CN102485767A - Polyester/low-filling hybrid carbon nanotube composite material and preparation method thereof - Google Patents
Polyester/low-filling hybrid carbon nanotube composite material and preparation method thereof Download PDFInfo
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- CN102485767A CN102485767A CN2010105712841A CN201010571284A CN102485767A CN 102485767 A CN102485767 A CN 102485767A CN 2010105712841 A CN2010105712841 A CN 2010105712841A CN 201010571284 A CN201010571284 A CN 201010571284A CN 102485767 A CN102485767 A CN 102485767A
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Abstract
The invention relates to a polyester/low-filling hybrid carbon nanotube composite material and a preparation method thereof. The carbon nanotube composite material is prepared from the following raw materials, by weight, 0.05-5 parts of carbon nanotubes, 78 parts of dimetyl terephthalate, 50-100 parts of a diol, 0.0078-0.78 parts of an ester exchange catalyst and 0.0078-0.78 parts of a polymerization catalyst. According to the composite material prepared in the invention, advantages of long carbon nanotubes and short carbon nanotubes, which are greatly performed through the optimized combination of the long carbon nanotubes and the short carbon nanotubes, and the low system viscosity and vigorous mechanical stirring in the in situ polymerization process allow the carbon nanotubes to be uniformly dispersed in the system, so the low filling of the carbon nanotubes allows good mechanical performances, thermal performances and electric performances of the composite material to be reached. The method for preparing the high-electricity-conduction high-thermal-conduction low-filling composite material is an in situ polymerization method without any solvents, so the method is greatly convenient for the industrialized production.
Description
Technical field
The invention belongs to materials science field, relate to a kind of polyester/low filling and mix carbon nano tube compound material and preparation method thereof.
Background technology
For a long time, macromolecular material be considered to always the conduction and heat conduction on purposes less, this mainly is generally 10 because of its volume specific resistance
10～10
20Between Ω/cm, do not reach minimum conduction requirement far away; Equally, its thermal conductivity also differs greatly, and is about 1/500～1/600 of metal.This has limited the purposes of macromolecular material on the root greatly.Yet; Present numerous areas all requires very high to conduction, heat conduction, although metals such as argent, copper, aluminium have good conductive and heat-conductive ability, and used at wide spectrum; But it is than great; Limitations such as expensive have limited its range of application, and especially various plant and instrument have all stepped into the development track of miniaturized, high performance, and this makes with heavy metal as conduction or heat conduction some imbalance that seems.And polymer just in time has advantages such as light specific gravity and easy processing.The first-selection that has been combined into interior preparation conduction of a very long time and thermally conductive material of polymer and metal.
Over nearly more than 20 years, be matrix with the polymkeric substance, some conductions, heat conduction particle such as graphite, metal powder etc. have caused people's attention for the matrix material of filling.But these all only just have electrical and thermal conductivity preferably when high filler loading capacity, and price is raise, and can cause whole matrix material comprehensive mechanical property to reduce as bigger fragility, and this certainly will influence its range of application.
Since Japanese expert's Iijima (lijima) accident in 1991 is found carbon nanotube; Because its particular structural; Bigger length-to-diameter ratio (nano level diameter, micron-sized length) and remarkable performance are like extremely superior mechanics, heat conduction and conductivity; With macromolecule matrix density about the same, since coming to light, just become focus academic and that industrial community is paid close attention to always.Property research, study on the modification and applied research become the research focus of a very long time.Yet specific surface area that it is high and unreactiveness and the thin and long kindliness that is showed make and are difficult to and macromolecule matrix is well compatible and disperse.Certainly, also just be difficult to reach theoretical desired effect.A lot of relevant researchs also only rest on the experimental study stage.The carbon nanotube of producing at present roughly has following several kinds of sorting techniques: be that standard can be divided into: single wall, double-walled and multi-walled carbon nano-tubes with the wall; With length for being divided into: short and long carbon nanotube; With surface group for being divided into: unmodified carbon nanotube and modified carbon nano-tube (generally including carboxylic carbon nano-tube and hydroxylation carbon nanotube).Obviously, the longer carbon nanotube of short carbon nanometer tube is easier to disperse, but long carbon nanotube conducting heat conductivility is more outstanding; Consistency also should be variant in same Polymer Systems for the carbon nanotube of different surface treatment.
Summary of the invention
The objective of the invention is for a kind of low filling polyester-mix carbon nano tube compound material and preparation method thereof is provided.
The object of the invention mainly is to realize through following technical scheme: comprise the processing of two core links: the one, and optimum combination length wall carbon nano tube; Bring into play short carbon nanometer tube and long carbon nanotube advantage separately as far as possible, prepare carbon nano tube suspension by ultra-sonic dispersion; The 2nd, utilize in-situ polymerization to be beneficial to dispersive characteristics and violent mechanical stirring, make the dispersion state of carbon nanotube keep consistent as far as possible with carbon nano tube suspension, mix carbon nanotube enhancing, conduction, heat-conductive composite material thereby prepare low filling of polyester.
A kind of polyester/low filling mixes carbon nano tube compound material, prepared by following raw material and component:
The composition weight umber
Carbon nanotube 0.05-5
DMT. Dimethyl p-benzenedicarboxylate 78
Glycol 50-100
Transesterification catalyst 0.0078-0.78
Polymerizing catalyst 0.0078-0.78.
Described glycol is a terepthaloyl moietie, small molecules aliphatic dialcohols such as Ucar 35 or butyleneglycol.
Described carbon nanotube is carboxylated single wall, carboxylated double-walled or carboxylated multi-walled carbon nano-tubes or hydroxylation single wall, hydroxylation double-walled or hydroxylation multi-walled carbon nano-tubes; The shortwall length of carbon nanotube is 0.5-2 μ m; Long carbon nanotube is 10-50 μ m, and diameter is 2-100nm; Its carboxyl-content of carboxylic carbon nano-tube is 0.73～3.24%; Its hydroxy radical content of hydroxylation carbon nanotube is 0.73～3.24%; Shortwall carbon nanotube and longwell carbon nanotube mass ratio are 1: 10～10: 1.
Described transesterification catalyst is Antimony Trioxide: 99.5Min, tetra-n-butyl titanate, K
2TiF
6Deng in one or more mixtures.The weight ratio of transesterification catalyst and DMT. Dimethyl p-benzenedicarboxylate is (0.0078～0.78): 78.
Described polymerizing catalyst is venus crystals, magnesium acetate or zinc acetate etc.The weight ratio of polymerizing catalyst and DMT. Dimethyl p-benzenedicarboxylate is (0.0078～0.78): 78.
A kind of above-mentioned polyester/low method that mixes carbon nano tube compound material of filling for preparing comprises step:
(1) transesterify: a certain amount of DMT. Dimethyl p-benzenedicarboxylate, glycol and transesterification catalyst are mixed, with the three-necked flask that the mixture that obtains places band to stir, open and stir, control reaction temperature is 140～205 ℃, carries out transesterification reaction;
(2) polymerization: when amount that step (1) steams methyl alcohol be higher than theoretical value (DMT. Dimethyl p-benzenedicarboxylate amount 2 times) more than 80% after, add polymerizing catalyst, then to wherein adding carbon nanotube; Elevated temperature to 240～280 ℃; Regulate vacuum tightness to carrying out polycondensation below the 40Pa, the reaction times is 4～6h, and it is 60-80 ℃ that polycondensation finishes the back controlled temperature; Vacuum-drying 24～48h promptly gets Pdyester/carbon nano tube composite material, and wherein the content of carbon nanotube accounts for 0.05-5wt%.
The invention has the advantages that:
Compared with prior art; The polyester of the present invention's preparation/low filling mixes carbon nano tube compound material and preparation method thereof; Good use two kinds of carbon nanotubes advantages separately, i.e. relatively easy dispersion and the better conductive and heat-conductive ability of long carbon nanotube of short carbon nanometer tube.Utilize simultaneously in the in-situ polymerization process because the relatively low and violent mechanical stirring of system viscosity; Be convenient to the better dispersion of carbon nanotube and in whole process of preparation, exempted worries with the solvent dispersion carbon nanotube; Having prepared low filling enhancing, conduction, heat conduction polyester mixes carbon nano tube compound material, but is a kind of method of suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated, rather than limits scope of the present invention.
Embodiment 1
(1) with the 78g DMT. Dimethyl p-benzenedicarboxylate, churned mechanically 250ml three-necked flask is equipped with in the positive four butyl esters adding of 50g terepthaloyl moietie and 0.03g metatitanic acid, and control reaction temperature is 200 ℃ and carries out transesterify;
(2) after the quantity of methyl alcohol that steams of transesterify reaches 25.4g; Add the 0.03g zinc acetate, the 0.05g diameter is that (wherein, mass ratio is the carboxylated SWCN of 10-20nm: short carbon nanometer tube (about 2 microns of length)/long carbon nanotube (about 20 microns of length)=1/1); Controlled temperature is 280 ℃; Polycondensation 4h under less than the pressure of 40Pa, polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h, is polyethylene terephthalate/carbon nano tube compound material.Content of carbon nanotubes is 0.05wt% in the matrix material.With gained sample hot pressing film forming under 265 ℃ of conditions, the power of measure sample, conduction and heat conductivility.Numerical value such as table 1.
Embodiment 2
(1) with the 78g DMT. Dimethyl p-benzenedicarboxylate, churned mechanically 250ml three-necked flask is equipped with in the positive four butyl esters adding of 50g terepthaloyl moietie and 0.03g metatitanic acid, and control reaction temperature is 200 ℃ and carries out transesterify;
(2) after the quantity of methyl alcohol that steams of transesterify reaches 25.4g; Add the 0.03g zinc acetate, the 0.5g diameter is that (wherein, mass ratio is the carboxylated SWCN of 10-20nm: short carbon nanometer tube (about 2 microns of length)/long carbon nanotube (about 20 microns of length)=1/1); Controlled temperature is 280 ℃; Polycondensation 4h under less than the pressure of 40Pa, polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h, is polyethylene terephthalate/carbon nano tube compound material.Content of carbon nanotubes is 0.5wt% in the matrix material.With gained sample hot pressing film forming under 265 ℃ of conditions, the power of measure sample, conduction and heat conductivility.Numerical value such as table 1.
Embodiment 3
(1) with the 78g DMT. Dimethyl p-benzenedicarboxylate, churned mechanically 250ml three-necked flask is equipped with in the positive four butyl esters adding of 50g terepthaloyl moietie and 0.03g metatitanic acid, and control reaction temperature is 200 ℃ and carries out transesterify;
(2) after the quantity of methyl alcohol that steams of transesterify reaches 25.4g; Add the 0.03g zinc acetate, the 5g diameter is that (wherein, mass ratio is the carboxylated SWCN of 10-20nm: short carbon nanometer tube (about 2 microns of length)/long carbon nanotube (about 20 microns of length)=1/1); Controlled temperature is 280 ℃; Polycondensation 4h under less than the pressure of 40Pa, polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h, is polyethylene terephthalate/carbon nano tube compound material.Content of carbon nanotubes is 5wt% in the matrix material.With gained sample hot pressing film forming under 265 ℃ of conditions, the power of measure sample, conduction and heat conductivility.Numerical value such as table 1.
Comparative example 1
(1) with the 78g DMT. Dimethyl p-benzenedicarboxylate, churned mechanically 250ml three-necked flask is equipped with in the positive four butyl esters adding of 50g terepthaloyl moietie and 0.03g metatitanic acid, and control reaction temperature is 200 ℃ and carries out transesterify;
(2) after the quantity of methyl alcohol that steams of transesterify reaches 25.4g; Add the 0.03g zinc acetate; The 5g diameter is the carboxylated short SWCN of 10-20nm, and controlled temperature is 280 ℃, polycondensation 4h under less than the pressure of 40Pa; Polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h, is polyethylene terephthalate/weak point SWCN matrix material.Content of carbon nanotubes is 5wt% in the matrix material.With gained sample hot pressing film forming under 265 ℃ of conditions, the power of measure sample, conduction and heat conductivility.Numerical value such as table 1.
Comparative example 2
(1) with the 78g DMT. Dimethyl p-benzenedicarboxylate, churned mechanically 250ml three-necked flask is equipped with in the positive four butyl esters adding of 50g terepthaloyl moietie and 0.03g metatitanic acid, and control reaction temperature is 200 ℃ and carries out transesterify;
(2) after the quantity of methyl alcohol that steams of transesterify reaches 25.4g; Add the 0.03g zinc acetate; The 5g diameter is the carboxylated long SWCN of 10-20nm, and controlled temperature is 280 ℃, polycondensation 4h under less than the pressure of 40Pa; Polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h, is polyethylene terephthalate/long SWCN matrix material.Content of carbon nanotubes is 5wt% in the matrix material.With gained sample hot pressing film forming under 265 ℃ of conditions, the power of measure sample, conduction and heat conductivility.Numerical value such as table 1.
Embodiment 4
(1) with the 78g DMT. Dimethyl p-benzenedicarboxylate, 70g 1, and churned mechanically 250ml three-necked flask is equipped with in ammediol and the adding of 0.0078g Antimony Trioxide: 99.5Min, and control reaction temperature is 195 ℃ and carries out transesterify;
(2) after the quantity of methyl alcohol that steams of transesterify reaches 25.4g; Add the 0.0078g magnesium acetate, the 2g diameter is that (wherein, mass ratio is the carboxylated double-walled carbon nano-tube of 20-30nm: short carbon nanometer tube (about 2 microns of length)/long carbon nanotube (about 20 microns of length)=10/1); Controlled temperature is 255 ℃; Polycondensation 4h under less than the pressure of 40Pa, polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h, is PTT/carbon nano tube compound material.Content of carbon nanotubes is 2wt% in the matrix material.With gained sample hot pressing film forming under 245 ℃ of conditions, the power of measure sample, conduction and heat conductivility.Numerical value such as table 1.
Embodiment 5
(1) with the 78g DMT. Dimethyl p-benzenedicarboxylate, 75g 1, ammediol and 0.78g K
2TiF
6Add churned mechanically 250ml three-necked flask is housed, control reaction temperature is 195 ℃ and carries out transesterify;
(2) after the quantity of methyl alcohol that steams of transesterify reaches 25.4g; Add 0.78g venus crystals 2g diameter and be the carboxylated many carbon nanotubes of 30-50nm (wherein; Mass ratio is: short carbon nanometer tube (about 2 microns of length)/long carbon nanotube (about 20 microns of length)=1/10), controlled temperature is 255 ℃, polycondensation 4h under less than the pressure of 40Pa; Polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h, is PTT/carbon nano tube compound material.Content of carbon nanotubes is 2wt% in the matrix material.With gained sample hot pressing film forming under 245 ℃ of conditions, the power of measure sample, conduction and heat conductivility.Numerical value such as table 1.
Comparative example 3
(1) with the 78g DMT. Dimethyl p-benzenedicarboxylate, 65g 1, and churned mechanically 250ml three-necked flask is equipped with in the positive four butyl esters adding of ammediol and 0.055g metatitanic acid, and control reaction temperature is 190 ℃ and carries out transesterify;
(2) after the quantity of methyl alcohol that steams of transesterify reaches 25.4g, add the 0.055g zinc acetate, controlled temperature is 255 ℃, polycondensation 4h under less than the pressure of 40Pa, and polycondensation finishes the back and promptly gets PTT in 90 ℃ of vacuum-drying 30h.With gained sample hot pressing film forming under 245 ℃ of conditions, the power of measure sample, conduction and heat conductivility.Numerical value such as table 1.
Embodiment 6
(1) with the 78g DMT. Dimethyl p-benzenedicarboxylate, 72g 1, and churned mechanically 250ml three-necked flask is equipped with in 4-butyleneglycol and the adding of 0.0078g Antimony Trioxide: 99.5Min, and control reaction temperature is 195 ℃ and carries out transesterify;
(2) after the quantity of methyl alcohol that steams of transesterify reaches 25.4g; Add the 0.0078g magnesium acetate, the 0.05g diameter is that (wherein, mass ratio is 2-10nm hydroxylation SWCN: short carbon nanometer tube (about 2 microns of length)/long carbon nanotube (about 20 microns of length)=1/1); Controlled temperature is 255 ℃; Polycondensation 4h under less than the pressure of 40Pa, polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h, is polybutylene terephthalate/carbon nano tube compound material.Content of carbon nanotubes is 0.05wt% in the matrix material.With gained sample hot pressing film forming under 245 ℃ of conditions, the power of measure sample, conduction and heat conductivility.Numerical value such as table 1.
Embodiment 7
(1) with the 78g DMT. Dimethyl p-benzenedicarboxylate, 95g 1,4-butyleneglycol and 0.0.045g K
2TiF
6Add churned mechanically 250ml three-necked flask is housed, control reaction temperature is 195 ℃ and carries out transesterify;
(2) after the quantity of methyl alcohol that steams of transesterify reaches 25.4g; Add 0.045g zinc acetate 2g diameter and be 20-30nm hydroxylation double-carbon nanotube (wherein; Mass ratio is: short carbon nanometer tube (about 2 microns of length)/long carbon nanotube (about 20 microns of length)=10/1), controlled temperature is 255 ℃, polycondensation 4h under less than the pressure of 40Pa; Polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h, is polybutylene terephthalate/carbon nano tube compound material.Content of carbon nanotubes is 2wt% in the matrix material.With gained sample hot pressing film forming under 245 ℃ of conditions, the power of measure sample, conduction and heat conductivility.Numerical value such as table 1.
Embodiment 8
(1) with the 78g DMT. Dimethyl p-benzenedicarboxylate, 100g 1,4-butyleneglycol and 0.078g K
2TiF
6Add churned mechanically 250ml three-necked flask is housed, control reaction temperature is 195 ℃ and carries out transesterify;
(2) after the quantity of methyl alcohol that steams of transesterify reaches 25.4g; Add 0.078g venus crystals 5g diameter and be the many carbon nanotubes of 30-50nm hydroxyl baseization (wherein; Mass ratio is: short carbon nanometer tube (about 2 microns of length)/long carbon nanotube (about 20 microns of length)=1/10), controlled temperature is 255 ℃, polycondensation 4h under less than the pressure of 40Pa; Polycondensation finishes the back and promptly gets product in 80 ℃ of vacuum-drying 24h, is polybutylene terephthalate/carbon nano tube compound material.Content of carbon nanotubes is 5wt% in the matrix material.With gained sample hot pressing film forming under 245 ℃ of conditions, the power of measure sample, conduction and heat conductivility.Numerical value such as table 1.
Comparative example 4
(1) with the 78g DMT. Dimethyl p-benzenedicarboxylate, 100g 1, and churned mechanically 250ml three-necked flask is equipped with in the positive four butyl esters adding of 4-butyleneglycol and 0.025g metatitanic acid, and control reaction temperature is 190 ℃ and carries out transesterify;
(2) after the quantity of methyl alcohol that steams of transesterify reaches 25.2g, add the 0.025g zinc acetate, controlled temperature is 255 ℃, polycondensation 4h under less than the pressure of 40Pa, and polycondensation finishes the back and promptly gets polybutylene terephthalate in 80 ℃ of vacuum-drying 24h.With gained sample hot pressing film forming under 245 ℃ of conditions, the power of measure sample, conduction and heat conductivility.Numerical value such as table 1.
Table 1
Through the comparison of instance 1-3 in the table one and comparative example 1 and 2, we find in same content of carbon nanotubes, and length carbon pipe mixes more singlely has better effect with long carbon nanotube or short carbon nanometer tube.
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. polyester/low filling mixes carbon nano tube compound material, it is characterized in that: prepared by following raw material and component:
The composition weight umber
Carbon nanotube 0.05-5
DMT. Dimethyl p-benzenedicarboxylate 78
Glycol 50-100
Transesterification catalyst 0.0078-0.78
Polymerizing catalyst 0.0078-0.78.
2. polyester according to claim 1/low filling mixes carbon nano tube compound material, and it is characterized in that: described glycol is terepthaloyl moietie, Ucar 35 or butyleneglycol.
3. polyester according to claim 1/low filling mixes carbon nano tube compound material, and it is characterized in that: described carbon nanotube is carboxylated single wall, carboxylated double-walled or carboxylated multi-walled carbon nano-tubes or hydroxylation single wall, hydroxylation double-walled or hydroxylation multi-walled carbon nano-tubes; The shortwall length of carbon nanotube is 0.5-2 μ m; Long carbon nanotube is 10-50 μ m, and diameter is 2-100nm; Its carboxyl-content of carboxylic carbon nano-tube is 0.73～3.24%; Its hydroxy radical content of hydroxylation carbon nanotube is 0.73～3.24%; Shortwall carbon nanotube and longwell carbon nanotube mass ratio are 1: 10～10: 1.
4. polyester according to claim 1/low filling mixes carbon nano tube compound material, and it is characterized in that: described transesterification catalyst is one or more mixtures among Antimony Trioxide: 99.5Min, tetra-n-butyl titanate, the K2TiF6; The weight ratio of transesterification catalyst and DMT. Dimethyl p-benzenedicarboxylate is 0.0078～0.78: 78.
5. polyester according to claim 1/low filling mixes carbon nano tube compound material, and it is characterized in that: described polymerizing catalyst is venus crystals, magnesium acetate or zinc acetate; The weight ratio of polymerizing catalyst and DMT. Dimethyl p-benzenedicarboxylate is (0.0078～0.78): 78.
6. one kind prepares arbitrary described polyester among the claim 1-5/low method that mixes carbon nano tube compound material of filling, and it is characterized in that: comprise step:
(1) transesterify: a certain amount of DMT. Dimethyl p-benzenedicarboxylate, glycol and transesterification catalyst are mixed, with the three-necked flask that the mixture that obtains places band to stir, open and stir, control reaction temperature is 140～205 ℃, carries out transesterification reaction;
(2) polymerization: be higher than when amount that step (1) steams methyl alcohol 2 times of theoretical value DMT. Dimethyl p-benzenedicarboxylate amount more than 80% after, add polymerizing catalyst, then to wherein adding carbon nanotube; Elevated temperature to 240～280 ℃; Regulate vacuum tightness to carrying out polycondensation below the 40Pa, the reaction times is 4～6h, and it is 60-80 ℃ that polycondensation finishes the back controlled temperature; Vacuum-drying 24～48h, the content that promptly gets carbon nanotube accounts for the Pdyester/carbon nano tube composite material of 0.05-5wt%.
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Cited By (4)
| 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 |
| CN107987218A (en) * | 2017-12-08 | 2018-05-04 | 仲恺农业工程学院 | A kind of preparation method of in-situ polymerization modified unsaturated polyester resin |
| CN109608859A (en) * | 2018-12-17 | 2019-04-12 | 特塑（大连）高分子材料有限公司 | A kind of carbon nano-tube modification engineering plastics 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101314637A (en) * | 2007-05-31 | 2008-12-03 | 中国科学院化学研究所 | Poly-p-benzene dicarboxylic acid 1,2-propylene glycol ester and copolyester, and preparation thereof |
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| CN101314637A (en) * | 2007-05-31 | 2008-12-03 | 中国科学院化学研究所 | Poly-p-benzene dicarboxylic acid 1,2-propylene glycol ester and copolyester, and preparation 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 |
| CN107987218A (en) * | 2017-12-08 | 2018-05-04 | 仲恺农业工程学院 | A kind of preparation method of in-situ polymerization modified unsaturated polyester resin |
| CN107987218B (en) * | 2017-12-08 | 2020-07-28 | 仲恺农业工程学院 | Preparation method of in-situ polymerization modified unsaturated polyester resin |
| CN109608859A (en) * | 2018-12-17 | 2019-04-12 | 特塑（大连）高分子材料有限公司 | A kind of carbon nano-tube modification engineering plastics 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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| CN102485767B (en) | 2014-07-09 |
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