CN103937154A - Super-hydrophobic epoxy solid buoyancy material, and preparation method thereof - Google Patents
Super-hydrophobic epoxy solid buoyancy material, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a super-hydrophobic epoxy solid buoyancy material, and a preparation method thereof. The super-hydrophobic epoxy solid buoyancy material comprises, by mass, 100 parts of epoxy resin, 5 to 20 parts of a diluents, 2 to 20 parts of a flexibilizer, 60 to 80 parts of a curing agent, 0.5 to 5 parts of a catalyst, 10 to 80 parts of hollow microsphere, and 2 to 15 parts of a fluorated acrylic acid prepolymer. The fluorated acrylic prepolymer is a novel fluorine-modified acrylic acid prepolymer; comprises one or a plurality of compounds selected from a fluorine-modified acrylic acid prepolymer A, a fluorine-modified acrylic acid prepolymer B, and a fluorine-modified acrylic acid prepolymer C; and is prepared via successive synthesis of the fluorine-modified acrylic acid prepolymer A, the fluorine-modified acrylic acid prepolymer B, and the fluorine-modified acrylic acid prepolymer C, and hot-press curing molding with other formula ingredients. The super-hydrophobic epoxy solid buoyancy material possesses excellent selt-cleaning performance, water resistance, and corrosion resistance; the preparation method is simple; repeatability is high; cost is low; complex chemical processing processes are not needed; and industrialized application prospect is promising.
Description
Technical field
The invention belongs to functional nonmetallic composite technical field, relate in particular to a kind of super-hydrophobic epoxy group(ing) solid buoyancy material and preparation method thereof.
Background technology
Super hydrophobic material generally refers to that surface-stable contact angle is greater than 150 °, the material that rolling contact angle is less than 10 °.Super-hydrophobic research derives from " lotus leaf effect " that the people such as Barthlott propose, find after deliberation, why lotus leaf can go out mud and not dye, and reason is that lotus leaf surface has one deck super hydrophobic material, poly-strand of current rolled and can not permeate, thereby making lotus leaf there is the characteristic on self-cleaning blade face.In recent years, very extensive for the research of super hydrophobic material, as super hydrophobic material can anti-accumulated snow for outdoor antenna, can be antifouling and anticorrosion for ocean-going vessel, for petroleum transportation pipeline, microsyringe needle point can effectively antifouling and waterproof.On super hydrophobic surface; water droplet or sewage (as muddy water, ink etc.) can form the glistening spherical globule conventionally; the globule can not be penetrated into base material the inside; inclined surface or under micro-wind action a little; the globule will tumble rapidly from surface at once; when the globule tumbles, by being deposited on surperficial dust, take away, play self-cleaning effect.Super hydrophobic surface can keep dry for a long time, can effectively suppress various generations of take the corrosion reaction that water is medium, effectively extends the work-ing life of super hydrophobic surface and base material thereof.
In the last few years, along with the progress of oceanology and ocean science, more and more higher for the demand of solid buoyancy material at aspects such as oceanic resources, marine instrument and equipment, bathyscaph and petroleum pipe line coatings.Solid buoyancy material generally refers to have high strength or superstrength water pressure resistance, and density is far smaller than the polymer composite of water, as patent 200410030821.6 discloses PU-Epoxy porous plastics solid buoyancy material; Patent 200610007987.5 discloses the PU-Epoxy solid buoyancy material that a kind of glass microballon adds, these materials all have excellent compressive property, can meet the application of deep-sea research, yet in the research work of current solid buoyancy material, be all the research based on higher withstand voltage deep-sea application aspect, specific functional solid buoyancy material is rare.In the face of day by day complicated ocean environment, the microorganism of especially causing due to Marine Environmental Pollution and the threat of algae are more and more serious, and then solid buoyancy material is had higher requirement, the research of super-hydrophobic solid buoyancy material extremely has necessity and significance thus.
Summary of the invention
The object of the invention is to: a kind of super-hydrophobic epoxy group(ing) solid buoyancy material and preparation method thereof is provided, merged " super-hydrophobic " technique means, adopting process is simple, favorable reproducibility, without any expensive device, do not need the preparation method of complicated chemical treating process yet, prepare a kind of super-hydrophobic epoxy group(ing) solid buoyancy material with excellent automatically cleaning, waterproof, the performance such as anticorrosive.
To achieve these goals, the present invention adopts following technical scheme:
A kind of super-hydrophobic epoxy group(ing) solid buoyancy material, it is characterized in that: with mass fraction, calculate, this material comprises following component: 100 parts of epoxy resin, 5～20 parts of thinners, 2～20 parts of toughner, 60～80 parts, solidifying agent, 0.5～5 part of catalyzer, 10～80 parts of cenospheres, 2～15 parts of fluorinated acrylamide acids prepolymers.
Wherein, described epoxy resin is a kind of in dihydroxyphenyl propane based epoxy resin, novolac epoxy, aliphatic epoxy resin or hydridization type epoxy resin; Described thinner is acetone, ethyl acetate, butylacetate, butylglycidyl ether, 1,4-butanediol diglycidyl ether, ethylene glycol diglycidylether, phenyl glycidyl ether, polypropylene glycol diglycidyl ether, fatty glycidyl ether, benzyl glycidyl ether, 1, one or more in 6-hexanediol diglycidyl ether, propylene oxide o-cresyl ether or o-tolyl glycidyl ether, neopentylglycol diglycidyl ether; Described toughner is to be one or more in rubber-like toughner, thermoplastic elastomer class toughner, Versamid and low molecular nonactive toughner; Described solidifying agent be for alkaline amine curing agent, acid acid anhydride type curing agent, fatty amines, low molecular polyamides class add-on type solidifying agent or imidazole curing agent one or more; Described cenosphere is that ultimate compression strength is 30～125MPa, and real density is 0.125～0.6g/cm3, and particle diameter is 10～120 μ m, inner chamber be filled with gas or for vacuum through silane coupling agent KH560 surface-treated hollow glass micropearl or hollow ceramic microspheres.
A kind of super-hydrophobic epoxy group(ing) solid buoyancy material, it is characterized in that: described fluorinated acrylamide acids prepolymer is a kind of novel fluorin modified crylic acid class prepolymer, comprise one or more in its fluorin modified crylic acid class prepolymer A, fluorin modified crylic acid class prepolymer B and fluorin modified crylic acid class prepolymer C.
Further, described fluorin modified crylic acid class prepolymer A adopts synthetic with the following method: the 11 fluorine normal hexane-1-alcohol and 1 that are 1:2 by mol ratio, hexamethylene-diisocyanate mixes, under nitrogen protection, under 60oC condition, react after 3～5h, mixed solution is joined in dimethyl formamide solution, until solution clear obtains pre-polymer solution, the ratio that the mol ratio of again epoxy acrylate and prepolymer being take is 2.07:1 joins in prepolymer mixing solutions, it is 85% (w/v) that solution solid content is controlled, continue to stir, under nitrogen protection, under 60oC condition, react 12～24h, after finally the mixing solutions solvent free obtaining being processed, prepare fluorin modified crylic acid class prepolymer A.
Described fluorin modified crylic acid class prepolymer B adopts synthetic with the following method: the 11 fluorine normal hexane-1-alcohol that are 1:2 by mol ratio mix with tolylene diisocyanate, under nitrogen protection, under 60oC condition, react after 3～5h, mixed solution is joined in dimethyl formamide solution, until solution clear obtains pre-polymer solution, the ratio that the mol ratio of again epoxy acrylate and prepolymer being take is 2.07:1 joins in prepolymer mixing solutions, solution solid content is controlled at 85% (w/v), continue to stir, under nitrogen protection, under 60oC condition, react 12～24h, after finally the mixing solutions solvent free obtaining being processed, prepare fluorin modified crylic acid class prepolymer B.
Described fluorin modified crylic acid class prepolymer C adopts synthetic with the following method: the 11 fluorine normal hexane-1-alcohol and 4 that are 1:2 by mol ratio, 4'-diphenylmethanediisocyanate mixes, under nitrogen protection, and react after 3～5h under 60oC condition, mixed solution is joined in dimethyl formamide solution, until solution clear obtains pre-polymer solution, the ratio that the mol ratio of again epoxy acrylate and prepolymer being take is 2.07:1 joins in prepolymer mixing solutions, solution solid content is controlled at 85% (w/v), continue to stir, under nitrogen protection, under 60oC condition, react 12～24h, after finally the mixing solutions solvent free obtaining being processed, obtain fluorin modified crylic acid class prepolymer C.
A super-hydrophobic epoxy group(ing) solid buoyancy material, is characterized in that: described super-hydrophobic epoxy group(ing) solid buoyancy material surface and the contact angle of water are between 150～170 °, and the roll angle of water droplet on solid buoyancy material surface is less than 5 °.
A preparation method for super-hydrophobic epoxy group(ing) solid buoyancy material, concrete steps are as follows:
(1) surface treatment of cenosphere
Cenosphere is joined in 50% sodium hydroxide solution, under room temperature, stir 2～4h, filter and take out cenosphere, first with the aqueous acetic acid that volume percent is 0.1%, cenosphere is washed, with after deionized water wash, by the cenosphere obtaining vacuum-drying 12h under 80oC, then joined in the ethanolic soln of silane coupling agent KH560 again, and at room temperature stir 5h, finally take out cenosphere and be placed in the dry 24h of baking oven of 80oC;
(2) prepare super-hydrophobic epoxy group(ing) solid buoyancy material
By the epoxy resin of described mass fraction, thinner, toughner, join in vacuum mixer through silane coupling agent KH560 surface-treated cenosphere and synthetic fluorinated acrylamide acids prepolymer A, one or more in B, C, in the vacuum mixer of 60～80oC, stir 20～30min, then add solidifying agent and the catalyzer of respective quality umber and continue to stir 20min, finally gained mixture is injected to mould, curing molding under the pressure of 20MPa, program curing is followed successively by 2h under 110oC, 4h under 140oC, 4h under 160oC.
Inventive principle and beneficial effect:
Waterproof based on fluorochemical, dirt-removing functions, the present invention introduces fluorine-containing acrylic acid or the like prepolymer in epoxy group(ing) solid buoyancy material, and the method that adopts hot-press solidifying moulding prepares hydrophobic epoxy group(ing) solid buoyancy material, this material has good automatically cleaning, waterproof, corrosion resistance; Meanwhile, preparation method's of the present invention technique is simple, favorable reproducibility, without any expensive device, do not need complicated chemical treating process yet, have advantages of that cost is low.
Accompanying drawing explanation
Fig. 1 is the contact angle test result of epoxy group(ing) solid buoyancy material and super-hydrophobic epoxy group(ing) solid buoyancy material surface and water.
Embodiment
Below in conjunction with specific examples, technical scheme of the present invention is described further.
As shown in Figure 1, (a) be the contact angle test result of epoxy group(ing) solid buoyancy material surface and water, concrete numerical value is 73.3 °; (b) be the prepared super-hydrophobic epoxy group(ing) solid buoyancy material surface of embodiment 1 and the contact angle test result of water, concrete numerical value is 157.3 °; (c) be the prepared super-hydrophobic epoxy group(ing) solid buoyancy material surface of embodiment 2 and the contact angle test result of water, concrete numerical value is 162.8 °.
Embodiment 1
A kind of super-hydrophobic epoxy group(ing) solid buoyancy material, with mass fraction, calculate, this material comprises following component: 100 parts of epoxy resin, 15 parts of thinners, 10 parts of toughner, 60 parts, solidifying agent, 1 part of catalyzer, 40 parts of cenospheres, 15 parts of fluorinated acrylamide acids prepolymers.
Described epoxy resin is epoxy resin E51.
Described thinner is ethylene glycol diglycidylether type epoxide diluent.
Described toughner is acrylonitrile-butadiene-styrene copolymer (ABS) toughner.
Described solidifying agent is MALEIC ANHYDRIDE.
Described catalyzer is diethylenetriamine.
Described cenosphere is through KH560 surface-treated hollow glass micropearl K37.
Described fluorinated acrylamide acids prepolymer is fluorinated acrylamide acids prepolymer A.
According to above-mentioned formula, get the raw materials ready, then adopt following technique preparation:
(1) surface treatment of hollow glass micropearl K37
Hollow glass micropearl K37 is joined in 50% sodium hydroxide solution, under room temperature, stir 2～4h, filter and take out hollow glass micropearl K37, the aqueous acetic acid that is first 0.1% by volume percent washs hollow glass micropearl K37, again with after deionized water wash, by the hollow glass micropearl K37 obtaining vacuum-drying 12h under 80oC, then joined in the ethanolic soln of silane coupling agent KH560, and at room temperature stir 5h, finally take out hollow glass micropearl K37 and be placed in the dry 24h of baking oven of 80oC;
(2) synthetic fluorinated acrylamide acids prepolymer A
The 11 fluorine normal hexane-1-alcohol and 1 that are 1:2 by mol ratio, hexamethylene-diisocyanate mixes, under nitrogen protection, under 60oC condition, react after 3～5h, mixed solution is joined in dimethyl formamide solution, until solution clear obtains pre-polymer solution, the ratio that the mol ratio of again epoxy acrylate and prepolymer being take is 2.07:1 joins in prepolymer mixing solutions, it is 85% (w/v) that solution solid content is controlled, continue to stir, under nitrogen protection, under 60oC condition, react 12～24h, after finally the mixing solutions solvent free obtaining being processed, prepare fluorin modified crylic acid class prepolymer A.
(3) prepare super-hydrophobic epoxy group(ing) solid buoyancy material
By the epoxy resin of described mass fraction, thinner, toughner, join in vacuum mixer through silane coupling agent KH560 surface-treated hollow glass micropearl K37 and synthetic fluorinated acrylamide acids prepolymer A, in the vacuum mixer of 60～80oC, stir 20～30min, then add solidifying agent and the catalyzer of respective quality umber and continue to stir 20min, finally gained mixture is injected to mould, curing molding under the pressure of 20MPa, program curing is followed successively by 2h under 110oC, 4h under 140oC, 4h under 160oC.
Embodiment 2
A kind of super-hydrophobic epoxy group(ing) solid buoyancy material, with mass fraction, calculate, this material comprises following component: 100 parts of epoxy resin, 15 parts of thinners, 10 parts of toughner, 60 parts, solidifying agent, 1 part of catalyzer, 40 parts of cenospheres, 15 parts of fluorinated acrylamide acids prepolymers.
Described epoxy resin is epoxy resin E51.
Described thinner is ethylene glycol diglycidylether type epoxide diluent.
Described toughner is acrylonitrile-butadiene-styrene copolymer (ABS) toughner.
Described solidifying agent is MALEIC ANHYDRIDE.
Described catalyzer is diethylenetriamine.
Described cenosphere is through KH560 surface-treated hollow glass micropearl K37.
Described fluorinated acrylamide acids prepolymer is fluorinated acrylamide acids prepolymer C.
According to above-mentioned formula, get the raw materials ready, then adopt following technique preparation:
(1) surface treatment of hollow glass micropearl K37
Hollow glass micropearl K37 is joined in 50% sodium hydroxide solution, under room temperature, stir 2～4h, filter and take out hollow glass micropearl K37, the aqueous acetic acid that is first 0.1% by volume percent washs hollow glass micropearl K37, again with after deionized water wash, by the hollow glass micropearl K37 obtaining vacuum-drying 12h under 80oC, then joined in the ethanolic soln of silane coupling agent KH560, and at room temperature stir 5h, finally take out hollow glass micropearl K37 and be placed in the dry 24h of baking oven of 80oC;
(3) synthetic fluorinated acrylamide acids prepolymer C
The 11 fluorine normal hexane-1-alcohol and 4 that are 1:2 by mol ratio, 4'-diphenylmethanediisocyanate mixes, under nitrogen protection, and react after 3～5h under 60oC condition, mixed solution is joined in dimethyl formamide solution, until solution clear obtains pre-polymer solution, the ratio that the mol ratio of again epoxy acrylate and prepolymer being take is 2.07:1 joins in prepolymer mixing solutions, solution solid content is controlled at 85% (w/v), continue to stir, under nitrogen protection, under 60oC condition, react 12～24h, after finally the mixing solutions solvent free obtaining being processed, obtain fluorin modified crylic acid class prepolymer C.
(3) prepare super-hydrophobic epoxy group(ing) solid buoyancy material
By the epoxy resin of described mass fraction, thinner, toughner, join in vacuum mixer through silane coupling agent KH560 surface-treated hollow glass micropearl K37 and synthetic fluorinated acrylamide acids prepolymer C, in the vacuum mixer of 60～80oC, stir 20～30min, then add solidifying agent and the catalyzer of respective quality umber and continue to stir 20min, finally gained mixture is injected to mould, curing molding under the pressure of 20MPa, program curing is followed successively by 2h under 110oC, 4h under 140oC, 4h under 160oC.
As can be seen from Figure 1, in existing epoxy group(ing) solid buoyancy material, add after fluorinated acrylamide acids prepolymer A or C, all there is very large change in the contact angle of material surface and water, thereby being conducive to water droplet tumbles and adhesion, realized and reduced the object of water-intake rate, and then reached the effect of waterproof, self-cleaning.And comparative example 1 and 2 contact and can see, after adding fluorinated acrylamide acids prepolymer A and C, contact angle changes, but change little, illustrate that the super-hydrophobic epoxy group(ing) solid buoyancy material that adopts technical solution of the present invention to prepare has satisfactory stability and reproducibility, is suitable for industrial expanding production.
Claims (7)
1. a super-hydrophobic epoxy group(ing) solid buoyancy material, it is characterized in that: with mass fraction, calculate, this material comprises following component: 100 parts of epoxy resin, 5～20 parts of thinners, 2～20 parts of toughner, 60～80 parts, solidifying agent, 0.5～5 part of catalyzer, 10～80 parts of cenospheres, 2～15 parts of fluorinated acrylamide acids prepolymers.
2. a kind of super-hydrophobic epoxy group(ing) solid buoyancy material as claimed in claim 1, it is characterized in that: described fluorinated acrylamide acids prepolymer is a kind of novel fluorin modified crylic acid class prepolymer, comprise one or more in its fluorin modified crylic acid class prepolymer A, fluorin modified crylic acid class prepolymer B and fluorin modified crylic acid class prepolymer C.
3. a kind of super-hydrophobic epoxy group(ing) solid buoyancy material as claimed in claim 2 fluorinated acrylamide acids prepolymer A used, it is characterized in that: the synthetic method of this fluorinated acrylamide acids prepolymer A is: the 11 fluorine normal hexane-1-alcohol and 1 that are 1:2 by mol ratio, hexamethylene-diisocyanate mixes, under nitrogen protection, under 60oC condition, react after 3～5h, mixed solution is joined in dimethyl formamide solution, until solution clear obtains pre-polymer solution, the ratio that the mol ratio of again epoxy acrylate and prepolymer being take is 2.07:1 joins in prepolymer mixing solutions, it is 85% (w/v) that solution solid content is controlled, continue to stir, under nitrogen protection, under 60oC condition, react 12～24h, after finally the mixing solutions solvent free obtaining being processed, prepare fluorin modified crylic acid class prepolymer A.
4. a kind of super-hydrophobic epoxy group(ing) solid buoyancy material as claimed in claim 2 fluorinated acrylamide acids prepolymer B used, it is characterized in that: the synthetic method of this fluorinated acrylamide acids prepolymer B is: the 11 fluorine normal hexane-1-alcohol that are 1:2 by mol ratio mix with tolylene diisocyanate, under nitrogen protection, under 60oC condition, react after 3～5h, mixed solution is joined in dimethyl formamide solution, until solution clear obtains pre-polymer solution, the ratio that the mol ratio of again epoxy acrylate and prepolymer being take is 2.07:1 joins in prepolymer mixing solutions, solution solid content is controlled at 85% (w/v), continue to stir, under nitrogen protection, under 60oC condition, react 12～24h, after finally the mixing solutions solvent free obtaining being processed, prepare fluorin modified crylic acid class prepolymer B.
5. a kind of super-hydrophobic epoxy group(ing) solid buoyancy material as claimed in claim 2 fluorinated acrylamide acids prepolymer C used, it is characterized in that: the synthetic method of this fluorinated acrylamide acids prepolymer C is: the 11 fluorine normal hexane-1-alcohol and 4 that are 1:2 by mol ratio, 4'-diphenylmethanediisocyanate mixes, under nitrogen protection, and react after 3～5h under 60oC condition, mixed solution is joined in dimethyl formamide solution, until solution clear obtains pre-polymer solution, the ratio that the mol ratio of again epoxy acrylate and prepolymer being take is 2.07:1 joins in prepolymer mixing solutions, solution solid content is controlled at 85% (w/v), continue to stir, under nitrogen protection, under 60oC condition, react 12～24h, after finally the mixing solutions solvent free obtaining being processed, obtain fluorin modified crylic acid class prepolymer C.
6. a kind of super-hydrophobic epoxy group(ing) solid buoyancy material as claimed in claim 1, it is characterized in that: described super-hydrophobic epoxy group(ing) solid buoyancy material surface and the contact angle of water are between 150～170 °, and the roll angle of water droplet on solid buoyancy material surface is less than 5 °.
7. a preparation method for super-hydrophobic epoxy group(ing) solid buoyancy material according to claim 1, is characterized in that: this preparation method's concrete steps are as follows:
(1) surface treatment of cenosphere
Cenosphere is joined in 50% sodium hydroxide solution, under room temperature, stir 2～4h, filter and take out cenosphere, first with the aqueous acetic acid that volume percent is 0.1%, cenosphere is washed, with after deionized water wash, by the cenosphere obtaining vacuum-drying 12h under 80oC, then joined in the ethanolic soln of silane coupling agent KH560 again, and at room temperature stir 5h, finally take out cenosphere and be placed in the dry 24h of baking oven of 80oC;
(2) prepare super-hydrophobic epoxy group(ing) solid buoyancy material
By the epoxy resin of described mass fraction, thinner, toughner, join in vacuum mixer through silane coupling agent KH560 surface-treated cenosphere and synthetic fluorinated acrylamide acids prepolymer A, one or more in B, C, in the vacuum mixer of 60～80oC, stir 20～30min, then add solidifying agent and the catalyzer of respective quality umber and continue to stir 20min, finally gained mixture is injected to mould, curing molding under the pressure of 20MPa, program curing is followed successively by 2h under 110oC, 4h under 140oC, 4h under 160oC.
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| CN201410050317.6A CN103937154B (en) | 2014-02-13 | A kind of super-hydrophobic epoxy radicals solid buoyancy material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410050317.6A CN103937154B (en) | 2014-02-13 | A kind of super-hydrophobic epoxy radicals solid buoyancy material and preparation method thereof |
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| CN103937154A true CN103937154A (en) | 2014-07-23 |
| CN103937154B CN103937154B (en) | 2016-11-30 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105254997A (en) * | 2015-09-01 | 2016-01-20 | 上海大学 | Manufacture method for super-hydrophobic plastic |
| CN107083022A (en) * | 2017-05-23 | 2017-08-22 | 苏州轩朗塑料制品有限公司 | A kind of preparation method of shock absorbing foam plastic material |
| CN109456575A (en) * | 2018-11-21 | 2019-03-12 | 兰州工业学院 | A kind of ceramic composite and preparation method thereof |
| US10611100B2 (en) | 2015-06-12 | 2020-04-07 | 3M Innovative Properties Company | Buoyancy module |
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| CN1844236A (en) * | 2006-04-08 | 2006-10-11 | 海洋化工研究院 | Workable solid buoyancy material for deep sea and method for preparing same |
| CN102039984A (en) * | 2010-11-23 | 2011-05-04 | 哈尔滨工业大学 | Super-buoyancy superhydrophobic aramid fiber bundle ship and manufacturing method thereof |
| CN103172975A (en) * | 2013-04-03 | 2013-06-26 | 上海海事大学 | Preparation method of high-impact-resistance solid buoyancy material |
| CN103483773A (en) * | 2013-09-24 | 2014-01-01 | 滕州市华海新型保温材料有限公司 | Deep-sea solid buoyancy material and manufacture method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1844236A (en) * | 2006-04-08 | 2006-10-11 | 海洋化工研究院 | Workable solid buoyancy material for deep sea and method for preparing same |
| CN102039984A (en) * | 2010-11-23 | 2011-05-04 | 哈尔滨工业大学 | Super-buoyancy superhydrophobic aramid fiber bundle ship and manufacturing method thereof |
| CN103172975A (en) * | 2013-04-03 | 2013-06-26 | 上海海事大学 | Preparation method of high-impact-resistance solid buoyancy material |
| CN103483773A (en) * | 2013-09-24 | 2014-01-01 | 滕州市华海新型保温材料有限公司 | Deep-sea solid buoyancy material and manufacture method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10611100B2 (en) | 2015-06-12 | 2020-04-07 | 3M Innovative Properties Company | Buoyancy module |
| CN105254997A (en) * | 2015-09-01 | 2016-01-20 | 上海大学 | Manufacture method for super-hydrophobic plastic |
| CN107083022A (en) * | 2017-05-23 | 2017-08-22 | 苏州轩朗塑料制品有限公司 | A kind of preparation method of shock absorbing foam plastic material |
| CN109456575A (en) * | 2018-11-21 | 2019-03-12 | 兰州工业学院 | A kind of ceramic composite and preparation method thereof |
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