CN103159611A - Preparation method of flame-retardant separant - Google Patents
Preparation method of flame-retardant separant Download PDFInfo
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- CN103159611A CN103159611A CN2011104199326A CN201110419932A CN103159611A CN 103159611 A CN103159611 A CN 103159611A CN 2011104199326 A CN2011104199326 A CN 2011104199326A CN 201110419932 A CN201110419932 A CN 201110419932A CN 103159611 A CN103159611 A CN 103159611A
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- separant
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- rubber
- flame retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 46
- 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 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920001971 elastomer Polymers 0.000 claims abstract description 45
- 239000005060 rubber Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 33
- -1 unsaturated fatty acids acid anhydrides Chemical class 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 229920000126 latex Polymers 0.000 claims description 18
- 235000021355 Stearic acid Nutrition 0.000 claims description 16
- 239000004816 latex Substances 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
- 239000008117 stearic acid Substances 0.000 claims description 16
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 14
- 239000002174 Styrene-butadiene Substances 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 13
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- 230000001143 conditioned effect Effects 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound 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
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 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
- 239000003513 alkali Substances 0.000 claims description 5
- 229920000459 Nitrile rubber Polymers 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
- 238000007127 saponification reaction Methods 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
- 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 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
- 238000005054 agglomeration Methods 0.000 claims 1
- 230000002776 aggregation Effects 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 17
- 230000002269 spontaneous effect Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 description 15
- 239000002002 slurry Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003860 storage Methods 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000000839 emulsion Substances 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
- 230000007246 mechanism Effects 0.000 description 2
- 229940096992 potassium oleate Drugs 0.000 description 2
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-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
- 241001122126 Carex secta Species 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 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
- 239000012757 flame retardant agent Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 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
- 238000002955 isolation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 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
- 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
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention provides a preparation method of a flame-retardant separant 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 preparation method of functional type separant, specifically a kind of preparation method with separant that is applicable to the powdered rubber preparation of anti-flaming function.
Background technology
The preparation method of powdered rubber mainly contains mechanical crushing method, spray-drying process and cohesion coating method etc.Three kinds of methods all need be used separant, and the separant effect is to prevent rubber particles surface adhesion, mainly divides inorganics and the large class of inorganics two, inorganics, as: calcium carbonate, talcum powder, carbon black, white carbon black, water glass etc.; Organism, as: macromolecule resin, divalence soap etc.No matter be inorganic separant or organic separant, only play the antiseized effect of isolation in the powdered rubber production process, do not retrieve the bibliographical information that separant has flame retardant resistance.
At present, the flame resistant method in niggerhead field mainly contains and adds fire retardant and fire two kinds of methods of blend rubber with difficulty.Adding fire retardant has inorganic combustion inhibitor and organic fire-retardant, the general tool cooling of inorganic combustion inhibitor and iris action, and it is that thing and molybdenum are thing etc. that common kind has aluminium hydroxide, magnesium hydroxide, boron; Take brominated, chlorine or phosphorous organic compound as main, brominated flame retardant can discharge hydrogen bromide to organic fire-retardant in burning, serve as a barrier against oxygen.Yu Zhi etc. proposed in " flame retardant rubber simple analysis " (world rubber industry, the 31st the 39th page of the 4th phase of volume), 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, can obtain flame retardant resistance sizing material preferably.Li Ang etc. proposed in " rubber flame-retarded and fire retardant " (specialty elastomer goods, the 23rd the 25th page of the 3rd phase of volume), with brominated phosphoric acid ester, aromatic bromide, Sb
2O
3With 4 kinds of fire retardants of ammonium chloride and use, join in SBR, can obtain the good sizing material of flame retardant effect.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, can obtain the good sizing material of flame retardant effect.Difficult combustion rubber is mainly some glue kinds that contain halogen, as chloroprene rubber, polyvinyl chloride, epichlorohydrin rubber, chlorosulfonated polyethylene etc.
Inorganic combustion inhibitor has the large shortcoming of consumption, and the organic fire-retardant expense is high again, even do not consider these factors, adds fire retardant and also is difficult for realizing in the production process of powdered rubber.When powdered rubber was produced, the inorganic combustion inhibitor and the latex system that add were incompatible, and fire retardant is with Precipitation; And add organic fire-retardant, and because fire retardant is small molecule component, easily separate out from the powdered rubber surface, cause the secondary adhesion of powder particle.Sacrifice to a certain extent again the characteristic of sizing material itself during with other difficult combustion blend rubber.
Summary of the invention
The present invention be directed to the problem that easily causes spontaneous combustion in the powdered rubber storage and transport process, a kind of preparation method of flame retardant type separant is provided, the separant with fire-retardant group that is synthesized uses in the emulsion condensation powdering process, separant evenly is coated on the surface of powdered rubber, fire-retardant group also is evenly distributed on the powdered rubber particle surface, therefore give powdered rubber certain flame retardant properties, thereby guaranteed the safety of storage and transport process.
A kind of preparation method of flame retardant type separant is characterized in that comprising the following steps:
1) be (0.1～6) with the unsaturated fatty acids acid anhydrides according to mol ratio with halogenic donator: 1 ratio is mixed, stir, add initiator, the mol ratio of initiator and unsaturated fatty acids acid anhydrides is (0～3): 1, carry out the addition reaction of 0.5～5 hour at 30～150 ℃ of temperature;
2) to step 1) reaction solution in add excessive dilute alkaline aqueous solution, the pH value of conditioned reaction liquid stirs and made the product saponification in 0.1～2 hour, thereby prepare the separant with flame retardant resistance greater than 8.
Halogenic donator of the present invention is tetracol phenixin, hydrogenchloride, chlorine, hydrogen bromide or bromine etc., and the mode that adopts circulation to advertise when halogenic donator is gas passes in reactive component.Described unsaturated fatty acids acid anhydrides is selected from the olefin(e) acid acid anhydride of saturation ratio scarcely that has 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 as halogen acceptor.
Described initiator is benzoyl peroxide ((PhCO
2)
2), dicumyl peroxide, di-isopropylbenzene hydroperoxide or oxygen etc.
Step 2 of the present invention) alkali aqueous solution described in is sodium hydroxide, potassium hydroxide or ammoniacal liquor etc., acid anhydrides after alkali aqueous solution and halogenation reacts and generates the flame retardant type separant, separant is monovalent base metal or ammonium salt, so it is soluble in water to have hydrophilic radical, separant pH value is greater than 8, and the mass concentration of alkali aqueous solution is 2%～30%.
Flame retardant type separant of the present invention can be applicable to the condensation powdering of the latex such as styrene-butadiene latex, nitrile rubber, natural rubber latex, polybutadiene latex, thereby preparation has the powdered rubber of anti-flaming function.
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
4Addition reaction occurs; 2. reaction is saponification reaction, and the halogen-containing fatty acid anhydride that 1. reaction is generated carries out the function that saponification makes it to have rubber-coated particle in the aqueous solution; 3. reaction is condensation powdering mechanism, and the separant hydrophobic end is coated on the rubber particles surface, and water-wet side is at Ca
2+Become the hydrophobic side under effect, thereby the rubber latex breakdown of emulsion forms the powdered rubber particle.
The fire retardant mechanism of the powdered rubber that the flame retardant type separant coats is as follows:
It is very fierce oxidizing reaction that powdered rubber burns under aerobic conditions, is also chain chemical reaction, generates the free free radical of active HO-during burning, Formed hydrogen compound and water when HO-free radical and rubber molecule meet.Under aerobic conditions, hydrocarbon polymer can continue decomposition and generate again the HO-free radical, thereby forms chain reaction, and burning is continued.Stoping rubber combustion or it is extinguished must blocking-up oxygen or reduction 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 further be eliminated the HO-free radical, thereby reduce the HO-number of free radical, combustionvelocity are slowed down until extinguish.
The invention provides a kind of separant with anti-flaming function, use its oxygen index of powder styrene butadiene rubber of this separant preparation to bring up to 23%～25% by 18%～20%, make powdered rubber be difficult for spontaneous combustion in storage and transport process.
Description of drawings
Fig. 1 is the structural representation of flame retardant type separant cladding powder rubber of the present invention.
Embodiment
" % (w) " expression mass concentration hereinafter described.
The flame retardant effect of a kind of flame retardant type separant of the present invention is estimated as follows, get the rubber latex of 500g, add the described flame retardant type separant of 10～200g, stirring makes it to mix, then add 10～200g flocculation agent, condensation temperature is 10～80 ℃, and the acquisition slurry makes the surface and is coated with the powdered rubber product with anti-flaming function separant after washing drying.Characterize its flame retardant effect by the test oxygen index, the oxygen index test is carried out according to the described method of GB 10707-89.
Embodiment 1:
Add 10mol monoene stearic acid acid anhydride and 20mol CCl in reactor
4Mix, add (the PhCO of 0.1mol
2)
2Initiator, controlling temperature of reaction is 40 ℃, adding the pH value of the NaOH solution conditioned reaction liquid of 5% (w) in the backward reactor of reaction 60min is 8.5, gets separant after stirring 20min stand-by.Get the styrene-butadiene latex 500g of 20% (w), add the foregoing separant of 40g, stirring makes it to mix, then adds 50gCaCl
2Condense, controlling cohesion still temperature is 40 ℃, obtains slurry and get powdered rubber after washing drying, and surveying its oxygen index is 23.5%, difficult combustion.
Comparative Examples 1:
Add 10mol monoene stearic acid acid anhydride in reactor, adding the pH value of the NaOH solution conditioned reaction liquid of 5% (w) is 8.5, gets separant after stirring 20min stand-by.Get 20% (w) styrene-butadiene latex 500g, add the foregoing separant of 40g, stirring makes it to mix, and adds 50gCaCl
2Condense, controlling cohesion still temperature is 40 ℃, obtains slurry and get powdered rubber after washing drying, surveys its oxygen index and is 18.7%, inflammable.
Embodiment 2:
Add 10mol diene stearic acid acid anhydride and 1molCCl in reactor
4Mix, add (the PhCO of 0.05mol
2)
2Be initiator, controlling temperature of reaction is 30 ℃, and adding the pH value of the NaOH solution conditioned reaction liquid of 50% (w) in the backward reactor of reaction 30min is 8.5, gets separant after stirring 6min stand-by.Get 20% (w) styrene-butadiene latex 500g, add the foregoing separant of 10g, stirring makes it to mix, and adds 200g CaCl
2Condense, controlling cohesion still temperature is 45 ℃, obtains slurry and get powdered rubber after washing drying, and surveying its oxygen index is 24.8%, difficult combustion.
Comparative Examples 2:
Add 10mol diene stearic acid acid anhydride in reactor, adding the pH value of the NaOH solution conditioned reaction liquid of 50% (w) is 8.5, gets separant after stirring 6min stand-by.Get 20% (w) styrene-butadiene latex 500g, add the foregoing separant of 10g, stirring makes it to mix, and adds 200g CaCl
2Condense, controlling cohesion still temperature is 45 ℃, obtain slurry after washing drying powdered rubber, sneak into the clorafin fire retardant of 10 mass parts in this powdered rubber, surveying its oxygen index is 20.1%.
Embodiment 3:
Add 10mol triolefin stearic acid acid anhydride and 60mol CCl in reactor
4Mix, add (the PhCO of 0.3mol
2)
2Be initiator, controlling temperature of reaction is 90 ℃, and adding the pH value of the NaOH solution conditioned reaction liquid of 25% (w) in the backward reactor of reaction 180min is 8.9, gets separant after stirring 120min stand-by.Get 20% (w) natural rubber latex 500g, add the foregoing separant of 200g, stirring makes it to mix, and adds 10g CaCl
2Condense, controlling cohesion still temperature is 55 ℃, obtains slurry and get powdered rubber after washing drying, and surveying its oxygen index is 25.8%, difficult combustion.
Comparative Examples 3:
Add 10mol triolefin stearic acid acid anhydride in reactor, adding the pH value of the NaOH solution conditioned reaction liquid of 25% (w) is 8.9, gets separant after stirring 120min stand-by.Get 20% (w) natural rubber latex 500g, add the foregoing separant of 200g, add 10g clorafin fire retardant, stirring makes it to mix, and adds 10g CaCl
2Condense, controlling cohesion still temperature is 55 ℃, obtains slurry and get powdered rubber after washing drying, surveys its oxygen index and is 20.6%, inflammable.
Embodiment 4:
Add 10mol monoene stearic acid acid anhydride in reactor, be blown into 10mol HCl stirring and make it to mix, be blown into 20mol O
2Be initiator, controlling temperature of reaction is 120 ℃, and adding the pH value of the NaOH solution conditioned reaction liquid of 3% (w) in the backward reactor of reaction 30min is 8.6, gets separant after stirring 60min stand-by.Get 20% (w) nitrile rubber 500g, add the foregoing separant of 50g, stirring makes it to mix, and adds 60gMgCl
2Condense, controlling cohesion still temperature is 60 ℃, obtains slurry and get powdered rubber after washing drying, and surveying its oxygen index is 25.5%, difficult combustion.
Comparative Examples 4:
Get 20% (w) nitrile rubber 500g, add the commercially available separant sodium stearate of 50g, stirring makes it to mix, and adds 60g MgCl
2Condense, controlling cohesion still temperature is 60 ℃, obtain slurry after washing drying powdered rubber, add the sample preparation after blend with it of 0.5g commodity fire retardant tributyl phosphate, surveying its oxygen index is 23.4%, flame retardant effect is poor.
Embodiment 5:
Add 10mol monoene stearic acid acid anhydride in reactor, be blown into 30mol HBr stirring and make it to mix, be blown into 15mol O
2Be initiator, controlling temperature of reaction is 150 ℃, and adding the pH value of the NaOH solution conditioned reaction liquid of 30% (w) in the backward reactor of reaction 240min is 8.3, gets separant after stirring 30min stand-by.Get 20% (w) butadiene latex 500g, add the foregoing separant of 100g, stirring makes it to mix, and adds 120gCaCl
2Condense, controlling cohesion still temperature is 80 ℃, obtains slurry and get powdered rubber after washing drying, and surveying its oxygen index is 23.8%, difficult combustion.
Comparative Examples 5:
Get 20% (w) butadiene latex 500g, add the commercially available separant potassium oleate of 100g, stirring makes it to mix, and adds 120g CaCl
2Condense, controlling cohesion still temperature is 80 ℃, obtains slurry and get powdered rubber after washing drying, adds the blend sample preparation with it of 0.5g commodity fire retardant hexabromocyclododecane, surveys its oxygen index and is 20.1%, inflammable.
Embodiment 6:
The Br that adds 10mol monoene stearic acid acid anhydride and 50mol in reactor
2Stirring makes it to mix, and does not add initiator, and controlling temperature of reaction is 150 ℃, and adding the pH value of the NaOH solution conditioned reaction liquid of 5% (w) in the backward reactor of reaction 120min is 10, gets separant after stirring 120min stand-by.Get 20% (w) styrene-butadiene latex 500g, add the foregoing separant of 30g, stirring makes it to mix, and adds 200g MgSO
4Condense, controlling cohesion still temperature is 10 ℃, obtains slurry and get powdered rubber after washing drying, and surveying its oxygen index is 22.9%, difficult combustion.
Comparative Examples 6:
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, and adds 200g MgSO
4Condense, controlling cohesion still temperature is 10 ℃, obtains slurry and get powdered rubber after washing drying, and surveying its oxygen index is 21.9%, and flame retardant effect is not good.
Embodiment 7:
Add 10mol monoene stearic acid acid anhydride and the Cl that is blown into 60mol in reactor
2Stirring makes it to mix, and controlling temperature of reaction is 30 ℃, and adding the pH value of the NaOH solution conditioned reaction liquid of 25% (w) in the backward reactor of reaction 300min is 9.5, gets separant after stirring 10min stand-by.Get 20% (w) styrene-butadiene latex 500g, add the foregoing separant of 200g, stirring makes it to mix, and adds 100g Al
2(SO
4)
3Condense, controlling cohesion still temperature is 80 ℃, obtains slurry and get powdered rubber after washing drying, and surveying its oxygen index is 22.7%, difficult combustion.
Comparative Examples 7:
Get 20% (w) styrene-butadiene latex 500g, add the commercially available separant potassium rosinate of 200g, add 0.5g commodity TDE, stirring makes it to mix, and adds 100g Al
2(SO
4)
3Condense, controlling cohesion still temperature is 80 ℃, obtains slurry and get powdered rubber after washing drying, and surveying its oxygen index is 20.8%, and flame retardant effect is not good.
Claims (7)
1. the preparation method of a flame retardant type separant is characterized in that comprising the following steps:
1) be (0.1～6) with the unsaturated fatty acids acid anhydrides according to mol ratio with halogenic donator: 1 ratio is mixed, stir, add initiator, the mol ratio of initiator and unsaturated fatty acids acid anhydrides is (0～3): 1, carry out the addition reaction of 0.5～5 hour at 30～150 ℃ of temperature;
2) to step 1) reaction solution in add excessive dilute alkaline aqueous solution, the pH value of conditioned reaction liquid stirs and made the product saponification in 0.1～2 hour greater than 8, makes the flame retardant type separant.
2. preparation method as claimed in claim 1, is characterized in that described halogenic donator is tetracol phenixin, hydrogenchloride, chlorine, hydrogen bromide, bromine.
3. preparation method as claimed in claim 1, is characterized in that the mode that adopts circulation to advertise when described halogenic donator is gas passes in reactive component.
4. preparation method as claimed in claim 1, is characterized in that 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.
5. preparation method as claimed in claim 1, is characterized in that described initiator is benzoyl peroxide, dicumyl peroxide, di-isopropylbenzene hydroperoxide or oxygen.
6. preparation method as claimed in claim 1, is characterized in that described alkali aqueous solution is sodium hydroxide, potassium hydroxide or ammoniacal liquor, and the mass concentration of alkali aqueous solution is 2%～50%.
One kind adopt that method as claimed in claim 1 makes the application of flame retardant type separant in styrene-butadiene latex, nitrile rubber, natural rubber latex or polybutadiene latex agglomeration process, for the preparation of the powdered rubber with anti-flaming function.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104448446A (en) * | 2013-09-18 | 2015-03-25 | 中国石油天然气股份有限公司 | Preparation method of environment-friendly flame-retardant powdered styrene butadiene rubber |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5938206A (en) * | 1982-08-30 | 1984-03-02 | Toyo Soda Mfg Co Ltd | Prevention of coagulation of powdered rubber |
| CN1569906A (en) * | 2003-07-17 | 2005-01-26 | 中国石油天然气股份有限公司 | Method for preparing powdered rubber through continuous coagulation |
| CN1704439A (en) * | 2004-06-02 | 2005-12-07 | 中国石油天然气股份有限公司 | Method for producing powdered rubber |
| CN102070789A (en) * | 2009-11-25 | 2011-05-25 | 中国石油天然气股份有限公司 | Preparation method of powdered rubber |
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2011
- 2011-12-15 CN CN201110419932.6A patent/CN103159611B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5938206A (en) * | 1982-08-30 | 1984-03-02 | Toyo Soda Mfg Co Ltd | Prevention of coagulation of powdered rubber |
| CN1569906A (en) * | 2003-07-17 | 2005-01-26 | 中国石油天然气股份有限公司 | Method for preparing powdered rubber through continuous coagulation |
| CN1704439A (en) * | 2004-06-02 | 2005-12-07 | 中国石油天然气股份有限公司 | Method for producing powdered rubber |
| CN102070789A (en) * | 2009-11-25 | 2011-05-25 | 中国石油天然气股份有限公司 | Preparation method of powdered rubber |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448446A (en) * | 2013-09-18 | 2015-03-25 | 中国石油天然气股份有限公司 | Preparation method of environment-friendly flame-retardant powdered styrene butadiene rubber |
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