CN108329656A - A kind of high tenacity solid buoyancy material and preparation method thereof containing elastic microsphere - Google Patents
A kind of high tenacity solid buoyancy material and preparation method thereof containing elastic microsphere Download PDFInfo
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- CN108329656A CN108329656A CN201810018626.3A CN201810018626A CN108329656A CN 108329656 A CN108329656 A CN 108329656A CN 201810018626 A CN201810018626 A CN 201810018626A CN 108329656 A CN108329656 A CN 108329656A
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
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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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
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Abstract
A kind of high tenacity solid buoyancy material and preparation method thereof containing elastic microsphere, according to mass percent, it is made of 100 parts of epoxy resin, 0 20 parts of reactive diluent, 60 120 parts of curing agent, 01 parts of accelerating agent, 0 20 parts of toughener and 10 100 parts of elastic microsphere.The present invention is used as the filler of solid buoyancy material using the elastic microsphere for being coated with mineral shell, and to make the toughness of final products be greatly improved, and its resistance to pressure and heat resistance have also obtained certain promotion；Meanwhile after surface modifier is added, surface modification can be carried out at the same time to matrix resin and elastic microsphere, and then improve binding force between elastic microsphere surface mineral shell and epoxy resin-base, so as to improve the overall flexibility of solid buoyancy material.
Description
Technical field
It is specifically a kind of containing elastic microsphere the present invention relates to the Feature Engineering Material Field of marine environment
High tenacity solid buoyancy material and preparation method thereof.
Background technology
With flourishing for marine economy, China proposes completely new requirement to the further deep development of ocean.As
The special engineered material in important ocean, solid buoyancy material under water robot, bathyscaph, submerged buoy system, underwater collecting machine,
It is used widely on the ocean development such as offshore oil exploration and exploitation marine riser equipment.The density of solid buoyancy material is low, pressure-resistant
Intensity is high, not hygroscopic, corrosion resistance and good, is typical structure-function integration material.
Currently, solid buoyancy material is mainly using liquid epoxies as matrix, using hollow glass micropearl as filler, by altogether
It is prepared by the techniques such as mixed, molding, solidification.Although material compression strength itself is higher, but still belongs to fragile material, removed after production
It is easy to be collided or impact to destroy during fortune, installation, use.Therefore, it is necessary to improve the toughness of material
Ensure the safety during being used for a long time.
Chinese patent CN1844236 is described using addition plasticized modifier such as polysulfide rubber, liquid nitrile rubber or fourth
The method of hydroxyl is come the method that improves the toughness of epoxy resin-base to improve material overall flexibility.But poor hollow of toughness
Glass microballoon is still unique filler used and mass fraction accounting is larger, so performance improvement very unobvious.
Chinese patent CN103172975 describes micro- using surface modified ultra-high molecular weight polyethylene particle and hollow glass
Pearl is blended improves the method for toughness of material for filler.The toughness of buoyant material made from this method is carried to a certain extent
Height, but since the poor hollow glass micropearl of toughness still occupies major portion in filler, performance improves smaller.
Chinese patent CN106380786 describes whole to improve material for filler using tiny balloon and foam microspheres blending
The method of body toughness.This method mainly utilizes the thermal expansion of foam microspheres to reduce density, by the thermoplasticity ball wall of foam microspheres
Improve toughness, although improving toughness of material to a certain extent, foam microspheres cure after material progress（Generally higher than 100
℃）Shi Fasheng gross distortions so that more defect occurs in inside, substantially influences compressive resistance.
It is filler, polyethers, butyronitrile rubber that Chinese patent CN103665768, which is described and is blended using tiny balloon and fiber bead,
The method that glue, polybutadiene etc. improve material overall flexibility for toughening modifying resin matrix.Buoyant material made from this method
Toughness be highly improved compared to pure buoyant material, but due to the diameter of fiber bead and rigidity it is larger, specific surface area is also remote
Much smaller than tiny balloon, therefore interfacial failure easily occurs when material compression.
The above patent is all made of hollow glass micro-ball or tiny balloon is used as filler production solid buoyancy material, but by
It is poor in itself toughness, so causing the toughness of the solid buoyancy material finished product of its final production also not satisfactory.
Invention content
It is tough to be used as product caused by filler to solve solid buoyancy material in the prior art using hollow glass micro-ball
The undesirable problem of property, the present invention provides a kind of high tenacity solid buoyancy material and preparation method thereof containing elastic microsphere,
It is used as the filler of solid buoyancy material using the elastic microsphere for being coated with mineral shell, to make the toughness of final products obtain
To being greatly improved, and its resistance to pressure and heat resistance have also obtained certain promotion；Meanwhile surface modifier is added
Afterwards, matrix resin and elastic microsphere can be carried out at the same time surface modification, and then improve elastic microsphere surface mineral shell with
Binding force between epoxy resin-base, so as to improve the overall flexibility of solid buoyancy material.
Used technical solution is the present invention to solve above-mentioned technical problem：A kind of high tenacity containing elastic microsphere is solid
Body buoyant material, according to mass percent, by 100 parts of epoxy resin, 0-20 parts of reactive diluent, 60-120 parts of solidification
Agent, 0-1 parts of accelerating agent, 0-20 parts of toughener and 10-100 parts of elastic microsphere are made.
As another preferred embodiment of the present invention, the epoxy resin is bisphenol A type epoxy resin or bisphenol-f type
Epoxy resin, it is one kind in E44, E51, E54,170 that the trade mark, which may be used,.
As another preferred embodiment of the present invention, the reactive diluent is allyl glycidyl ether（AGE）、
Butyl glycidyl ether（BGE）, diglycidylaniline（DGA）Or butanediol diglycidyl ether（BDGE）, acting on is
The viscosity for reducing epoxy resin improves the mobility of resin, increases the amount of filler of elastic microballon, reduces high tenacity solid buoyancy material
The density of material.
As another preferred embodiment of the present invention, the curing agent is and the matching used anhydride of epoxy resin
Or amine curing agent, such as methyl tetrahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, low molecular weight polycaprolactone
Amide 650 or aromatic polyamine DDM；
As another preferred embodiment of the present invention, the accelerating agent is match with the curing agent imidazoles used or uncle
Amine type accelerator, may be selected 2-ethyl-4-methylimidazole, 1- benzyl -2- ethyl imidazol(e)s, 1- amino-ethyls -2-methylimidazole,
The one of which of DMP-30 or benzyl dimethylamine.
As the present invention another preferred embodiment, the toughener be liquid nbr carboxyl terminal (CTBN),
Epoxy terminated nitrile rubber (ETBN), polysulfide rubber, polyether-ether-ketone（PEEK）It is arbitrary with one or more of polyether sulfone (PES)
The mixing of ratio.
As another preferred embodiment of the present invention, also containing 0-20 parts in the high tenacity solid buoyancy material
Surface modifier, the surface modifier be JN114 titanate coupling agents, KH560 silane coupling agents, 414 aluminate coupling agents and
The mixing of one or more of laurel alcohol ether phosphate anionic surfactant arbitrary proportion.
The preparation method of the above-mentioned high tenacity solid buoyancy material containing elastic microsphere, includes the following steps：
1）Each material is weighed according to the ratio, it is spare；
2）Remaining component other than elastic microsphere is made to resin adhesive liquid after mixing at normal temperatures, it is spare；
3）By step 1）The elastic microsphere weighed is added to step 2）In in resin adhesive liquid obtained, in the rotating speed of 25-50r/min
It is lower to be uniformly mixed, it is spare to obtain raw mixture；
4）By step 3）Raw mixture obtained is sent into mold, in the forming under the pressure of 5-20MPa, in 80-100 after molding
Solidification is not less than 48h at a temperature of DEG C, and then demoulding obtains material base, spare；
5）By step 4）Solidification is not less than for 24 hours again at a temperature of 120-140 DEG C for obtained material base, and natural cooling is after solidification
Obtain product.
Elastic microsphere used in the present invention refers to that surface is coated with the polymer microballoon of mineral shell, compared to traditional
Hollow glass micropearl, under same density, toughness greatly improves, and resistance to pressure and heat resistance, which are also significantly larger than, common to be had
The polymer microballoon of machine beyond the region of objective existence shell, material carry out it is required after solidification when will not occur polymer microballoon size distortion so as to cause
The case where internal flaw, occurs；10-120 microns of average grain diameter, density 0.10-0.20g/cm may be selected3, compressive resistance 10-
It is one or more in the acrylonitrile polymers microballoon of the calcium carbonate of 20MPa, talcum or titanium-oxide-coated.
In the present invention, reactive diluent effect is to reduce the viscosity of epoxy resin, improves the mobility of resin, increases elasticity
The amount of filler of microballon reduces the density of high tenacity solid buoyancy material；Toughener is floating to improve from modified matrix resin angle
The overall flexibility of dead-wood material；And surface modifier is between raising elastic microsphere surface mineral shell and epoxy resin-base
Binding force improves the overall flexibility of buoyant material.
Compared with prior art, the invention has the advantages that：
1）The present invention is used as the filler of solid buoyancy material using the elastic microsphere for being coated with mineral shell, final to make
The toughness of product is greatly improved, and its resistance to pressure and heat resistance have also obtained certain promotion；
2）The present invention adds surface modifier wherein, and surface modification can be carried out at the same time to matrix resin and elastic microsphere,
And then binding force between elastic microsphere surface mineral shell and epoxy resin-base is improved, so as to improve solid buoyancy material
Overall flexibility；
3）By detection, product of the invention not only maintains the low-density of solid buoyancy material（0.45-0.55g/cm3）, it is high
Intensity（20-40MPa）And low water absorption（No more than 1%）Characteristic, it is also larger to improve toughness of material（Elongation at break reaches
6-8%）.
Specific implementation mode
Technical scheme of the present invention is clearly and completely described below in conjunction with specific embodiment, it is clear that described
Embodiment be only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ability
The every other embodiment that domain those of ordinary skill is obtained without making creative work, belongs to guarantor of the present invention
The range of shield.
Embodiment 1
A kind of high tenacity solid buoyancy material containing elastic microsphere, according to mass percent, by 100 parts of epoxy resin, 60
The curing agent and 10 parts of elastic microsphere of part are made, wherein epoxy resin selects E51, curing agent to select aromatic polyamine
DDM, toughener select liquid nbr carboxyl terminal, and it is 40 microns that elastic microsphere, which selects average grain diameter, density 0.20g/cm3
Calcium carbonate coat acrylonitrile polymer microballoon；
Preparation method is：
1）Each material is weighed according to the ratio, it is spare；
2）Remaining component other than elastic microsphere is made to resin adhesive liquid after mixing at normal temperatures, it is spare；
3）By step 1）The elastic microsphere weighed is added to step 2）In in resin adhesive liquid obtained, under the rotating speed of 25r/min
It is uniformly mixed, it is spare to obtain raw mixture；
4）By step 3）Raw mixture obtained is sent into mold, in the forming under the pressure of 5MPa, in 80 DEG C of temperature after molding
Degree is lower to cure 58h, and then demoulding obtains material base, spare；
5）By step 4）Obtained material base cures 30h again at a temperature of 120 DEG C, and natural cooling obtains product after solidification.
Embodiment 2
A kind of high tenacity solid buoyancy material containing elastic microsphere, according to mass percent, by 100 parts of epoxy resin, 20
The reactive diluent, 120 parts of curing agent, 1 part of accelerating agent, 20 parts of toughener and 100 parts of elastic microsphere of part are made,
In, epoxy resin selects E54, reactive diluent to select AGE, curing agent that dodecenylsuccinic anhydride, accelerating agent is selected to select 2-
Ethyl -4-methylimidazole, toughener select epoxy terminated nitrile rubber, and it is 80 microns, density that elastic microsphere, which selects average grain diameter,
For 0.20g/cm3Talcum coat acrylonitrile polymer microballoon；
Preparation method is：
1）Each material is weighed according to the ratio, it is spare；
2）Remaining component other than elastic microsphere is made to resin adhesive liquid after mixing at normal temperatures, it is spare；
3）By step 1）The elastic microsphere weighed is added to step 2）In in resin adhesive liquid obtained, under the rotating speed of 50r/min
It is uniformly mixed, it is spare to obtain raw mixture；
4）By step 3）Raw mixture obtained is sent into mold, in the forming under the pressure of 20MPa, at 100 DEG C after molding
At a temperature of cure 86h, then demoulding obtain material base, it is spare；
5）By step 4）Obtained material base cures 48h again at a temperature of 140 DEG C, and natural cooling obtains product after solidification.
Embodiment 3
A kind of high tenacity solid buoyancy material containing elastic microsphere, according to mass percent, by 100 parts of epoxy resin, 10
The reactive diluent, 90 parts of curing agent, 0.5 part of accelerating agent, 10 parts of toughener and 55 parts of elastic microsphere of part are made,
In, epoxy resin selects No. 170 epoxy resin, reactive diluent to select DGA, curing agent to select Versamid 650, promote
Agent selects DMP-30, toughener to select polyether-ether-ketone, and it is 120 microns that elastic microsphere, which selects average grain diameter, density 0.15g/cm3
Titanium-oxide-coated acrylonitrile polymer microballoon；
Preparation method is：
1）Each material is weighed according to the ratio, it is spare；
2）Remaining component other than elastic microsphere is made to resin adhesive liquid after mixing at normal temperatures, it is spare；
3）By step 1）The elastic microsphere weighed is added to step 2）In in resin adhesive liquid obtained, under the rotating speed of 40r/min
It is uniformly mixed, it is spare to obtain raw mixture；
4）By step 3）Raw mixture obtained is sent into mold, in the forming under the pressure of 12MPa, in 90 DEG C of temperature after molding
Degree is lower to cure 49h, and then demoulding obtains material base, spare；
5）By step 4）Obtained material base cures 25h again at a temperature of 130 DEG C, and natural cooling obtains product after solidification.
Embodiment 4
A kind of high tenacity solid buoyancy material containing elastic microsphere, according to mass percent, by 100 parts of epoxy resin, 5 parts
Reactive diluent, 75 parts of curing agent, 0.4 part of accelerating agent, 15 parts of toughener, 40 parts of elastic microsphere and with 10 parts
Surface modifier is made, wherein epoxy resin selects E44, reactive diluent that BDGE, curing agent is selected to select methyl nadic acid
Acid anhydride, accelerating agent selection 1- amino-ethyls -2-methylimidazole, toughener selection polysulfide rubber, elastic microsphere selection average grain diameter are
10 microns, density 0.20g/cm3Calcium carbonate coat acrylonitrile polymer microballoon, surface modifier select JN114 titanate esters
Coupling agent；
Preparation method is：
1）Each material is weighed according to the ratio, it is spare；
2）Remaining component other than elastic microsphere is made to resin adhesive liquid after mixing at normal temperatures, it is spare；
3）By step 1）The elastic microsphere weighed is added to step 2）In in resin adhesive liquid obtained, under the rotating speed of 40r/min
It is uniformly mixed, it is spare to obtain raw mixture；
4）By step 3）Raw mixture obtained is sent into mold, in the forming under the pressure of 10MPa, in 85 DEG C of temperature after molding
Degree is lower to cure 56h, and then demoulding obtains material base, spare；
5）By step 4）Obtained material base cures 40h again at a temperature of 125 DEG C, and natural cooling obtains product after solidification.
Embodiment 5
A kind of high tenacity solid buoyancy material containing elastic microsphere, according to mass percent, by 100 parts of epoxy resin, 15
Part reactive diluent, 90 parts of curing agent, 0.8 part of accelerating agent, 5 parts of toughener, 60 parts of elastic microsphere and 20 parts
Surface modifier is made, wherein epoxy resin selects E54, reactive diluent that AGE, curing agent is selected to select methyl tetrahydrochysene neighbour's benzene
Dicarboxylic acid anhydride, accelerating agent selection 1- benzyl -2- ethyl imidazol(e)s, toughener selection polyether sulfone, elastic microsphere selection average grain diameter are
40 microns, density 0.10g/cm3Titanium-oxide-coated acrylonitrile polymer microballoon, surface modifier selects 414 Aluminates even
Join agent；
Preparation method is：
1）Each material is weighed according to the ratio, it is spare；
2）Remaining component other than elastic microsphere is made to resin adhesive liquid after mixing at normal temperatures, it is spare；
3）By step 1）The elastic microsphere weighed is added to step 2）In in resin adhesive liquid obtained, in the rotating speed of 25-50r/min
It is lower to be uniformly mixed, it is spare to obtain raw mixture；
4）By step 3）Raw mixture obtained is sent into mold, in the forming under the pressure of 15MPa, in 95 DEG C of temperature after molding
Degree is lower to cure 72h, and then demoulding obtains material base, spare；
5）By step 4）Obtained material base cures 28h again at a temperature of 135 DEG C, and natural cooling obtains product after solidification.
Properties test is carried out to the solid buoyancy material obtained by each embodiment, test result is as follows：
Embodiment 1：Density is 0.49g/cm3, compressive strength 25MPa, water absorption rate 0.9%, elongation at break 7.3%；
Embodiment 2：Density is 0.47g/cm3, compressive strength 27MPa, water absorption rate 0.5%, elongation at break 6.5%；
Embodiment 3：Density is 0.53g/cm3, compressive strength 33MPa, water absorption rate 0.7%, elongation at break 6.9%；
Embodiment 4：Density is 0.51g/cm3, compressive strength 38MPa, water absorption rate 0.6%, elongation at break 8.3%；
Embodiment 5：Density is 0.49g/cm3, compressive strength 41MPa, water absorption rate 0.5%, elongation at break 8.5%.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Profit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent requirements of the claims
Variation is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiment being appreciated that.
Claims (8)
1. a kind of high tenacity solid buoyancy material containing elastic microsphere, it is characterised in that：According to mass percent, by 100 parts
Epoxy resin, 0-20 parts of reactive diluent, 60-120 parts of curing agent, 0-1 parts of accelerating agent, 0-20 parts of toughener and
10-100 parts of elastic microsphere is made.
2. a kind of high tenacity solid buoyancy material containing elastic microsphere according to claim 1, it is characterised in that：It is described
Epoxy resin is bisphenol A type epoxy resin or bisphenol f type epoxy resin.
3. a kind of high tenacity solid buoyancy material containing elastic microsphere according to claim 1, it is characterised in that：It is described
Reactive diluent shrinks sweet for allyl glycidyl ether, butyl glycidyl ether, diglycidylaniline or butanediol two
Oily ether.
4. a kind of high tenacity solid buoyancy material containing elastic microsphere according to claim 1, it is characterised in that：It is described
Curing agent be and the matching used anhydride of epoxy resin or amine curing agent.
5. a kind of high tenacity solid buoyancy material containing elastic microsphere according to claim 1, it is characterised in that：It is described
Accelerating agent is match with the curing agent imidazoles used or tertiary amines accelerating agent.
6. a kind of high tenacity solid buoyancy material containing elastic microsphere according to claim 1, it is characterised in that：It is described
Toughener is one kind in liquid nbr carboxyl terminal, epoxy terminated nitrile rubber, polysulfide rubber, polyether-ether-ketone and polyether sulfone
Or the mixing of several arbitrary proportions.
7. a kind of high tenacity solid buoyancy material containing elastic microsphere according to claim 1, it is characterised in that：It is described
Also containing 0-20 parts of surface modifier in high tenacity solid buoyancy material, the surface modifier be JN114 titanate coupling agents,
KH560 silane coupling agents, 414 aluminate coupling agents and one kind or several in laurel alcohol ether phosphate anionic surfactant
The mixing of kind arbitrary proportion.
8. a kind of preparation method of high tenacity solid buoyancy material containing elastic microsphere according to claim 1 or claim 7,
It is characterized in that, includes the following steps：
1）Each material is weighed according to the ratio described in claim 1 or 7, it is spare；
2）Remaining component other than elastic microsphere is made to resin adhesive liquid after mixing at normal temperatures, it is spare；
3）By step 1）The elastic microsphere weighed is added to step 2）In in resin adhesive liquid obtained, in the rotating speed of 25-50r/min
It is lower to be uniformly mixed, it is spare to obtain raw mixture；
4）By step 3）Raw mixture obtained is sent into mold, in the forming under the pressure of 5-20MPa, in 80-100 after molding
Solidification is not less than 48h at a temperature of DEG C, and then demoulding obtains material base, spare；
5）By step 4）Solidification is not less than for 24 hours again at a temperature of 120-140 DEG C for obtained material base, and natural cooling is after solidification
Obtain product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112961570A (en) * | 2021-02-06 | 2021-06-15 | 杭州每步材料科技有限公司 | Environment-friendly underwater toughening epoxy resin adhesive and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023183119A2 (en) * | 2022-03-01 | 2023-09-28 | Huntsman Advanced Materials Americas Llc | Surface tolerant adhesive |
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| JPH03166929A (en) * | 1989-11-27 | 1991-07-18 | Yokohama Rubber Co Ltd:The | Buoyancy material |
| CN106832789A (en) * | 2017-03-21 | 2017-06-13 | 钟东南 | A kind of integrated molding solid buoyancy material and preparation method thereof |
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2018
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03166929A (en) * | 1989-11-27 | 1991-07-18 | Yokohama Rubber Co Ltd:The | Buoyancy material |
| CN106832789A (en) * | 2017-03-21 | 2017-06-13 | 钟东南 | A kind of integrated molding solid buoyancy material and preparation method thereof |
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| Title |
|---|
| 吴培熙: "《聚合物共混改性》", 31 August 2017, 华南理工大学出版社 * |
| 梁基照: "《聚合物复合材料增强增韧理论》", 30 April 2012, 中国轻工业出版社 * |
| 苗琦: "耐水型环氧树脂增韧剂的制备及应用", 《塑料科技》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112961570A (en) * | 2021-02-06 | 2021-06-15 | 杭州每步材料科技有限公司 | Environment-friendly underwater toughening epoxy resin adhesive and preparation method thereof |
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