CN101220191B - Grease-proof, heat-resistant expansion type flame-proof rubber - Google Patents
Grease-proof, heat-resistant expansion type flame-proof rubber Download PDFInfo
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- CN101220191B CN101220191B CN2008100570921A CN200810057092A CN101220191B CN 101220191 B CN101220191 B CN 101220191B CN 2008100570921 A CN2008100570921 A CN 2008100570921A CN 200810057092 A CN200810057092 A CN 200810057092A CN 101220191 B CN101220191 B CN 101220191B
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Abstract
This invention discloses an expansion fire-retardant rubber with resistance to oil and heat, particularly being applicable to fire safety protection of conductor bundles in all enclosed spaces, and relates to the technical field of the fire-retardant rubber which is composed by the components with the following portions by weight: 40 to 60 percent of oil-resistant rubber, 5 to 10 percent of resin viscosity regulator, 20 to 40 percent of ammonium polyphosphate, 3 to 10 percent of melamine, 2 to 8 percent of zinc borate, 5 to 20 percent of nano-inorganic and 1 to 5 percent of silica white. The fuel immersion swelling rate of the fire-retardant rubber is zero; when the rubber thickness is less than or equal to 1.0mm, the fire resistance duration is more than or equal to 5 min with the flame temperature of 1200 DEG C and the protected substrate temperature of being less than or equal to 300 DEG C. The fire-retardant rubber of the invention has resistance to heat and ageing, and flexibility and can be used for the fire safety protection of various the conductor bundles.
Description
Technical field
The present invention relates to the flame retardant rubber technical field, this expansion type flame-proof rubber is particularly useful for the fire safety evaluating protection of various enclosed space inside conductor bundles.
Background technology
At present, the halogen-free flameproof of conventional rubber mainly contains two classes: (1) adding the system of inorganic metal oxyhydroxide fire retardant, as based on aluminium hydroxide, magnesium hydroxide, and composite a small amount of zinc borate, red phosphorus, organophosphate, organosilicon etc.; (2) add expansion type flame retardant, typical expansion type flame-retarding system is ammonium polyphosphate (acid source), tetramethylolmethane (charcoal source), trimeric cyanamide (source of the gas), can composite a certain amount of titanium dioxide, silicon-dioxide, talcum powder, nano imvite etc. improve the expandable flame retardant effect of heat insulation.Because the expansion type flame-retarding system is under flame interaction, acid source, charcoal source, source of the gas can be by chemical reaction and physical action by the superficial expansions of protective material, form the very low porous dense char layer of thermal conductivity, thereby have the effect that intercepts flame heat regulating conduction and thermal oxidation resistance.In addition, the expansion type flame-retarding system also have flame retarding efficiency height, the amount of being fuming few, do not have advantage such as drippage, be one of important system of present halogen-free fire retardant plastic, rubber and coating.
Patent CN1884367 has adopted nitrogen-phosphorus composite flame-retardant agent and a small amount of nano-inorganic substance compound expansion type flame-retarding system flame-proofed thermoplastic styrene-butadiene rubber(SBR) (SEBS), has the advantage of good flame retardation effect, LSZH.But this flame retardant rubber does not have oil resistant, heat-stable characteristic.Patent CN1730525 has announced a kind of Microencapsulation Intumescent Flame-Retardant Rubber And Its Preparation Method, and its rubber matrix is a kind of or mixture of natural rubber, styrene-butadiene rubber(SBR), paracril or polyurethane elastomer; Its fire retardant core is ammonium polyphosphate, tetramethylolmethane, trimeric cyanamide, and the capsule material is a terpolycyantoamino-formaldehyde resin.The introducing of capsule material has improved the expandable flame retardant effect of flame retardant rubber, and its oxygen index is 27.5%, has the good mechanical performance simultaneously.Although this patented technology has been used the resin-coated material, the poor heat resistance of tetramethylolmethane, the easy moisture absorption in ammonium phosphate, tetramethylolmethane, the trimeric cyanamide expandable flame retardant system; Simultaneously do not have grease-proof characteristic yet, its application is restricted.Patent CN1036390 provides a kind of insulation oil resistant and heat-stable flame retardant rubber, owing to adopted paracril, chloroprene rubber, chlorosulfonated polyethylene rubber base material and crosslinking technological, oil immersion 24h does not have distortion, fire-retardant rank reaches from fire and puts out rank certainly, and thermotolerance is no abnormal at 100 ℃～250 ℃ following 20min.But this patent does not have the heat insulation performance of high temperature resistant flame.
In sum, at present the expandable flame retardant rubber that provides of patent of invention is both not fire-retardant, again both multifunctionalities of oil resistant, heat-resisting, high temperature resistant flame.Its reason is to prepare oil resistant, expandable flame retardant rubber heat-resisting, the high temperature resistant flame of softish exists a technical barrier, be that oil resisting rubber is crosslinked fast in decomposes initial stage system, cause source of the gas to be difficult to bring into play expansion, non-bloating flame retardant rubber does not just possess good high temperature resistant flame ability.Simultaneously, the performance that the existence of charcoal source tetramethylolmethane will be lost the heat-resisting of expandable flame retardant rubber and humidity environment in the present expansion type flame retardant system.
Summary of the invention
The purpose of this invention is to provide a kind of flexible flame retardant rubber with good oil resistant, heat-resisting, high temperature resistant accelerated deterioration, ultra-thin high temperature resistant flame.This expandable flame retardant rubber of≤1mm thickness is compressed on the steel plate of 1mm thickness, under 1200 ℃ of hydrocarbon fuel gas torch flame combustion conditionss, can keeps being protected temperature≤300 ℃ of substrate surface in the 5min.
The present invention can adopt the synthetic viton of the special type of oil resistant, excellent heat resistance or modification viton or ethylene-vinyl acetate rubber (EVM, VA content 〉=70%) is the system matrix resin charcoal source of holding concurrently, with the high-polymerization degree ammonium polyphosphate is acid source, trimeric cyanamide is a source of the gas, constitutes main expandable flame retardant system; Add zinc borate simultaneously and become the charcoal ability for becoming charcoal promotor, resin viscosity conditioning agent to increase the expandable flame retardant rubber material rapid expansion, add the ability of inorganic heat-resisting nano material raising charcoal layer withstand high temperatures flame impingement, add the mechanical strength that white carbon black improves system.
The objective of the invention is to be achieved through the following technical solutions: adopt twin-roll plastic mixing mill mixing, 70～100 ℃ of melting temperatures, mixing time 6～12min; Adopt vulcanizing press, with expandable flame retardant rubber compression moulding, 80～120 ℃ of press temperatures, press time 2～6min, expandable flame retardant rubber thickness of sample 1mm.
A kind of oil resistant fire-resistant expansible flame retardant rubber of the present invention is made of the component of following weight per-cent:
Oil resisting rubber 40～60%
Resin viscosity conditioning agent 5～10%
Ammonium polyphosphate 20～40%
Trimeric cyanamide 3～10%
Zinc borate 2～8%
Nano-inorganic substance 5～20%
White carbon black 1～5%
Oil resisting rubber is the viton that vinylidene (VDF) and perfluoro propylene (HFP) copolymerization form, and density is 1.80-1.84g/cm
3, Mooney viscosity 10-50 (ML 1+10,121 ℃);
The resin viscosity conditioning agent is made up of weight percent 1～5% thermosetting resin 663UE (molecular weight 1800), 1～5%KR120 resin, 2～8% triphenylphosphates.
Nano-inorganic substance is the mixture of nano titanium oxide, nano-sized magnesium hydroxide.
Above-mentioned oil resisting rubber can be the viton that vinylidene (VDF) and perfluoro propylene (HFP) copolymerization form, and density is 1.80-1.84g/cm
3, Mooney viscosity 10-50 (ML 1+10,121 ℃).
Oil resisting rubber among the present invention has good heat-resisting, oil resistant, weather-proof, electrical insulating property and physical and mechanical properties, is the vector resin of expansion type flame retardant system, simultaneously as the charcoal source of expanding fire retardant system.
The resin viscosity conditioning agent by following raw materials according by mass percentage content constitute: 1～5% thermosetting resin 663UE (molecular weight 1800), 1～5%KR120 resin, 2～8% triphenylphosphates; This resin viscosity conditioning agent has the processing of improvement rheological, the function of reduction system burning molten state viscosity is also arranged and the effect that is easy to expand into charcoal is arranged.Acid source high-polymerization degree ammonium polyphosphate heat decomposition temperature 〉=270 ℃, the Tripyrophosphoric acid that produces by thermolysis promotes the dehydration of resin charcoal source, crosslinked, one-tenth charcoal.Source of the gas trimeric cyanamide heat decomposition temperature 〉=280 ℃, crosslinked in system, become charcoal to be under the condition of molten state to discharge gas, impel system to form expansible porous charcoal layer.Zinc borate is a kind of multifunctional inorganic fire retardant, can play enhancement to expansion charcoal layer physical structure after the dehydration of zinc borate thermolysis in the present invention, can prevent that hair line from appearring in the charcoal layer, also has the cigarette effect of pressing down simultaneously.
The inorganic nano-filler that the present invention uses is made up of titanium dioxide and/or magnesium hydroxide, and the use of inorganic nano-filler can improve the charcoal layer to the reflection of thermal-flame and the ability of thermal oxidation resistance.White carbon black has enhancement to expansion type flame-proof rubber, also has simultaneously the collaborative fireproof effect of expandable flame retardant system.
The factor that the present invention has the greatest impact to the flame retardant rubber oil resistance is a resin matrix; What resistance toheat was played restrictive function is the thermostability of high-polymerization degree ammonium polyphosphate and resin viscosity conditioning agent; The factor that high temperature resistant flame performance is played a decisive role is the ratio matching of resin matrix and high-polymerization degree ammonium polyphosphate, trimeric cyanamide, mineral filler.
The present invention and existing flame retardant rubber relatively have following advantage:
(1) is matrix and charcoal source with the oil-resisting and heat-resisting resin, utilizes the ratio of high-polymerization degree ammonium polyphosphate and trimeric cyanamide to be adjusted to charcoal resin speed of expansion and carbon layer;
(2) utilize the melt viscosity of resin viscosity conditioning agent control expandable flame retardant system, make speed that source of the gas discharges gas with acid source dehydrated crosslinking, expansion, become the speed of charcoal to be complementary;
(3) utilize the matching of inorganic and Nano filling to strengthen the performance of charcoal layer high temperature resistance flame impingement.
Adopt the technology of above-mentioned three aspects to realize that oil resistant flame retardant rubber rapid expansion becomes the performance of charcoal and high temperature resistant flame; Make flame retardant rubber keep the characteristic of good oil resistant, heat-resisting and high temperature resistant accelerated deterioration simultaneously.Table 1 has listed that expandable flame retardant rubber of the present invention is fire-resistant, oil resistant, heat-resisting and high temperature resistant acceleration heat aging performance test result.Wherein the oil resistance test is carried out with reference to GA 181-1998 " industry standards of public safety cable fire-refractory coating general technical specifications " standard.
Table 1 flame retardant rubber of the present invention is fire-resistant, oil resistant, heat-resisting and heat aging performance test result
(flame retardant rubber thickness≤1mm, protection base material steel plate thickness 1.0mm)
In sum, expansion type flame-proof rubber of the present invention has anti-1200 ℃ of thermal-flames, oil resistant, heat-resisting, resistant to heat aging performance, and this flame retardant rubber has thermoplastic flexibility, component does not simultaneously have and move out, place good characteristics such as stable.Expansion type flame-proof rubber of the present invention can be compound with terylene or polyester-cotton blend base fabric, makes the fire safety evaluating protection that strapping tape is used for all kinds of bundle conductors, especially nacelle fuel oil environment bundle conductor.
Embodiment
Embodiment
Expansion type flame-proof rubber implementation example of the present invention is 100 parts of meterings with the matrix resin quality, and all the other components are in respect to 100 parts of resin contents (phr, per 100 parts of resins add the umber of filler).Expansion type flame-proof rubber recipe ingredient content and technical performance index are as shown in table 2.
Table 2 flame retardant rubber embodiment of the present invention component and performance index
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Oil resisting rubber | 100 | 100 | 100 | 100 |
| Resin viscosity conditioning agent/phr | 6 | 8 | 10 | 22 |
| Ammonium polyphosphate/phr | 80 | 80 | 80 | 80 |
| Trimeric cyanamide/phr | 8 | 8 | 8 | 10 |
| Zinc borate/phr | 8 | 8 | 8 | 8 |
| Inorganic nano-filler/phr | 8 | 12 | 14 | 14 |
| White carbon black/phr | 2 | 4 | ||
| Thickness of sample/mm | 0.90 | 0.85 | 0.92 | 0.96 |
| The butane blowtorch, protection base material 5min back of the body temperature/℃ | 298 | 280 | 283 | 255 |
| Gasoline blast burner, protection base material 5min back of the body temperature/℃ | 304 | 292 | 289 | 263 |
The preparation method of each embodiment is identical in the table 2, in table 2 recipe ingredient ratio batching, adopts SK-106B type twin-roll plastic mixing mill mixing, 90 ℃ of melting temperatures, mixing time 8min; Adopt QLB type vulcanizing press, it is on the steel plate of 100mm * 100mm that expandable flame retardant rubber is compressed on thick 1mm area, 100 ℃ of press temperatures, press time 3min, expandable flame retardant rubber thickness of sample≤1mm.
The high-temperature flame testing method is described below: adopt butane Gas blowtorch flame or gasoline blast burner flame to carry out fire-resistant test, butane flame diameter 20mm ± 5mm, length of flame 150mm ± 5mm; Gasoline blast burner flame diameter 60mm ± 5mm, length of flame 300mm ± 5mm.Torch flame vertical angle contact sample surfaces contacts tested sample with the outside blue flame of flame (about 1200 ℃).The expandable flame retardant rubber samples vertical that is compressed on the steel plate is installed on the homemade combustion testing equipment, and temperature thermocouple is equipped with at the sample back side.The data that record steel plate back temperature changed with combustion time in the time of flame contact expandable flame retardant rubber sample.
Claims (3)
1. an oil resistant, heat resistant fire-proof expansion type flame-proof rubber is characterized in that being made of the component of following weight per-cent:
Oil resisting rubber 40～60%
Resin viscosity conditioning agent 5～10%
Ammonium polyphosphate 20～40%
Trimeric cyanamide 3～10%
Zinc borate 2～8%
Nano-inorganic substance 5～20%
White carbon black 1～5%
Wherein oil resisting rubber is to be formed by vinylidene and perfluoro propylene copolymerization, and density is 1.80～1.84g/cm
3, ML 1+10, the Mooney viscosity 10～50 under 121 ℃; Wherein the resin viscosity conditioning agent is made up of thermosetting resin 663UE, 1～5%KR120 resin and 2～8% triphenylphosphates of weight percent 1～5% molecular weight 1800.
2. according to the described a kind of oil resistant of claim 1, heat resistant fire-proof expansion type flame-proof rubber, it is characterized in that: described nano-inorganic substance is the mixture of nano titanium oxide, nano-sized magnesium hydroxide.
3. according to the described a kind of oil resistant of claim 1, heat resistant fire-proof expansion type flame-proof rubber, it is characterized in that: the preparation method of this oil resistant, heat resistant fire-proof expansion type flame-proof rubber adopts twin-roll plastic mixing mill mixing, 70～100 ℃ of melting temperatures, mixing time 6～12min; Adopt vulcanizing press, with expandable flame retardant rubber compression moulding, 80～120 ℃ of press temperatures, press time 2～6min, expandable flame retardant rubber thickness of sample≤1mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100570921A CN101220191B (en) | 2008-01-29 | 2008-01-29 | Grease-proof, heat-resistant expansion type flame-proof rubber |
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| CN2008100570921A CN101220191B (en) | 2008-01-29 | 2008-01-29 | Grease-proof, heat-resistant expansion type flame-proof rubber |
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| CN101220191A CN101220191A (en) | 2008-07-16 |
| CN101220191B true CN101220191B (en) | 2011-05-18 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311631B (en) * | 2011-08-30 | 2013-01-09 | 芜湖禾田汽车工业有限公司 | Oil resistant rubber |
| CN102367329B (en) * | 2011-09-02 | 2012-12-19 | 芜湖禾田汽车工业有限公司 | Heat-resisting and oil-resisting rubber and preparation method thereof |
| CN103183848B (en) * | 2013-04-15 | 2016-01-06 | 桂林电子科技大学 | A kind of fast-curing low-smoke and halogen-free fire-retardant rubber CABLE MATERIALS and preparation method |
| CN103642158A (en) * | 2013-11-27 | 2014-03-19 | 太仓市晨洲塑业有限公司 | Cable protection pipe |
| CN104086973A (en) * | 2014-06-27 | 2014-10-08 | 匡铁铃 | Flame-retardant cold-resistant rubber |
| EP3690000B1 (en) * | 2017-11-02 | 2024-02-07 | Daikin Industries, Ltd. | Fluorine-containing elastomer composition for heat dissipation material and sheet thereof |
| CN108864691A (en) * | 2018-06-27 | 2018-11-23 | 滁州环球聚氨酯科技有限公司 | A kind of compound polyurethane material of oil-resisting and heat-resisting |
| CN114672266B (en) * | 2020-12-24 | 2024-02-20 | 深圳科创新源新材料股份有限公司 | Fireproof plugging plate and preparation method and application thereof |
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