CN107805318A - The preparation method of the big ball of solid buoyancy material composite material hollow and hollow big ball - Google Patents

The preparation method of the big ball of solid buoyancy material composite material hollow and hollow big ball Download PDF

Info

Publication number
CN107805318A
CN107805318A CN201711065185.4A CN201711065185A CN107805318A CN 107805318 A CN107805318 A CN 107805318A CN 201711065185 A CN201711065185 A CN 201711065185A CN 107805318 A CN107805318 A CN 107805318A
Authority
CN
China
Prior art keywords
big ball
hollow
composite
resin
shell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201711065185.4A
Other languages
Chinese (zh)
Inventor
贺湘伟
王梦晨
李�远
陈彰斌
周明
董晶晶
黄自华
张亚新
姜其斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhuzhou Times New Material Technology Co Ltd
Original Assignee
Zhuzhou Times New Material Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhuzhou Times New Material Technology Co Ltd filed Critical Zhuzhou Times New Material Technology Co Ltd
Priority to CN201711065185.4A priority Critical patent/CN107805318A/en
Publication of CN107805318A publication Critical patent/CN107805318A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36After-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/34Chemical features in the manufacture of articles consisting of a foamed macromolecular core and a macromolecular surface layer having a higher density than the core
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36After-treatment
    • C08J9/38Destruction of cell membranes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/14Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02Homopolymers or copolymers of hydrocarbons
    • C08J2325/04Homopolymers or copolymers of styrene
    • C08J2325/06Polystyrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/06Elements
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/14Glass

Abstract

The invention provides a kind of preparation method of the big ball of solid buoyancy material composite material hollow, comprise the following steps:(1) expansion type particle and foaming agent are added in spherical die, matched moulds foamable obtains the spheroid of foaming and intumescing;(2) spheroid of the foaming and intumescing obtained in step (1) is cooled down, obtains core;(3) core obtained in step (2) is put into roller and rolled, add aathermoset resin system material and fibrous material, rolling obtains the big ball with shell;(4) the big ball with shell obtained in step (3) is heating and curing, obtains hollow big ball.Present invention also offers the hollow big ball that a kind of above-mentioned preparation method is prepared.The present invention is spherical close to perfection using the hollow big ball that drum process is prepared, and surface zero defect is damaged, and then the compressive resistance that can be born is high, and in the case where meeting compressive resistance, the diameter of hollow big ball can be bigger, and density can be lower, and weight is lighter.

Description

The preparation method of the big ball of solid buoyancy material composite material hollow and hollow big ball
Technical field
The invention belongs to solid buoyancy material manufacturing field, more particularly to the preparation method of a kind of hollow big ball and hollow big Ball.
Background technology
Solid buoyancy material is a kind of low-density, high intensity, the polymer composite of low water suction, is widely used in underwater To provide buoyancy in various plant machineries, such as have in oil gas deepwater drilling, habitata apparatus, deep-sea pipeline and umbilical cables Widely use.After solid buoyancy material loss of weight, the apparatus operated in deep-sea is able to break away from the load that self gravitation is brought, and makes Obtaining these apparatuses can go slick, and therefore, be either obtained in military domain or civil area, solid buoyancy material It is widely recognized as and uses.
The starting of development abroad solid buoyancy material is more early, and development is more ripe, and largest is Australian company Matrix, it is absorbed in marine riser solid buoyancy material, and production density of having the ability is 0.37-0.47g/cm3, it is using the depth of water 1000-3000m solid buoyancy material, water pressure resistance reach more than 30MPa;Swedish company Te Ruibao, the solid buoyancy material of production Material is widely used in underwater robot and various underwater cables, and a series of products can be applied to from the 1000m depth of waters to 11000m water Deep various situations, density is minimum can be to 0.4g/cm3, compression strength can reach more than 110MPa.
Domestic solid buoyancy material starts to walk to be earliest Qingdao Haiyang chemical research institute, early just to be sent out in the early 1990s with chemical Bubble method successfully have developed " SBM-300 " solid buoyancy material, available for shallow sea operation.Chinese patent CN100378166C is green grass or young crops The disclosed patent on solid buoyancy material of island Inst. of Marine Chemical Engineering, which describes the preparation of several solid buoyancy materials Technique, condition and raw material, wherein, a kind of product density is 0.4-0.47g/cm3, resistance to hydrostatic pressure intensity reaches more than 12MPa, Water absorption rate is less than 1%;Another product density is 0.54-0.56g/cm3, resistance to hydrostatic pressure intensity reaches more than 55MPa, water absorption rate Less than 1%;Close also a kind of product is 0.67-0.69g/cm3, resistance to hydrostatic pressure intensity reaches more than 70MPa, and water absorption rate is less than 1%.
Current deep water is roughly divided into two kinds with solid buoyancy material, and one kind is resin hybrid glass microballon, Qingdao Haiyang Chemical research institute's production is exactly this solid buoyancy material, and another kind is resin mixing compound material ball, and the country there is no at present Using the matured product of such technology.
Between solid buoyancy material is generally 2~450mm with hollow ball size, general more than industry regulation 30mm is big Ball, below 30mm are bead.Chinese patent CN101709130B describes a kind of expansion type extremely-low density buoyant material, the material It is divided into core and plane materiel, can reaches 0.12g/ using Polymethacrylimide and epoxide resin material, density minimum respectively cm3, compressive strength 1.5MPa, water absorption rate is less than 1%, but this kind of buoyant material can only use in shallow water field, and the depth of water is excessive Can be by pressure break and then failure.Chinese patent CN103665615B describe a kind of fiber bead for solid buoyancy material and its Preparation method, the sphere diameter prepared in this way are 6-25mm, shell thickness 0.2-2.5mm, available for solid buoyancy To reduce density in material, but the sphere diameter generally can not meet to require, limit the length of the fiber of enhancing, and work as ball When body diameter is more than 15mm, deviation spheroid form that product can be larger, surface also has more defect.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to mention in background above technology and defect, there is provided a kind of The solid buoyancy material that surface zero defect is damaged, compressive resistance is high, density is low, shell thickness can be controlled accurately, product quality is stable The preparation method of the big ball of material composite material hollow and hollow big ball.In order to solve the above technical problems, technology proposed by the present invention Scheme is:
A kind of preparation method of the big ball of solid buoyancy material composite material hollow, comprises the following steps:
(1) expansion type particle and foaming agent are added in spherical die, matched moulds foamable obtains the spheroid of foaming and intumescing;
(2) spheroid of the foaming and intumescing obtained in step (1) is cooled down, obtains core;
(3) core obtained in step (2) is put into roller and rolled, add aathermoset resin system material and undulation degree Material, rolling obtain the big ball with shell;
(4) the big ball with shell obtained in step (3) is heating and curing, obtains hollow big ball.
The present invention is that hollow big ball is prepared based on following principle, and expansion type particle and foaming agent are put into mould first Foamable obtains core in tool, and core is put into roller again after cooling and rolled, aathermoset resin system is coated on core Material and fibrous material, finally heated, aathermoset resin system material solidification obtains shell, while the melting of core heat collapses, Obtain hollow big ball.In the present invention, during cooling, the spheroid of foaming and intumescing is cooled to less than 70 DEG C with mould, now spheroid It foaming, will not deform, then spheroid is removed from the molds natural cooling, in addition, there is releasing agent in mould, during taking-up It is easier to.Because the ball interior of foaming and intumescing contains foaming agent (such as pentane) in step (1), gas constantly volatilizees and sent out Bubble, gas played supporting role, so step (1) can obtain a spheroid, reactive blowing agent in core, stomata in step (4) Inner and outer air pressure is consistent, and plastics viscosity flow is melt into again when the foamed plastic (core) with loose structure is in its fusing point and the above State, volume significantly reduce, and become hollow ball from the medicine ball of coated with resins is made.
In above-mentioned preparation method, it is preferred that repeat the hollow big ball obtained in the step (4) instead of the core Step (3) and (4) are one or many to obtain the hollow big ball of multilayer shell.The number of number of repetition is decided by the thickness of shell Degree, the number of repetition can be adjusted in practical operation as needed.
In above-mentioned preparation method, it is preferred that the expansion type particle is expanded polystyrene (EPS), polyethylene foamed, foams and gather One kind in propylene, the particle diameter of the expansion type particle are not more than 4mm, and the foaming agent is volatile liquid, more preferably Pentane, the addition of the foaming agent are the 0.5-2% of the expansion type granular mass, more preferably 1%.General plastics Volume can increase by more than 6 times after grain foaming, due to big ball size it has been determined that the dosage of expansion type particle can not be too many, can cause The problems such as density of material is too big after can not foaming or foaming.The addition of foaming agent can not too much can not very little, if foaming agent Add very little, foaming effect is bad, adds too much, the spherome surface for foaming to obtain is easy to crack or the intensity of spheroid is too low to Load shows shell.
In above-mentioned preparation method, it is preferred that the density of the core is 0.03-0.1g/cm3, a diameter of 9-440mm.Through After crossing foaming, expansion type particle is expanded into spheroid in spherical die, passes through the addition of different moulds and expansion type particle It can obtain the core of different densities and diameter.
In above-mentioned preparation method, it is preferred that when adding aathermoset resin system material and fibrous material, control the thermosetting Property resin system material and fibrous material mass ratio be 1:0.4-1.2.How much the accounting of fibrous material determines the strong of shell Degree and density, fiber accounting is bigger, and shell modulus is bigger, and density is also bigger, it is contemplated that the combination property of hollow big ball, it should will The accounting of fibrous material is controlled in certain scope.
In above-mentioned preparation method, it is preferred that the expression by weight of the aathermoset resin system material includes such as the following group Point:
Resin 80-100 parts;
Curing agent 10-80 parts;
Diluent 0.2-25 parts;
Coupling agent 0.2-5 parts.
In above-mentioned preparation method, it is preferred that the resin is epoxy resin, phenolic resin, vinylite and polyester tree One or more in fat, the curing agent is the one or more in polynary amine type, modified amine type and acid anhydrides type material, described Diluent is the one or more in glycidol ethers material, the coupling agent be gamma-aminopropyl-triethoxy-silane and γ- One or both of (oxygen of 2,3- epoxies third) propyl trimethoxy silicane.The effect for adding curing agent is solidifying shell during heating Layer, add diluent effect and be to reduce resin viscosity, control heat release during curing reaction, add action of coupling agents and be to improve Fibrous material surface property, increase the conjugation of fiber surface and resin matrix, fibrous material is preferably combined with resin Together.
In above-mentioned preparation method, it is preferred that the fiber is in glass fibre, carbon fiber, metallic fiber and aramid fiber One or more, the length of the fiber is 50 μm -5000 μm.
In above-mentioned preparation method, it is preferred that in the step (1), the heating-up temperature is 90-150 DEG C, the step (4) described to be heating and curing using hot air in, the heating-up temperature is 100-150 DEG C.In step (1) during foamable, The effect of heating is foaming agent is volatilized, and so as to cause core plastic grain to foam, in foaming process, temperature gets over high-foaming speed Rate is faster, but can influence very much the stomata uniformity that foams soon, and temperature too low ratio foamed is too slow or does not foam, so temperature will in foaming Control is at 90-150 DEG C.
The hollow big ball that a kind of solid buoyancy material is prepared with the preparation method of the big ball of composite material hollow, the sky A diameter of 30-450mm of the big ball of the heart, density 0.15-1g/cm3, shell is 1-5 layers, and the thickness of every layer of shell is 0.05- 1mm。
The shell thickness of the hollow big ball of the present invention is with adding aathermoset resin system material in roller and fibrous material Amount, roll coating speed, time and number have it is very big contact, by accurately controlling the thermosetting tree of addition when coating each time The amount of resin system material and fibrous material, coating speed and time are to control the thickness of every layer of shell to be defined for 0.05-1mm.
Compared with prior art, the advantage of the invention is that:
1. the hollow big ball that preparation method of the present invention obtains can be held close to perfect spherical, surface zero defect breakage The compressive resistance received is high, and in the case where meeting compressive resistance, the diameter of hollow big ball can be bigger, and density can be lower, weight Amount is lighter.
2. the hollow big bulb diameter that preparation method of the present invention obtains is big, adjustable space is bigger, can adjust as needed big Bulb diameter.
3. the hollow big ball steady quality that preparation method of the present invention obtains, production efficiency is high, and the shell of hollow big ball is one One layer of coating of layer is got on, smaller per thickness degree, is easier to control hollow big ball in addition than existing paddling process using drum process Sphericity and every layer of thickness, shell thickness accurately control.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are the present invention Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis These accompanying drawings obtain other accompanying drawings.
Fig. 1 is prepared hollow big for the hollow big ball that drum process in the embodiment of the present invention 1 is prepared with conventional method The photo of ball (the big ball of black is prepared for drum process in figure, and the big ball of white is prepared for paddling process).
Embodiment
For the ease of understanding the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of preparation method of the big ball of solid buoyancy material composite material hollow, comprises the following steps:
(1) the expanded polystyrene (EPS) 7g that average diameter of particles is about 3mm is added to a diameter of 80mm ball with 0.07g pentanes In shape mould, matched moulds heats mould to 120 DEG C of foamings;
(2) spheroid of foaming and intumescing in step (1) is cooled down, obtains core;
(3) core obtained in step (2) is put into roller and rolled, spray into aathermoset resin system material and glass fibers Material is tieed up, rolling obtains the big ball with shell, wherein, 800 μm of the average length of glass fibre, 10 μm of average diameter;
(4) the big ball with shell obtained in step (3) is put in 80 DEG C of hot-airs and solidified 3 hours, obtained hollow big Ball;
(5) the hollow big ball obtained in step (4) is repeated into step (3) and (4) twice instead of core, obtains 3 layers of shell The hollow big ball of layer.
Shell formula is (numeral represents parts by weight) as shown in table 1 in the present embodiment.
Table 1:Shell formula in embodiment 1
Epoxy resin 100
Glass fibre 60
Phenolic aldehyde ethylenediamine 10
3,3,-diethyl -4,4,-diaminodiphenyl-methane 15
2,4,6 3 (dimethylamino methyl) phenol 0.2
Phenmethylol glycidol ether 15
Gamma-aminopropyl-triethoxy-silane 3
Solid buoyancy material manufactured in the present embodiment is 82mm with the average diameter of the big ball of composite material hollow, total shell Thickness average out to 2mm, apparent density are about 0.23g/cm3, resistance to hydrostatic pressure intensity 75MPa.The big ball of the composite material hollow is applicable In Intermediate Water Depth's solid buoyancy material, because its density is extremely low, the global density of material can be substantially reduced.
Fig. 1 is the sky that the hollow big ball (the big ball of black) that drum process is prepared in the present embodiment is prepared with conventional method The photo of the big ball of the heart (the big ball of white), as seen from the figure, the sphericity for the hollow big ball that the present embodiment is prepared is substantially more preferable, this Also the advantage of drum process is embodied.
Embodiment 2:
A kind of preparation method of the big ball of solid buoyancy material composite material hollow, comprises the following steps:
(1) the expanded polystyrene (EPS) 7g that average diameter of particles is about 3mm is added to a diameter of 80mm ball with 0.07g pentanes In shape mould, matched moulds heats mould to 120 DEG C of foamings;
(2) spheroid of foaming and intumescing in step (1) is cooled down, obtains core;
(3) core obtained in step (2) is put into roller and rolled, spray into aathermoset resin system material and carbon fiber Material, rolling obtain the big ball with shell, wherein, 100 μm of the average length of carbon fiber, 7 μm of average diameter;
(4) the big ball with shell obtained in step (3) is put in 80 DEG C of hot-airs and solidified 3 hours, obtained hollow big Ball;
(5) the hollow big ball obtained in step (4) is repeated into step (3) and (4) twice instead of core, obtains 3 layers of shell The hollow big ball of layer.
Shell formula is (numeral represents parts by weight) as shown in table 2 in the present embodiment.
Table 2:Shell formula in embodiment 2
Solid buoyancy material manufactured in the present embodiment is 82mm with the average diameter of the big ball of composite material hollow, total shell Thickness average out to 2mm, apparent density are about 0.21g/cm3, resistance to hydrostatic pressure intensity 90MPa.Composite in the present embodiment is empty The big ball of the heart can be used in the solid buoyancy material under Intermediate Water Depth's environment, due to having used carbon fiber, reinforcement and low-density side The excellent performance in face, compressive resistance is very high, and density is relatively low.
Embodiment 3:
A kind of preparation method of the big ball of solid buoyancy material composite material hollow, comprises the following steps:
(1) the expanded polystyrene (EPS) 7g that average diameter of particles is about 3mm is added to a diameter of 80mm ball with 0.07g pentanes In shape mould, matched moulds heats mould to 120 DEG C of foamings;
(2) spheroid of foaming and intumescing in step (1) is cooled down, obtains core;
(3) core obtained in step (2) is put into roller and rolled, spray into aathermoset resin system material and carbon fiber Material, rolling obtain the big ball with shell, wherein, 100 μm of the average length of carbon fiber, 7 μm of average diameter;
(4) the big ball with shell obtained in step (3) is put in 80 DEG C of hot-airs and solidified 3 hours, obtained hollow big Ball;
(5) the hollow big ball obtained in step (4) is repeated into step (3) and (4) twice instead of core, obtains 3 layers of shell The hollow big ball of layer.
Shell formula is (numeral represents parts by weight) as shown in table 3 in the present embodiment.
Table 3:Shell formula in embodiment 3
Phenolic resin 100
Carbon fiber 80
IPD 10
3,3,-diethyl -4,4,-diaminodiphenyl-methane 15
2,4,6 3 (dimethylamino methyl) phenol 0.2
Phenyl glycidyl ether diluent 15
Gamma-aminopropyl-triethoxy-silane 3
Solid buoyancy material manufactured in the present embodiment is 82mm with the average diameter of the big ball of composite material hollow, total shell Thickness average out to 2mm, apparent density are about 0.21g/cm3, resistance to hydrostatic pressure intensity 80MPa.Composite in the present embodiment is empty The big ball of the heart can be used in the solid buoyancy material under Intermediate Water Depth's environment, due to having used carbon fiber, reinforcement and low-density side The excellent performance in face, compressive resistance is very high, and density is relatively low.
Embodiment 4:
A kind of preparation method of the big ball of solid buoyancy material composite material hollow, comprises the following steps:
(1) the expanded polystyrene (EPS) 0.88g that average diameter of particles is about 3mm and 0.088g pentanes are added into a diameter of 40mm Spherical die in, matched moulds heats mould to 120 DEG C of foamings;
(2) spheroid of foaming and intumescing in step (1) is cooled down, obtains core;
(3) core obtained in step (2) is put into roller and rolled, spray into aathermoset resin system material and glass fibers Material is tieed up, rolling obtains the big ball with shell, wherein, 200 μm of the average length of glass fibre, 7 μm of average diameter;
(4) the big ball with shell obtained in step (3) is put in 80 DEG C of hot-airs and solidified 3 hours, obtained hollow big Ball;
(5) the hollow big ball obtained in step (4) is repeated into step (3) and (4) twice instead of core, obtains 3 layers of shell The hollow big ball of layer.
Shell formula is (numeral represents parts by weight) as shown in table 4 in the present embodiment.
Table 4:Shell formula in embodiment 4
Epoxy resin 100
Carbon fiber 60
651 polyamide 20
Phenolic aldehyde ethylenediamine 10
2,4,6 3 (dimethylamino methyl) phenol 0.2
Epoxy propane butyl ether diluent 15
Gamma-aminopropyl-triethoxy-silane 3
Solid buoyancy material manufactured in the present embodiment is 42mm with the average diameter of the big ball of composite material hollow, total shell Thickness average out to 2mm, apparent density are about 0.42g/cm3, resistance to hydrostatic pressure intensity 150MPa.Hollow big ball manufactured in the present embodiment For that can be used as in the solid buoyancy material under ultra-deep water environment, the excellent performance in terms of reinforcement and low-density, compressive resistance is very high, Density is relatively low.
Embodiment 5:
A kind of preparation method of the big ball of solid buoyancy material composite material hollow, comprises the following steps:
(1) the expanded polystyrene (EPS) 65.62g and 0.984g pentanes that average diameter of particles is about 3mm are added a diameter of In 200mm spherical die, matched moulds heats mould to 120 DEG C of foamings;
(2) spheroid of foaming and intumescing in step (1) is cooled down, obtains core;
(3) core obtained in step (2) is put into roller and rolled, spray into aathermoset resin system material and glass fibers Material is tieed up, rolling obtains the big ball with shell, wherein, 200 μm of the average length of glass fibre, 7 μm of average diameter;
(4) the big ball with shell obtained in step (3) is put in 80 DEG C of hot-airs and solidified 3 hours, obtained hollow big Ball;
(5) the hollow big ball obtained in step (4) is repeated into step (3) and (4) four times instead of core, obtains 5 layers of shell The hollow big ball of layer.
Shell formula is (numeral represents parts by weight) as shown in table 5 in the present embodiment.
Table 5:Shell formula in embodiment 5
Epoxy resin 100
Carbon fiber 60
651 polyamide 20
Phenolic aldehyde ethylenediamine 10
2,4,6 3 (dimethylamino methyl) phenol 0.2
Epoxy propane butyl ether diluent 15
Gamma-aminopropyl-triethoxy-silane 3
Solid buoyancy material manufactured in the present embodiment is 203mm with the average diameter of the big ball of composite material hollow, and shell is put down Equal thickness is 3mm, and apparent density is about 0.18g/cm3, resistance to hydrostatic pressure intensity 32MPa.Hollow big ball manufactured in the present embodiment is There can be preferable loss of weight or so, resistance to pressure can also meet most of bar as in the solid buoyancy material under shallow water depth of water environment The requirement of part.

Claims (10)

1. a kind of preparation method of the big ball of solid buoyancy material composite material hollow, it is characterised in that comprise the following steps:
(1) expansion type particle and foaming agent are added in spherical die, matched moulds foamable obtains the spheroid of foaming and intumescing;
(2) spheroid of the foaming and intumescing obtained in step (1) is cooled down, obtains core;
(3) core obtained in step (2) is put into roller and rolled, add aathermoset resin system material and fibrous material, Rolling obtains the big ball with shell;
(4) the big ball with shell obtained in step (3) is heating and curing, obtains hollow big ball.
2. the preparation method of the big ball of composite material hollow according to claim 1, it is characterised in that by the step (4) In obtained hollow big ball repeat step (3) instead of the core and (4) are one or many.
3. the preparation method of the big ball of composite material hollow according to claim 1 or 2, it is characterised in that the expansion type Particle is one kind in expanded polystyrene (EPS), polyethylene foamed, expanded polypropylene, and the particle diameter of the expansion type particle is not more than 4mm, the foaming agent are volatile liquid, and the addition of the foaming agent is the 0.5-2% of the expansion type granular mass.
4. the preparation method of the big ball of composite material hollow according to claim 1 or 2, it is characterised in that the core Density is 0.03-0.1g/cm3, a diameter of 9-440mm.
5. the preparation method of the big ball of composite material hollow according to claim 1 or 2, it is characterised in that add thermosetting When resin system material and fibrous material, the mass ratio for controlling the aathermoset resin system material and fibrous material is 1:0.4- 1.2。
6. the preparation method of the big ball of composite material hollow according to claim 5, it is characterised in that the thermosetting resin The expression by weight of system material includes following component:
Resin 80-100 parts;
Curing agent 10-80 parts;
Diluent 0.2-25 parts;
Coupling agent 0.2-5 parts.
7. the preparation method of the big ball of composite material hollow according to claim 6, it is characterised in that the resin is epoxy One or more in resin, phenolic resin, vinylite and polyester resin, the curing agent are polynary amine type, modified amine One or more in type and acid anhydrides type material, the diluent is the one or more in glycidol ethers material, described Coupling agent is one kind or two in gamma-aminopropyl-triethoxy-silane and γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane Kind.
8. the preparation method of the big ball of composite material hollow according to claim 1 or 2, it is characterised in that the fiber is One or more in glass fibre, carbon fiber, metallic fiber and aramid fiber, the length of the fiber is 50 μm -5000 μm.
9. the preparation method of the big ball of composite material hollow according to claim 1 or 2, it is characterised in that the step (1) In, the heating-up temperature is 90-150 DEG C, described to be heating and curing using hot air in the step (4), the heating temperature Spend for 100-150 DEG C.
10. the hollow big ball that a kind of preparation method according to any one of claim 1-9 is prepared, its feature exist In a diameter of 30-450mm, density 0.15-1g/cm of the hollow big ball3, shell is 1-5 layers, the thickness of every layer of shell For 0.05-1mm.
CN201711065185.4A 2017-11-02 2017-11-02 The preparation method of the big ball of solid buoyancy material composite material hollow and hollow big ball Pending CN107805318A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711065185.4A CN107805318A (en) 2017-11-02 2017-11-02 The preparation method of the big ball of solid buoyancy material composite material hollow and hollow big ball

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711065185.4A CN107805318A (en) 2017-11-02 2017-11-02 The preparation method of the big ball of solid buoyancy material composite material hollow and hollow big ball

Publications (1)

Publication Number Publication Date
CN107805318A true CN107805318A (en) 2018-03-16

Family

ID=61590621

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711065185.4A Pending CN107805318A (en) 2017-11-02 2017-11-02 The preparation method of the big ball of solid buoyancy material composite material hollow and hollow big ball

Country Status (1)

Country Link
CN (1) CN107805318A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105037789A (en) * 2015-09-22 2015-11-11 台州中浮新材料科技股份有限公司 Fiber-reinforced resin composite material hollow ball and preparation method thereof
CN105542219A (en) * 2016-02-26 2016-05-04 天津中材工程研究中心有限公司 Preparation method for light high-strength composite hollow sphere
CN106046412A (en) * 2016-06-30 2016-10-26 台州中浮新材料科技股份有限公司 Hollow ball with ball wall made from composite material and layer-by-layer coating method for manufacturing hollow ball

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105037789A (en) * 2015-09-22 2015-11-11 台州中浮新材料科技股份有限公司 Fiber-reinforced resin composite material hollow ball and preparation method thereof
CN105542219A (en) * 2016-02-26 2016-05-04 天津中材工程研究中心有限公司 Preparation method for light high-strength composite hollow sphere
CN106046412A (en) * 2016-06-30 2016-10-26 台州中浮新材料科技股份有限公司 Hollow ball with ball wall made from composite material and layer-by-layer coating method for manufacturing hollow ball

Similar Documents

Publication Publication Date Title
EP2197665B1 (en) Composite laminated article and manufacture thereof
EP2197666B1 (en) Composite laminated article and manufacture thereof
CN107283711B (en) A kind of thermoplastic polymer expanded bead formed body and preparation method thereof
JP5303115B2 (en) Method for manufacturing an outer tube for a thermally insulated conduit
US20080233332A1 (en) Thermal Insulation Material
CN105037789A (en) Fiber-reinforced resin composite material hollow ball and preparation method thereof
CN103694625B (en) A kind of modified phenolic foam body
CN105542219B (en) A kind of preparation method of high-strength light composite hollow ball
CN106317782B (en) A kind of preparation method of composite buoyancy material
CN102504322A (en) Method for preparing supercritical fluid reinforced fluorine-containing polymer product
CN107805318A (en) The preparation method of the big ball of solid buoyancy material composite material hollow and hollow big ball
CN107117257B (en) A kind of composite element and its manufacturing process
US20130251924A1 (en) Macrosphere carbon fiber reduction
CN205208043U (en) Continuous fibers hot oil line
KR20180119298A (en) Manufacturing method for large-size composite structure
CN105985610A (en) Method for producing solid buoyancy material
CN106380786A (en) Composite buoyancy material
CN207128360U (en) A kind of core filled composite material
CN109627690A (en) A kind of solid buoyancy material and preparation method thereof containing three-dimensional fiber reinforcement
CN103910975B (en) A kind of method utilizing rumbatron to prepare deep-sea buoyancy material fast
CN107687544A (en) A kind of self-heat conserving solid wall pipe
CN205118634U (en) Composite board
CN106566192A (en) Foaming material
CN109591267A (en) A kind of three layers of compound XPS prefabricated thermal insulation heat supply plastic pipe preparation method
JP4227683B2 (en) Plastic foam composite

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20180316

RJ01 Rejection of invention patent application after publication