CN104292525B - A kind of flame retardant rubber and preparation method thereof - Google Patents
A kind of flame retardant rubber and preparation method thereof Download PDFInfo
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- CN104292525B CN104292525B CN201410604313.8A CN201410604313A CN104292525B CN 104292525 B CN104292525 B CN 104292525B CN 201410604313 A CN201410604313 A CN 201410604313A CN 104292525 B CN104292525 B CN 104292525B
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- flame retardant
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- retardant rubber
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 68
- 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 title claims abstract description 44
- 229920001971 elastomer Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 41
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 41
- 229920001194 natural rubber Polymers 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 8
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- -1 organo montmorillonite Chemical compound 0.000 claims description 27
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 17
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 8
- 238000004513 sizing Methods 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000006957 Michael reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 238000010074 rubber mixing Methods 0.000 claims description 5
- 238000005987 sulfurization reaction Methods 0.000 claims description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000412 dendrimer Substances 0.000 claims description 4
- 229920000736 dendritic polymer Polymers 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 3
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical compound [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 claims description 3
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 claims description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 230000004580 weight loss Effects 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 239000013536 elastomeric material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229940059260 amidate Drugs 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- AIRPJJGSWHWBKS-UHFFFAOYSA-N hydroxymethylphosphanium;chloride Chemical compound [Cl-].OC[PH3+] AIRPJJGSWHWBKS-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 125000001453 quaternary ammonium group Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004760 silicates Polymers 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- LOZAIRWAADCOHQ-UHFFFAOYSA-N triphosphazene Chemical compound PNP=NP LOZAIRWAADCOHQ-UHFFFAOYSA-N 0.000 description 1
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
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
- B29B7/726—Measuring properties of mixture, e.g. temperature or density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
- B29B7/728—Measuring data of the driving system, e.g. torque, speed, power, vibration
-
- 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
- C08K3/346—Clay
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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)
- Mechanical Engineering (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of flame retardant rubber and preparation method thereof, prepared by the raw material of following component and weight part content: natural rubber matrix 100; Vulcanizing agent 2 ~ 4; Promotor 2 ~ 4; Fire retardant 1 ~ 10; Processing aid 2 ~ 6; Anti-aging agent 3 ~ 5.Compared with prior art, the thermal weight loss core temperature of the flame retardant rubber that the present invention prepares is 396.3 DEG C, rate of combustion is 19.48mm*min, achieve with the organic imvite modified natural rubber of dendriform, obtain the Flame-retardant natural rubber that the performances such as fire-retardant, thermally-stabilised and mechanics are all excellent, and the controlled stripping of polynite achieved wherein and dispersed in polymeric matrix thereof and the excellent compatibility with polymkeric substance.
Description
Technical field
The invention belongs to technical field of rubber material, especially relate to a kind of flame retardant rubber and preparation method thereof.
Background technology
The natural high moleculer eompound of natural rubber to be a kind of with polyisoprene be main component, molecular formula is (C5H8) n, in its composition, 91% ~ 94% is rubber hydrocarbon (polyisoprene), and all the other are the nonrubber materials such as protein, lipid acid, ash content, carbohydrate.Natural rubber is most widely used conventional rubber.Natural rubber, as general elastomeric material, is widely used in automobile, plane tyre, adhesive tape, sebific duct, water-proof material, and rubber overshoes, gloves, electrical accessorie etc., and the life of people is closely bound up.But general natural rubber oxygen index is about 17%, and easily burn, and can discharge a large amount of black smoke in combustion, therefore fire-retardant the and thermal stability of natural rubber is extremely important.
Traditional halogen fire retardant can reach good flame retardant effect, but it can discharge poisonous hydrogen halide in combustion, works the mischief to human body, environment; And inorganic fire-retarded filler often needs very high addition could meet flame-retardancy requirements, but affect the use properties of material.The fire-retardant fire retardant mostly still adopted containing halogen of current natural rubber, along with people are to environmental protection and the raising to material performance requirement, develops the focus that novel effective, eco-friendly fire retardant systems has become research.
In recent years, along with people are to the further investigation of nanotechnology, utilize some special effectses of the size of nanometer fire-retardant to realize, cause the attention of people.Nano-meter flame retardants, generally comprises nano-powder and the large class of layered silicate two.Nano-powder is mainly nano-sized magnesium hydroxide, nano-aluminum hydroxide etc., but their addition generally all will reach more than 30 parts just shows good flame retardant effect.And the organic layered silicate salt/polymer nanocomposites utilizing intercalation technique to prepare is compared with traditional filled polymer, the mechanical property of polymeric matrix, gas barrier property and solvent resistance can not only be improved, also there is potential flame retardant resistance and burn from putting out the features such as feature.
Result of study shows, the dendriform organo montmorillonite price that both alternative or Some substitute was traditional is higher, environment is unfriendly and the fire-retardant and supporting material of other performance of infringement polymkeric substance, as: halogen flame, expansion type flame retardant, hydroxide flame retardant, white carbon black and carbon black etc., can improve again the performances such as the fire-retardant of elastomeric material and mechanics.But how to use dendriform organo montmorillonite to carry out modification to natural rubber, realize the controlled stripping of polynite and the dispersed and consistency in polymeric matrix thereof, obtain the Flame-retardant natural rubber that flame retardant effect, thermostability and mechanical property are all excellent, relevant report that so far there are no.
Chinese patent CN101792544 discloses environment-friendly flame retardant rubber material and preparation method thereof, its component comprises rubber matrix, vulcanizing agent, promotor, stearic acid, zinc oxide, anti-aging agent, fire retardant etc., the flame retardant rubber good flame retardation effect prepared, mechanical property and wear resisting property relative good.What above-mentioned fire retardant was chosen is quaternary ammonium salt and polynite react make organo montmorillonite, its mechanical property and flame retardant effect are comparatively worse than the dendriform montmorillonite flame-retardant agent in this patent.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and a kind of application requiring meeting natural rubber is provided.
Object of the present invention can be achieved through the following technical solutions:
A kind of flame retardant rubber, is prepared by the raw material of following component and weight part content:
Natural rubber matrix 100; Vulcanizing agent 2 ~ 4; Promotor 2 ~ 4; Fire retardant 1 ~ 10; Processing aid 2 ~ 6; Anti-aging agent 3 ~ 5.
Described fire retardant is dendriform organo montmorillonite, this organo montmorillonite take hexachlorocyclotriphosphazene as core by the Michael reaction of quadrol and methyl acrylate, the dendritic polymer of synthesis containing phosphorus nitrogen, and undertaken organically-modified by MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, synthesis organo montmorillonite, finally carries out modification to the Amino End Group synthesizing the dendritic polymer obtained.
Sodium methylate is added as catalyzer in described Michael reaction.
Described vulcanizing agent is sulphur.
Described promotor is 2-benzothiazolyl mercaptan and Sodium dimethyldithiocarbamate 40min is 2: 1 ~ 6: 1 compound formed in mass ratio.
Described processing aid is stearic acid and zinc oxide 1: 3 ~ 3: 1 compound formed in mass ratio.
Described anti-aging agent is N-sec.-propyl-N '-diphenyl-para-phenylene diamine.
The preparation method of flame retardant rubber adopts following steps:
A) regulate the roller temperature of rubber mixing mill between 30 ~ 60 DEG C, natural rubber matrix, promotor, processing aid and anti-aging agent are dropped in mill carry out mixing 20 ~ 30min successively;
B) adjust the roll spacing of mill to 0.5 ~ 1.5mm, add fire retardant, smash glue, mixing 5 ~ 15min;
C) adjust the roll spacing of mill again to 3 ~ 5mm, continue mixing 10 ~ 20min, until form the sizing material of smooth zero-clearance;
D) by step c) gained sizing material roll-in slice, after film at room temperature naturally cooling, again drops in mill, adds vulcanizing agent, carry out discharging, sulfuration, prepare flame retardant rubber.
The present invention adopts dendriform polynite as fire retardant, mainly there is the hexachlorocyclotriphosphazene of higher thermal temperature performance for core with phosphorous, nitrogen, the dendritic flame-retardant polymkeric substance of 24 arm ends is synthesized by the Michael addition of methyl acrylate that replaces and the amidate action of quadrol, and react with the organo montmorillonite after quaternary ammonium salt-MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) intercalation with high thermal stability, final dendritic flame-retardant polynite.The final residual volume of this dendritic flame-retardant polynite is 61%, and thermal weight loss core temperature is 200.2 DEG C.And the dendritic flame-retardant polynite in Zhao Yi master thesis carries out organic modification by Tetrakis hydroxymethyl phosphonium chloride (THPC) to sodium-based montmorillonite, modified organo montmorillonite and AB
2intermediate (diethanolamine and methyl acrylate generation Michael reaction, thus prepare end group and contain hydroxyl, and there is the compound of ester group one end) step reaction, final dendritic flame-retardant polynite.Because the thermal stability of this intermediate is lower, so the thermal stability of dendritic flame-retardant polynite is lower.
Compared with prior art, the thermal weight loss core temperature of the flame retardant rubber that the present invention prepares is 396.3 DEG C, rate of combustion is 19.48mm*min, achieve with the organic imvite modified natural rubber of dendriform, obtain the Flame-retardant natural rubber that the performances such as fire-retardant, thermally-stabilised and mechanics are all excellent, and the controlled stripping of polynite achieved wherein and dispersed in polymeric matrix thereof and the excellent compatibility with polymkeric substance, and use safety environmental protection, there is potential economic benefit and social effect.
Embodiment
Below in conjunction with embodiment and comparative example, technical scheme of the present invention is described in further detail and completely.Organo montmorillonite described in embodiment and dendriform organo montmorillonite are all adopt following methods to prepare: the inorganic polynite of 20g adds in deionized water, is mixed with the suspension that massfraction is 5%; Gained suspension is placed in the water bath with thermostatic control of 60 DEG C, 30g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is added in suspension, finishes, insulation reaction 5h under violent stirring, filters, with deionized water wash filter cake to existing without Cl-, 80 DEG C of oven dry, obtain the organo montmorillonite of modification.In flask, add 2.5g massfraction is that the G-1 of 20% is for the methanol aqueous solution of Amino End Group polyamidoamine Triphosphazene dendritic macromole; under N2 protection; the organo montmorillonite 10g that modification obtains slowly is added at 50 DEG C; finish; insulation reaction 7h under violent stirring; filter, dry pale powder solid, be high heat-resisting, the high fire retardant pressing down cigarette.Embodiment is tested the physical and mechanical properties of obtained flame-retardant natural rubber and flame retardant properties with reference to GB528-83 and GB/T10707 standard.Adopt the thermogravimetry that " nano composite polymer/laminated silicate material theory and practice " (QiZongNeng, Shang Wenyu writes, Chemical Industry Press, 2002) specifies, the thermal weight loss core temperature of test Flame-retardant natural rubber, T
max.
Embodiment 1
Regulate the roller temperature of rubber mixing mill to 30 DEG C, successively 100g natural rubber matrix, 2g captax, 0.5g promotor S, 1g stearic acid, 1g zinc oxide, 3g antioxidant 4010 A are dropped in mill, mixing 20min;
Adjustment roll spacing, to 0.5mm, adds 1g dendriform organo montmorillonite, smashes glue, mixing 5min; Adjust roll spacing again to 3mm, continue mixing about 10min, until form the glue-line of smooth zero-clearance;
By gained sizing material roll-in slice, treat film at room temperature naturally cooling 8h, again drop in mill, add 2g sulphur, carry out discharging, sulfuration, obtain described Flame-retardant natural rubber.
The tensile strength of gained natural rubber, elongation at break, horizontal burn rate and thermal weight loss core temperature (T
max) test data in table 1.
Comparative example 1
By 100g natural rubber, 2g sulphur, 2g captax, 0.5g promotor S, 1g organo montmorillonite, 1g stearic acid, 1g zinc oxide and 3g antioxidant 4010NA, drop in mill, evenly mixing at 30 DEG C, obtain common natural rubber.
The tensile strength of common natural rubber, elongation at break, horizontal burn rate and thermal weight loss core temperature (T
max) test data in table 1.
Embodiment 2
Regulate the roller temperature of rubber mixing mill to 45 DEG C, successively by 100g natural rubber, 2.5g captax, 0.7g promotor S, 2g stearic acid, 2g zinc oxide, 4g antioxidant 4010NA, drop in mill, mixing 25min;
Adjustment roll spacing, to 1mm, adds 5g dendriform organo montmorillonite, smashes glue, mixing 10min; Adjust roll spacing again to 4mm, continue mixing 15min, until form the glue-line of smooth zero-clearance;
By gained sizing material roll-in slice, treat film at room temperature naturally cooling 16h, again drop in mill, add 3g sulphur, carry out discharging, sulfuration, obtain described Flame-retardant natural rubber.
The tensile strength of gained natural rubber, elongation at break, horizontal burn rate and thermal weight loss core temperature (T
max) test data in table 1.
Comparative example 2
100g natural rubber, 3g sulphur, 2.5g captax, 0.7g promotor S, 5g organo montmorillonite, 2g stearic acid, 2g zinc oxide and 4g antioxidant 4010NA are dropped in mill, evenly mixing at 45 DEG C, obtain common natural rubber.
The tensile strength of common natural rubber, elongation at break, horizontal burn rate and thermal weight loss core temperature (T
max) test data in table 1.
Embodiment 3
Regulate the roller temperature of rubber mixing mill to 60 DEG C, successively by 100g natural rubber, 3g captax, 0.9g promotor S, 3g stearic acid, 3g zinc oxide, 5g antioxidant 4010NA, drop in mill, mixing 30min;
Adjustment roll spacing, to 1.5mm, adds 10g dendriform organo montmorillonite, smashes glue, mixing 15min; Adjust roll spacing again to 5mm, continue mixing 20min, until form the glue-line of smooth zero-clearance;
By gained sizing material roll-in slice, treat film at room temperature naturally cooling 24h, again drop in mill, add 4g sulphur, carry out discharging, sulfuration, obtain described Flame-retardant natural rubber.
The tensile strength of gained natural rubber, elongation at break, horizontal burn rate and thermal weight loss core temperature (T
max) test data in table 1.
Comparative example 3
100g natural rubber, 4g sulphur, 3g captax, 0.9g promotor S, 10g organo montmorillonite, 3g stearic acid, 3g zinc oxide and 5g antioxidant 4010NA are dropped in mill, evenly mixing at 60 DEG C, obtain common natural rubber.
The tensile strength of common natural rubber, elongation at break, horizontal burn rate and thermal weight loss core temperature (T
max) test data in table 1.
Table 1
Can be shown by the test result of table 1: present invention achieves with the organic imvite modified natural rubber of dendriform, obtain fire-retardant, that the performance such as thermostability and mechanics is all excellent Flame-retardant natural rubber, and the controlled stripping of polynite achieved wherein and dispersed in polymeric matrix thereof and the excellent compatibility with polymkeric substance, significantly improve the smoke suppressing effect of natural gum.Visible, dendriform organo montmorillonite/natural rubber nano composite material a kind of novelly has flame-retarded efficiency and eco-friendly fire retardant material.
Finally be necessary described herein: above embodiment is only for being described in more detail technical scheme of the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (9)
1. a flame retardant rubber, is characterized in that, is prepared by the raw material of following component and weight part content:
Natural rubber matrix 100; Vulcanizing agent 2 ~ 4; Promotor 2 ~ 4; Fire retardant 1 ~ 10; Processing aid 2 ~ 6; Anti-aging agent 3 ~ 5;
Described fire retardant is dendriform organo montmorillonite, this organo montmorillonite take hexachlorocyclotriphosphazene as core by the Michael reaction of quadrol and methyl acrylate, the dendritic polymer of synthesis containing phosphorus nitrogen, and undertaken organically-modified by MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, synthesis organo montmorillonite, finally carries out modification to the Amino End Group synthesizing the dendritic polymer obtained.
2. a kind of flame retardant rubber according to claim 1, is characterized in that, adds sodium methylate as catalyzer in described Michael reaction.
3. a kind of flame retardant rubber according to claim 1, is characterized in that, described vulcanizing agent is sulphur.
4. a kind of flame retardant rubber according to claim 1, is characterized in that, described promotor is the compound that 2-benzothiazolyl mercaptan and Sodium dimethyldithiocarbamate 40min form for 2:1 ~ 6:1 in mass ratio.
5. a kind of flame retardant rubber according to claim 1, is characterized in that, described processing aid is stearic acid and the zinc oxide compound that forms of 1:3 ~ 3:1 in mass ratio.
6. a kind of flame retardant rubber according to claim 1, is characterized in that, described anti-aging agent is N-sec.-propyl-N '-diphenyl-para-phenylene diamine.
7. the preparation method of the flame retardant rubber according to any one of claim 1-6, is characterized in that, adopts following steps:
A) regulate the roller temperature of rubber mixing mill between 30 ~ 60 DEG C, evenly mixing by carrying out in natural rubber matrix, promotor, processing aid and the mill of anti-aging agent input successively;
B) adjust the roll spacing of mill to 0.5 ~ 1.5mm, add fire retardant, smash glue, mixing 5 ~ 15min;
C) adjust the roll spacing of mill again to 3 ~ 5mm, continue mixing, until form the sizing material of smooth zero-clearance;
D) by step c) gained sizing material roll-in slice, after film at room temperature naturally cooling, again drops in mill, adds vulcanizing agent, carry out discharging, sulfuration, prepare flame retardant rubber.
8. the preparation method of a kind of flame retardant rubber according to claim 7, is characterized in that, step a) middle mixing time is 20 ~ 30min.
9. the preparation method of a kind of flame retardant rubber according to claim 7, is characterized in that, step c) in mixing time be 10 ~ 20min.
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