube is dispersed in macromolecule matrix must to carry out necessary modification to carbon nanotube in order to improve, this has improved carbon nanotube and high molecular interaction force, but the while also reduced carbon nanotube induce the nucleation ability.
Summary of the invention
The purpose of this invention is to provide a kind of Pdyester/carbon nano tube-nucleator matrix material.
Another object of the present invention provides the preparation method of a kind of above-mentioned Pdyester/carbon nano tube-nucleator matrix material.
Technical scheme of the present invention is following:
The invention provides a kind of Pdyester/carbon nano tube-nucleator matrix material, this matrix material comprises following component and weight part:
The composition weight umber
DMT. Dimethyl p-benzenedicarboxylate 78
1, ammediol 61-100
Transesterification catalyst 0.0078-0.78
Polymerizing catalyst 0.0078-0.78
Carbon nanotube 0.05-5
Nucleator 0.02-2
Said transesterification catalyst is selected from Antimony Trioxide: 99.5Min, tetra-n-butyl titanate or hexafluoro and closes potassium titanate (K
2TiF
6) one or more mixtures in waiting.
Said polymerizing catalyst is selected from one or more mixtures in venus crystals, magnesium acetate or the zinc acetate etc.
Said carbon nanotube is selected from one or more the mixture in carboxylated SWCN, carboxylated double-walled carbon nano-tube, carboxylated multi-walled carbon nano-tubes, hydroxylation SWCN, hydroxylation double-walled carbon nano-tube or the hydroxylation multi-walled carbon nano-tubes; Length of carbon nanotube is 0.5-50 μ m; Diameter is 2-100nm, and carboxyl or hydroxy radical content are 0.73-3.24wt%.
Said nucleator is selected from Natural manganese dioxide, sodium-based montmorillonite, lime carbonate or with one or more mixtures in organic type of nucleator such as long-chain linear saturated carboxylic acid sodium salt (carbon atom quantity is between 28-32 on the main chain).
The present invention also provides the preparation method of a kind of above-mentioned Pdyester/carbon nano tube-nucleator matrix material, and this method may further comprise the steps:
(1) transesterify: with 78 parts of DMT. Dimethyl p-benzenedicarboxylates, 61～100 part 1; Ammediol and 0.0078-0.78 part transesterification catalyst mix, and with the three-necked flask that the mixing solutions that obtains places band to stir, open and stir; Control reaction temperature is 140～205 ℃, carries out transesterification reaction;
(2) polymerization: in the mixing solutions behind 92% the methyl alcohol that steams theoretical value (DMT. Dimethyl p-benzenedicarboxylate amount 2 times) through transesterify; Add 0.0078-0.78 part polymerizing catalyst; Then to wherein adding 0.05-5 part carbon nanotube and 0.02-2 part nucleator; Vacuum tightness is regulated to carrying out polycondensation below the 40Pa in elevated temperature to 240～270 ℃, and the reaction times is 4～6h; It is 80 ℃ that polycondensation finishes the back controlled temperature, and vacuum-drying 24～48h promptly gets Pdyester/carbon nano tube-nucleator matrix material.
The present invention compares with prior art, has following advantage and beneficial effect:
1, matrix material provided by the invention because the adding of nucleator has strengthened the heterogeneous nucleation crystallizing power, has improved crystallization velocity, has reduced the spherulite size of poly terephthalic acid dimethyl ester, has improved mechanical property; Its enhancing toughened ability will be mainly brought into play in the adding of carbon nanotube this moment, thereby make less filling just can reach the raising by a relatively large margin of composite property, thereby expand the Application Areas of matrix material greatly.
2, matrix material of the present invention does not use any solvent in the preparation process, be beneficial to suitability for industrialized production.
3, matrix material of the present invention, because carbon nanotube has the excellent comprehensive physicals, high length-to-diameter ratio can significantly improve the mechanical property of PTT.
4, the present invention utilizes the lower characteristics of in-situ polymerization system viscosity, helps the dispersion of nucleator and carbon nanotube, and performance advantage separately strengthens toughening effect preferably to such an extent as to low filling can reach to greatest extent.
5, the present invention is intended to utilize the synergy of nucleator and carbon nanotube, promptly utilizes the mechanical property of the high excellence that length-to-diameter ratio embodied of nucleator raising crystallization rate and carbon nanotube, toughness reinforcing PTT.
Embodiment
Below in conjunction with illustrated embodiment the present invention is further described.
Embodiment 1
(1) with 78 parts of DMT. Dimethyl p-benzenedicarboxylates, 76 part 1, ammediol and 0.015 part of positive four butyl esters adding of metatitanic acid are equipped with in the churned mechanically 250ml three-necked flask, open and stir, and control reaction temperature is 190 ℃ and carries out transesterify;
(2) quantity of methyl alcohol that steams of transesterify reaches in the mixing solutions behind 92% the methyl alcohol of transesterify theoretical value (DMT. Dimethyl p-benzenedicarboxylate amount 2 times); Add 0.015 part of polymerizing catalyst zinc acetate; Adding 0.05 part of diameter is the carboxylated SWCN of 2-10nm and 0.02 part of sodium-based montmorillonite; Controlled temperature is 255 ℃, polycondensation 4h under less than the pressure of 40Pa, and polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h.With gained sample hot pressing film forming under 245 ℃ of conditions, the mechanical property of measure sample.Numerical value such as table 1.
Embodiment 2
(1) with 78 parts of DMT. Dimethyl p-benzenedicarboxylates, 76 part 1, ammediol and 0.015 part of positive four butyl esters adding of metatitanic acid are equipped with in the churned mechanically 250ml three-necked flask, open and stir, and control reaction temperature is 190 ℃ and carries out transesterify;
(2) quantity of methyl alcohol that steams of transesterify reaches in the mixing solutions behind 92% the methyl alcohol of transesterify theoretical value (DMT. Dimethyl p-benzenedicarboxylate amount 2 times); Add 0.015 part of polymerizing catalyst zinc acetate; Adding 1 part of diameter is the carboxylated SWCN of 2-10nm and 0.02 part of sodium-based montmorillonite; Controlled temperature is 255 ℃, polycondensation 4h under less than the pressure of 40Pa, and polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h.With gained sample hot pressing film forming under 245 ℃ of conditions, the mechanical property of measure sample.Numerical value such as table 1.
Embodiment 3
(1) with 78 parts of DMT. Dimethyl p-benzenedicarboxylates, 76 part 1, ammediol and 0.015 part of positive four butyl esters adding of metatitanic acid are equipped with in the churned mechanically 250ml three-necked flask, open and stir, and control reaction temperature is 190 ℃ and carries out transesterify;
(2) quantity of methyl alcohol that steams of transesterify reaches in the mixing solutions behind 92% the methyl alcohol of transesterify theoretical value (DMT. Dimethyl p-benzenedicarboxylate amount 2 times); Add 0.015 part of polymerizing catalyst zinc acetate; Adding 5 parts of diameters is the carboxylated SWCN of 2-10nm and 0.02 part of sodium-based montmorillonite; Controlled temperature is 255 ℃, polycondensation 4h under less than the pressure of 40Pa, and polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h.With gained sample hot pressing film forming under 245 ℃ of conditions, the mechanical property of measure sample.Numerical value such as table 1.
Comparative example 1
(1) with 78 parts of DMT. Dimethyl p-benzenedicarboxylates, 78 part 1, ammediol and 0.015 part of positive four butyl esters adding of metatitanic acid are equipped with in the churned mechanically 250ml three-necked flask, open and stir, and control reaction temperature is 190 ℃ and carries out transesterify;
(2) quantity of methyl alcohol that steams of transesterify reaches in the mixing solutions behind 92% the methyl alcohol of transesterify theoretical value (DMT. Dimethyl p-benzenedicarboxylate amount 2 times); Add 0.015 part of zinc acetate; Controlled temperature is 255 ℃; Polycondensation 4h under less than the pressure of 40Pa, polycondensation finishes the back and promptly gets pure PTT in 80 ℃ of vacuum-drying 24h.With gained sample hot pressing film forming under 245 ℃ of conditions, the mechanical property of measure sample.Numerical value such as table 1.
Comparative example 2
(1) with 78 parts of DMT. Dimethyl p-benzenedicarboxylates, 78 part 1, ammediol and 0.015 part of positive four butyl esters adding of metatitanic acid are equipped with in the churned mechanically 250ml three-necked flask, open and stir, and control reaction temperature is 190 ℃ and carries out transesterify;
(2) quantity of methyl alcohol that steams of transesterify reaches in the mixing solutions behind 92% the methyl alcohol of transesterify theoretical value (DMT. Dimethyl p-benzenedicarboxylate amount 2 times); Add 0.015 part of polymerizing catalyst zinc acetate; Add 0.02 part of sodium-based montmorillonite; Controlled temperature is 255 ℃, polycondensation 4h under less than the pressure of 40Pa, and polycondensation finishes the back and promptly gets product (PTT/sodium-based montmorillonite matrix material) in 80 ℃ of vacuum-drying 24h.With gained sample hot pressing film forming under 245 ℃ of conditions, the mechanical property of measure sample.Numerical value such as table 1.
Comparative example 3
(1) with 78 parts of DMT. Dimethyl p-benzenedicarboxylates, 78 part 1, ammediol and 0.015 part of positive four butyl esters adding of metatitanic acid are equipped with in the churned mechanically 250ml three-necked flask, open and stir, and control reaction temperature is 190 ℃ and carries out transesterify;
(2) quantity of methyl alcohol that steams of transesterify reaches in the mixing solutions behind 92% the methyl alcohol of transesterify theoretical value (DMT. Dimethyl p-benzenedicarboxylate amount 2 times); Add 0.015 part of polymerizing catalyst zinc acetate; Adding 5 parts of diameters is the carboxylated SWCN of 10-20nm; Controlled temperature is 255 ℃, polycondensation 4h under less than the pressure of 40Pa, and polycondensation finishes the back and promptly gets product (PTT/SWCN matrix material) in 80 ℃ of vacuum-drying 24h.With gained sample hot pressing film forming under 245 ℃ of conditions, the mechanical property of measure sample.Numerical value such as table 1.
Embodiment 4
(1) with 78 parts of DMT. Dimethyl p-benzenedicarboxylates, 61 part 1, ammediol and 0.03 part of Antimony Trioxide: 99.5Min adding are equipped with in the churned mechanically 250ml three-necked flask, open and stir, and control reaction temperature is 190 ℃ and carries out transesterify;
(2) quantity of methyl alcohol that steams of transesterify reaches in the mixing solutions behind 92% the methyl alcohol of transesterify theoretical value (DMT. Dimethyl p-benzenedicarboxylate amount 2 times); Add 0.03 part of polymerizing catalyst magnesium acetate; Adding 2 parts of diameters is the carboxylated double-walled carbon nano-tube of 10-20nm and 1 part of lime carbonate; Controlled temperature is 255 ℃, polycondensation 4h under less than the pressure of 40Pa, and polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h.With gained sample hot pressing film forming under 245 ℃ of conditions, the mechanical property of measure sample.Numerical value such as table 1.
Embodiment 5
(1) with 78 parts of DMT. Dimethyl p-benzenedicarboxylates, 70 part 1, ammediol and 0.03 part of Antimony Trioxide: 99.5Min adding are equipped with in the churned mechanically 250ml three-necked flask, open and stir, and control reaction temperature is 190 ℃ and carries out transesterify;
(2) quantity of methyl alcohol that steams of transesterify reaches in the mixing solutions behind 92% the methyl alcohol of transesterify theoretical value (DMT. Dimethyl p-benzenedicarboxylate amount 2 times); Add 0.03 part of polymerizing catalyst magnesium acetate; Adding 5 parts of diameters is the carboxylated multi-walled carbon nano-tubes of 30-50nm and 2 parts of lime carbonate; Controlled temperature is 255 ℃, polycondensation 4h under less than the pressure of 40Pa, and polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h.With gained sample hot pressing film forming under 245 ℃ of conditions, the mechanical property of measure sample.Numerical value such as table 1.
Embodiment 6
(1) with 78 parts of DMT. Dimethyl p-benzenedicarboxylates, 80 part 1, ammediol and 0.0078 part of K
2TiF
6Add and be equipped with in the churned mechanically 250ml three-necked flask, open and stir, control reaction temperature is 190 ℃ and carries out transesterify;
(2) quantity of methyl alcohol that steams of transesterify reaches in the mixing solutions behind 92% the methyl alcohol of transesterify theoretical value (DMT. Dimethyl p-benzenedicarboxylate amount 2 times); Add 0.0078 part of polymerizing catalyst venus crystals; Add 0.05 part of diameter and be 2-10nm hydroxylation SWCN and 0.02 part of main chain and contain the long-chain linear saturated carboxylic acid sodium salt of 30 carbon; Controlled temperature is 255 ℃, polycondensation 4h under less than the pressure of 40Pa, and polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h.With gained sample hot pressing film forming under 245 ℃ of conditions, the mechanical property of measure sample.Numerical value such as table 1.
Embodiment 7
(1) with 78 parts of DMT. Dimethyl p-benzenedicarboxylates, 90 part 1, ammediol and 0.015 part of K
2TiF
6Add and be equipped with in the churned mechanically 250ml three-necked flask, open and stir, control reaction temperature is 190 ℃ and carries out transesterify;
(2) quantity of methyl alcohol that steams of transesterify reaches in the mixing solutions behind 92% the methyl alcohol of transesterify theoretical value (DMT. Dimethyl p-benzenedicarboxylate amount 2 times); Add 0.015 part of polymerizing catalyst venus crystals; Add 2 parts of diameters and be 10-20nm hydroxylation double-walled carbon nano-tube and 0.5 part of main chain and contain the long-chain linear saturated carboxylic acid sodium salt of 28 carbon; Controlled temperature is 255 ℃, polycondensation 4h under less than the pressure of 40Pa, and polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h.With gained sample hot pressing film forming under 245 ℃ of conditions, the mechanical property of measure sample.Numerical value such as table 1.
Embodiment 8
(1) with 78 parts of DMT. Dimethyl p-benzenedicarboxylates, 100 part 1, ammediol and 0.78 part of K
2TiF
6Add and be equipped with in the churned mechanically 250ml three-necked flask, open and stir, control reaction temperature is 190 ℃ and carries out transesterify;
(2) quantity of methyl alcohol that steams of transesterify reaches in the mixing solutions behind 92% the methyl alcohol of transesterify theoretical value (DMT. Dimethyl p-benzenedicarboxylate amount 2 times); Add 0.78 part of polymerizing catalyst venus crystals; Add 5 parts of diameters and be 30-50nm hydroxylation multi-walled carbon nano-tubes and 2 parts of main chains and contain the long-chain linear saturated carboxylic acid sodium salt of 32 carbon; Controlled temperature is 255 ℃, polycondensation 4h under less than the pressure of 40Pa, and polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h.With gained sample hot pressing film forming under 245 ℃ of conditions, the mechanical property of measure sample.Numerical value such as table 1.
Table 1
| Example | Notched Izod impact strength (J/m) |
| Embodiment 1 | 70 |
| Embodiment 2 | 97 |
| Embodiment 3 | 123 |
| Comparative example 1 | 35 |
| Comparative example 2 | 44 |
| Comparative example 3 | 45 |
| Embodiment 4 | 115 |
| Embodiment 5 | 155 |
| Embodiment 6 | 55 |
| Embodiment 7 | 100 |
| Embodiment 8 | 165 |
Find that through " comparative example 1-3 " being compared we no matter be to add sodium-based montmorillonite separately or add carbon nanotube separately, all the notched Izod impact strength to the poly terephthalic acid dimethyl ester has the raising effect, only increase rate is less relatively; Embodiment 1-3 is a fixed sodium base montmorillonite content, changes the amount of carbon nanotube, and the result finds to improve with content of carbon nanotubes, and notched Izod impact strength significantly improves; Embodiment 1 is the comprehensive of comparative example 2 and 3, and embodiment 1 is that hit intensity improves 35J/m in the comparative example 1 with respect to pure polyester, and comparative example 2 and 3 is that hit intensity improves 9 and 10J/m respectively in the comparative example 1 with respect to pure polyester.Obviously, the coordination plasticizing effect is more obvious.
The above-mentioned description to embodiment is can understand and use the present invention for ease of the those of ordinary skill of this technical field.The personnel of skilled obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (6)
1. Pdyester/carbon nano tube-nucleator matrix material, it is characterized in that: this matrix material comprises following component and weight part,
The composition weight umber
DMT. Dimethyl p-benzenedicarboxylate 78
1, ammediol 61-100
Transesterification catalyst 0.0078-0.78
Polymerizing catalyst 0.0078-0.78
Carbon nanotube 0.05-5
Nucleator 0.02-2
2. Pdyester/carbon nano tube according to claim 1-nucleator matrix material is characterized in that: said transesterification catalyst is selected from Antimony Trioxide: 99.5Min, tetra-n-butyl titanate or hexafluoro and closes one or more mixtures in the potassium titanate.
3. Pdyester/carbon nano tube according to claim 1-nucleator matrix material is characterized in that: said polymerizing catalyst is selected from one or more mixtures in venus crystals, magnesium acetate or the zinc acetate.
4. Pdyester/carbon nano tube according to claim 1-nucleator matrix material; It is characterized in that: said carbon nanotube is selected from one or more the mixture in carboxylated SWCN, carboxylated double-walled carbon nano-tube, carboxylated multi-walled carbon nano-tubes, hydroxylation SWCN, hydroxylation double-walled carbon nano-tube or the hydroxylation multi-walled carbon nano-tubes; Length of carbon nanotube is 0.5-50 μ m; Diameter is 2-100nm, and carboxyl or hydroxy radical content are 0.73-3.24wt%.
5. Pdyester/carbon nano tube according to claim 1-nucleator matrix material is characterized in that: said nucleator is selected from Natural manganese dioxide, sodium-based montmorillonite, lime carbonate or with one or more the mixture in the organic type of nucleator of carbon atom quantity between 28-32 on its main chain of long-chain linear saturated carboxylic acid sodium salt.
6. the preparation method of the arbitrary described Pdyester/carbon nano tube of claim 1 to 5-nucleator matrix material, it is characterized in that: this method may further comprise the steps,
(1) transesterify: with 78 parts of DMT. Dimethyl p-benzenedicarboxylates, 61～100 part 1; Ammediol and 0.0078-0.78 part transesterification catalyst mix, and with the three-necked flask that the mixing solutions that obtains places band to stir, open and stir; Control reaction temperature is 140～205 ℃, carries out transesterification reaction;
(2) polymerization: to steaming theoretical value through transesterify; In the mixing solutions behind 2 times of the DMT. Dimethyl p-benzenedicarboxylate amount 92% the methyl alcohol; Add 0.0078-0.78 part polymerizing catalyst, then to wherein adding 0.05-5 part carbon nanotube and 0.02-2 part nucleator, elevated temperature to 240～270 ℃; Regulate vacuum tightness to carrying out polycondensation below the 40Pa; Reaction times is 4～6h, and it is 80 ℃ that polycondensation finishes the back controlled temperature, and vacuum-drying 24～48h promptly gets Pdyester/carbon nano tube-nucleator matrix material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102964604A (en) * | 2012-11-23 | 2013-03-13 | 张家港顺昌化工有限公司 | Preparation method of nanometer fire retardant |
| CN105199339A (en) * | 2015-10-19 | 2015-12-30 | 福建师范大学 | PBS (poly butylenes succinate)/PBAT (poly butyleneadipate-co-terephthalate)/CNTs (Carbon Nanotubes) material for 3D printing and preparation method of PBS/PBAT/CNTs material |
| CN110948988A (en) * | 2019-11-05 | 2020-04-03 | 浙江旗声电子科技股份有限公司 | Diaphragm material for loudspeaker and preparation method thereof |
| CN111995846A (en) * | 2020-09-16 | 2020-11-27 | 贺州学院 | PTT/artificial granite waste residue composite material and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964604A (en) * | 2012-11-23 | 2013-03-13 | 张家港顺昌化工有限公司 | Preparation method of nanometer fire retardant |
| CN105199339A (en) * | 2015-10-19 | 2015-12-30 | 福建师范大学 | PBS (poly butylenes succinate)/PBAT (poly butyleneadipate-co-terephthalate)/CNTs (Carbon Nanotubes) material for 3D printing and preparation method of PBS/PBAT/CNTs material |
| CN110948988A (en) * | 2019-11-05 | 2020-04-03 | 浙江旗声电子科技股份有限公司 | Diaphragm material for loudspeaker and preparation method thereof |
| CN110948988B (en) * | 2019-11-05 | 2022-04-01 | 浙江旗声电子科技股份有限公司 | Diaphragm material for loudspeaker and preparation method thereof |
| CN111995846A (en) * | 2020-09-16 | 2020-11-27 | 贺州学院 | PTT/artificial granite waste residue composite material and preparation method thereof |
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