CN106009700A - Heat-resistant ablation-resistant rubber composite material with temperature responsive self-expansion characteristic and preparation method thereof - Google Patents
Heat-resistant ablation-resistant rubber composite material with temperature responsive self-expansion characteristic and preparation method thereof Download PDFInfo
- Publication number
- CN106009700A CN106009700A CN201610644650.9A CN201610644650A CN106009700A CN 106009700 A CN106009700 A CN 106009700A CN 201610644650 A CN201610644650 A CN 201610644650A CN 106009700 A CN106009700 A CN 106009700A
- Authority
- CN
- China
- Prior art keywords
- parts
- rubber
- rubber composite
- composite material
- expansion
- 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.)
- Granted
Links
Classifications
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-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
- C08J9/14—Working-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
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- 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
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
-
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- 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
- C08K2003/2231—Oxides; Hydroxides of metals of tin
-
- 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
- C08K2003/2248—Oxides; Hydroxides of metals of copper
-
- 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
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
-
- 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
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a rubber composite material. The rubber composite material comprises, by weight, 80-120 parts of rubber, 20-35 parts of silica, 10-30 parts of a metal oxide, 2-30 parts of foaming microspheres and 0.8-1.5 parts of a cross-linking agent. Through specific composition and ratio, the rubber composite material has the temperature responsive self-expansion characteristic. An initial expansion temperature, an expansion rate and an expanded multiplication rate of the material can be conveniently controlled and adjusted. The expanded material still retains excellent ablation resistance and satisfies some special application requirements so that in a specific environment, the rubber composite material satisfies self-expansion heatproof sealing and ablation resistance requirements such as heat transfer channel automatic enclosing, heat transmission isolation and effective resistance to further external ablation in a fire environment or in a substantial heating process and thus the rubber composite material produces protection effects on a specific mechanism.
Description
Technical field
The present invention relates to a kind of rubber composite of resistance to ablation with temperature-responsive self-expanding characteristic and preparation method thereof.
Background technology
Flexible heat resistant anti-yaw damper material has more application in all kinds of engineerings, thermal protection and fire proof construction and plays
Key player, but its function is the most single, and some special and key position thermal protections often must also meet the merit in design
Can property requirement.Temperature-responsive expanding material then refers to when ambient temperature changes a lot, and material volume changes, thus can
To realize certain function, it is divided into repeatable thermal expansion material, and its swell increment is typically small, and non-repeatability thermal expansion material
Material, but its swell increment is generally large, if the latter combined with flexible anti-yaw damper material, then can prepare a kind of brand-new tool
The heat-resistant ablation rubber composite of temperature-responsive self-expanding characteristic, imparting rubber composite is had to have oneself of temperature-responsive
Expansion characteristics, the material after it expands simultaneously remains to keep excellent ablation resistance so that it is disclosure satisfy that some special applications
Requirement, can realize the anti-heat seal of the automatic expansion of material and ablation resistance requirement, such as naval vessel etc. under specific environment similar narrow
The fire damping of little complex space, the thermal protection etc. of particular organization, its fire environment or during notable temperature rise occurs by heat
Transmission channels self-closed, isolation heat transmits and is effective against further external ablation, thus blocks burning or to specific
Mechanism plays a protective role.
But, existing material is typically only capable to meet the requirement in one side face, there are no at present on can meeting simultaneously
State temperature-responsive self-expanding characteristic and the rubber packing material of heat-resistant ablation aspect performance requirement.And, it is generally the case that material
Density after material expands declines, and can cause significantly reducing of material ablation resistance, and this increases acquisition undoubtedly can expire simultaneously
The difficulty of the material of the above-mentioned two aspect performance requirements of foot.
Summary of the invention
It is an object of the invention to provide and a kind of there is temperature-responsive self-expanding characteristic and the rubber composite of resistance to ablation.
A kind of rubber composite that the present invention provides, it includes the component of following parts by weight: 80 parts～120 portions of rubbers
Glue, 20 parts～35 parts of silicon dioxide, 10 parts～30 parts of metal-oxides, 2 parts～30 parts of foam microspheres, 0.8 part～1.5 parts of crosslinkings
Agent.
Further, it is made up of the component of following parts by weight: 80 parts～120 parts of rubber, 20 parts～35 parts of dioxies
SiClx, 10 parts～30 parts of metal-oxides, 2 parts～30 parts of foam microspheres, 0.8 part～1.5 parts of cross-linking agent.
Further, the particle diameter of described silicon dioxide is 5nm～100nm；Preferably, the particle diameter of described silicon dioxide is
10nm～40nm.
Further, described metal-oxide is selected from Fe3O4、M12O3、M2O、M3O2In any one or two kinds with
On；Wherein, M1 is Fe, Al, Co or Ni, and M2 is Mg, Ca, Cu or Ba, and M3 is Sn, Ti, Pb or Zr.
Further, described metal-oxide is made up of the component of following parts by weight: 1 part～5 parts of Fe3O4, 3 parts
～15 parts of M12O3, 4 parts～10 parts of M2O, 0 part～15 parts of M3O2；Wherein, M1 is Fe, Al, Co or Ni, and M2 is Mg, Ca, Cu or Ba,
M3 is Sn, Ti, Pb or Zr.
Further, the initial blowing temperature of described foam microspheres is 80 DEG C～220 DEG C；Preferably, described foam microspheres
Initial blowing temperature be 110 DEG C～150 DEG C.
Further, described rubber is selected from silicone rubber, fluorubber, natural rubber, butadiene-styrene rubber, nitrile rubber, suitable fourth
In rubber, isoprene rubber, EP rubbers, neoprene any one or two or more；Described cross-linking agent is selected from peroxidating
Dibenzoyl, cumyl peroxide, di-isopropylbenzene hydroperoxide, 2,5-dimethyl-2,5 di-t-butyl hexane peroxide, two
In tert-butyl peroxide any one or two or more.
Wherein, described silicone rubber is selected from dimethyl silicone rubber, methyl vinyl silicone rubber, methyl phenyl vinyl silicon rubber
In glue any one or two or more.
Present invention also offers a kind of method preparing above-mentioned rubber composite, it comprises the following steps:
A, take rubber and silicon dioxide, mixing, add metal-oxide, mixing, add cross-linking agent, mixing, add foaming
Microsphere, mixing, obtain mixed material；
B, step a gained mixed material is aged more than 24 hours the most naturally；
C, step b is aged after material, 100 DEG C, under the conditions of 8MPa～12MPa, hot-press vulcanization 15min～25min
After, cooling, obtain hot-press vulcanization moulded products；
D, by step c gained hot-press vulcanization moulded products room temperature place more than 12 hours.
Present invention also offers a kind of compositions improving ablation resistance, it is by the component group of following parts by weight
Become: 10 parts～30 parts of metal-oxides, 2 parts～30 parts of foam microspheres.
Further, described metal-oxide is selected from Fe3O4、M12O3、M2O、M3O2In any one or two kinds with
On；Wherein, M1 is Fe, Al, Co or Ni, and M2 is Mg, Ca, Cu or Ba, and M3 is Sn, Ti, Pb or Zr.
Further, described metal-oxide is made up of the component of following parts by weight: 1 part～5 parts of Fe3O4, 3 parts
～15 parts of M12O3, 4 parts～10 parts of M2O, 0 part～15 parts of M3O2；Wherein, M1 is Fe, Al, Co or Ni, and M2 is Mg, Ca, Cu or Ba,
M3 is Sn, Ti, Pb or Zr.
Further, the initial blowing temperature of described foam microspheres is 80 DEG C～220 DEG C；Preferably, described foam microspheres
Initial blowing temperature be 110 DEG C～150 DEG C.
Present invention also offers above-mentioned composition application in preparing above-mentioned rubber composite.
The rubber composite of the present invention, by using specific composition and proportioning, gives composite and has temperature sound
The self-expanding characteristic answered, the expansion characteristics such as the initial expansion temperature of material, expansion rate, expansion multiplying power can be controlled easily
System adjusts so that it is disclosure satisfy that some special applications requirements, the material after it expands simultaneously remain to keep excellent ablation resistance
Can, can realize the anti-heat seal of the automatic expansion of material and ablation resistance requirement under specific environment, such as fire environment or appearance
By heat transfer pathway self-closed during notable temperature rise, isolation heat transmission also can be effective against outside burning
Erosion, thus particular organization is played a protective role.Meanwhile, the rubber composite performance designability of the present invention is good, stores steady
Fixed, multiple application demand can be met, have a extensive future.
Foam microspheres is a kind of by thermoplastic resin (1,1-dichloroethylene system, acrylic, the homopolymerization of acrylic monomer
Thing or copolymer etc.) shell and Nei Bao low boiling point organic solvent (iso-butane, normal butane, pentane, isopentane, petroleum ether etc.) core
The microsphere particle of composition.According to the difference of application purpose, its microsphere diameter is from 5～100 μm.Along with the rising of temperature, core
Material vaporizes rapidly, produces high internal pressure, and meanwhile, sheathing material is by thermal softening, thus whole microsphere is swollen under intrinsic pressure promotion
It is expanded into big abscess.Typically, the diameter of microsphere can increase to original several times, and volume can increase to 10 times even 100 times.This
Expended microsphere has metastable shape, without retracting because of cooling.
Obviously, according to the foregoing of the present invention, according to ordinary technical knowledge and the customary means of this area, without departing from
Under the present invention above-mentioned basic fundamental thought premise, it is also possible to make the amendment of other various ways, replace or change.
The detailed description of the invention of form by the following examples, remakes the most specifically the foregoing of the present invention
Bright.But this should not being interpreted as, the scope of the above-mentioned theme of the present invention is only limitted to Examples below.All based on foregoing of the present invention
The technology realized belongs to the scope of the present invention.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention 1 gained rubber composite expansion multiplying power at 120 DEG C is schemed over time.
Fig. 2 is that the embodiment of the present invention 2 gained rubber composite expansion multiplying power at 120 DEG C is schemed over time.
Fig. 3 is that the embodiment of the present invention 3 gained rubber composite expansion multiplying power at 120 DEG C is schemed over time.
Fig. 4 is that the embodiment of the present invention 1 gained rubber composite expansion multiplying power at 130 DEG C is schemed over time.
Fig. 5 is that the embodiment of the present invention 4 gained rubber composite expansion multiplying power at 140 DEG C is schemed over time.
Fig. 6 is that the embodiment of the present invention 5 gained rubber composite expansion multiplying power at 140 DEG C is schemed over time.
Fig. 7 is that the embodiment of the present invention 4 gained rubber composite expansion multiplying power at 150 DEG C is schemed over time.
Fig. 8 is that comparative example 1 is without the expansion multiplying power change in time at 120 DEG C of foam microspheres gained rubber composite
Change figure.
Fig. 9 is the microscopic appearance figure before and after the embodiment of the present invention 1 gained rubber composite expands.
Figure 10 is the thickness variation diagram before and after the embodiment of the present invention 1 gained rubber composite expands.
Detailed description of the invention
The raw material, the equipment that use in the specific embodiment of the invention are known product, obtain by buying commercially available prod.
Such as, foam microspheres can obtain by buying commercially available prod, it is also possible to by literature method or in detail below
Preparation method obtains:
1, the preparation of low-temp foaming microsphere (LTE)
(1), preparation aqueous dispersion liquid: be sequentially added into 1.05g sodium hydroxide, 3.00g six hydration in 27.5g deionized water
Magnesium chloride, 0.5g lauryl sodium sulfate aqueous solution (1wt%), be stirred vigorously half an hour, forms stable suspension protection liquid；
(2), preparation oil phase dispersion liquid: toward beaker in addition 6.20g acrylonitrile (AN), 3.10g acrylic acid methyl ester. (MA),
1.03g vinyl acetate (VAc), 2.53g foaming agent (normal hexane), 0.19g initiator (azodiisobutyronitrile, AIBN),
0.045g cross-linking agent (ethylene glycol dimethacrylate, EGDMA)；
(3) above-mentioned oil phase being added aqueous phase, being stirred vigorously until obtaining stable suspension, seal, 63 DEG C of reaction 20h, fall
Temperature, discharging, remove Surface Hydrogen magnesium oxide with dilute hydrochloric acid washing, be placed in 55 DEG C of baking ovens being dried, obtain faint yellow or white product
Product, are low-temp foaming microsphere (LTE), and its initial blowing temperature is about 110～125 DEG C.
2, the preparation of middle temperature foam microspheres (MTE)
(1) preparation aqueous dispersion liquid: by 275.0g deionized water, 5.0g sodium lauryl sulphate (1wt%), 3.0g nanometer
Silicon dioxide, 15.0g sodium chloride mix, and high-speed stirred is uniform, obtains the aqueous phase needed for suspension polymerisation；
(2) preparation oil phase dispersion liquid: toward beaker in addition 63.0g acrylonitrile (AN), 21.g methacrylic acid (MAA),
21.0g methyl methacrylate, 41.0g foaming agent (isopentane), 1.10g initiator (benzoyl peroxide, BPO), 0.35g second
Diol dimethacrylate (EGDMA)；
(3) above-mentioned oil phase being added aqueous phase, being stirred vigorously until obtaining stable suspension, seal, tie after 69 DEG C of reaction 19h
Shu Fanying, product is scrubbed, filter after, put in baking oven 55 DEG C and be dried, finally obtain white or light yellow product, in being
Temperature foam microspheres (MTE), its initial blowing temperature is about 130～150 DEG C.
Embodiment 1, the rubber composite of the preparation present invention
1, mixing
According to each component specified in table 1 and weight proportion, take raw material；
Room temperature logical cooling water double roll mill, measures in mixing process and guarantees that temperature of charge is less than 60 DEG C, mixing time
Total is not less than 20min, and step is as follows:
(1), adjust double roller gap, add rubber (methyl vinyl silicone rubber: weight average molecular weight 45～700,000, vinyl
Content is 0.15wt%～0.17wt%) mixing, the most progressively it is slowly added to silicon dioxide (particle diameter is 20nm～30nm),
Mixing 1min is continued after adding complete range estimation mix homogeneously；
(2), add metal-oxide, after adding complete range estimation mix homogeneously, continue mixing 1min, typically add from raw material
Entering and feed to next step, its incorporation time is 5min；
(3), cross-linking agent (dibenzoyl peroxide, BPO), mixing 5min are added.
(4), tune up double roller gap, add foam microspheres (low-temp foaming microsphere, LTE), to adding complete range estimation mixing all
Mixing 1min, natural cooling after blanking is continued after even.
2, ageing one: the natural digestion time at ambient temperature of the material after compounding procedure is not less than 24h.
3, hot-press vulcanization molding
(1) (typically with alcohol washes, part spot uses toothpaste to remove) after, mould carefully cleans；
(2), uniform spreading enters die cavity after sizing material is colded pressing and is cut into bar, strict controls material total amount, is less than with flash amount
3% is advisable, and to guarantee the dimensional stability of shaped article, must pay attention to the uniformity of paving, to guarantee uniform mold filling；
(3), mould matched moulds hot-press vulcanization, curing temperature controls at 100 DEG C, pressure 10MPa, and the time is 20min；
(4), 5min is cooled down under 10MPa cold press.
4, ageing two: heat cure moulded products naturally cools to room temperature placement and is not less than 12h, the rubber obtaining the present invention is multiple
Condensation material.
Embodiment 2, the rubber composite of the preparation present invention
The method repeating embodiment 1 according to each component specified in table 1 and weight proportion (reducing the consumption of foam microspheres),
Obtain the rubber composite of the present invention.
Embodiment 3, the rubber composite of the preparation present invention
The method repeating embodiment 1 according to each component specified in table 1 and weight proportion (increasing the consumption of foam microspheres),
Obtain the rubber composite of the present invention.
Embodiment 4, the rubber composite of the preparation present invention
The method repeating embodiment 1 according to each component specified in table 1 and weight proportion, and by middle temperature foam microspheres
(MTE) the low-temp foaming microsphere (LTE) in alternative embodiment 1, obtains the rubber composite of the present invention.
Embodiment 5, the rubber composite of the preparation present invention
The method repeating embodiment 1 according to each component specified in table 1 and weight proportion (reducing the consumption of foam microspheres),
And with the low-temp foaming microsphere (LTE) in middle temperature foam microspheres (MTE) alternative embodiment 1, obtain the rubber combined material of the present invention
Material.
Embodiment 6, the rubber composite of the preparation present invention
The method repeating embodiment 1 according to each component specified in table 1 and weight proportion, obtains the rubber combined of the present invention
Material.
Embodiment 7, the rubber composite of the preparation present invention
The method repeating embodiment 1 according to each component specified in table 1 and weight proportion, and with dimethyl silicone rubber (or
Methyl phenyl vinyl silicone rubber) methyl vinyl silicone rubber in alternative embodiment 1, obtain the rubber combined material of the present invention
Material.
Embodiment 8, the rubber composite of the preparation present invention
The method repeating embodiment 1 according to each component specified in table 1 and weight proportion, and with fluorubber (or butylbenzene rubber
Glue, or nitrile rubber) methyl vinyl silicone rubber in alternative embodiment 1, obtain the rubber composite of the present invention.
Comparative example 1, without foam microspheres
The method repeating embodiment 1 according to each component specified in table 2 and weight proportion, obtains the rubber combined of comparative example
Material.
Comparative example 2, without foam microspheres
The method repeating embodiment 1 according to each component specified in table 2 and weight proportion, obtains the rubber combined of comparative example
Material.
Comparative example 3, without metal-oxide
The method repeating embodiment 1 according to each component specified in table 2 and weight proportion, obtains the rubber combined of comparative example
Material.
Each component that table 1, the embodiment of the present invention 1～8 are specified and weight proportion
Each component that table 2, comparative example 1～3 are specified and weight proportion
Below by way of test example beneficial effects of the present invention is described:
Test example 1, swell
1.1, expansion multiplying power test
Measure expansion multiplying power by the following method: at a fixed temperature, the thickness of every 10s sample of test, and remember
Record is got off.
The computing formula of expansion multiplying power: (dt-d0)/d0, wherein dtFor the thickness that t sample is corresponding, d0At the beginning of sample
Beginning thickness.
Embodiment 1, embodiment 2, embodiment 3 gained rubber composite carry out foaming and intumescing respectively at 120 DEG C, implement
Example 1 gained rubber composite carries out foaming and intumescing at 130 DEG C, and its result is respectively such as Fig. 1～Fig. 4.
Embodiment 4, embodiment 5 gained rubber composite carry out foaming and intumescing, embodiment 4 gained respectively at 140 DEG C
Rubber composite carries out foaming and intumescing at 150 DEG C, and its result is respectively such as Fig. 5～Fig. 7.
Comparative example 1 carries out foaming and intumescing without foam microspheres gained rubber composite at 120 DEG C, and result is shown in Fig. 8.
The above results shows, the rubber composite of the present invention, has temperature-responsive self-expanding characteristic (to different temperature
Condition, material can occur different expansion behaviors to respond), the initial expansion temperature of material, expansion rate, expansion multiplying power etc.
Expansion characteristics can be controlled easily and adjust, it is possible to effectively stop or the conduction of retarding heat, plays sealing and protects
The effect of protection unit particularly critical component, meets some particular/special requirements of reality application.
1.2, the microscopic appearance before and after expanding
Sem test (SEM): use NEC JSM-7500 scanning electron microscopic observation sample to quench the microcosmic shape of section
Looks, accelerating potential is 5kV.
The embodiment of the present invention 1 gained rubber composite, (is placed on 120 after the microscopic appearance before expansion, and expansion
At DEG C, 180s obtains sample expanded) microscopic appearance, see Fig. 9；Result shows, after the rubber composite of the present invention expands, and bubble
Hole substantially becomes big, and dispersed in the base, be highly suitable as encapsulant.
1.3, the thickness change test before and after expanding
At room temperature, monthly silicone rubber of test expands the thickness change of both front and back batten, and records.
The embodiment of the present invention 1 gained rubber composite, (is placed on 180s at 120 DEG C to obtain before expanding and after expanding
To sample expanded) thickness change test result see that Figure 10, result show, either expand before, or expand after, rubber of the present invention
The thickness of glue composite can keep stable, it is not easy to retraction deformation occurs, has good dimensional stability.
Test example 2, ablation resistance are tested
Embodiment 1, comparative example 1, comparative example 2 and comparative example 3 carry out ablation property after expanding 180s at 120 DEG C respectively real
Test；Embodiment 4 carries out ablation property experiment after expanding 180s at 140 DEG C.
Ablation property is tested:
Measuring linear ablative rate the most respectively, evaluate the ablation resistance of material, the numerical value of linear ablative rate is more
Little, the ablation resistance of illustrative material is the best.
Linear ablative rate test condition: vertically rushed by oxy-acetylene flame stream and burn on sample, ablation temperature is 1500 DEG C, nozzle
With sample interval 2cm, ablation time 30s.
Computing formula is as follows: Rd=Δ d/t=(d1-d2)/t
Wherein, Rd is sample line ablating rate, mm/s；D1 is sample original thickness, mm；D2 is the thickness after sample ablation,
mm；T is the ablation time, s.
Test result is shown in Table 3.
Table 3, the test result of linear ablative rate
The above results shows, the present invention by foam microspheres and metal-oxide with the use of so that rubber combined material
Linear ablative rate after material expansion can reach the lowest numerical value, far below the linear ablative rate of the material being used alone, is greatly promoted
Expand the ablation resistance of silicon rubber composite material, it is possible to meet specific environment to the automatic expansion anti-heat seal of material and resistance to
The requirements at the higher level of ablation property, for instance, it is possible to isolation heat transmits and is effective against external ablation, meet fire environment or appearance
The notable elevated temp protection requirement to particular elements.
In sum, the rubber composite of the present invention, by using specific composition and proportioning, give composite tool
Having the self-expanding characteristic of temperature-responsive, the expansion characteristics such as the initial expansion temperature of material, expansion rate, expansion multiplying power can facilitate
Be controlled adjusting so that it is disclosure satisfy that some special applications requirements, the material after it expands simultaneously remains to keep excellent
Ablation resistance, can realize the anti-heat seal of the automatic expansion of material and ablation resistance requirement under specific environment, such as fire ring
Border or during notable temperature rise occurs by heat transfer pathway self-closed, isolation heat transmission also can be effective against further
External ablation, thus particular organization is played a protective role.Meanwhile, the rubber composite performance designability of the present invention is good,
Stable storing, can meet multiple application demand, have a extensive future.
Claims (10)
1. a rubber composite, it is characterised in that: it includes the component of following parts by weight: 80 parts～120 parts of rubber, 20
Part～35 parts of silicon dioxide, 10 parts～30 parts of metal-oxides, 2 parts～30 parts of foam microspheres, 0.8 part～1.5 parts of cross-linking agent.
Rubber composite the most according to claim 1, it is characterised in that: it is by the component group of following parts by weight
Become: 80 parts～120 parts of rubber, 20 parts～35 parts of silicon dioxide, 10 parts～30 parts of metal-oxides, 2 parts～30 parts of foam microspheres,
0.8 part～1.5 parts of cross-linking agent.
Rubber composite the most according to claim 1 and 2, it is characterised in that: the particle diameter of described silicon dioxide be 5nm～
100nm；Preferably, the particle diameter of described silicon dioxide is 10nm～40nm.
Rubber composite the most according to claim 1 and 2, it is characterised in that: described metal-oxide is selected from Fe3O4、
M12O3、M2O、M3O2In any one or two or more；Wherein, M1 is Fe, Al, Co or Ni, and M2 is Mg, Ca, Cu or Ba, M3
For Sn, Ti, Pb or Zr.
Rubber composite the most according to claim 4, it is characterised in that: described metal-oxide is by following weight
The component composition of number: 1 part～5 parts of Fe3O4, 3 parts～15 parts of M12O3, 4 parts～10 parts of M2O, 0 part～15 parts of M3O2；Wherein, M1
For Fe, Al, Co or Ni, M2 is Mg, Ca, Cu or Ba, and M3 is Sn, Ti, Pb or Zr.
Rubber composite the most according to claim 1 and 2, it is characterised in that: the initial foaming temperature of described foam microspheres
Degree is 80 DEG C～220 DEG C；Preferably, the initial blowing temperature of described foam microspheres is 110 DEG C～150 DEG C.
Rubber composite the most according to claim 1 and 2, it is characterised in that: described rubber is selected from silicone rubber, fluorine rubber
Any one in glue, natural rubber, butadiene-styrene rubber, nitrile rubber, butadiene rubber, isoprene rubber, EP rubbers, neoprene
Or it is two or more；Described cross-linking agent selected from dibenzoyl peroxide, cumyl peroxide, di-isopropylbenzene hydroperoxide, 2,
In 5-dimethyl-2,5 di-t-butyl hexane peroxide, di-tert-butyl peroxide any one or two or more.
8. prepare the method for rubber composite described in claim 1～7 any one for one kind, it is characterised in that: it include with
Lower step:
A, take rubber and silicon dioxide, mixing, add metal-oxide, mixing, add cross-linking agent, mixing, add foam microspheres,
Mixing, obtains mixed material；
B, step a gained mixed material is aged more than 24 hours the most naturally；
C, step b is aged after material, 100 DEG C, under the conditions of 8MPa～12MPa, after hot-press vulcanization 15min～25min, cold
But, hot-press vulcanization moulded products is obtained；
D, by step c gained hot-press vulcanization moulded products room temperature place more than 12 hours.
9. the compositions improving ablation resistance, it is characterised in that: it is made up of the component of following parts by weight: 10 parts
～30 parts of metal-oxides, 2 parts～30 parts of foam microspheres.
10. the application in rubber composite described in preparation claim 1～7 any one of the compositions described in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610644650.9A CN106009700B (en) | 2016-08-08 | 2016-08-08 | A kind of heat-resisting anti-ablation rubber composite material and preparation method thereof with temperature-responsive self-expanding characteristic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610644650.9A CN106009700B (en) | 2016-08-08 | 2016-08-08 | A kind of heat-resisting anti-ablation rubber composite material and preparation method thereof with temperature-responsive self-expanding characteristic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106009700A true CN106009700A (en) | 2016-10-12 |
| CN106009700B CN106009700B (en) | 2019-09-20 |
Family
ID=57135043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610644650.9A Active CN106009700B (en) | 2016-08-08 | 2016-08-08 | A kind of heat-resisting anti-ablation rubber composite material and preparation method thereof with temperature-responsive self-expanding characteristic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106009700B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589622A (en) * | 2016-12-09 | 2017-04-26 | 湖北航天化学技术研究所 | Ablation-resistant rubber type thermal insulation layer and preparation method thereof |
| CN108623262A (en) * | 2018-06-29 | 2018-10-09 | 佛山市高明区爪和新材料科技有限公司 | A kind of heat-insulated gap filler |
| CN109021335A (en) * | 2018-07-14 | 2018-12-18 | 桂林理工大学 | A kind of formula of microballoon free foaming acrylonitrile butadiene packing material |
| CN109021571A (en) * | 2018-06-12 | 2018-12-18 | 西北橡胶塑料研究设计院有限公司 | A kind of thermal response self-expanding silastic material of resistance to ablation |
| CN109721762A (en) * | 2018-12-17 | 2019-05-07 | 航天材料及工艺研究所 | A kind of anti-heat-insulation composite material of resin base ablation and preparation method thereof |
| CN109880379A (en) * | 2019-02-22 | 2019-06-14 | 四川大学 | A kind of resistance to ablative composite material of flexibility |
| CN109880368A (en) * | 2019-02-22 | 2019-06-14 | 四川大学 | A kind of flexibility preparation method of an ablation-resisting composite material |
| CN111704800A (en) * | 2020-06-24 | 2020-09-25 | 步阳集团有限公司 | High-temperature ceramic blocking fireproof door sealing strip |
| CN112457511A (en) * | 2019-09-06 | 2021-03-09 | 艾比尔艺术工业有限公司 | Polyethylene terephthalate film coated with foamed rubber |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103874726A (en) * | 2011-10-25 | 2014-06-18 | 埃克森美孚化学专利公司 | Composition, foam, and article made therefrom |
-
2016
- 2016-08-08 CN CN201610644650.9A patent/CN106009700B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103874726A (en) * | 2011-10-25 | 2014-06-18 | 埃克森美孚化学专利公司 | Composition, foam, and article made therefrom |
Non-Patent Citations (1)
| Title |
|---|
| RUI LI 等: ""Study on the thermal stability and ablation properties of metallic oxide-filled silicone rubber composites using uniform design method"", 《JOURNAL OF POLYMER ENGINEERING》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589622B (en) * | 2016-12-09 | 2019-06-21 | 湖北航天化学技术研究所 | A kind of resistance to ablation rubber-type heat insulation layer and preparation method thereof |
| CN106589622A (en) * | 2016-12-09 | 2017-04-26 | 湖北航天化学技术研究所 | Ablation-resistant rubber type thermal insulation layer and preparation method thereof |
| CN109021571A (en) * | 2018-06-12 | 2018-12-18 | 西北橡胶塑料研究设计院有限公司 | A kind of thermal response self-expanding silastic material of resistance to ablation |
| CN108623262A (en) * | 2018-06-29 | 2018-10-09 | 佛山市高明区爪和新材料科技有限公司 | A kind of heat-insulated gap filler |
| CN109021335A (en) * | 2018-07-14 | 2018-12-18 | 桂林理工大学 | A kind of formula of microballoon free foaming acrylonitrile butadiene packing material |
| CN109721762A (en) * | 2018-12-17 | 2019-05-07 | 航天材料及工艺研究所 | A kind of anti-heat-insulation composite material of resin base ablation and preparation method thereof |
| CN109721762B (en) * | 2018-12-17 | 2022-06-03 | 航天材料及工艺研究所 | Resin-based ablation heat-insulation-prevention composite material and preparation method thereof |
| CN109880368A (en) * | 2019-02-22 | 2019-06-14 | 四川大学 | A kind of flexibility preparation method of an ablation-resisting composite material |
| CN109880368B (en) * | 2019-02-22 | 2021-06-15 | 四川大学 | Preparation method of flexible ablation-resistant composite material |
| CN109880379B (en) * | 2019-02-22 | 2021-09-10 | 四川大学 | Flexible ablation-resistant composite material |
| CN109880379A (en) * | 2019-02-22 | 2019-06-14 | 四川大学 | A kind of resistance to ablative composite material of flexibility |
| CN112457511A (en) * | 2019-09-06 | 2021-03-09 | 艾比尔艺术工业有限公司 | Polyethylene terephthalate film coated with foamed rubber |
| CN111704800A (en) * | 2020-06-24 | 2020-09-25 | 步阳集团有限公司 | High-temperature ceramic blocking fireproof door sealing strip |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106009700B (en) | 2019-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106009700A (en) | Heat-resistant ablation-resistant rubber composite material with temperature responsive self-expansion characteristic and preparation method thereof | |
| CN102391588B (en) | High-flame-retardant low-smoke-density polystyrene foam compound heat insulating material and preparation method thereof | |
| CN106810778B (en) | A kind of preparation method of polystyrene board | |
| CN107857935A (en) | A kind of preparation method of grey high fire-retardance polypropylene foaming beads | |
| CN109879652A (en) | A kind of feedstock composition and insulation board containing polystyrene | |
| CN103113651A (en) | Method for producing high-foaming EPE pearl wool by use of carbon dioxide foaming agent | |
| US2888407A (en) | Manufacture of cellular material from bitumen and styrene | |
| CN103102579A (en) | Halogen-free expanded flame retardant cable outer sheath material composition and preparation method thereof | |
| CN110305412B (en) | Chiral silica fiber reinforced foamed polypropylene composite material | |
| CN111978587A (en) | Flame-retardant polystyrene material and preparation method thereof | |
| CN109722038A (en) | A kind of silica gel foam and preparation method thereof | |
| KR100878877B1 (en) | Composition for making rubber gasket for the plate type heat exchanger and method for making the gasket in use of the compositon | |
| CN105348635A (en) | Nano cooperative intumescent flame retardant and toughening polypropylene blend composite material and preparation method thereof | |
| CN103333403A (en) | Halogen-free intumescent flame retardant polyolefine cable sheath material and preparation method thereof | |
| WO2021017580A1 (en) | Lightweight polystyrene foamed material having small pore diameter and preparation method therefor | |
| CN106893326A (en) | A kind of silicon rubber/resistance to ablative composite material of benzoxazine colophony/zirconium boride and preparation method thereof | |
| CN106243321A (en) | A kind of functional urethane elastomeric material and preparation method thereof | |
| CN103589081A (en) | Novel expanded polystyrene resin | |
| CN109912285B (en) | Manufacturing process of flexible heat-insulation board | |
| CN110373906B (en) | High-strength heat-conducting GMT composite board and preparation method thereof | |
| CN103665420A (en) | Propylene-ethylene-butylene high-melt-strength polypropylene foamed bead and preparation method thereof | |
| CN103613873B (en) | A kind of modified polystyrene foam | |
| CN103613872A (en) | High flame retardant polystyrene insulation foam material | |
| CN109553978A (en) | Retarding chamber temperature vulcanizable silicone rubber compounding and fire-retardant room temperature vulcanized silicone rubber | |
| CN115304836A (en) | Low-sulfur rubber-plastic sponge product and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |