CN104804373A - Preparation method of aminated carbon nanotube/polyetheretherketone composite material - Google Patents
Preparation method of aminated carbon nanotube/polyetheretherketone composite material Download PDFInfo
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- CN104804373A CN104804373A CN201510206691.5A CN201510206691A CN104804373A CN 104804373 A CN104804373 A CN 104804373A CN 201510206691 A CN201510206691 A CN 201510206691A CN 104804373 A CN104804373 A CN 104804373A
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Abstract
The invention relates to a preparation method of an aminated carbon nanotube/polyetheretherketone composite material. The preparation method comprises the following steps: taking carbon nanotubes and polyetheretherketone as raw materials, firstly performing acidification and amination treatment on the carbon nanotubes and synthesizing the carbon nanotube/polyetheretherketone composite material through a solution co-blending method. As the carbon nanotubes are uniformly dispersed in a polyetheretherketone substrate, the strength, the high temperature resistance, the oxidation resistance and the corrosion resistance of the polyetheretherketone are effectively improved, and the friction coefficients of the composite material are reduced. The preparation method provided by the invention is advanced and reasonable in process, detailed and accurate in data, good in product quality and high in purity which reaches 98 percent, the prepared polyetheretherketone substrate composite material can be applied to various industrial fields, and the preparation method is a very ideal enhanced preparation method of the polyetheretherketone composite material.
Description
Technical field
The present invention relates to a kind of preparation method of amination carbon nano-tube/poly polyetherether ketone composite, belong to the technical field of the preparations and applicatio of carbon material/polymer composites.
Background technology
Polymer matrix composite is a kind of desirable friction materials, polyether-ether-ketone is material the most frequently used in special engineering plastics, compared with other engineering plastics, polyether-ether-ketone has high temperature resistant, intensity is high, good toughness, good rigidly, self lubricity is good, good corrosion resistance, there is flame retardant resistance, be easy to processing, there is insulativity, wear resistance, this makes polyether-ether-ketone resin in aerospace, automotive industry, mechanical industry, electronic apparatus and medical instruments field have broad application prospects, but pure polyether-ether-ketone resin fragility is large, cutting performance is poor, use temperature is low, and it is expensive, limit its range of application.
For the defect of the chemical physics performance of polyether-ether-ketone, the normal method adopting other chemical substances of doping, but owing to selecting, material is unreasonable, technical parameter is inaccurate, preparation method's imprecision, makes the unstable properties of polyether-ether-ketone, does not reach real requirement.
Summary of the invention
Goal of the invention
The object of the invention is the practical situation for background technology, carbon nanotube and polyether-ether-ketone is adopted to carry out solution blending, by oxide treatment, the modifying and decorating of carbon nanotube, matrix material is made with polyether-ether-ketone solution blending, to increase substantially the chemical physics performance of polyether-ether-ketone, strengthen acidproof, alkali resistance and crocking resistance, expand the range of application of polyether-ether-ketone.
Technical scheme
The chemical substance material that the present invention uses is: carbon nanotube, polyether-ether-ketone, sulfuric acid, nitric acid, thanomin, N, N-dicyclohexylcarbodiimide, N, dinethylformamide, dehydrated alcohol, deionized water, it is as follows that its combination prepares consumption: with gram, milliliter for measure unit
Preparation method is as follows:
(1) selected chemical substance material
To carry out selected to the chemical substance material that preparation uses, and carry out quality purity, concentration control:
(2) grind, sieve, thinning processing carbon nanotube
Carbon nanotube agate mortar, pestle are ground, then sieve with 650 eye mesh screens, grind, sieving repeats, grinding becomes fine powder after sieving;
(3) oxide treatment carbon nanotube
Oxide treatment carbon nanotube carries out in there-necked flask, is in ultrasonic wave separating apparatus, completes in heating, ultrasonic disperse process;
1. open ultrasonic wave separating apparatus, ultrasonic frequency is 50kHz, Heating temperature to 50 DEG C ± 2 DEG C; Take carbon nanotube 3g ± 0.001g, measure sulfuric acid 180mL ± 1mL, nitric acid 60mL ± 1mL, add in there-necked flask;
2. there-necked flask is placed in ultrasonic wave separating apparatus and carries out ultrasonic disperse, ultrasonic disperse time 120min ± 2min, become oxide solution;
Carbon nanotube will carry out chemical reaction in oxidation reaction process, and reaction formula is as follows:
In formula: C-COOH: carboxylic oxide/carbon nanometer tube
SO
2: sulfurous gas
NO
2: nitrogen peroxide
CO
2: carbonic acid gas
3., after oxidizing reaction, close ultrasonic wave separating apparatus, the oxide solution in there-necked flask is cooled to 25 DEG C with bottle; Then oxide solution is placed in beaker, adds deionized water 1000mL, become mixed solution, leave standstill 12h;
4. suction filtration, is placed in the Büchner funnel on filter flask by mixed solution, carry out suction filtration with millipore filtration, remaining product filter cake on filter membrane, and filtrate is evacuated in filter flask, discards;
5. washing, suction filtration, be placed in beaker by filter cake, add deionized water 300mL, agitator treating 5min, then carry out suction filtration with millipore filtration, retains filter cake, discard washings, and washing, suction filtration repeat three times;
6. vacuum-drying, is placed in quartz container by filter cake, is then placed in vacuum drying oven, drying temperature 80 DEG C, vacuum tightness 10Pa, and time of drying, 24h, obtained after drying: carboxylic oxide/carbon nanometer tube;
(4) amination carbon nanotube is prepared
Preparation amination carbon nanotube carries out in there-necked flask, completes in water-bath, heating, ultrasonic disperse process;
1. take carboxylic oxide/carbon nanometer tube 0.3g ± 0.001g, N, N-dicyclohexylcarbodiimide 0.1g ± 0.001g, measure dehydrated alcohol 75mL ± 0.1mL, add in there-necked flask;
2. be placed on cleansing bath tub by there-necked flask, be placed in by cleansing bath tub on ultrasonic wave separating apparatus, the water-bath water in cleansing bath tub will flood 4/5 of there-necked flask volume;
3. open ultrasonic wave separating apparatus, carry out ultrasonic disperse, ultrasonic frequency 50KHz, ultrasonic disperse time 20min;
4. ultrasonic wave separating apparatus well heater is opened, Heating temperature 50 DEG C ± 2 DEG C, and constant temperature insulation 30min;
5. measure thanomin 0.3mL ± 0.001mL, dehydrated alcohol 75mL ± 0.1mL, add in there-necked flask, stir 10min, proceed ultrasonic disperse 10h, become mixing solutions;
6. will there is chemical reaction in mixing solutions in heating, stirring, ultrasonic disperse process;
Thanomin carries out chemical reaction to occur in modification process to carbon nanotube, and reaction formula is as follows:
In formula: C-COO (CH
2)
2nH
2: amination carbon nanotube
Close well heater after reaction, make mixing solutions be cooled to 25 DEG C with bottle;
7. suction filtration, is placed in the Büchner funnel on filter flask by cooled mixing solutions, carry out suction filtration with millipore filtration, retains filter cake, discards filtrate;
8. absolute ethanol washing, suction filtration, be placed in beaker by filter cake, adds dehydrated alcohol 200mL, agitator treating 10min, then carries out suction filtration with millipore filtration, retains filter cake, discard washings, and washing, suction filtration repeat three times;
9. deionized water wash, suction filtration, be placed in beaker by filter cake, adds deionized water 200mL, agitator treating 10min, then carries out suction filtration with millipore filtration, retains filter cake, discard washings, and washing, suction filtration repeat three times;
10. vacuum-drying, is placed in quartz container by filter cake, is then placed in vacuum drying oven, drying temperature 80 DEG C, vacuum tightness 10Pa, and time of drying, 24h, obtained amination carbon nanotube after drying;
(5) amination carbon nano-tube/poly polyetherether ketone composite is prepared
1. drying treatment polyether-ether-ketone, is placed in quartz container by polyether-ether-ketone 100g ± 0.001g, is then placed in vacuum drying oven, drying temperature 80 DEG C, vacuum tightness 10Pa, time of drying 12h;
2. take polyether-ether-ketone 7.2g ± 0.001g, amination carbon nanotube 0.3g ± 0.001g, measure DMF 20mL ± 1mL, add in beaker, be uniformly mixed 30min, become mixed solution;
3. be placed on cooking-vessel by the beaker filling mixed solution, heat, Heating temperature 30 DEG C ± 1 DEG C, heat-up time, 30min, became pasty mixture;
4. dry, pasty mixture is placed in bar shaped quartz container, is then placed in loft drier, drying temperature 80 DEG C, time of drying 12h, product into strips after drying;
5. pelletizing, is placed in strip product on dicing machine and carries out cutting, is≤bar shaped the particle of 10mm × 2mm × 6mm, is carbon nano-tube/poly polyetherether ketone composite after cutting;
6. vacuum-drying, is placed in quartz container by carbon nano-tube/poly ether ether ketone bar shaped particle, is then placed in vacuum drying oven dry, drying temperature 80 DEG C, vacuum tightness 10Pa, and time of drying, 12h, was amination carbon nano-tube/poly polyetherether ketone composite after dry;
(6) detect, analyze, characterize
The pattern of amination carbon nano-tube/poly polyetherether ketone composite of preparation, structure, composition, chemical physics performance, mechanical property are detected, analyze, characterized;
Morphology analysis is carried out with field emission scanning electron microscope;
Surface functional group analysis is carried out with infrared spectrometer;
Thermal stability analysis is carried out with thermogravimetric analyzer;
Dynamic properties analysis is carried out with dynamic mechanical analyzer;
Analysis on Friction Performance is carried out with frictional testing machines;
Conclusion: amination carbon nano-tube/poly polyetherether ketone composite is black bar shaped particles, is of a size of≤10mm × 2mm × 6mm, smooth surface, and the frictional coefficient of matrix material can reduce by 12%, and product purity reaches 98%;
(7) product storage
Be stored in the Glass Containers of amber transparent to the amination carbon nano-tube/poly polyetherether ketone composite of preparation, airtightly keep in Dark Place, waterproof, sun-proof, moistureproof, anti-acid-alkali salt to corrode, storing temp 20 DEG C, relative humidity≤10%.
Beneficial effect
The present invention has obvious advance compared with background technology, with carbon nanotube, polyether-ether-ketone is raw material, first carbon nanotube is oxidized, amination treatment, by solution blended process synthesis amination carbon nano-tube/poly polyetherether ketone composite, amination even carbon nanotube is dispersed in polyether-ether-ketone matrix, obtain finely dispersed matrix material, improve the intensity of polyether-ether-ketone, high temperature resistant, anti-oxidant, corrosion resistance nature, the frictional coefficient of matrix material can be reduced, this preparation method's technique is tight, rationally advanced, informative data is accurate, product purity is good, the polyether-ether-ketone of preparation can be applied at multiple industrial circle, the enhancing preparation method of very good polyether-ether-ketone composite material.
Accompanying drawing explanation
Fig. 1 prepares amination carbon nanotube state figure
Fig. 2 amination carbon nano-tube/poly polyetherether ketone composite amplifies 10000 times of scanning shape appearance figures
Fig. 3 amination carbon nano-tube/poly polyetherether ketone composite dynamic properties graphic representation
Fig. 4 amination carbon nano-tube/poly polyetherether ketone composite frictional behaviour graphic representation
Shown in Fig. 1, list of numerals is as follows:
1, ultrasonic wave separating apparatus, 2, display screen, 3, ultrasonic wave controller, 4, heating temperature control, 5, mixing control device, 6, pilot lamp, 7, cleansing bath tub, 8, anchor, 9, there-necked flask, 10, agitator, 11, water-bath water, 12, mixing solutions, 13, addition funnel, 14, control valve, 15, water cycle prolong, 16, water-in, 17, water outlet, 18, air outlet, 19, power switch.
Embodiment
Below in conjunction with accompanying drawing, the present invention will be further described:
Shown in Fig. 1, be preparation amination carbon nanotube state figure, each position, annexation will correctly, according to quantity proportioning, operate according to the order of sequence.
The value of the chemical substance that preparation uses determines by the scope pre-set, with gram, milliliter for measure unit.
Preparation amination carbon nanotube carries out in there-necked flask, completes in water-bath, heating, ultrasonic wave dispersion process;
Ultrasonic wave separating apparatus 1 top arranges cleansing bath tub 7, there-necked flask 9 is put on cleansing bath tub 7 top, and fixed by anchor 8, be water-bath water 11 in cleansing bath tub 7, water-bath water 11 will flood 4/5 of there-necked flask 9 volume, there-necked flask 9 top sets gradually addition funnel 13 and control valve 14, agitator 10, water cycle prolong 15 and water-in 16, water outlet 17, air outlet 18 from left to right, is mixing solutions 12 in there-necked flask 9; Ultrasonic wave separating apparatus 1 arranges display screen 2, pilot lamp 6, mixing control device 5, heating temperature control 4, ultrasonic wave controller 3, power switch 19.
Shown in Fig. 2, for amination carbon nano-tube/poly polyetherether ketone composite amplifies 10000 times of shape appearance figures, known in figure: amination even carbon nanotube is dispersed in polyether-ether-ketone matrix, ruler units 1 μm.
Shown in Fig. 3, for amination carbon nano-tube/poly polyetherether ketone composite dynamic properties graphic representation, ordinate zou is temperature, X-coordinate is storage modulus, a curve is the storage modulus curve of polyether-ether-ketone, b curve is the storage modulus curve of amination carbon nano-tube/poly polyetherether ketone composite, before matrix material b temperature is increased to softening temperature by-100 DEG C, storage modulus is apparently higher than the storage modulus of polyether-ether-ketone.
Shown in Fig. 4, for amination carbon nano-tube/poly polyetherether ketone composite tribological property graphic representation, ordinate zou is frictional coefficient, X-coordinate is wearing-in period, c curve is the friction coefficient curve of polyether-ether-ketone, d curve is the friction coefficient curve of carbon nano-tube/poly polyetherether ketone composite, the average friction coefficient of matrix material d reduces 12%, and the wear resisting property of matrix material significantly improves.
Claims (2)
1. the preparation method of an amination carbon nano-tube/poly polyetherether ketone composite, it is characterized in that: the chemical substance material of use is: carbon nanotube, polyether-ether-ketone, sulfuric acid, nitric acid, thanomin, N, N '-dicyclohexylcarbodiimide, N, dinethylformamide, dehydrated alcohol, deionized water, it is as follows that its combination prepares consumption: with gram, milliliter for measure unit
Preparation method is as follows:
(1) selected chemical substance material
To carry out selected to the chemical substance material that preparation uses, and carry out quality purity, concentration control:
(2) grind, sieve, thinning processing carbon nanotube
Carbon nanotube agate mortar, pestle are ground, then sieve with 650 eye mesh screens, grind, sieving repeats, grinding becomes fine powder after sieving;
(3) oxide treatment carbon nanotube
Oxide treatment carbon nanotube carries out in there-necked flask, is in ultrasonic wave separating apparatus, completes in heating, ultrasonic disperse process;
1. open ultrasonic wave separating apparatus, ultrasonic frequency is 50kHz, Heating temperature to 50 DEG C ± 2 DEG C; Take carbon nanotube 3g ± 0.001g, measure sulfuric acid 180mL ± 1mL, nitric acid 60mL ± 1mL, add in there-necked flask;
2. there-necked flask is placed in ultrasonic wave separating apparatus and carries out ultrasonic disperse, ultrasonic disperse time 120min ± 2min, become oxide solution;
Carbon nanotube will carry out chemical reaction in oxidation reaction process, and reaction formula is as follows:
In formula: C-COOH: carboxylic oxide/carbon nanometer tube
SO
2: sulfurous gas
NO
2: nitrogen peroxide
CO
2: carbonic acid gas
3., after oxidizing reaction, close ultrasonic wave separating apparatus, the oxide solution in there-necked flask is cooled to 25 DEG C with bottle; Then oxide solution is placed in beaker, adds deionized water 1000mL, become mixed solution, leave standstill 12h;
4. suction filtration, is placed in the Büchner funnel on filter flask by mixed solution, carry out suction filtration with millipore filtration, remaining product filter cake on filter membrane, and filtrate is evacuated in filter flask, discards;
5. washing, suction filtration, be placed in beaker by filter cake, add deionized water 300mL, agitator treating 5min, then carry out suction filtration with millipore filtration, retains filter cake, discard washings, and washing, suction filtration repeat three times;
6. vacuum-drying, is placed in quartz container by filter cake, is then placed in vacuum drying oven, drying temperature 80 DEG C, vacuum tightness 10Pa, and time of drying, 24h, obtained after drying: carboxylic oxide/carbon nanometer tube;
(4) amination carbon nanotube is prepared
Preparation amination carbon nanotube carries out in there-necked flask, completes in water-bath, heating, ultrasonic disperse process;
1. take carboxylic oxide/carbon nanometer tube 0.3g ± 0.001g, N, N-dicyclohexylcarbodiimide 0.1g ± 0.001g, measure dehydrated alcohol 75mL ± 0.1mL, add in there-necked flask;
2. be placed on cleansing bath tub by there-necked flask, be placed in by cleansing bath tub on ultrasonic wave separating apparatus, the water-bath water in cleansing bath tub will flood 4/5 of there-necked flask volume;
3. open ultrasonic wave separating apparatus, carry out ultrasonic disperse, ultrasonic frequency 50KHz, ultrasonic disperse time 20min;
4. ultrasonic wave separating apparatus well heater is opened, Heating temperature 50 DEG C ± 2 DEG C, and constant temperature insulation 30min;
5. measure thanomin 0.3mL ± 0.001mL, dehydrated alcohol 75mL ± 0.1mL, add in there-necked flask, stir 10min, proceed ultrasonic disperse 10h, become mixing solutions;
6. will there is chemical reaction in mixing solutions in heating, stirring, ultrasonic disperse process;
Thanomin carries out chemical reaction to occur in modification process to carbon nanotube, and reaction formula is as follows:
In formula: C-COO (CH
2)
2nH
2: amination carbon nanotube
Close well heater after reaction, make mixing solutions be cooled to 25 DEG C with bottle;
7. suction filtration, is placed in the Büchner funnel on filter flask by cooled mixing solutions, carry out suction filtration with millipore filtration, retains filter cake, discards filtrate;
8. absolute ethanol washing, suction filtration, be placed in beaker by filter cake, adds dehydrated alcohol 200mL, agitator treating 10min, then carries out suction filtration with millipore filtration, retains filter cake, discard washings, and washing, suction filtration repeat three times;
9. deionized water wash, suction filtration, be placed in beaker by filter cake, adds deionized water 200mL, agitator treating 10min, then carries out suction filtration with millipore filtration, retains filter cake, discard washings, and washing, suction filtration repeat three times;
10. vacuum-drying, is placed in quartz container by filter cake, is then placed in vacuum drying oven, drying temperature 80 DEG C, vacuum tightness 10Pa, and time of drying, 24h, obtained amination carbon nanotube after drying;
(5) amination carbon nano-tube/poly polyetherether ketone composite is prepared
1. drying treatment polyether-ether-ketone, is placed in quartz container by polyether-ether-ketone 100g ± 0.001g, is then placed in vacuum drying oven, drying temperature 80 DEG C, vacuum tightness 10Pa, time of drying 12h;
2. take polyether-ether-ketone 7.2g ± 0.001g, amination carbon nanotube 0.3g ± 0.001g, measure DMF 20mL ± 1mL, add in beaker, be uniformly mixed 30min, become mixed solution;
3. be placed on cooking-vessel by the beaker filling mixed solution, heat, Heating temperature 30 DEG C ± 1 DEG C, heat-up time, 30min, became pasty mixture;
4. dry, pasty mixture is placed in bar shaped quartz container, is then placed in loft drier, drying temperature 80 DEG C, time of drying 12h, product into strips after drying;
5. pelletizing, is placed in strip product on dicing machine and carries out cutting, is≤bar shaped the particle of 10mm × 2mm × 6mm, is carbon nano-tube/poly polyetherether ketone composite after cutting;
6. vacuum-drying, is placed in quartz container by carbon nano-tube/poly ether ether ketone bar shaped particle, is then placed in vacuum drying oven dry, drying temperature 80 DEG C, vacuum tightness 10Pa, and time of drying, 12h, was amination carbon nano-tube/poly polyetherether ketone composite after dry;
(6) detect, analyze, characterize
The pattern of amination carbon nano-tube/poly polyetherether ketone composite of preparation, structure, composition, chemical physics performance, mechanical property are detected, analyze, characterized;
Morphology analysis is carried out with field emission scanning electron microscope;
Surface functional group analysis is carried out with infrared spectrometer;
Thermal stability analysis is carried out with thermogravimetric analyzer;
Dynamic properties analysis is carried out with dynamic mechanical analyzer;
Analysis on Friction Performance is carried out with frictional testing machines;
Conclusion: amination carbon nano-tube/poly polyetherether ketone composite is black bar shaped particles, is of a size of≤10mm × 2mm × 6mm, smooth surface, and the frictional coefficient of matrix material can reduce by 12%, and product purity reaches 98%;
(7) product storage
Be stored in the Glass Containers of amber transparent to the amination carbon nano-tube/poly polyetherether ketone composite of preparation, airtightly keep in Dark Place, waterproof, sun-proof, moistureproof, anti-acid-alkali salt to corrode, storing temp 20 DEG C, relative humidity≤10%.
2. the preparation method of a kind of amination carbon nano-tube/poly polyetherether ketone composite according to claim 1, is characterized in that: preparation amination carbon nanotube carries out in there-necked flask, completes in heating in water bath, ultrasonic wave dispersion process, ultrasonic wave separating apparatus (1) top arranges cleansing bath tub (7), there-necked flask (9) is put on cleansing bath tub (7) top, and fixed by anchor (8), be water-bath water (11) in cleansing bath tub (7), water-bath water (11) will flood 4/5 of there-necked flask (9) volume, there-necked flask (9) top sets gradually addition funnel (13) and control valve (14) from left to right, agitator (10), water cycle prolong (15) and water-in (16), water outlet (17), air outlet (18), be mixing solutions (12) in there-necked flask (9), ultrasonic wave separating apparatus (1) arranges display screen (2), pilot lamp (6), mixing control device (5), heating temperature control (4), ultrasonic wave controller (3), power switch (19).
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Cited By (5)
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| CN105597568A (en) * | 2016-02-23 | 2016-05-25 | 天津大学 | Chloromethylated polyether-ether-ketone/imidazole carbon nano tube hybrid membrane, preparation and application |
| CN105838086A (en) * | 2016-06-20 | 2016-08-10 | 太原理工大学 | Preparation method of sulfonated carbon nano tube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material |
| CN105873254A (en) * | 2016-06-14 | 2016-08-17 | 中科电力装备（安徽）智能化科技有限公司 | Chemical-corrosion-resistant self temperature limiting heat tracing cable |
| CN106421922A (en) * | 2016-10-09 | 2017-02-22 | 太原理工大学 | Modified hydroxyapatite/carbon nanotube/polyetheretherketon composite material and preparation method thereof |
| CN107629344A (en) * | 2017-09-14 | 2018-01-26 | 苏州聚慧邦新材料科技有限公司 | One kind building foaming thermal-insulating and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597568A (en) * | 2016-02-23 | 2016-05-25 | 天津大学 | Chloromethylated polyether-ether-ketone/imidazole carbon nano tube hybrid membrane, preparation and application |
| CN105597568B (en) * | 2016-02-23 | 2018-07-20 | 天津大学 | Chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film and preparation and application |
| CN105873254A (en) * | 2016-06-14 | 2016-08-17 | 中科电力装备（安徽）智能化科技有限公司 | Chemical-corrosion-resistant self temperature limiting heat tracing cable |
| CN105838086A (en) * | 2016-06-20 | 2016-08-10 | 太原理工大学 | Preparation method of sulfonated carbon nano tube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material |
| CN105838086B (en) * | 2016-06-20 | 2020-06-05 | 太原理工大学 | Preparation method of sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material |
| CN106421922A (en) * | 2016-10-09 | 2017-02-22 | 太原理工大学 | Modified hydroxyapatite/carbon nanotube/polyetheretherketon composite material and preparation method thereof |
| CN106421922B (en) * | 2016-10-09 | 2019-08-16 | 太原理工大学 | A kind of modified hydroxylapatite/carbon nano-tube/poly polyetherether ketone composite and preparation method thereof |
| CN107629344A (en) * | 2017-09-14 | 2018-01-26 | 苏州聚慧邦新材料科技有限公司 | One kind building foaming thermal-insulating and preparation method thereof |
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Application publication date: 20150729 |