CN102115072A - Organic tin functionalized carbon nano tube and application of organic tin functionalized carbon nano tube in polyester compound material preparation - Google Patents
Organic tin functionalized carbon nano tube and application of organic tin functionalized carbon nano tube in polyester compound material preparation Download PDFInfo
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Abstract
The invention relates to an organic tin functionalized carbon nano tube, a carbon-nano-tube-based polyester nucleating agent and a preparation method of a carbon nano tube/polyester compound material. The preparation method of the carbon nano tube/polyester compound material comprises the following steps: reacting the carbon nano tube with an organic tin compound; initiating cyclic oligoester to carry out ring-opening polymerization based on the functionalized carbon nano tube as a macromolecule initiator so as to obtain the nucleating agent subjected to carbon nano tube surface polyester modification; and carrying out an in-situ polymerization reaction on the organic tin functionalized carbon nano tube and cyclic oligomer of polybutylene terephthalate so as to generate the carbon nano tube/polyester compound material. Compared with the prior art, in the method, a polymer is introduced to be firmly coated on the surface of the carbon nano tube, thereby increasing the interactive function between the carbon nano tube and a polymer substrate and improving the dispersion of the carbon nano tube in the substrate so as to achieve ideal nucleating efficiency and in-situ compatibilization.
Description
Technical field
The present invention relates to the preparation method of a kind of organotin functionalized carbon nanotube, carbon nanotube-based polyester nucleator and carbon nano-tube/poly ester matrix material.
Background technology
From Sumio Iijima in 1991 since significant article is delivered about carbon nanotube, carbon nanotube becomes the hot issue in chemistry, material field rapidly because of characteristics such as its superpower mechanical property, unique photoelectric properties and specific surface area are big.But carbon nanotube is easily reunited, thereby is difficult to be scattered in matrix and is insoluble to any solvent owing to there is stronger Van der Waals force effect between self, makes its application be subjected to serious restriction.
The most frequently used nucleator of polyester is a macromole carboxylate salt nucleator at present, for example poly-(ethylene-propylene ester sodium salt) multipolymer and various small molecules carboxylate salt nucleator, the nucleogenesis of such nucleator is in the course of processing of polyester and polyester carries out chemical reaction, make the polyester molecule splitting of chain, meanwhile, connect the carboxylic acid sodium ionic end groups at molecule chain end.Thereby what really work is the polyester ionic end groups that generates in the reaction process, or the ion cluster that is formed by ionic end groups.This class nucleator is referred to as " chemical nucleation " mechanism type nucleator, though its nucleation efficient height unavoidably causes the molecular weight of polyesters degraded, thus infringement polyester performance.
As everyone knows, carbon nanotube is a kind of good heterogeneous nucleation agent, and very high crystallization nucleation efficient is arranged under the finely disseminated situation, and consumption seldom can reach very high nucleation rate.But because strong Van der Waals force interacts between the carbon nanotube itself, carbon nanotube is easily reunited, and the carbon nanotube of reunion can not be brought into play its due nucleation efficient.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of simple and convenient, the preparation method of the organotin functionalized carbon nanotube of good product performance, carbon nanotube-based polyester nucleator and carbon nano-tube/poly ester matrix material 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 organotin functionalized carbon nanotube is characterized in that described method specifically may further comprise the steps:
(1) take by weighing after the carbon nanotube drying and thionyl chloride heating reflux reaction 12-48 hour, the excessive thionyl chloride of underpressure distillation, suction filtration obtains the acidylate carbon nanotube after the anhydrous tetrahydro furan washing;
(2) will be after the acidylate carbon nanotube drying with dibasic alcohol 100-130 ℃ of reaction 8-15 hour down, filter, wash the carbon nanotube of hydroxyl functionalization;
(3) with the carbon nanotube of hydroxyl functionalization and organic tin compound under the condition that dewatering agent exists, be heated to 100-150 ℃, react 8-12 hour, filtration, wash the organotin functionalized carbon nanotube.
The described carbon nanotube of step (1) is carboxylated carbon nanotube, and the mass ratio of described carbon nanotube of step (1) and thionyl chloride is 1: (40-60).
The described dibasic alcohol of step (2) comprises ethylene glycol, 1, ammediol or 1, and the 4-butyleneglycol, the mass ratio of described acidylate carbon nanotube of step (2) and dibasic alcohol is 1: (30-60).
The described organic tin compound of step (3) comprises dibutyltin oxide, Mono-n-butyltin or stannous octoate, described dewatering agent is a toluene, and the carbon nanotube of the described hydroxyl functionalization of step (3) and the mass ratio of organic tin compound are 1: (0.5-1.0).
A kind of preparation method of carbon nanotube-based polyester nucleator, it is characterized in that, this method reacts described organotin functionalized carbon nanotube to 20-60min as macromole evocating agent and cyclic oligoester under 180-220 ℃ temperature, cause the cyclic oligoester ring-opening polymerization, obtain the nucleator of carbon nano tube surface polyester modification, concrete reaction process is as shown below:
Described cyclic oligoester is polybutylene terephthalate cyclic oligomer, polyethylene terephthalate cyclic oligomer, Poly(Trimethylene Terephthalate) cyclic oligomer or L-lactic acid, and the mass ratio of described organotin functionalized carbon nanotube and cyclic oligoester is 1: (40-50).
A kind of preparation method of carbon nano-tube/poly ester matrix material is characterized in that, this method may further comprise the steps:
(a) adopt high purity nitrogen that the air in the reactor is driven out of, in the cyclic oligomer input reactor with polybutylene terephthalate, be heated to 180-200 ℃, make its complete fusion, obtain clear solution;
(b) in the cyclic oligomer of the polybutylene terephthalate of per 100 weight parts, add the described organotin functionalized carbon nanotube of exsiccant 0.5-1.5 weight part;
(c) mechanical stirring is warming up to 220-250 ℃ of reaction 20-60min after evenly, adds ester catalyst and ester stabilizer, reacts 20-60min again, obtains the carbon nano-tube/poly ester matrix material of the original position increase-volume of macromolecule.
The described ester catalyst of step (c) is tributyl oxyethyl group tin, butyl dihydroxyl tin chloride or positive metatitanic acid four (2-ethylhexyl) ester, its add-on is the 0.1-0.3% of the cyclic oligomer weight of polybutylene terephthalate, the described ester stabilizer of step (c) is antioxidant 1010 or three (2, the 4-DI-tert-butylphenol compounds) phosphorous acid ester, its add-on are the 1-3% of the cyclic oligomer weight of polybutylene terephthalate.
Compared with prior art, the present invention utilizes the carbon nanotube can be as the characteristic of good heterogeneous nucleation agent, but because it is difficult to disperse in polyester matrix, do not play due effect, thereby the present invention adopts way to surface modification of carbon nanotube to improve the dispersion of carbon nanotube in matrix, resulting carbon nanotube-based polyester nucleator can effectively promote crystallizing polyester, add in the polyester system, do not react with polyester, do not cause the molecular weight of polyesters degraded, this kind nucleator can be referred to as " non-chemical nucleation " mechanism type nucleator.The present invention is intended to improve the group of carbon nano tube surface, introduces polymkeric substance and firmly is coated on carbon nano tube surface, increases the interaction of carbon nanotube and polymeric matrix, improves the dispersion of carbon nanotube in matrix, thereby reaches ideal nucleation efficient.
Compared with prior art, the homemade organotin functionalized carbon nanotube that the present invention adopts, can cause the ring-opening reaction of cyclic oligoester because of the organotin of its surface grafting, the formation carbon nanotube grafts of energy original position, this grafts in system as the original position expanding material, increase the interaction of carbon nanotube and polymeric matrix, thereby improved the dispersiveness of carbon nanotube in polymeric matrix.
In addition, the raw material that is adopted among the present invention is the cyclic oligomer CBT of PBT, and CBT is made by Cyclic company, and its outstanding advantage is that melt viscosity is extremely low, as water, is beneficial to processing.Add catalyzer under suitable temperature, CBT can aggregate into high-molecular weight PBT resin, and no low molecular weight substance is emitted in the reaction process.Simultaneously, low melt viscosity that CBT had and polar characteristics are nano-sized filler, and as splendid " solvent " of nanoclay, carbon Nano filling, carbon nanotube, thereby Nano filling can well be scattered in the CBT melt.Having simplified production technique greatly, shortened the production cycle, also can avoid the use of solvent, is a kind of environmental friendliness production technique.
Can prepare the carbon nano-tube/poly ester nano composite material of original position increase-volume by introducing carbon nano tube modified in the process of the present invention, by the original position increase-volume, resulting nano composite material characterizes carbon nanotube homogeneous dispersion in substrate polyester as can be seen by transmission electron microscope, is nano level and disperses.Because carbon nano tube surface is through the organotin grafting, can be as the macromole evocating agent of cyclic oligoester, thereby played the effect of original position increase-volume.
Description of drawings
Fig. 1 is the TEM figure of the carbon nano-tube/poly mutual-phenenyl two acid bromide two alcohol ester nano composite material 2 μ m of content of carbon nanotubes 0.5wt%;
Fig. 2 is the TEM figure of the carbon nano-tube/poly mutual-phenenyl two acid bromide two alcohol ester nano composite material 0.2 μ m of content of carbon nanotubes 0.5wt%;
Fig. 3 is the TEM figure of the carbon nano-tube/poly mutual-phenenyl two acid bromide two alcohol ester nano composite material 100nm of content of carbon nanotubes 0.5wt%;
Fig. 4 is the TEM figure of the carbon nano-tube/poly mutual-phenenyl two acid bromide two alcohol ester nano composite material 2 μ m of content of carbon nanotubes 0.75wt%;
Fig. 5 is the TEM figure of the carbon nano-tube/poly mutual-phenenyl two acid bromide two alcohol ester nano composite material 0.2 μ m of content of carbon nanotubes 0.75wt%;
Fig. 6 is the TEM figure of the carbon nano-tube/poly mutual-phenenyl two acid bromide two alcohol ester nano composite material 100nm of content of carbon nanotubes 0.75wt%.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1:
A kind of organotin functionalized carbon nanotube and preparation method thereof, realize as follows:
(1) take by weighing the 1g carboxylic carbon nano-tube, the 40g thionyl chloride, heating reflux reaction 24 hours, the excessive thionyl chloride of underpressure distillation, suction filtration, the anhydrous tetrahydro furan washing gets the acidylate carbon nanotube for several times.
(2) take by weighing 1g acidylate carbon nanotube, 30g 1, and the 4-butyleneglycol is heated to 120 ℃ of reactions 12 hours, suction filtration, and washing gets the hydroxylation carbon nanotube for several times.
(3) take by weighing 1g hydroxylation carbon nanotube, the 0.5g dibutyltin oxide, extremely anhydrous generation of refluxing toluene band water reaction, suction filtration, drying gets the organotin functionalized carbon nanotube.
Embodiment 2:
A kind of organotin functionalized carbon nanotube and preparation method thereof, realize as follows:
(1) take by weighing the 1g carboxylic carbon nano-tube, the 60g thionyl chloride, heating reflux reaction 12 hours, the excessive thionyl chloride of underpressure distillation, suction filtration, the anhydrous tetrahydro furan washing gets the acidylate carbon nanotube for several times.
(2) take by weighing 1g acidylate carbon nanotube, 60g1, ammediol is heated to 130 ℃ of reactions 8 hours, suction filtration, washing gets the hydroxylation carbon nanotube for several times.
(3) take by weighing 1g hydroxylation carbon nanotube, the 1g Mono-n-butyltin, extremely anhydrous generation of refluxing toluene band water reaction, suction filtration, drying gets the organotin functionalized carbon nanotube.
Embodiment 3
A kind of preparation method of organotin functionalized carbon nanotube specifically may further comprise the steps:
(1) takes by weighing after the carboxylated carbon nanotube drying and thionyl chloride heating reflux reaction 48 hours, the mass ratio of carbon nanotube and thionyl chloride is 1: 50, the excessive thionyl chloride of underpressure distillation, suction filtration obtains black acidylate carbon nanotube after the anhydrous tetrahydro furan washing;
(2) be 1: 50 acidylate carbon nanotube and ethylene glycol with mass ratio 100 ℃ of reactions 15 hours down, filter, wash the carbon nanotube of hydroxyl functionalization;
(3) with mass ratio be 1: 0.75 the carbon nanotube of hydroxyl functionalization and stannous octoate under the condition that dewatering agent toluene exists, be heated to 100 ℃, react 12 hours, filtration, wash the organotin functionalized carbon nanotube.
Embodiment 4
A kind of preparation method of carbon nanotube-based polyester nucleator specifically may further comprise the steps:
(1) takes by weighing after the carboxylated carbon nanotube drying and thionyl chloride heating reflux reaction 30 hours, the mass ratio of carbon nanotube and thionyl chloride is 1: 45, the excessive thionyl chloride of underpressure distillation, suction filtration obtains black acidylate carbon nanotube after the anhydrous tetrahydro furan washing;
(2) with mass ratio be 1: 40 acidylate carbon nanotube and 1, ammediol filters 110 ℃ of reactions 10 hours down, wash the carbon nanotube of hydroxyl functionalization;
(3) with mass ratio be 1: 0.85 the carbon nanotube of hydroxyl functionalization and Mono-n-butyltin under the condition that dewatering agent toluene exists, be heated to 150 ℃, react 8 hours, filtration, wash the organotin functionalized carbon nanotube;
(4) the organotin functionalized carbon nanotube is reacted 20min as macromole evocating agent and polyethylene terephthalate cyclic oligomer under 180 ℃ temperature, the mass ratio of organotin functionalized carbon nanotube and polyethylene terephthalate cyclic oligomer is 1: 50, obtains the nucleator of carbon nano tube surface polyester modification.
Embodiment 5
A kind of preparation method of carbon nanotube-based polyester nucleator specifically may further comprise the steps:
(1) takes by weighing after the carboxylated carbon nanotube drying and thionyl chloride heating reflux reaction 36 hours, the mass ratio of carbon nanotube and thionyl chloride is 1: 55, the excessive thionyl chloride of underpressure distillation, suction filtration obtains black acidylate carbon nanotube after the anhydrous tetrahydro furan washing;
(2) with mass ratio be 1: 35 acidylate carbon nanotube and 1, the 4-butyleneglycol filters 125 ℃ of reactions 13 hours down, wash the carbon nanotube of hydroxyl functionalization;
(3) with mass ratio be 1: 0.9 the carbon nanotube of hydroxyl functionalization and stannous octoate under the condition that dewatering agent toluene exists, be heated to 120 ℃, react 9 hours, filtration, wash the organotin functionalized carbon nanotube;
(4) the organotin functionalized carbon nanotube is reacted 60min as macromole evocating agent and Poly(Trimethylene Terephthalate) cyclic oligomer under 220 ℃ temperature, the mass ratio of organotin functionalized carbon nanotube and Poly(Trimethylene Terephthalate) cyclic oligomer is 1: 40, obtains the nucleator of carbon nano tube surface polyester modification.
Embodiment 6
A kind of carbon nanotube the in-situ preparing of polyester composite and the method for original position increase-volume, realize as follows:
(1) takes by weighing 20g CBT, drive air in the system away with high purity nitrogen before feeding intake, repeat this action three times, get rid of totally to guarantee the air in the system, with anti-oxidation.Be heated to 190 ℃, stir and make the complete fusion of CBT.
(2) take by weighing 0.15g exsiccant organotin functionalized carbon nanotube, nitrogen protection adds down.Mechanical stirring 1h, ultra-sonic dispersion 1h.
(3) be warming up to 240 ℃ of reaction 30min after, add 0.04g tributyl oxyethyl group tin and 0.4g antioxidant 1010, react 30min once more.The nitrogen protection bottom discharge, the nano composite material of the son amount that secures satisfactory grades.
Embodiment 7
The application of organotin functionalized carbon nano-tube in the preparation polyester composite, this application may further comprise the steps:
(a) adopt high purity nitrogen that the air in the reactor is driven out of, in the cyclic oligomer input reactor with polybutylene terephthalate, be heated to 180 ℃, make its complete fusion, obtain clear solution;
(b) in the cyclic oligomer of the polybutylene terephthalate of 100g, add the described organotin functionalized carbon nanotube of exsiccant 0.5g;
(c) mechanical stirring is warming up to 220 ℃ of reaction 60min after evenly, adds 0.1g ester catalyst butyl dihydroxyl tin chloride and 1g ester stabilizer antioxidant 1010, reacts 20min again, obtains the carbon nano-tube/poly ester matrix material of the original position increase-volume of macromolecule.
Embodiment 8
The application of organotin functionalized carbon nano-tube in the preparation polyester composite, this application may further comprise the steps:
(a) adopt high purity nitrogen that the air in the reactor is driven out of, in the cyclic oligomer input reactor with polybutylene terephthalate, be heated to 200 ℃, make its complete fusion, obtain clear solution;
(b) in the cyclic oligomer of the polybutylene terephthalate of every 100g, add the described organotin functionalized carbon nanotube of exsiccant 1.5g;
(c) mechanical stirring is warming up to 250 ℃ of reaction 20min after evenly, add 0.3g ester catalyst positive metatitanic acid four (2-ethylhexyl) ester and 3g ester stabilizer three (2, the 4-DI-tert-butylphenol compounds) phosphorous acid ester reacts 60min again, obtains the carbon nano-tube/poly ester matrix material of the original position increase-volume of macromolecule.
The preparation carbon nanotube polyester composite, by the deployment conditions (see accompanying drawing 1-6) of tem observation carbon nanotube in matrix.Shown in accompanying drawing 1-6, carbon nanotube homogeneous in matrix PBT disperses as can be seen, is nano level and disperses.
Claims (8)
1. the preparation method of organotin functionalized carbon nano-tube is characterized in that, described method specifically may further comprise the steps:
(1) take by weighing after the carbon nanotube drying and thionyl chloride heating reflux reaction 12-48 hour, the excessive thionyl chloride of underpressure distillation, suction filtration obtains the acidylate carbon nanotube after the anhydrous tetrahydro furan washing;
(2) will be after the acidylate carbon nanotube drying with dibasic alcohol 100-130 ℃ of reaction 8-15 hour down, filter, wash the carbon nanotube of hydroxyl functionalization;
(3) with the carbon nanotube of hydroxyl functionalization and organic tin compound under the condition that dewatering agent exists, be heated to 100-150 ℃, react 8-12 hour, filtration, wash the organotin functionalized carbon nanotube.
2. the preparation method of organotin functionalized carbon nano-tube according to claim 1 is characterized in that, the described carbon nanotube of step (1) is carboxylated carbon nanotube, and the mass ratio of described carbon nanotube of step (1) and thionyl chloride is 1: (40-60).
3. the preparation method of organotin functionalized carbon nano-tube according to claim 1; it is characterized in that the described dibasic alcohol of step (2) comprises ethylene glycol, 1, ammediol or 1; the 4-butyleneglycol, the mass ratio of described acidylate carbon nanotube of step (2) and dibasic alcohol is 1: (30-60).
4. the preparation method of organotin functionalized carbon nano-tube according to claim 1, it is characterized in that, the described organic tin compound of step (3) comprises dibutyltin oxide, Mono-n-butyltin or stannous octoate, described dewatering agent is a toluene, and the carbon nanotube of the described hydroxyl functionalization of step (3) and the mass ratio of organic tin compound are 1: (0.5-1.0).
5. the preparation method of a carbon nanotube-based polyester nucleator, it is characterized in that, this method reacts described organotin functionalized carbon nanotube to 20-60min as macromole evocating agent and cyclic oligoester under 180-220 ℃ temperature, cause the cyclic oligoester ring-opening polymerization, obtain the nucleator of carbon nano tube surface polyester modification.
6. the preparation method of a kind of carbon nanotube-based polyester nucleator according to claim 5, it is characterized in that, described cyclic oligoester is polybutylene terephthalate cyclic oligomer, polyethylene terephthalate cyclic oligomer, Poly(Trimethylene Terephthalate) cyclic oligomer or L-lactic acid, and the mass ratio of described organotin functionalized carbon nanotube and cyclic oligoester is 1: (40-50).
7. the application of organotin functionalized carbon nano-tube in the preparation polyester composite is characterized in that this application may further comprise the steps:
(a) adopt high purity nitrogen that the air in the reactor is driven out of, in the cyclic oligomer input reactor with polybutylene terephthalate, be heated to 180-200 ℃, make its complete fusion, obtain clear solution;
(b) in the cyclic oligomer of the polybutylene terephthalate of per 100 weight parts, add the described organotin functionalized carbon nanotube of exsiccant 0.5-1.5 weight part;
(c) mechanical stirring is warming up to 220-250 ℃ of reaction 20-60min after evenly, adds ester catalyst and ester stabilizer, reacts 20-60min again, obtains the carbon nano-tube/poly ester matrix material of the original position increase-volume of macromolecule.
8. the application of organotin functionalized carbon nano-tube according to claim 7 in the preparation polyester composite, it is characterized in that, the described ester catalyst of step (c) is tributyl oxyethyl group tin, butyl dihydroxyl tin chloride or positive metatitanic acid four (2-ethylhexyl) ester, its add-on is the 0.1-0.3% of the cyclic oligomer weight of polybutylene terephthalate, the described ester stabilizer of step (c) is antioxidant 1010 or three (2, the 4-DI-tert-butylphenol compounds) phosphorous acid ester, its add-on are the 1-3% of the cyclic oligomer weight of polybutylene terephthalate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718988A (en) * | 2012-06-28 | 2012-10-10 | 东华大学 | Polybutylece terephthalate (PBT) coated functional powder and preparation method thereof |
| CN102719931A (en) * | 2012-06-28 | 2012-10-10 | 东华大学 | Preparation method of functionalized polyester fiber |
| CN102952385A (en) * | 2012-10-29 | 2013-03-06 | 暨南大学 | Modified halloysite nanotube / biodegradable polyester composite material and preparation method thereof |
| CN110028771A (en) * | 2019-04-12 | 2019-07-19 | 江苏华信新材料股份有限公司 | A kind of novel transparent card polycarbonate protective film and preparation method thereof |
| CN111393744A (en) * | 2020-03-26 | 2020-07-10 | 南京京锦元科技实业有限公司 | TPE material with antibacterial conductivity and preparation method thereof |
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2009
- 2009-12-30 CN CN2009102476420A patent/CN102115072A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718988A (en) * | 2012-06-28 | 2012-10-10 | 东华大学 | Polybutylece terephthalate (PBT) coated functional powder and preparation method thereof |
| CN102719931A (en) * | 2012-06-28 | 2012-10-10 | 东华大学 | Preparation method of functionalized polyester fiber |
| CN102952385A (en) * | 2012-10-29 | 2013-03-06 | 暨南大学 | Modified halloysite nanotube / biodegradable polyester composite material and preparation method thereof |
| CN102952385B (en) * | 2012-10-29 | 2014-06-04 | 暨南大学 | Modified halloysite nanotube / biodegradable polyester composite material and preparation method thereof |
| CN110028771A (en) * | 2019-04-12 | 2019-07-19 | 江苏华信新材料股份有限公司 | A kind of novel transparent card polycarbonate protective film and preparation method thereof |
| CN111393744A (en) * | 2020-03-26 | 2020-07-10 | 南京京锦元科技实业有限公司 | TPE material with antibacterial conductivity and preparation method thereof |
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Application publication date: 20110706 |