CN103159867B - Preparation method of flame-retardant powdered rubber - Google Patents
Preparation method of flame-retardant powdered rubber Download PDFInfo
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- CN103159867B CN103159867B CN201110421192.XA CN201110421192A CN103159867B CN 103159867 B CN103159867 B CN 103159867B CN 201110421192 A CN201110421192 A CN 201110421192A CN 103159867 B CN103159867 B CN 103159867B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 84
- 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 62
- 229920001971 elastomer Polymers 0.000 title claims abstract description 59
- 239000005060 rubber Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 34
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 32
- -1 unsaturated fatty acids acid anhydrides Chemical class 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 229920000126 latex Polymers 0.000 claims description 20
- 235000021355 Stearic acid Nutrition 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- 239000008117 stearic acid Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000004816 latex Substances 0.000 claims description 15
- 239000002174 Styrene-butadiene Substances 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 13
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical group C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 10
- 239000011115 styrene butadiene Substances 0.000 claims description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 8
- 229920000459 Nitrile rubber Polymers 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000005189 flocculation Methods 0.000 claims description 6
- 230000016615 flocculation Effects 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 4
- 229920006173 natural rubber latex Polymers 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- NWADXBLMWHFGGU-UHFFFAOYSA-N dodecanoic anhydride Chemical compound CCCCCCCCCCCC(=O)OC(=O)CCCCCCCCCCC NWADXBLMWHFGGU-UHFFFAOYSA-N 0.000 claims description 2
- PKHMTIRCAFTBDS-UHFFFAOYSA-N hexanoyl hexanoate Chemical compound CCCCCC(=O)OC(=O)CCCCC PKHMTIRCAFTBDS-UHFFFAOYSA-N 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 9
- 230000002269 spontaneous effect Effects 0.000 abstract description 4
- 239000000843 powder Substances 0.000 description 30
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- 238000005070 sampling Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 229940096992 potassium oleate Drugs 0.000 description 4
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 241001122126 Carex secta Species 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention provides a preparation method of flame-retardant powdered rubber aiming at the phenomenon that spontaneous combustion is easily caused by improper handling in the process of storing and transporting powdered rubber.
Description
Technical field
The present invention relates to a kind of powdered rubber preparation method, specifically a kind of preparation method with flame-retarding characteristic powdered rubber.
Background technology
Powdered rubber median size is about 1mm, and its specific surface area is about 6 × 10
-4m
2/ g, in powdered rubber and air, the contact area of oxygen is much bigger compared with niggerhead, at the easy oxidized rejected heat of stacking states powder surface and then cause spontaneous combustion.Such as, the oxygen index of powder styrene butadiene rubber is 18% ~ 20%, belongs to flammable rubber, once powder styrene butadiene rubber dieseling occurs in storage process.
Due to powdered rubber or a kind of new type rubber product, seldom there is the bibliographical information about its flame retardant resistance.The flame resistant method in current niggerhead field mainly contains additional fire retardant and fires blend rubber two kinds of methods with difficulty.Additional fire retardant has inorganic combustion inhibitor and organic fire-retardant, the general tool cooling of inorganic combustion inhibitor and iris action, and common kind has aluminium hydroxide, magnesium hydroxide, boron system thing and molybdenum system thing etc.; Organic fire-retardant is then based on brominated, chlorine or phosphorous organic compound, and brominated flame retardant can discharge hydrogen bromide in burning, serves as a barrier against oxygen.Yu Zhi etc. proposed in " flame retardant rubber simple analysis " (world rubber industry, the 31st volume the 4th phase the 39th page), added 15 parts of Sb in SBR
2o
3with 30 parts of clorafins or 5 parts of Sb
2o
3, 20 parts of clorafin and 25 parts of Al (OH)
3, the good sizing material of flame retardant resistance can be obtained.Li Ang etc. propose in " rubber flame-retarded and fire retardant " (specialty elastomer goods, the 23rd volume the 3rd phase the 25th page), by brominated phosphoric acid ester, aromatic bromide, Sb
2o
3with ammonium chloride 4 kinds of fire retardants and use, join in SBR, the good sizing material of flame retardant effect can be obtained.With 5 ~ 10 parts of dialkyl phenyl organic phosphates, 10 ~ 15 parts of Sb
2o
3with the flame retardant agent of 3 ~ 10 parts of iodine, add in SBR, the sizing material that flame retardant effect is good can be obtained.Difficult combustion rubber more mainly contains the glue kind of halogen, as chloroprene rubber, polyvinyl chloride, epichlorohydrin rubber, chlorosulfonated polyethylene etc.
The shortcoming that inorganic combustion inhibitor has consumption large, organic fire-retardant expense is high again, even if do not consider these factors, additional fire retardant also not easily realizes in the production process of powdered rubber.When powdered rubber is produced, the inorganic combustion inhibitor added is incompatible with latex system, and fire retardant is by Precipitation; And add organic fire-retardant, due to fire retardant system small molecule component, easily separate out from powdered rubber surface, cause the secondary adhesion of powder particle.The characteristic of sizing material itself is sacrificed again to a certain extent when firing blend rubber with other difficulty.
Summary of the invention
The present invention be directed to the problem easily causing spontaneous combustion in powdered rubber storage and transport process, provide a kind of preparation method of flame retardant type powdered rubber, the separant with fire-retardant group synthesized by this invention uses in emulsion condensation powdering process, separant is evenly coated on the surface of powdered rubber, fire-retardant group is also evenly distributed on powdered rubber particle surface, therefore impart the flame retardant properties that powdered rubber is certain, thus ensure the safety of storage and transport process.
A preparation method for flame retardant type powdered rubber, is characterized in that comprising the following steps:
Step 1, the preparation of flame retardant type separant: be (0.1 ~ 6) with unsaturated fatty acids acid anhydrides according to mol ratio by halogenic donator: the ratio of 1 mixes, stir, add initiator, the mol ratio of initiator and unsaturated fatty acids acid anhydrides is (0 ~ 3): 1, carries out the addition reaction of 0.5 ~ 5 hour at 30 ~ 150 DEG C of temperature; In reaction solution, add excessive dilute alkaline aqueous solution, regulate the pH value of reaction solution to be greater than 8, stir and make product in 0.1 ~ 2 hour, thus prepare the separant with flame retardant resistance, stand-by;
Step 2, the preparation of flame retardant type powdered rubber: the rubber latex getting 500g, add the flame retardant type separant described in 10 ~ 200g step 1, stirring makes it to mix, then 0 ~ 200g flocculation agent is added, condensation temperature is-20 ~ 95 DEG C, and obtaining slurry obtained Surface coating after washing drying has the powdered rubber product with anti-flaming function separant.
Halogenic donator of the present invention is tetracol phenixin, hydrogenchloride, chlorine, hydrogen bromide or bromine etc., adopts the mode advertised that circulates to pass in reactive component when halogenic donator is gas.Described unsaturated fatty acids acid anhydrides, as halogen acceptor, is selected from the olefin(e) acid acid anhydride with saturation ratio scarcely of the different carbon chain lengths such as acrylic anhydride, iso-butylene acid anhydrides, monoene caproic anhydride, monoene lauric anhydride, monoene stearic acid acid anhydride, diene stearic acid acid anhydride or triolefin stearic acid acid anhydride and structure.
Initiator of the present invention is benzoyl peroxide ((PhCO
2)
2), dicumyl peroxide, di-isopropylbenzene hydroperoxide or oxygen etc.
Alkali aqueous solution described in step 1 of the present invention is sodium hydroxide, potassium hydroxide or ammoniacal liquor etc., acid anhydrides after alkali aqueous solution and halogenation carries out reaction and generates flame retardant type separant, separant is monovalent base metal or ammonium salt, there is hydrophilic radical so soluble in water, separant pH value is greater than 8, and the mass concentration of alkali aqueous solution is 2% ~ 30%.
Described rubber latex is styrene-butadiene latex, nitrile rubber, natural rubber latex, polybutadiene latex etc.
Flocculation agent of the present invention can be CaCl
2, MgSO
4, Mg Cl
2, Al
2sO
4, FeCl
3, CuCl
2, Ca (HSO
4)
2deng soluble metal salt and composition thereof.
The principle of foundation of the present invention is as follows:
①
②[Cl
3C-CH
2-CHCl-(CH
2)
n-CO]
2O+2NaOH→2Cl
3C-CH
2-CHCl-(CH
2)
n-COONa+H
2O
③2[Cl
3C-CH
2-CHCl-(CH
2)
n-COONa]+CaCl
2→[Cl
3C-CH
2-CHCl-(CH
2)
n-COO]
2Ca+2NaCl
1. chemical equation is unsaturated fatty acids acid anhydrides [CH
2=CH-(CH
2)
n-CO]
2o is at initiator (PhCO
2)
2effect under with halogenic donator CCl
4there is addition reaction; 2. reaction is saponification reaction, carries out reacting the halogen-containing fatty acid anhydride 1. generated the function that saponification makes it to have rubber-coated particle in aqueous; 3. reaction is condensation powdering mechanism, and separant hydrophobic end is coated on rubber particles surface, and water-wet side is at Ca
2+hydrophobic side is become, rubber latex breakdown of emulsion thus form powdered rubber particle under effect.
The fire retardant mechanism of the powdered rubber that flame retardant type separant is coated is as follows:
It is very fierce oxidizing reaction that powdered rubber burns under aerobic conditions, is also chain chemical reaction, generates active HO-and to dissociate free radical, Formed hydrogen compound and water when HO-free radical and rubber molecule meet during burning.Under aerobic conditions, hydrocarbon polymer can continue to decompose generation HO-free radical again, thus forms chain reaction, and burning is continued.Stop rubber combustion or make it extinguish and must block oxygen or reduce HO-number of free radical.Flame retardant type separant decomposes discharges halogen gas and hydrogen halide, and halogen can play the effect of certain blocking-up oxygen; Halogenation Hydrogen Energy and HO-free radical reaction generate water and halide-ions, and halide-ions can generate hydrogen halide with hydrocarbon reaction, and hydrogen halide can eliminate HO-free radical further, thus reduce HO-number of free radical, combustionvelocity are slowed down until extinguish.
The invention provides a kind of separant with anti-flaming function, its oxygen index of powder styrene butadiene rubber using this separant to prepare can bring up to 23% ~ 25% by 18% ~ 20%, makes powdered rubber not easily spontaneous combustion in storage and transport process.In the present invention, oxygen index test is carried out according to method described in GB 10707-89.
Accompanying drawing explanation
Fig. 1 is the structural representation of flame retardant type separant cladding powder rubber of the present invention.
Embodiment
" % (w) " hereinafter described represents mass concentration.
Embodiment 1:
Step 1, the preparation of flame retardant type separant: add 10mol monoene stearic acid acid anhydride and 20molCCl in the reactor
4be uniformly mixed, add (the PhCO of 0.1mol
2)
2initiator, controlling temperature of reaction is 40 DEG C, and the NaOH solution adding 5% (w) after reaction 60min in reactor regulates the pH value of reaction solution to be 8.5, obtains separant stand-by after stirring 20min.
Step 2, the preparation of flame retardant type powdered rubber: the styrene-butadiene latex 500g getting 20% (w), adds the separant of 40g step 1, stirs and makes it to mix, then add 100gCaCl
2condense, controlling condensing field temperature is 40 DEG C, obtains slurry and obtain flame retardant type powder styrene butadiene rubber after washing drying.
Sampling, surveying fire-retardant powder styrene butadiene rubber oxygen index is 23.5%, difficult combustion.
Comparative example 1:
Step 1, the preparation of flame retardant type separant: add 10mol monoene stearic acid acid anhydride in the reactor, the NaOH solution adding 5% (w) regulates the pH value of reaction solution to be 8.5, obtains separant stand-by after stirring 20min.
Step 2, the preparation of flame retardant type powdered rubber: get 20% (w) styrene-butadiene latex 500g, add the separant of 40g step 1, stirs and makes it to mix, add 100gCaCl
2condense, controlling condensing field temperature is 40 DEG C, obtains slurry and obtain flame retardant type powder styrene butadiene rubber after washing drying.
Sampling, surveying powder styrene butadiene rubber oxygen index is 18.7%, inflammable.
Embodiment 2:
Step 1, the preparation of flame retardant type separant: add 10mol diene stearic acid acid anhydride and 1molCCl in the reactor
4be uniformly mixed, add (the PhCO of 0.05mol
2)
2for initiator, controlling temperature of reaction is 30 DEG C, and the NaOH solution adding 50% (w) after reaction 30min in reactor regulates the pH value of reaction solution to be 8.5, obtains separant stand-by after stirring 6min.
Step 2, the preparation of flame retardant type powdered rubber: get 20% (w) styrene-butadiene latex 500g, add the separant of 10g step 1, stirs and makes it to mix, add 200g MgCl
2condense, controlling condensing field temperature is 45 DEG C, obtains slurry and obtain powder styrene butadiene rubber after washing drying.
Sampling, surveying fire-retardant powder styrene butadiene rubber oxygen index is 24.8%, difficult combustion.
Comparative example 2:
Step 1, the preparation of flame retardant type separant: add 10mol diene stearic acid acid anhydride in the reactor, the NaOH solution adding 50% (w) regulates the pH value of reaction solution to be 8.5, obtains separant stand-by after stirring 6min.
Step 2, the preparation of flame retardant type powdered rubber: get 20% (w) styrene-butadiene latex 500g, add the separant of 10g step 1, stirs and makes it to mix, add 200g MgCl
2condense, controlling condensing field temperature is 45 DEG C, obtains slurry and obtain powder styrene butadiene rubber after washing drying.
In this powder styrene butadiene rubber, be mixed into the clorafin fire retardant of 10 mass parts, surveying its oxygen index after sample preparation is 20.1%, and flame retardant effect is not good.
Embodiment 3:
Step 1, the preparation of flame retardant type separant: add 10mol triolefin stearic acid acid anhydride and 60molCCl in the reactor
4be uniformly mixed, add (the PhCO of 0.3mol
2)
2for initiator, controlling temperature of reaction is 90 DEG C, and the NaOH solution adding 25% (w) after reaction 180min in reactor regulates the pH value of reaction solution to be 8.9, obtains separant stand-by after stirring 120min.
Step 2, the preparation of flame retardant type powdered rubber: get 20% (w) natural rubber latex 500g, add the separant of 200g step 1, stirs and makes it to mix, add 10g CuCl
2condense, controlling condensing field temperature is 55 DEG C, obtains slurry and obtain powder natural rubber after washing drying.
Sampling, surveying fire-retardant powder natural rubber oxygen index is 25.8%, difficult combustion.
Comparative example 3:
Step 1, the preparation of flame retardant type separant: add 10mol triolefin stearic acid acid anhydride in the reactor, the NaOH solution adding 25% (w) regulates the pH value of reaction solution to be 8.9, obtains separant stand-by after stirring 120min.
Step 2, the preparation of flame retardant type powdered rubber: get 20% (w) natural rubber latex 500g, add the separant of 200g step 1, adds 10g clorafin fire retardant, stirs and makes it to mix, add 10g CuCl
2condense, controlling condensing field temperature is 55 DEG C, obtains slurry and obtain powder natural rubber after washing drying.
Sampling, surveying powder natural rubber oxygen index is 20.6%, inflammable.
Embodiment 4:
Step 1, the preparation of flame retardant type separant: add 10mol monoene stearic acid acid anhydride in the reactor, is blown into 10mol HCl stirring and makes it mixing, be blown into 20mol O
2for initiator, controlling temperature of reaction is 120 DEG C, and the NaOH solution adding 3% (w) after reaction 30min in reactor regulates the pH value of reaction solution to be 8.6, obtains separant stand-by after stirring 60min.
Step 2, the preparation of flame retardant type powdered rubber: get 20% (w) nitrile rubber 500g, add the separant of 50g step 1, stirs and makes it to mix, add 60g MgSO
4condense, control condensing field temperature and be-20 DEG C, obtain slurry and obtain Powdered acrylonitrile-butadiene rubber after washing drying.
Sampling, surveying flame retardant type Powdered acrylonitrile-butadiene rubber oxygen index is 25.5%, difficult combustion.
Comparative example 4:
Step 1, the preparation of flame retardant type separant: commercially available separant sodium stearate, stand-by;
Step 2, the preparation of flame retardant type powdered rubber: get 20% (w) nitrile rubber 500g, adds the commercially available separant sodium stearate of 50g, stirs and makes it to mix, add 60g MgSO
4condense, control condensing field temperature and be-20 DEG C, obtain slurry and obtain Powdered acrylonitrile-butadiene rubber after washing drying.
In gained Powdered acrylonitrile-butadiene rubber, add the blended rear sample preparation with it of 0.5g commodity fire retardant tributyl phosphate, surveying its oxygen index is 23.4%, and flame retardant effect is not good.
Embodiment 5:
Step 1, the preparation of flame retardant type separant: add 10mol monoene stearic acid acid anhydride in the reactor, is blown into 30mol HBr stirring and makes it mixing, be blown into 15mol O
2for initiator, controlling temperature of reaction is 150 DEG C, and the NaOH solution adding 30% (w) after reaction 240min in reactor regulates the pH value of reaction solution to be 8.3, obtains separant stand-by after stirring 30min.
Step 2, the preparation of flame retardant type powdered rubber: get 20% (w) butadiene latex 500g, add the separant of 100g step 1, stirs and makes it to mix, add 120g Al
2sO
4condense, controlling condensing field temperature is 95 DEG C, obtains slurry and obtain powder divinyl rubber after washing drying.
Sampling, surveying fire-retardant powder divinyl rubber oxygen index is 23.8%, difficult combustion.
Comparative example 5:
Step 1, the preparation of flame retardant type separant: commercially available separant potassium oleate, stand-by.
Step 2, the preparation of flame retardant type powdered rubber: get 20% (w) butadiene latex 500g, adds the commercially available separant potassium oleate of 100g, stirs and makes it to mix, add 120g Al
2sO
4condense, controlling condensing field temperature is 95 DEG C, obtains slurry and obtain powder divinyl rubber after washing drying.
In gained powder divinyl rubber, add the blended sample preparation with it of 0.5g commodity fire retardant hexabromocyclododecane, surveying its oxygen index is 20.1%, inflammable.
Embodiment 6:
Step 1, the preparation of flame retardant type separant: the Br2 adding 10mol monoene stearic acid acid anhydride and 50mol in the reactor stirs and makes it mixing, do not add initiator, controlling temperature of reaction is 150 DEG C, the NaOH solution adding 5% (w) after reaction 120min in reactor regulates the pH value of reaction solution to be 10, obtains separant stand-by after stirring 120min.
Step 2, the preparation of flame retardant type powdered rubber: get 20% (w) styrene-butadiene latex 500g, add the separant of 30g step 1, stirring makes it to mix, do not add flocculation agent and carry out mechanical coalescence, controlling condensing field temperature is 10 DEG C, obtains slurry and obtain powder styrene butadiene rubber after washing drying.
Sampling, surveying flame retardant type powder styrene butadiene rubber oxygen index is 22.9%, difficult combustion.
Comparative example 6:
Step 1, the preparation of flame retardant type separant: commercially available separant potassium oleate, stand-by.
Step 2, the preparation of flame retardant type powdered rubber: get 20% (w) styrene-butadiene latex 500g, add the commercially available separant potassium oleate of 30g, add 0.5g commodity fire retardant tributyl phosphate, stirring makes it to mix, do not add flocculation agent and carry out mechanical coalescence, controlling condensing field temperature is 10 DEG C, obtains slurry and obtain powder styrene butadiene rubber after washing drying.
Sampling, surveying powder styrene butadiene rubber oxygen index is 21.9%, and flame retardant effect is not good.
Embodiment 7:
Step 1, the preparation of flame retardant type separant: add 10mol monoene stearic acid acid anhydride and the Cl being blown into 60mol in the reactor
2stirring makes it to mix, and controlling temperature of reaction is 30 DEG C, and the NaOH solution adding 25% (w) after reaction 300min in reactor regulates the pH value of reaction solution to be 9.5, obtains separant stand-by after stirring 10min.
Step 2, the preparation of flame retardant type powdered rubber: get 20% (w) styrene-butadiene latex 500g, add the separant of 200g step 1, stirs and makes it to mix, add 100g Al
2(SO
4)
3condense, controlling condensing field temperature is 80 DEG C, obtains slurry and obtain powder styrene butadiene rubber after washing drying.
Sampling, surveying flame retardant type powder styrene butadiene rubber oxygen index is 22.7%, difficult combustion.
Comparative example 7:
Step 1, the preparation of flame retardant type separant: commercially available separant potassium rosinate, stand-by.
Step 2, the preparation of flame retardant type powdered rubber: get 20% (w) styrene-butadiene latex 500g, adds the commercially available separant potassium rosinate of 200g, adds 0.5g commodity TDE, stirs and makes it to mix, add 100g Al
2(SO
4)
3condense, controlling condensing field temperature is 80 DEG C, obtains slurry and obtain powder styrene butadiene rubber after washing drying.
Sampling, surveying powder styrene butadiene rubber oxygen index is 20.8%, and flame retardant effect is not good.
Claims (6)
1. a preparation method for flame retardant type powdered rubber, is characterized in that comprising the following steps:
The first step: the preparation of flame retardant type separant: be (0.1 ~ 6) with unsaturated fatty acids acid anhydrides according to mol ratio by halogenic donator: the ratio of 1 mixes, stir, add initiator, the mol ratio of initiator and unsaturated fatty acids acid anhydrides is (0 ~ 3): 1, carries out the addition reaction of 0.5 ~ 5 hour at 30 ~ 150 DEG C of temperature; In reaction solution, add excessive dilute alkaline aqueous solution, regulate the pH value of reaction solution to be greater than 8, stir and make product in 0.1 ~ 2 hour, thus prepare the separant with flame retardant resistance, stand-by;
Second step: the preparation of flame retardant type powdered rubber: the rubber latex getting 500g, add the flame retardant type separant described in 10 ~ 200g the first step, stirring makes it to mix, then 0 ~ 200g flocculation agent is added, condensation temperature is-20 ~ 95 DEG C, and obtaining slurry obtained Surface coating after washing drying has the powdered rubber product with anti-flaming function separant;
Described halogenic donator is tetracol phenixin, hydrogenchloride, chlorine, hydrogen bromide, bromine; Described unsaturated fatty acids acid anhydrides is selected from acrylic anhydride, iso-butylene acid anhydrides, monoene caproic anhydride, monoene lauric anhydride, monoene stearic acid acid anhydride, diene stearic acid acid anhydride or triolefin stearic acid acid anhydride.
2. preparation method as claimed in claim 1, adopts the mode advertised that circulates to pass in reactive component when it is characterized in that described halogenic donator is gas.
3. preparation method as claimed in claim 1, is characterized in that described initiator is benzoyl peroxide, dicumyl peroxide, di-isopropylbenzene hydroperoxide or oxygen.
4. preparation method as claimed in claim 1, it is characterized in that described alkali aqueous solution is sodium hydroxide, potassium hydroxide or ammoniacal liquor, the mass concentration of alkali aqueous solution is 2% ~ 50%.
5. preparation method as claimed in claim 1, is characterized in that described rubber latex is styrene-butadiene latex, nitrile rubber, natural rubber latex or polybutadiene latex.
6. preparation method as claimed in claim 1, is characterized in that described flocculation agent is CaCl
2, MgSO
4, Mg Cl
2, Al
2(SO
4)
3, FeCl
3, CuCl
2or Ca (HSO
4)
2.
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| CN104448452B (en) * | 2013-09-18 | 2016-07-13 | 中国石油天然气股份有限公司 | Preparation method of halogenated acylation low-smoke flame-retardant powder styrene butadiene rubber |
| CN104448661B (en) * | 2013-09-18 | 2017-03-15 | 中国石油天然气股份有限公司 | Preparation method of low-smoke high-flame-retardant powder styrene butadiene rubber |
| CN104448662B (en) * | 2013-09-18 | 2017-01-11 | 中国石油天然气股份有限公司 | Preparation method of low-smoke high-flame-retardant powder styrene butadiene rubber |
| CN104448447B (en) * | 2013-09-18 | 2017-01-04 | 中国石油天然气股份有限公司 | Preparation method of environment-friendly low-smoke flame-retardant powdered styrene butadiene rubber |
| CN104448663B (en) * | 2013-09-18 | 2017-01-11 | 中国石油天然气股份有限公司 | Preparation method of environment-friendly low-smoke flame-retardant powdered styrene butadiene rubber |
| CN104448453B (en) * | 2013-09-18 | 2016-04-06 | 中国石油天然气股份有限公司 | Preparation method of halogenated acylation low-smoke flame-retardant powdered styrene butadiene rubber |
| CN104448446B (en) * | 2013-09-18 | 2016-08-17 | 中国石油天然气股份有限公司 | Preparation method of environment-friendly flame-retardant powdered styrene butadiene rubber |
| CN105733157B (en) * | 2014-12-11 | 2018-02-02 | 中国石油天然气股份有限公司 | Preparation method of flame-retardant powdered styrene butadiene rubber |
| CN105733054B (en) * | 2014-12-11 | 2017-09-01 | 中国石油天然气股份有限公司 | Preparation process of flame-retardant powdered styrene-butadiene rubber |
| CN106032434B (en) * | 2015-03-18 | 2019-12-20 | 中国石油化工股份有限公司 | Powder rubber and vulcanized powder rubber and preparation method thereof |
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| CN1175603A (en) * | 1997-05-24 | 1998-03-11 | 华南理工大学 | Method for preparing high-molecular coating agent and use thereof |
| CN1394881A (en) * | 2001-07-08 | 2003-02-05 | 汪立波 | Industrial production method of chlorinated rubber by adopting water phase suspension method and its product |
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|---|---|---|---|---|
| JPS5938206A (en) * | 1982-08-30 | 1984-03-02 | Toyo Soda Mfg Co Ltd | Prevention of coagulation of powdered rubber |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1175603A (en) * | 1997-05-24 | 1998-03-11 | 华南理工大学 | Method for preparing high-molecular coating agent and use thereof |
| CN1394881A (en) * | 2001-07-08 | 2003-02-05 | 汪立波 | Industrial production method of chlorinated rubber by adopting water phase suspension method and its product |
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| Title |
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| JP昭59-38206A 1984.03.02 * |
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