CN1322044C - Microcapsulized expansion type flame-proof rubber and its preparation method - Google Patents
Microcapsulized expansion type flame-proof rubber and its preparation method Download PDFInfo
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- CN1322044C CN1322044C CNB2005100288397A CN200510028839A CN1322044C CN 1322044 C CN1322044 C CN 1322044C CN B2005100288397 A CNB2005100288397 A CN B2005100288397A CN 200510028839 A CN200510028839 A CN 200510028839A CN 1322044 C CN1322044 C CN 1322044C
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 45
- 239000005060 rubber Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003063 flame retardant Substances 0.000 claims abstract description 62
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 39
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 15
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008117 stearic acid Substances 0.000 claims abstract description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 23
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 18
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 18
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 18
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 17
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 14
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229940059574 pentaerithrityl Drugs 0.000 claims description 14
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 14
- 238000005538 encapsulation Methods 0.000 claims description 13
- 239000003094 microcapsule Substances 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002775 capsule Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- -1 nano zine oxide Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 3
- 229920003052 natural elastomer Polymers 0.000 claims description 3
- 229920001194 natural rubber Polymers 0.000 claims description 3
- 229920013649 Paracril Polymers 0.000 claims description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 2
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 2
- 230000003712 anti-aging effect Effects 0.000 abstract 1
- 239000011787 zinc oxide Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229960004279 formaldehyde Drugs 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000779 smoke Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000013536 elastomeric material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003340 retarding agent Substances 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000003913 Coccoloba uvifera Nutrition 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 244000286663 Ficus elastica Species 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 240000008976 Pterocarpus marsupium Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000003351 stiffener Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses a microencapsulation expansion type flame retardant rubber and a preparation method thereof. The method comprises the following steps: rubber elements, nanometer zinc oxide, stearic acid, an accelerating agent M, an accelerating agent DM, an accelerating agent CZ, an antiaging agent A, a microencapsulation flame retardant, light calcium carbonate, a vulcanizing agent, etc. in a proportion are sequentially put into a rubber mill and compounded at a temperature condition of 30 to 85 DEG C for 0.5 to 1 hour by adopting a traditional method for obtaining the rubber of the present invention. Due to the adoption of the microencapsulation flame retardant, the rubber has excellent interface compatibility efficiency and flame-retardant synergistic effect so that the mechanical properties and the flame retardant property of the rubbery material can be improved to a great extent.
Description
Technical field
The present invention relates to a kind of flame retardant rubber, be specifically related to rubber that contains microcapsule intumescent flame retardant and preparation method thereof.
Background technology
Natural rubber and most of synthetic rubber all are combustible or inflammable, especially with hydrocarbon rubbers for very, this is rubber and the major defect of goods on using thereof.Electric wire, cable sheathing, sheath, rope, the conveying belt that mine uses down, sebific duct, wheel lining, ventilating duct, the string rubber that uses on the vacuum pump, the various rubber items that use on electronics, the electrical equipment industry, the India-rubber strip that uses on the elevator door, and the rubber item that uses on the automobile, aircraft, steamer, hospital, station, kino, the rubber plate that public places such as railway carriage use, the most important property of their fire-retardantization is conspicuous.
It is fire-retardant that most anti-flaming rubber products all uses additive flame retardant to carry out.
Expansion type flame retardant is a kind ofly can generate layer of even carbonaceous foam layer on the surface when superpolymer is heated, and heat insulation, oxygen barrier, presses down cigarette, and can prevent to produce the novel additive type fire retardant of molten drop, has good flame retardancy.But the physical and mechanical properties of material itself is descended greatly as if it is directly applied to.For this reason, people wish to improve its flame retardant properties under the prerequisite of the physical and mechanical properties of not destroying material itself.
The domestic typical patent that at present not only relates to microcapsule but also relate to expansion type flame retardant has two.(CN 02114073.1) discloses a kind of micro-encapsulated expansion-type N-P flame-retarding agent production method.This method is that nitrogen-phosphorus fire retardant is crushed to particle diameter less than 400 orders, be scattered in the inert solvent with unsaturated polyester resin then, add initiator, be warmed up to 80-100 ℃, make unsaturated polyester resin generation curing reaction, thereby obtain the nitrogen-phosphorus fire retardant microcrystals, form the product of the extremely thin resin of one deck on its surface, i.e. the microcapsule expansion-type N-P flame-retarding agent.This product and IFR-2000 are suitable, when 0.20% during its water-soluble during by original 20 ℃ 0.12%, 100 ℃ is reduced to 20 ℃ 0.04%, 100 ℃ the time 0.07%.
(CN 03116283.5) discloses a kind of method about the ammonium polyphosphate micro encapsulation.This method is suspended in the ammonium polyphosphate powder in the dispersion liquid in reactor, under 60-150 ℃, add melamine-formaldehyde prepolymer or directly add melamine and formaldehyde is done resin-coated, and stiffening agent, stirring reaction adds the formaldehyde benefit again and catches agent after reaction finishes, continued stirring reaction 10-30 minute at 30-60 ℃, filter and the dry reaction product, promptly get the ammonium polyphosphate powder that microcapsule coat.This microcapsule-coated ammonium polyphosphate does not obviously increase the particulate good fluidity with comparing of not coating, median size, coating is evenly fine and close, and water-soluble reduction greatly can be used as polyolefine, the fire retardant of macromolecular materials such as urethane also can be used for the fire-retardant of paper, timber, fabric etc.
The technology of above-mentioned patent disclosure also exists and can not satisfy the defective of people to Flame Retardancy energy demand side, for example: aspect the expanded thickness of type, the proportioning of each component of expansion type flame retardant (acid source, source of the gas and charcoal source) and the final charcoal layer that caused, can't satisfy the application requiring in relevant field fully, need improve.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of Microencapsulation Intumescent Flame-Retardant Rubber And Its Preparation Method, are used for overcoming the defective of current material.
Technical scheme of the present invention
The elastomeric material that contains microcapsule intumescent flame retardant of the present invention, its component is basic identical with conventional rubber, and the parts by weight of each component are as follows:
Rubber matrix 100
Vulcanizing agent 1.5～4
Captax 0.5～1.5
Altax 0.3～1.0
Accelerant CZ 0.5～1.5
Stearic acid 0.8～2.0
Nano zine oxide 1～3
Antioxidant A 0.5～1.5
Light calcium carbonate 20～60
Microcapsule intumescent flame retardant 40～80
Rubber matrix comprises natural rubber, styrene-butadiene rubber(SBR), paracril, polyurethane elastomer or its mixture;
Vulcanizing agent is a sulphur;
The chemical name of captax is the 2-benzothiazolyl mercaptan;
The chemical name of altax is a dibenzothiazyl disulfide;
The chemical name of accelerant CZ is a N cyclohexyl 2 benzothiazole sulfenamide;
Nano zine oxide and stearic acid are vulcanization leveller, and wherein, the particle diameter of nano zine oxide is 10～80nm;
The chemical name of antioxidant A is the N-phenyl-a-naphthylamine;
Microcapsule intumescent flame retardant is a kind of micro encapsulation material, and capsule-core is a fire retardant, and the weight ratio of composition is:
Ammonium polyphosphate: tetramethylolmethane: trimeric cyanamide=3: 1～2: 1～2;
Capsule nuclear consists of terpolycyantoamino-formaldehyde resin, and particle diameter is 1～500 μ m;
Said capsule nuclear is wrapped in outside the capsule-core, constitutes a kind of microcapsule intumescent flame retardant;
Capsule nuclear with the weight ratio of capsule-core is: capsule nuclear: capsule-core=1: 4～5.
The preparation method of above-mentioned microcapsulized expansion type flame-proof rubber comprises the steps:
(1) preparation of microcapsule intumescent flame retardant:
Ammonium polyphosphate, tetramethylolmethane and trimeric cyanamide are scattered in the water, add the melmac prepolymer again, stir, obtain a kind of stable dispersion liquid, be heated to 90～100 ℃, be 2～4 hours heat-up time, at this moment form the fine and close continuously resin film of one deck on the fire retardant surface, whole system becomes thick material, puts into loft drier, dry under 100～110 ℃ temperature, the micro encapsulation fire retardant that gets final product requiredly;
Contain in the aqueous solution of ammonium polyphosphate, tetramethylolmethane and trimeric cyanamide, the total weight concentration of ammonium polyphosphate, tetramethylolmethane and trimeric cyanamide is 60～80%; The weight consumption of melmac prepolymer is 20～25% of ammonium polyphosphate, tetramethylolmethane and a trimeric cyanamide gross weight;
Said melmac prepolymer is a kind of low viscous polymkeric substance, and the preparation method of this melmac prepolymer has had disclosed report in CN 03116283.5 patent, and the present invention repeats no more;
(2) successively rubber matrix, nano zine oxide, stearic acid, captax, altax, accelerant CZ, antioxidant A, micro encapsulation fire retardant, light calcium carbonate and vulcanizing agent etc. are dropped in the mill under temperature is 30～85 ℃ condition according to aforementioned proportion, use conventional methods mixing 0.5～1 hour, promptly obtain rubber of the present invention.
Because adopt the micro encapsulation fire retardant, good interface co-operative effect and flame retardant synergistic effect that it shows make that the mechanical property of elastomeric material and flame retardant properties are improved largely.
Embodiment
Comparative Examples 1
With 3
#Smoke sheet rubber: 100 parts; Sulphur: 1.5 parts; Captax: 0.5 part; Altax: 0.3 part; Stearic acid: 0.8 part; Nano zine oxide: 1 part; Antioxidant A: 0.5 part; Light calcium carbonate: 60 parts; Expansion type flame retardant (ammonium polyphosphate: trimeric cyanamide: tetramethylolmethane=3: 2: 2, weight ratio): 40 parts, place mill, mixing under 55 ℃ temperature (mixing take traditional method) promptly gets flame retardant rubber.
According to GB 528-83, GB/T1689 and GB/T10707 standard are carried out physical mechanical and flame retardant properties test, result such as table 1.
Comparative Examples 2
With 3
#Smoke sheet rubber: 100 parts; Sulphur: 1.5 parts; Captax: 0.5 part; Altax: 0.5 part; Stearic acid: 1.2 parts; Nano zine oxide: 2 parts; Antioxidant A: 1 part; Light calcium carbonate: 60 parts; Expansion type flame retardant (ammonium polyphosphate: trimeric cyanamide: tetramethylolmethane=3: 1: 1, weight ratio): 50 parts, place mill, mixing under 55 ℃ temperature (mixing take traditional method) promptly gets flame retardant rubber.
According to GB 528-83, GB/T1689 and GB/T10707 standard are carried out physical mechanical and flame retardant properties test, result such as table 1.
Comparative Examples 3
With 3
#Smoke sheet rubber: 100 parts; Sulphur: 4 parts; Captax: 1.5 parts; Altax: 1 part; Stearic acid: 2 parts; Nano zine oxide: 3 parts; Antioxidant A: 1.5 parts; Light calcium carbonate: 60 parts; Expansion type flame retardant (ammonium polyphosphate: trimeric cyanamide: tetramethylolmethane=3: 2: 1, weight ratio): 60 parts, place mill, mixing under 55 ℃ temperature (mixing take traditional method) promptly gets flame retardant rubber.
According to GB 528-83, GB/T1689 and GB/T10707 standard are carried out physical mechanical and flame retardant properties test, result such as table 1.
Embodiment 1
Have in the 250ml there-necked flask of agitator, reflux condensing tube, thermometer one, the formaldehyde solution that adds 80g, 8g methyl alcohol and 19g diethanolamine with this mixture heating up to 90 ℃, keep 2h, then the 21g trimeric cyanamide is added wherein, said mixture is being warming up to 90 ℃, is keeping 6h, making the melamino-for maldehyde polycondensate, add 40ml water again, make the melmac prepolymer.
Get 30g expansion type flame retardant (ammonium polyphosphate: trimeric cyanamide: tetramethylolmethane=3: 2: 2, weight ratio) and be scattered in the 75ml water, add the above-mentioned preshrunk liquid of 10ml again, stir, make it to become a kind of stable dispersion liquid, be heated to 100 ℃, keep 1h.In this process, the preshrunk thing becomes gradually insoluble (overflowing with formaldehyde), slowly forms the fine and close continuously resin film of one deck simultaneously uniformly on the fire retardant surface, and whole system becomes thick material, puts into loft drier 100 ℃ of dryings.Grind into powder promptly gets required micro encapsulation fire retardant then.
With 3
#Smoke sheet rubber: 100 parts; Sulphur: 1.5 parts; Captax: 0.5 part; Altax: 0.3 part; Stearic acid: 0.8 part; Nano zine oxide: 1 part; Antioxidant A: 0.5 part; Light calcium carbonate: 60 parts; The micro encapsulation fire retardant: 40 parts, place mill, under 55 ℃ temperature mixing 1 hour, (mixing take traditional method) promptly obtained rubber of the present invention.
According to GB 528-83, GB/T1689 and GB/T10707 standard are carried out physical mechanical and flame retardant properties test, result such as table 1.
Embodiment 2
Have in the 250ml there-necked flask of agitator, reflux condensing tube, thermometer one, the formaldehyde solution that adds 90g, 10g methyl alcohol and 23g diethanolamine with this mixture heating up to 90 ℃, keep 3h, then the 25g trimeric cyanamide is added wherein, said mixture is being warming up to 90 ℃, is keeping 6h, making the melamino-for maldehyde polycondensate, add 50ml water again, make the melmac prepolymer.
Get 40g expansion type flame retardant (ammonium polyphosphate: trimeric cyanamide: tetramethylolmethane=3: 1: 1, weight ratio) and be scattered in the 85ml water, add the above-mentioned preshrunk liquid of 20ml again, stir, make it to become a kind of stable dispersion liquid, be heated to 100 ℃, keep 3h.In this process, the preshrunk thing becomes gradually insoluble (overflowing with formaldehyde), slowly forms the fine and close continuously resin film of one deck simultaneously uniformly on the fire retardant surface, and whole system becomes thick material, puts into loft drier 105 ℃ of dryings.Grind into powder promptly gets required micro encapsulation fire retardant then.
With 3
#Smoke sheet rubber: 100 parts; Sulphur: 1.5 parts; Captax: 0.5 part; Altax: 0.5 part; Stearic acid: 1.2 parts; Nano zine oxide: 2 parts; Antioxidant A: 1 part; Light calcium carbonate: 60 parts; Light calcium carbonate: 60 parts; Micro encapsulation fire retardant: 50 parts.Place mill, under 85 ℃ temperature mixing 0.5 hour, (mixing take traditional method) promptly obtained rubber of the present invention.
According to GB 528-83, GB/T1689 and GB/T10707 standard are carried out physical mechanical and flame retardant properties test, result such as table 1.
Embodiment 3
Have in the 250ml there-necked flask of agitator, reflux condensing tube, thermometer one, the formaldehyde solution that adds 100g, 12g methyl alcohol and 28g diethanolamine with this mixture heating up to 90 ℃, keep 4h, then the 30g trimeric cyanamide is added wherein, said mixture is being warming up to 90 ℃, is keeping 6h, making the melamino-for maldehyde polycondensate, add 60ml water again, make the melmac prepolymer.
Get 50g expansion type flame retardant (ammonium polyphosphate: trimeric cyanamide: tetramethylolmethane=3: 2: 1, weight ratio) and be scattered in the 95ml water, add the above-mentioned preshrunk liquid of 30ml again, stir, make it to become a kind of stable dispersion liquid, be heated to 100 ℃, keep 2h.In this process, the preshrunk thing becomes gradually insoluble (overflowing with formaldehyde), slowly forms the fine and close continuously resin film of one deck simultaneously uniformly on the fire retardant surface, and whole system becomes thick material, puts into loft drier 110 ℃ of dryings.Grind into powder promptly gets required micro encapsulation fire retardant then.
With 3
#Smoke sheet rubber: 100 parts; Sulphur: 4 parts; Captax: 1.5 parts; Altax: 1 part; Stearic acid: 2 parts; Nano zine oxide: 3 parts; Antioxidant A: 1.5 parts; Light calcium carbonate: 60 parts; Micro encapsulation fire retardant: 60 parts.Place mill, mixing 0.75 hour (mixing take traditional method) promptly obtains rubber of the present invention under 65 ℃ temperature.
According to GB 528-83, GB/T1689 and GB/T10707 standard are carried out physical mechanical and flame retardant properties test, result such as table 1.
Table 1
| Embodiment | Tensile strength/MPa | Elongation at break/% | Abrasion volume/cm 3 | Limiting oxygen index(LOI)/% |
| Comparative Examples 1 | 7.79 | 470 | 1.0924 | 20.2 |
| Comparative Examples 2 | 7.66 | 469 | 1.2536 | 21.4 |
| Comparative Examples 3 | 6.25 | 456 | 1.4897 | 22.6 |
| Embodiment 1 | 8.07 | 579 | 0.4276 | 23.5 |
| Embodiment 2 | 11.55 | 740 | 0.2451 | 25.6 |
| Embodiment 3 | 9.59 | 730 | 0.2882 | 27.5 |
Claims (8)
1. microcapsulized expansion type flame-proof rubber is characterized in that, the parts by weight of component are as follows:
Rubber matrix 100
Vulcanizing agent 1.5～4
Captax 0.5～1.5
Altax 0.3～1.0
Accelerant CZ 0.5～1.5
Stearic acid 0.8～2.0
Nano zine oxide 1～3
Antioxidant A 0.5～1.5
Light calcium carbonate 20～60
Microcapsule intumescent flame retardant 40～80
The chemical name of captax is the 2-benzothiazolyl mercaptan;
The chemical name of altax is a dibenzothiazyl disulfide;
The chemical name of accelerant CZ is a N cyclohexyl 2 benzothiazole sulfenamide;
The chemical name of antioxidant A is the N-phenyl-a-naphthylamine;
The capsule-core of microcapsule intumescent flame retardant is a fire retardant, and the weight ratio of composition is:
Ammonium polyphosphate: tetramethylolmethane: trimeric cyanamide=3: 1～2: 1～2;
Capsule nuclear is terpolycyantoamino-formaldehyde resin;
Said capsule nuclear is wrapped in outside the capsule-core.
2. microcapsulized expansion type flame-proof rubber according to claim 1 is characterized in that, rubber matrix comprises a kind of or its mixture in natural rubber, styrene-butadiene rubber(SBR), paracril or the polyurethane elastomer.
3. microcapsulized expansion type flame-proof rubber according to claim 1 is characterized in that, vulcanizing agent is a sulphur.
4. microcapsulized expansion type flame-proof rubber according to claim 1 is characterized in that, the particle diameter of nano zine oxide is 10～80nm.
5. microcapsulized expansion type flame-proof rubber according to claim 1 is characterized in that, the capsule karyosome directly is 1～500 μ m.
6. microcapsulized expansion type flame-proof rubber according to claim 1 is characterized in that, capsule nuclear with the weight ratio of capsule-core is: capsule nuclear: capsule-core=1: 4～5.
7. according to the preparation method of each described microcapsulized expansion type flame-proof rubber of claim 1～6, it is characterized in that, comprise the steps:
(1) preparation of microcapsule intumescent flame retardant:
Ammonium polyphosphate, tetramethylolmethane and trimeric cyanamide are scattered in the water, add the melmac prepolymer again, stir, obtain dispersion liquid, be heated to 90～100 ℃, drying obtains the micro encapsulation fire retardant;
(2) be mixing under 30～85 ℃ the condition successively with rubber matrix, nano zine oxide, stearic acid, captax, altax, accelerant CZ, antioxidant A, micro encapsulation fire retardant, light calcium carbonate and vulcanizing agent, promptly obtain product in temperature.
8. method according to claim 7 is characterized in that, the weight consumption of melmac prepolymer is 20～25% of ammonium polyphosphate, tetramethylolmethane and a trimeric cyanamide gross weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100288397A CN1322044C (en) | 2005-08-16 | 2005-08-16 | Microcapsulized expansion type flame-proof rubber and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100288397A CN1322044C (en) | 2005-08-16 | 2005-08-16 | Microcapsulized expansion type flame-proof rubber and its preparation method |
Publications (2)
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| CN101392075B (en) * | 2007-09-21 | 2010-08-25 | 丹阳市金晟医用橡塑制品有限公司 | Formula for synthesizing rubber injection member for disposable infusion device and method for producing the same |
| CN101173079B (en) * | 2007-10-19 | 2010-04-14 | 东北林业大学 | Xylem filber-polyvinyl chloride composite material and method for producing the same |
| CN101475730B (en) * | 2009-01-15 | 2012-08-15 | 中国石油大学(北京) | Preparation of bilaminar membrane sulfur microcapsule |
| CN101481471B (en) * | 2009-02-17 | 2012-11-14 | 中国石油大学(北京) | Raw materials formula for producing single-shell sulfur microcapsule |
| CN101792544B (en) * | 2010-03-30 | 2011-08-24 | 上海工程技术大学 | Environment-friendly flame retardant rubber material and preparation method thereof |
| EP2871208A1 (en) * | 2013-11-08 | 2015-05-13 | Carl-Eric Wilen | Sulfenamides, sulfinamides and sulfonamides as flame retardants |
| CN103724666B (en) * | 2013-12-26 | 2015-09-02 | 辽宁工程技术大学 | A kind of composite flame-retardant agent and preparation method containing microcapsule coated expanding fire retardant |
| CN104893035A (en) * | 2015-04-29 | 2015-09-09 | 安徽嘉木橡塑工业有限公司 | Roller rubber coated layer |
| SK288796B6 (en) * | 2016-04-16 | 2020-11-03 | Movychem S R O | Method of production of fire impregnation substance, mainly for construction products, fire impregnation substance and use of thereof |
| CN106009103A (en) * | 2016-06-23 | 2016-10-12 | 山东永泰集团有限公司 | Oil-resistant and flame-retardant rubber |
| CN108359149A (en) * | 2018-02-10 | 2018-08-03 | 石磊 | A kind of preparation method of expansion type flame-proof rubber |
| CN109227835A (en) * | 2018-10-18 | 2019-01-18 | 袁志伟 | A kind of novel environment friendly timber special environment protection fire retardant and its application method |
| CN110964232B (en) * | 2019-12-03 | 2021-07-16 | 苏州诺博恩新材料科技有限公司 | Efficient environment-friendly microcapsule flame retardant with multilayer structure and preparation method thereof |
| CN112724729A (en) * | 2020-12-24 | 2021-04-30 | 三棵树(上海)新材料研究有限公司 | Double-wall-layer intumescent fire retardant co-microcapsule and preparation method thereof |
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