CN106634574A - Graphene modified organic silicon coating as well as preparation method and application thereof - Google Patents
Graphene modified organic silicon coating as well as preparation method and application thereof Download PDFInfo
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- CN106634574A CN106634574A CN201611233823.4A CN201611233823A CN106634574A CN 106634574 A CN106634574 A CN 106634574A CN 201611233823 A CN201611233823 A CN 201611233823A CN 106634574 A CN106634574 A CN 106634574A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a graphene modified organic silicon coating as well as a preparation method and application thereof. The coating is mainly prepared from the following materials in parts by mass: 0.1-5 parts of graphene, 15-50 parts of an organic silicon emulsion, 5-35 parts of kaolin, 0.1-0.2 part of defoaming agents, 1-3 parts of thickening agents, 0.5-3 parts of dispersants and 0.07-3.5 parts of alkylphenol polyoxyethylene ether. The invention also discloses the preparation method and application of the coating. According to the graphene modified organic silicon coating, high strength and flexibility of a graphene material are used for making up for the defect of low strength of organic silicon; meanwhile, the organic silicon also has high ozone resistance and electrical insulation; the advantages of the graphene and the organic silicon are complementary, so that the prepared graphene modified organic silicon coating can be used to coat the surface of a material and can achieve high strength, high temperature resistance and weather resistance, ozone resistance and high electric insulation; compared with ordinary high-silica glass fiber, the strength, abrasion resistance and heat resistance of graphene modified high-silica glass fiber prepared by coating glass fiber with the graphene modified organic silicon coating are all improved to some extent.
Description
Technical field
The present invention relates to a kind of coating, more particularly to a kind of Graphene modified organosilicon paint and preparation method thereof with should
With.
Background technology
Resurrection glass fibre belongs to special glass fibre, typically by sodium borosilicate glass fibre Jing hot acid leachings,
Impurity beyond silicon is removed, is formed by sintering.Resurrection glass fibre intensity is very low, only the 1/10 of E glass fibres, but it
Resistance to elevated temperatures it is very good, can at 900 DEG C Long-Time Service, the short time is resistant to 1200 DEG C of high temperature, because it is a kind of excellent
High temperature resistant and resistant material, obtain application in terms of national defence, space flight, ferrous and nonferrous metals cleaning molten filtration.
Resurrection glass fibre intensity is very low in prior art, due to the acid leach technology used in preparation process, in system
The standby finished surface for obtaining has many holes residuals, forms defect, and surface area declines so that the intensity of resurrection glass fibre is entered
One step is reduced.
It would therefore be highly desirable to solve above-mentioned technical barrier.
The content of the invention
Goal of the invention：It is an object of the invention to provide a kind of Graphene by Graphene and organosilicon performance complement is modified having
Machine silicon coating and preparation method thereof, and using the coating with higher-strength, heat-resisting quantity, wearability, weatherability, resistance to smelly
Modified resurrection glass fibre of the Graphene of oxygen and electrical insulating property and preparation method thereof.
Technical scheme：A kind of Graphene modified organosilicon paint of the present invention, mainly by the material of following mass parts
Make：0.1～5 part of Graphene, 15～50 parts of organic silicon emulsion, 5～35 parts of kaolin, 0.1～0.2 part of defoamer, thickener 1
0.07～3.5 part of～3 parts, 0.5～3 part of dispersant and APES.
Further, the Graphene and the quality parts ratio of APES are 1:0.7.
It is further preferred that the thickener is hydroxypropyl cellulose, defoamer is tributyl phosphate, and dispersant is poly- carboxylic
Acid sodium-salt, organic silicon emulsion is MP-50E.
The preparation method of upper described Graphene modified organosilicon paint, comprises the following steps：
(1) Graphene and APES are blended in water, and carry out mixing 0.5～2h of ultrasonic disperse, shape
Into finely dispersed graphene aqueous solution；
(2) after being mixed and stirred for organic silica gel, dispersant, thickener and defoamer uniformly, kaolin is added, uniformly
Dispersed with stirring forms organosilicon compound；
(3) obtained graphene aqueous solution in step (1) is added in organosilicon compound obtained in step (2), stirring
Dispersion, obtains Graphene modified organosilicon paint.
Application of the above-mentioned Graphene modified organosilicon paint on the modified resurrection glass fibre of Graphene is prepared, including with
Lower step：
(1) glass batch is founded at 1300～1600 DEG C, and is divided into material block, then cooling material block；
(2) the material block after cooling is carried out into secondary fusion and wire drawing, then makes silk cylinder；
(3) silk cylinder is carried out into acid leach, to remove silicon beyond impurity；
(4) clean silk cylinder and remove surface hydrochloric acid solution, and dry；
(5) silk cylinder is sintered so that mass transfer is DB；
(6) Graphene modified organosilicon paint is obtained using the preparation method of above-mentioned Graphene modified organosilicon paint；
(7) Graphene modified organosilicon paint is sprayed on into silk cylinder surface, then in 50～150 DEG C of drying, obtains graphite
Alkene is modified resurrection glass fibre.
Further, the secondary fusion temperature described in above-mentioned steps (2) is 200～1150 DEG C.
Further, the solution of acid leach is the hydrochloric acid of concentration 5～15% in above-mentioned steps (3), and acid leach temperature is 50
～100 DEG C, the time is 0.5～40 hour.
Further, 400～900 DEG C of sintering temperature in above-mentioned steps (5).
Further, the drying time in above-mentioned steps (7) was controlled at 10～60 minutes.
Beneficial effect：Compared with prior art, significant advantage of the invention is：(1) Graphene modified organosilicon paint
Using the high intensity and pliability of grapheme material, the low intensive defect of organosilicon is compensate for, while organosilicon is also with good
Good ozone resistance and insulating properties, Graphene and organosilicon have complementary advantages so that made by Graphene modified organosilicon paint can
It is applied to material surface and plays high intensity, high-temperature resistant weatherability and good insulating properties；(2) by Graphene modified organosilicon paint
The coating modified resurrection glass fibre of obtained Graphene on the glass fibers is more common resurrection glass fibre intensity, wear-resisting
Property and heat resistance all increase.
Specific embodiment
Embodiment 1
It is that 5 parts of Graphenes and 3.5 parts of APESs are blended in 0.3 part of water to take mass parts, carries out ultrasound
Dispersion 120min, is obtained graphene aqueous solution；Again by 50 parts of MP-50E, 3 parts of polycarboxylate sodiums, 3 parts of hydroxypropyl celluloses and 0.2
Part tributyl phosphate mixing and stirring, continuously adds 35 parts of kaolin, and uniform stirring dispersion obtains organosilicon compound；Will
Finely dispersed graphene aqueous solution is added in organosilicon compound, and Graphene modified organosilicon paint is obtained.
Glass batch is put in electric melting furnace and is founded at 1600 DEG C, and if by expect stock be cut into siccative block, so
Block is expected in cooling afterwards；Material block after cooling is put in fiber drawing furnace carries out secondary fusion and wire drawing at 1150 DEG C, then makes silk
Cylinder；By silk cylinder in the hydrochloric acid that concentration is 15%, with 100 DEG C acid leach 0.5h is carried out, to remove silicon beyond impurity；It is clear with water
Wash silk cylinder and remove surface hydrochloric acid solution, and dry；Silk cylinder is sintered at 900 DEG C so that mass transfer is DB；Will be above-mentioned
Obtained Graphene modified organosilicon paint is sprayed on silk cylinder surface, then dries 60min at 150 DEG C, obtains Graphene and is modified
Resurrection glass fibre.
Embodiment 2
It is that 2 parts of Graphenes and 1.4 parts of APESs are blended in 42.95 parts of water to take mass parts, is surpassed
Sound disperses 80min, and graphene aqueous solution is obtained；Again by 30 parts of MP-50E, 1.5 parts of polycarboxylate sodiums, 2 parts of hydroxypropyl celluloses and
0.15 part of tributyl phosphate mixing and stirring, continuously adds 20 parts of kaolin, and uniform stirring dispersion obtains organosilicon mixing
Material；Finely dispersed graphene aqueous solution is added in organosilicon compound, Graphene modified organosilicon paint is obtained.
Glass batch is put in electric melting furnace and is founded at 1450 DEG C, and if by expect stock be cut into siccative block, so
Block is expected in cooling afterwards；Material block after cooling is put in fiber drawing furnace carries out secondary fusion and wire drawing at 800 DEG C, then makes silk
Cylinder；By silk cylinder in the hydrochloric acid that concentration is 10%, with 75 DEG C acid leach 10h is carried out, to remove silicon beyond impurity；Cleaned with water
Silk cylinder removes surface hydrochloric acid solution, and dries；Silk cylinder is sintered at 750 DEG C so that mass transfer is DB；By above-mentioned system
The Graphene modified organosilicon paint for obtaining is sprayed on silk cylinder surface, then dries 30min at 100 DEG C, obtains the modified height of Graphene
Silica glass.
Embodiment 3
It is that 0.1 part of Graphene and 0.07 part of APES are blended in 78.23 parts of water to take mass parts, is carried out
Ultrasonic disperse 30min, is obtained graphene aqueous solution；Again by 15 parts of MP-50E, 0.5 part of polycarboxylate sodium, 1 part of hydroxypropyl cellulose
With 0.1 part of tributyl phosphate mixing and stirring, 5 parts of kaolin are continuously added, uniform stirring dispersion obtains organosilicon mixing
Material；Finely dispersed graphene aqueous solution is added in organosilicon compound, Graphene modified organosilicon paint is obtained.
Glass batch is put in electric melting furnace and is founded at 1300 DEG C, and if by expect stock be cut into siccative block, so
Block is expected in cooling afterwards；Material block after cooling is put in fiber drawing furnace carries out secondary fusion and wire drawing at 200 DEG C, then makes silk
Cylinder；By silk cylinder in the hydrochloric acid that concentration is 5%, with 50 DEG C acid leach 40h is carried out, to remove silicon beyond impurity；Cleaned with water
Silk cylinder removes surface hydrochloric acid solution, and dries；Silk cylinder is sintered at 400 DEG C so that mass transfer is DB；By above-mentioned system
Graphene modified organosilicon paint be sprayed on silk cylinder surface, then dry 10min at 50 DEG C, obtain Graphene and be modified high silicon
Oxygen glass fibre.
Comparative example 1
Glass batch is put in electric melting furnace and is founded at 1600 DEG C, and if by expect stock be cut into siccative block, so
Block is expected in cooling afterwards；Material block after cooling is put in fiber drawing furnace carries out secondary fusion and wire drawing at 1150 DEG C, then makes silk
Cylinder；By silk cylinder in the hydrochloric acid that concentration is 15%, with 100 DEG C acid leach 0.5h is carried out, to remove silicon beyond impurity；It is clear with water
Wash silk cylinder and remove surface hydrochloric acid solution, and dry；Silk cylinder is sintered at 900 DEG C so that mass transfer is DB, obtains height
Silica glass.
Comparative example 2
Glass batch is put in electric melting furnace and is founded at 1450 DEG C, and if by expect stock be cut into siccative block, so
Block is expected in cooling afterwards；Material block after cooling is put in fiber drawing furnace carries out secondary fusion and wire drawing at 800 DEG C, then makes silk
Cylinder；By silk cylinder in the hydrochloric acid that concentration is 10%, with 75 DEG C acid leach 10h is carried out, to remove silicon beyond impurity；Cleaned with water
Silk cylinder removes surface hydrochloric acid solution, and dries；Silk cylinder is sintered at 750 DEG C so that mass transfer is DB, obtain high silicon
Oxygen glass fibre.
Comparative example 3
Glass batch is put in electric melting furnace and is founded at 1300 DEG C, and if by expect stock be cut into siccative block, so
Block is expected in cooling afterwards；Material block after cooling is put in fiber drawing furnace carries out secondary fusion and wire drawing at 200 DEG C, then makes silk
Cylinder；By silk cylinder in the hydrochloric acid that concentration is 5%, with 50 DEG C acid leach 40h is carried out, to remove silicon beyond impurity；Cleaned with water
Silk cylinder removes surface hydrochloric acid solution, and dries；Silk cylinder is sintered at 400 DEG C so that mass transfer is DB, obtain high silicon
Oxygen glass fibre.
The high silica glass in the modified resurrection glass fibre of Graphene and comparative example 1～3 in testing example 1～3
The heat resisting temperature of glass fiber, intensity and the intensity after abrasion, obtain table 1.
The performance test data table of table 1
| Strongly/N | Strength/N after abrasion | Strength reduction rate/% | Heat resisting temperature/DEG C | |
| Embodiment 1 | 32.2 | 19.3 | 40.0 | 1100 |
| Embodiment 2 | 33.1 | 21.5 | 35.0 | 1300 |
| Embodiment 3 | 32.1 | 17.7 | 44.9 | 1150 |
| Comparative example 1 | 28.5 | 11.4 | 60.0 | 900 |
| Comparative example 2 | 29.6 | 13.1 | 55.7 | 950 |
| Comparative example 3 | 27.9 | 10.1 | 63.8 | 900 |
It can be seen from table 1, it is modified high silica glass by Graphene obtained in the Graphene modified organosilicon paint of the present invention
The relatively conventional resurrection glass fibre of glass fiber, improves 15% or so in terms of intensity；Graphite after test abrasion
The relatively conventional resurrection glass fibre of the modified resurrection glass fibre of alkene, strength reduction rate declines 20% or so, and explanation passes through
The frayed impact of the modified resurrection glass fibre intensity of Graphene obtained in the Graphene modified organosilicon paint of the present invention compared with
Little, i.e., anti-wear performance is improved；And the relatively conventional resurrection glass fibre of the modified resurrection glass fibre of the Graphene is resistance to
Hot temperature improves 200～400 DEG C.
Claims (10)
1. a kind of Graphene modified organosilicon paint, it is characterised in that：Mainly it is made up of the material of following mass parts：Graphene
0.1～5 part, 15～50 parts of organic silicon emulsion, 5～35 parts of kaolin, 0.1～0.2 part of defoamer, 1～3 part of thickener, dispersion
0.07～3.5 part of 0.5～3 part of agent and APES.
2. the Graphene modified organosilicon paint described in claim 1, it is characterised in that：The Graphene and alkyl phenol polyoxy second
The quality parts ratio of alkene ether is 1:0.7.
3. the Graphene modified organosilicon paint described in claim 1, it is characterised in that：The thickener is hydroxy propyl cellulose
Element, defoamer is tributyl phosphate, and dispersant is polycarboxylate sodium, and organic silicon emulsion is MP-50E.
4. the preparation method of the Graphene modified organosilicon paint described in claim 1, it is characterised in that：Comprise the following steps：
(1) Graphene and APES are blended in water, and carry out mixing ultrasonic disperse, formed finely dispersed
Graphene aqueous solution；
(2) after being mixed and stirred for organic silica gel, dispersant, thickener and defoamer uniformly, kaolin, uniform stirring are added
Dispersion forms organosilicon compound；
(3) obtained graphene aqueous solution in step (1) is added in organosilicon compound obtained in step (2), dispersed with stirring,
Obtain Graphene modified organosilicon paint.
5. the preparation method of Graphene modified organosilicon paint according to claim 4, it is characterised in that：In step (1)
The ultrasonic disperse time is 0.5～2 hour.
6. the preparation method of the modified resurrection glass fibre of a kind of Graphene, it is characterised in that：Comprise the following steps：
(1) glass batch is founded at 1300～1600 DEG C, and is divided into material block, then cooling material block；
(2) the material block after cooling is carried out into secondary fusion and wire drawing at 200～1150 DEG C, then makes silk cylinder；
(3) silk cylinder is carried out into acid leach；
(4) clean silk cylinder and remove surface hydrochloric acid solution, and dry；
(5) silk cylinder is sintered；
(6) Graphene modified organosilicon paint is obtained using the preparation method described in claim 4；
(7) Graphene modified organosilicon paint is sprayed on into silk cylinder surface, then in 50～150 DEG C of drying, obtains Graphene and change
Property resurrection glass fibre.
7. the preparation method of the modified resurrection glass fibre of Graphene according to claim 6, it is characterised in that：Step
(3) solution of the acid leach is the hydrochloric acid of concentration 5～15%, and acid leach temperature is 50～100 DEG C, and the time is 0.5～40 little
When.
8. the preparation method of the modified resurrection glass fibre of Graphene according to claim 6, it is characterised in that：Step
(5) 400～900 DEG C of the sintering temperature in.
9. the preparation method of the modified resurrection glass fibre of Graphene according to claim 6, it is characterised in that：Step
(7) drying time in is 10～60 minutes.
10. the modified resurrection glass fibre of a kind of Graphene, it is characterised in that：The modified resurrection glass fibre of the Graphene passes through
The preparation method of the modified resurrection glass fibre of Graphene according to claim 5 is obtained.
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Cited By (5)
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|---|---|---|---|---|
| CN109161289A (en) * | 2018-08-24 | 2019-01-08 | 广东鑫皇冠新材料有限公司 | A kind of antistatic coating and preparation method thereof |
| CN109651816A (en) * | 2018-11-20 | 2019-04-19 | 兴业皮革科技股份有限公司 | A kind of compound emulsion method of graphene-based polysiloxanes |
| CN113683866A (en) * | 2021-08-26 | 2021-11-23 | 天长市康美达新型绝热材料有限公司 | Acid and alkali resistant glass fiber composite material and preparation method thereof |
| CN114292590A (en) * | 2022-01-11 | 2022-04-08 | 北京裕金科技有限公司 | Graphene oxide modified organic silicon coating and preparation method and application thereof |
| CN113683866B (en) * | 2021-08-26 | 2024-05-31 | 天长市康美达新型绝热材料有限公司 | Acid-alkali resistant glass fiber composite material and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109161289A (en) * | 2018-08-24 | 2019-01-08 | 广东鑫皇冠新材料有限公司 | A kind of antistatic coating and preparation method thereof |
| CN109651816A (en) * | 2018-11-20 | 2019-04-19 | 兴业皮革科技股份有限公司 | A kind of compound emulsion method of graphene-based polysiloxanes |
| CN109651816B (en) * | 2018-11-20 | 2021-06-15 | 兴业皮革科技股份有限公司 | Compound emulsification method of graphene-based polysiloxane |
| CN113683866A (en) * | 2021-08-26 | 2021-11-23 | 天长市康美达新型绝热材料有限公司 | Acid and alkali resistant glass fiber composite material and preparation method thereof |
| CN113683866B (en) * | 2021-08-26 | 2024-05-31 | 天长市康美达新型绝热材料有限公司 | Acid-alkali resistant glass fiber composite material and preparation method thereof |
| CN114292590A (en) * | 2022-01-11 | 2022-04-08 | 北京裕金科技有限公司 | Graphene oxide modified organic silicon coating and preparation method and application thereof |
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Application publication date: 20170510 |
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