CN104530650A - Submersible vehicle encapsulation composite foam filling materials and preparation method thereof - Google Patents
Submersible vehicle encapsulation composite foam filling materials and preparation method thereof Download PDFInfo
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- CN104530650A CN104530650A CN201410850850.0A CN201410850850A CN104530650A CN 104530650 A CN104530650 A CN 104530650A CN 201410850850 A CN201410850850 A CN 201410850850A CN 104530650 A CN104530650 A CN 104530650A
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Abstract
The invention discloses submersible vehicle encapsulation composite foam filling materials and a preparation method of the submersible vehicle encapsulation composite foam filling materials. The filling materials are composed of epoxy resin, polyether amine curing agents, silane coupling agents, polysiloxane defoamer, catalysts, thixotropic agents and hollow micro glass beads. The preparation method includes the steps of (1) pre-mixing of liquid materials, (2) preparation of slurry, (3) high-pressure air-free pouring, and (4) curing and performance test. The composite foam filling materials are low in system viscosity, good in flowing levelling property, long in construction period and suitable for a pouring encapsulation process, and can be cured at room temperature, the curing reaction heat release temperature peak is low, and condensate is tenacious, high in strength, small in contracting rate and good in adhesive property with steel and other materials. The composite foam filling materials are resistant to sea water soaking corrosion, good in effect after being tried, and suitable for encapsulation filling and water insulation sealing of a submarine non-water-sealing structure, a buoy, a subsurface buoy and other marine submersible vehicles.
Description
Technical field
The present invention relates to a kind of composite foam packing material, belong to ocean solid buoyancy material category, be specifically related to a kind of manufacture method of hollow glass micropearl filling epoxy resin light overpressure resistant packing material.
Background technology
Current marine survey technology is the important component part that marine resources development utilizes, low density, Bear high pressure intensity deep-sea solid buoyancy material, it is the important materials of marine survey technology, to dive device structural stability, stopping property and resistance to hydrostatic pressure performance to provide ocean, require pourable light overpressure resistant packing material, complement one another with prefabrication type solid buoyancy material.The light overpressure resistant packing material of external development adopts high-intensity resin as matrix, fills buoyancy adjustment medium as matrix, adopts special process to process.
Chinese patent CN102702679A has reported a kind of preparation method of deep diving High-strength solid buoyancy material, vibration self-assembling method is adopted to be filled in stainless steel forming mould ceramic hollow ball and/or hollow glass micropearl, through slight vibration jolt ramming, by low viscosity epoxy resin, solidifying agent, coupling agent, curing catalyst fully mixes according to a certain percentage and finds time degassed, then the epoxy resin slurry liquid booster pump mixed is injected die cavity from the bottom of stainless steel forming mould, be cured by predetermined solidification value and time and obtain light-high-strength packing material.Its ultimate compression strength can reach 80 ~ 120MPa, and density 0.45 ~ 0.65g/cm3, under high hydrostatic pressure, water-intake rate is less than 1%.
Chinese patent CN 103910974A reports a kind of tiny balloon filling epoxy resin composite foam material and manufacture method thereof, and its composition comprises polystyrene hollow spheres, hollow glass micropearl, liquid epoxies, amine hardener, thinner and coupling agent.Its manufacture method comprises the steps: the surface treatment b of a) hollow glass micropearl and polystyrene hollow spheres) batch mixing find time deaeration c) rerolling finds time deaeration d) vacuum pouring is in component die cavity e) curing molding.This composite foam material has lower density, higher hydrostatic pressure resistant intensity, for Deep-sea vessel light overpressure resistant composite foam packing material.
Manufacturing technology about ocean solid buoyancy material has multinomial Chinese patent report, its Patent 200410030821.6, solid buoyancy material prepared by a kind of chemical blowing process, patent 200610007987.5, a kind of glass microballon abscess composite foam structure buoyancy material, patent 200610043524.4, a kind of workable solid buoyancy material for deep sea and preparation method thereof, patent 200910230160.4 1 kinds of ultra-low density solid buoyant materials and making method.Above-mentioned patent is all the manufacture method of prefabrication type solid buoyancy material, has no the report about device embedding light overpressure resistant composite foam packing material manufacture method of diving at present.
Summary of the invention
Technical problem to be solved by this invention is to provide one and is applicable to latent device embedding composite foam packing material, is characterized in that material system viscosity is low, flowing good leveling property, and ambient temperature curable is applicable to pour into a mould dosing technology, has the longer pouring construction phase.Curing reaction exothermic temperature peak is low, and cured article is tough and tensile, low density, high strength, shrinking percentage are little, good with the material adhesive property such as iron and steel, can long-term sea water resistance immersion corrosion.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
Latent device embedding composite foam packing material provided by the invention comprises the component of following parts by weight: chemical constitution is by the epoxy resin of 100 mass parts: epoxy resin 100, polyetheramine solidifying agent 30--60, silane coupling agent 0.5--3.0, polysiloxane defoamers 1--3, catalyzer 0--2, thixotropic agent 0.5--1.5, hollow glass micropearl percent by volume 45--48%.
Preferably, epoxy resin described above be selected from following component one or more: liquid bisphenol A epoxy resin, low viscosity bisphenol F epoxy resin, cycloaliphatic epoxy resin; Wherein the epoxy equivalent (weight) of liquid bisphenol A epoxy resin is 184-225g/eq; The epoxy equivalent (weight) of low viscosity bisphenol F epoxy resin is 160-180g/eq, and viscosity is 25 DEG C/mpa.s700-1100; Cycloaliphatic epoxy resin be 3,4-epoxy-cyclohexane formic acid-3 ', 4 '-epoxy-cyclohexane methyl esters, its epoxy equivalent (weight) is 131-143g/eq; 3,4-epoxy group(ing)-6-cyclohexanecarboxylic acid-3 ', 4 '-epoxy group(ing)-6
,-methylcyclohexane methyl esters, its epoxy equivalent (weight) is 145-156g/eq.
Preferably, polyetheramine solidifying agent described above is selected from one or more in following component: polyoxypropylene diamine, trade mark D-230, molecular-weight average 230, total amine 8.45mmol/g, functionality 2; D-400, molecular-weight average 400, total amine 4.4mmol/g, functionality 2; D-2000, molecular-weight average 2000, total amine 1.0mmol/g, functionality 2; Polypropylene oxide triamine, trade mark T-403, molecular-weight average 440, total amine 6.4mmol/g, functionality 3; T-5000, molecular-weight average 5000, total amine 0.53mmol/g, functionality 3;
Preferably, catalyzer described above is selected from one or more in following component: 2,4,6 three (dimethylamino methyl) phenol (DMP-30), benzyldimethylamine, 2-ethyl-4-methylimidazole, nonyl phenol, Resorcinol.
Preferably, silane coupling agent described above be selected from following component one or more: γ-(2,3-glycidoxy) propyl trimethoxy silicane, γ-aminopropyl triethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-Mercapto propyl trimethoxy silicane.
Preferably, polysiloxane defoamers described above is selected from one or more in following component: Bi Ke (BYK) company, trade mark BYK-A530, BYK-088; Moral modest (Shanghai) chemical company, trade mark Defom5500, Defom6500, Defom6800.
Preferably, thixotropic agent described above is selected from one or more in following component: aerosil, organobentonite, polyamide wax, hydrogenated castor oil, diatomite, metal soap powder.
Preferably, hollow glass micropearl described above is selected from the product of following company: M company of the U.S. three, mine research institute of Ma'an Mountain and Bangbu frp industry design and research institute, density range 0.25-0.38g/cm
3, ultimate compression strength 5.17--41Mpa, material is soda-lime sodium borosilicate glass.
The present invention also provides the preparation technology of above-mentioned packing material, comprises the following steps:
(1) pre-mixing of liquid material: the epoxy resin of metering, polyetheramine solidifying agent, silane coupling agent, polysiloxane defoamers, catalyzer are dropped in mixing tank, with vacuum high speed dispersor, material stirring is even, and find time to remove bubble.
(2) preparation of slurry: drop into after thixotropic agent mixes in above-mentioned compound, then drop into hollow glass micropearl in batches, first low rate mixing makes microballon powder soak, and then moderate-speed mixer is even by powder lot dispersing, deaeration of finding time.
(3) high-pressure airless cast: be cast in mould by high-pressure airless injector and prepare test specimen.
(4) solidification and performance test: self-vulcanizing one week or 80 DEG C of solidifications prepare test specimen in 4 hours, carry out performance test.
The invention has the beneficial effects as follows:
Composite foam packing material of the present invention, system viscosity is low, and flowing good leveling property, has the longer construction time, is applicable to pour into a mould dosing technology.Ambient temperature curable, curing reaction exothermic temperature peak is low, and cured article is tough and tensile, high strength, shrinking percentage are little, good with material binding performances such as iron and steel.Sea water resistance immersion corrosion.Good through trial effect, be applicable to the non-watertight construction of submarine and the ocean such as buoy, subsurface buoy and dive the perfusion filling of device, water proof sealing.
Embodiment
Specific embodiment
Below in conjunction with concrete implementation column, the present invention is set forth further, but do not limit the present invention.
Embodiments of the invention, specifically describe the reliability and feasibility of this latent device embedding composite foam packing material further.But the present invention is not limited in following embodiment, below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1-4 composite foam packing material proportioning and performance are listed in table.
For embedding composite foam packing material, polyetheramine cured epoxy resin system viscosity is low, flowing good leveling property, and ambient temperature curable is applicable to pour into a mould dosing technology.Operable time is long the longer construction time, and curing reaction exothermic temperature peak is low, and cured article is tough and tensile, and shrinking percentage is little, with the material binding excellent property such as iron and steel.The requirement of embedding composite foam packing material performance index can be met.
As can be seen from the table, along with the increase of hollow glass micropearl volume fraction, buoyancy material density reduces, and compressive strength declines, and compressive strain increases, and snappiness reduces.The polyetheramine adopting higher functionality lower molecular weight is solidifying agent, and buoyancy material compressive strength increases relatively, and compressive strain reduces.
Embodiment 1 in table 1, with polyetheramine D230 for solidifying agent.100 its consumptions of mass parts epoxy resin are 30 mass parts, take nonyl phenol as catalyzer, and hollow glass micropearl volume fraction is 45%.Buoyancy material uniaxial compressive strength 81.6Mpa, compressive strain 17.4%.
Embodiment 2 in table 1, with polyetheramine D400 for solidifying agent.100 its consumptions of mass parts epoxy resin are 55 mass parts, take Resorcinol as catalyzer, and hollow glass micropearl volume fraction is 46%.Buoyancy material uniaxial compressive strength 64.6Mpa, compressive strain 26.8%.
Embodiment 3 in table 1, with polyetheramine D400 and T403 for solidifying agent.100 its consumptions of mass parts epoxy resin are 55 mass parts, take DMP-30 as catalyzer, and hollow glass micropearl volume fraction is 46%.Buoyancy material uniaxial compressive strength 71.5Mpa, compressive strain 24.5%.
Embodiment 4 in table 1, with polyetheramine D400 and D2000 for solidifying agent.100 its consumptions of mass parts epoxy resin are 60 mass parts, take benzyldimethylamine as catalyzer, and hollow glass micropearl volume fraction is 48%.Buoyancy material uniaxial compressive strength 56.4Mpa, compressive strain 76.8%.
Embodiment 1,2,3,4 pressurize water-intake rate of 24 hours under hydrostaticpressure 20Mpa is less than 0.2%, without compressive set, soaks 180 days outward appearances without considerable change in natural sea-water.
Claims (8)
1. a latent device embedding composite foam packing material, it is characterized in that, comprise the component of following masses number: chemical constitution is by the epoxy resin of 100 mass parts: epoxy resin 100, polyetheramine solidifying agent 30--60, silane coupling agent 0.5--3.0, polysiloxane defoamers 1--3, catalyzer 0--2, thixotropic agent 0.5--1.5, hollow glass micropearl percent by volume 45--48%.
2. latent device embedding composite foam packing material according to claim 1, is characterized in that, described epoxy resin be selected from following component one or more: liquid bisphenol A epoxy resin, low viscosity bisphenol F epoxy resin, cycloaliphatic epoxy resin.
3. latent device embedding composite foam packing material according to claim 2, it is characterized in that, cycloaliphatic epoxy resin is 3,4-epoxy-cyclohexane formic acid-3 ', 4 '-epoxy-cyclohexane methyl esters or 3,4-epoxy group(ing)-6-cyclohexanecarboxylic acid-3 ', 4 '-epoxy group(ing)-6
,one in-methylcyclohexane methyl esters or its mixture.
4. latent device embedding composite foam packing material according to claim 1, it is characterized in that, described polyetheramine solidifying agent comprises: polyoxypropylene diamine, trade mark D-230, molecular-weight average 230, total amine 8.45mmol/g, functionality 2; D-400, molecular-weight average 400, total amine 4.4mmol/g, functionality 2; D-2000, molecular-weight average 2000, total amine 1.0mmol/g, functionality 2; Polypropylene oxide triamine, trade mark T-403, molecular-weight average 440, total amine 6.4mmol/g, functionality 3; T-5000, molecular-weight average 5000, total amine 0.53mmol/g, functionality 3.
5. latent device embedding composite foam packing material according to claim 1, it is characterized in that, described catalyzer be selected from following component one or more: 2,4,6 three (dimethylamino methyl) phenol, benzyldimethylamine, 2-ethyl-4-methylimidazole, nonyl phenol, Resorcinol.
6. latent device embedding composite foam packing material according to claim 1, it is characterized in that, described silane coupling agent be selected from following component one or more: γ-(2,3-glycidoxy) propyl trimethoxy silicane, γ-aminopropyl triethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-Mercapto propyl trimethoxy silicane.
7. latent device embedding composite foam packing material according to claim 1, is characterized in that, thixotropic agent described above be selected from following component one or more: aerosil, organobentonite, polyamide wax, hydrogenated castor oil, diatomite, metal soap powder.
8. the method for the latent device embedding composite foam packing material of preparation described in above-mentioned any one claim, is characterized in that, comprise the following steps:
(1) pre-mixing of liquid material: the epoxy resin of metering, polyetheramine solidifying agent, silane coupling agent, polysiloxane defoamers, catalyzer are dropped in mixing tank, with vacuum high speed dispersor, material stirring is even, and find time to remove bubble;
(2) preparation of slurry: drop into after thixotropic agent mixes in above-mentioned compound, drop into hollow glass micropearl more in batches, first 60-80r/min stirring makes microballon powder soak at a slow speed, and then middling speed 500-600r/min stirs powder lot dispersing even, deaeration of finding time;
(3) high-pressure airless cast: be cast in mould by high-pressure airless injector and prepare test specimen;
(4) solidification and performance test: self-vulcanizing one week or 80 DEG C of solidifications prepare test specimen in 4 hours, carry out performance test.
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Cited By (7)
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CN106280257A (en) * | 2016-08-16 | 2017-01-04 | 梅庆波 | A kind of preparation method of lightweight homogeneous anti-impact epoxy fill-sealing materials |
CN107253328A (en) * | 2017-06-21 | 2017-10-17 | 巩义市泛锐熠辉复合材料有限公司 | A kind of preparation method without macroscopic interface density gradation type composite foam |
CN110951354A (en) * | 2019-10-24 | 2020-04-03 | 江苏兰陵高分子材料有限公司 | Epoxy resin-based intumescent steel structure fireproof coating for non-mechanical construction and preparation method thereof |
CN111187487A (en) * | 2019-12-23 | 2020-05-22 | 河南泛锐复合材料研究院有限公司 | High-damping composite foam and preparation method thereof |
CN111537057A (en) * | 2020-03-26 | 2020-08-14 | 中国船舶重工集团公司第七一五研究所 | 70 MPa-resistant standard hydrophone and manufacturing method thereof |
CN113201300A (en) * | 2021-03-26 | 2021-08-03 | 陕西黄河新兴设备有限公司 | Foam rubber and preparation method thereof |
CN113980425A (en) * | 2021-11-30 | 2022-01-28 | 苏州金枪新材料股份有限公司 | Foam filler and preparation method thereof |
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CN103709607A (en) * | 2013-12-26 | 2014-04-09 | 青岛海洋新材料科技有限公司 | Casting light composite foam floating material and preparation method thereof |
CN103788582A (en) * | 2013-12-26 | 2014-05-14 | 青岛海洋新材料科技有限公司 | Pouring type epoxy composite filling material and production method thereof |
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CN103709607A (en) * | 2013-12-26 | 2014-04-09 | 青岛海洋新材料科技有限公司 | Casting light composite foam floating material and preparation method thereof |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106280257A (en) * | 2016-08-16 | 2017-01-04 | 梅庆波 | A kind of preparation method of lightweight homogeneous anti-impact epoxy fill-sealing materials |
CN107253328A (en) * | 2017-06-21 | 2017-10-17 | 巩义市泛锐熠辉复合材料有限公司 | A kind of preparation method without macroscopic interface density gradation type composite foam |
CN110951354A (en) * | 2019-10-24 | 2020-04-03 | 江苏兰陵高分子材料有限公司 | Epoxy resin-based intumescent steel structure fireproof coating for non-mechanical construction and preparation method thereof |
CN110951354B (en) * | 2019-10-24 | 2022-01-11 | 江苏兰陵高分子材料有限公司 | Epoxy resin-based intumescent steel structure fireproof coating for non-mechanical construction and preparation method thereof |
CN111187487A (en) * | 2019-12-23 | 2020-05-22 | 河南泛锐复合材料研究院有限公司 | High-damping composite foam and preparation method thereof |
CN111537057A (en) * | 2020-03-26 | 2020-08-14 | 中国船舶重工集团公司第七一五研究所 | 70 MPa-resistant standard hydrophone and manufacturing method thereof |
CN113201300A (en) * | 2021-03-26 | 2021-08-03 | 陕西黄河新兴设备有限公司 | Foam rubber and preparation method thereof |
CN113980425A (en) * | 2021-11-30 | 2022-01-28 | 苏州金枪新材料股份有限公司 | Foam filler and preparation method thereof |
CN113980425B (en) * | 2021-11-30 | 2023-11-07 | 苏州金枪新材料股份有限公司 | Foam filler and preparation method thereof |
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