CN104448452B - The low cigarette of halogen acidylate, fire-retardant powder styrene butadiene rubber preparation method - Google Patents
The low cigarette of halogen acidylate, fire-retardant powder styrene butadiene rubber preparation method Download PDFInfo
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Abstract
The preparation method that the invention provides a kind of maximum smoke density is less than 150, oxygen index (OI) is more than 40% low cigarette, flame retardant type powder styrene butadiene rubber.This invention adopts styrene-butadiene latex to carry out acyl halogenation with anhydride and halogenating agent, then smoke suppressant is carried out esterification treatment, the method for direct condensation powdering after finally the styrene-butadiene latex of halogen acidylate and functionalization smoke suppressant being mixed.This method efficiently solves problems such as solving smoke suppressant dispersion inequality in rubber matrix, migration and precipitation, the molecular backbone of powder styrene butadiene rubber is embedded into fire-retardant group halogen simultaneously, imparts the low cigarette of powder styrene butadiene rubber fire resistance, efficient, lasting feature.
Description
Technical field
The preparation method that the present invention relates to a kind of fire-retardant powder styrene butadiene rubber, the preparation method being specifically related to a kind of halogen acidylate styrene-butadiene latex and functionalization smoke suppressant directly blended, the low cigarette of condensation powdering, fire-retardant powder styrene butadiene rubber.Background technology
It is known that, powder styrene butadiene rubber (PSBR) is a kind of hydrocarbon rubbers, its main chain all contains the elements such as substantial amounts of carbon, hydrogen, fuel gas it is easily generated during melted by heat, easily burning with oxygen effect when high temperature, cause its oxygen index (OI) low, fire resistance is poor, thus bring potential fire hazard, limit PSBR application in the fields such as mine, electronics, electrical equipment industry, automobile, aircraft, steamer.At present, the industrial commonly used halogen containing flame-retardant of China prepares flame retardant rubber, have an advantage in that there is higher anti-flammability, shortcoming produces a large amount of smog and toxicant when being burning, make adult respiratory distress, its hazardness is often even more serious than the consequence that burning produces, and is the primary risk factor causing people's injures and deaths in fire.In recent years, along with the reinforcement day by day of global safety environmental consciousness, people are more and more higher to the requirement of fire savety and the fire resistance of goods, develop novel low cigarette, the combustion elastomeric material of high fire-retardance has become study hotspot.
In prior art, prepare mainly by the method adding fire retardant and smoke suppressant about the low cigarette of elastomeric material, fire-retardant research.A kind of it is used in conjunction with each other with halogen-free flame retardants aluminium hydroxide (magnesium), antimony oxide and phosphorus flame retardant as: ZL96116942.7 discloses, by mixing blending technology, prepares low cigarette, low toxicity, environment-friendly type flame-retardant rubber floor that fire resistance is good.ZL201010136235.5 discloses a kind of efficient, environment friendly flame retardant adopting organic phosphorus flame retardant triaryl phosphate and the composite preparation of organic modified nano montmorillonite, and be applied in natural rubber system with 10～15wt% addition, prepare environment-friendly flame retardant rubber material.CN102040779A disclose a kind of with containing EPDM rubber, isocyanate-terminated polybutadiene, vulcanizing agent, hydroxide flame retardant mixture, obtain a kind of flame retardant rubber by mixing, sulfuration.The research such as Zhang Baowei finds that aluminium hydroxide processes, by silane coupler modified and particle diameter miniaturization, the oxygen index (OI) that can be effectively improved butadiene-styrene rubber." aluminium hydroxide Study of flame retardancy in butadiene-styrene rubber " (specific rubber goods, 2003,24 (2): 15～17).
Summary of the invention
The preparation method that the offer low cigarette that a kind of maximum smoke density is less than 150, oxygen index (OI) is more than 40%, flame retardant type powder styrene butadiene rubber are provided.This invention adopts styrene-butadiene latex to carry out acyl halogenation with anhydride and halogenating agent, then smoke suppressant is carried out esterification treatment, the method for direct condensation powdering after finally the styrene-butadiene latex of halogen acidylate and functionalization smoke suppressant being mixed.This method efficiently solves problems such as solving smoke suppressant dispersion inequality in rubber matrix, migration and precipitation, the molecular backbone of powder styrene butadiene rubber is embedded into fire-retardant group halogen simultaneously, imparts the low cigarette of powder styrene butadiene rubber fire resistance, efficient, lasting feature.
" part " of the present invention each means mass parts.
A kind of low cigarette of the present invention, fire-retardant powder styrene butadiene rubber preparation method, concrete preparation process is:
null(1) preparation of halogen acidylate styrene-butadiene latex: count for 100 parts with styrene-butadiene latex quality，Polymeric kettle is initially charged 100 parts of styrene-butadiene latexes、1～5 part of emulsifying agent、5～10 parts of solvents，Stirring、Heating，When still temperature to be polymerized reaches 25～50 DEG C，It is rapidly added 0.01～0.2 part of catalyst under agitation，Until adding 3～15 parts of anhydride when system becomes orange red，Stirring reaction 1～4h，Then 4～10 portions of halogenating agents are added，And (molar concentration of HCl is: 0.1～0.7mol/L) to drip methanol (CH3OH) solution of 0.1～0.5 part of HCl，After reacting 15～30h when 30～60 DEG C，Add the diluted hydrochloric acid aqueous solution that 10～15 parts of mass concentrations are 1.5%～5.0% and terminate reaction，Sucking filtration、Washing prepares halogen acidylate styrene-butadiene latex.
(2) preparation of functionalization smoke suppressant: count for 100 parts with smoke suppressant quality, 1～5 part of silane coupler and 50～100 parts of water, 5～10 parts of ethanol are joined in polymeric kettle and be uniformly mixed, it is 8～10 with buffer agent regulation system pH value, it is subsequently adding 100 parts of smoke suppressants, stirs mixing 10～30min；Add 10～20 parts of lauric acid polyol ester stirring mixing 30～60min；Dehydration, dry, grind and obtain functionalization smoke suppressant.
(3) preparation of fire-retardant powder styrene butadiene rubber: count for 100 parts with halogen acidylate styrene-butadiene latex quality; take 100 parts of halogen acidylate styrene-butadiene latexes and 10～25 parts of functionalization smoke suppressants, 50～100 parts of water join stirring mixing 10～30min in condensing field; when then heating to 50～60 DEG C; it is sequentially added into 2～5 portions of interleaving agents, 2～6 parts of flocculating agents; it is 8～11 with buffer agent regulation system pH value; stir 10～30min when being warming up to 70～90 DEG C and carry out ripening, finally scrubbed, dehydration, dry obtain low cigarette, fire-retardant powder styrene butadiene rubber product.
Anhydride of the present invention is dibasic acid anhydride compound, the one in succinic anhydride, maleic anhydride, phthalic anhydride, it is preferable that phthalic anhydride, and its addition is 3～15 parts, it is preferable that 7～12 parts.
Halogenating agent of the present invention is liquid chlorine, the one in bromine, it is preferable that bromine, and its addition is 4～10 parts.
Catalyst of the present invention is selected from aluminum trichloride (anhydrous) (AlCl3), boron trifluoride (BF3), butter of tin (SnCl4), zinc dichloride (ZnCl2) in one, it is preferable that AlCl3, its addition is 0.01～0.2 part, it is preferable that 0.05～0.15 part.
Solvent of the present invention can be selected from Carbon bisulfide (CS2), Nitrobenzol, petroleum ether, sym-tetrachloroethane, one in dichloroethanes, it is preferable that CS2。
Smoke suppressant of the present invention can be magnesium hydroxide [Mg (OH)2], aluminium hydroxide [Al (OH)3], calcium hydroxide, brucite [Mg6Al2(OH)16CO3·4H2O], calcium aluminate [3CaO Al2O3·6H2O], one in calcium carbonate, it is preferable that aluminium hydroxide.
Lauric acid polyol ester compounds of the present invention can be selected from one or more in lauric acid glycol ester, lauric acid propylene glycol ester, lauric acid glycerine ester, lauric acid butanediol ester, lauric acid pentaerythritol ester.
Silane coupler of the present invention can be selected from gamma-aminopropyl-triethoxy-silane (KH-550), 3-glycydoxy trimethoxy silane (KH-560), VTES (A-151), N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane (KH-602), γ-methacryloxypropyl trimethoxy silane (KH-570), N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane (KH-792), one or more in vinyltrimethoxy silane (A-171).
Styrene-butadiene latex of the present invention is to be polymerized copolymerization by conjugated diene hydrocarbon compound and aryl ethylene compounds by emulsion to form.Conjugated diene hydrocarbon compound is C4Class conjugated diene hydrocarbon compound.Aryl ethylene compounds can be styrene, α-methyl styrene, 2-propenyl benzene, ethyl styrene and their derivant.The wherein solid content 20～45% of styrene-butadiene latex.
The present invention emulsifying agent to adopting, interleaving agent, flocculating agent, buffer agent etc. are all not specially limited, all can adopt conven-tional adjuvants generally in the art, its addition be also those skilled in the art according to the consumption of latex can calculated conventional amount used, the present invention does not do particular determination yet.
Emulsifying agent as described in the present invention is conventionally known to one of skill in the art, it is possible to be one or more in anion emulsifier and nonionic emulsifier.As: can be selected from fatty acid soaps, RA rosin acid, dodecylbenzene sodium sulfonate, sodium lauryl sulphate, polyoxyethylene sorbitol acid anhydride list olein one or more, it is preferable that dodecylbenzene sodium sulfonate.
Interleaving agent of the present invention can be selected from one or more in potassium stearate, sodium stearate, potassium oleate, enuatrol, synthetic fatty acid potassium, sodium fat synthesis.
Flocculating agent of the present invention can be selected from one or more in univalent metal salt, divalent metal salt, divalent metal salt.Such as: one or more in sodium chloride, magnesium chloride, iron chloride, calcium chloride, magnesium sulfate, aluminum sulfate, Alumen.
Buffer agent of the present invention can be selected from the one in sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonia, ammonium hydrogen carbonate, it is preferable that sodium hydroxide.
First styrene-butadiene latex substrate has been carried out halogen acidylate and has processed by the present invention, on the one hand fire-retardant group halogen can be effectively embedding on the main chain of powder styrene butadiene rubber polymeric, imparts high efficiency and the persistency of powder styrene butadiene rubber fire resistance.A certain amount of polar group acid halide group is produced on the other hand on styrene-butadiene latex surface.Inorganic smoke suppressant surface is carried out functionalization simultaneously, by the addition of silane coupler and lauric acid polyol ester, give esterification treatment on its surface, thus forming alcohol terminal hydroxy group.Certain chemisorbed is there is in these alcohol terminal hydroxy groups with the acid halide group in halogen acidylate styrene-butadiene latex; so as the caking property improved between smoke suppressant particle and styrene-butadiene latex matrix; the compatibility of inorganic smoke suppressant and styrene-butadiene latex can be improved significantly; avoid particle to reunite in styrene-butadiene latex substrate, migrate and precipitate out the generation of phenomenon; drastically increase the smoke suppressing effect of inorganic smoke suppressant so that it is maximum smoke density is less than 150.
Secondly, inorganic smoke suppressant aluminium hydroxide etc. releases nonvolatile aluminium oxide at one layer of barrier layer of combustible Surface Creation when decomposes, it is possible to starvation, prevention burning.Simultaneously along with the very big improvement of smoke suppressant with the styrene-butadiene latex compatibility; cooperative effect definitely can be produced with the fire-retardant group halogen in halogen acidylate styrene-butadiene latex in improving the fire resistance of material; contribute to improving significantly the flame retardant effect of powder styrene butadiene rubber material, it is possible to prepare the oxygen index (OI) fire-retardant powder styrene butadiene rubber up to more than 40%.
Detailed description of the invention
Enumerate following example and comparative example so that the invention effect of the present invention to be described, but protection scope of the present invention is not limited in these embodiments and comparative example." part " described in embodiment and comparative example each means mass parts.
(1) raw material sources:
(2) analysis test method:
The mensuration of bromine content: the mensuration of the bromine content in halogen acidylate styrene-butadiene latex adopts alkali solution technique, uses AgNO3Standard solution titration, its concentration primary standard substance NaCl demarcates, eosin (C20H6O5BrNa2) for indicator, titration end-point solution is by pale red to lavender.Bromine content is calculated as follows:
In formula: C AgNO3The concentration of standard solution；V—AgNO3The volume that standard solution consumes；The molal quantity of acylate group in n halogen acidylate styrene-butadiene latex；The quality (g) of dry in m styrene-butadiene latex.
Embodiment 1
(1) preparation of halogen acidylate styrene-butadiene latex: be initially charged 100 parts of styrene-butadiene latex SBR1500,2.5 parts of dodecylbenzene sodium sulfonate, 6.0 parts of CS in polymeric kettle2, then stirring, heating, when still temperature rise to be polymerized is to 45 DEG C, rapidly join 0.08 part of AlCl3, until adding 7 parts of phthalic anhydrides, stirring reaction 3h when system becomes orange red, then adding 5 parts of bromines, and dripping 0.3 part of HCl-CH3(molar concentration of HCl is OH solution: 0.5mol/L) as catalyst, reacts 20h when 50 DEG C, is eventually adding the diluted hydrochloric acid aqueous solution that 12 parts of mass concentrations are 2.5% and terminates reaction, and sucking filtration, washing prepare bromine acidylate styrene-butadiene latex a.Sample analysis: the acylation degree recording bromine acidylate styrene-butadiene latex a is 13.7%；Bromine content is 18.7mol%.
(2) preparation of functionalization smoke suppressant: 2.0 parts of KH-550 and 70 parts of water, 6 parts of ethanol are joined in polymeric kettle and are uniformly mixed, is 8.5 with NaOH regulation system pH value, is subsequently adding 100 parts of aluminium hydroxide, stirring mixing 30min；Add 11 parts of lauric acid glycol ester stirring mixing 50min；Dehydration, dry obtain functionalization aluminium hydroxide a.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of bromine acidylate styrene-butadiene latex a and 10 parts of functionalization aluminium hydroxide a, 90 parts of water join stirring mixing 25min in condensing field; when then heating to 55 DEG C; it is sequentially added into 2.5 parts of potassium oleates, 3.5 parts of magnesium chlorides; it is 9 with NaOH regulation system pH value; stir 25min when being warming up to 80 DEG C and carry out ripening, finally scrubbed, dehydration, dry obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is in Table 1 after tested.
Embodiment 2
(1) preparation of halogen acidylate styrene-butadiene latex: with embodiment 1.
(2) preparation of functionalization smoke suppressant: with embodiment 1.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of bromine acidylate styrene-butadiene latex a and 12 parts of functionalization aluminium hydroxide a, 90 parts of water join stirring mixing 25min in condensing field; when then heating to 55 DEG C; it is sequentially added into 2.5 parts of potassium oleates, 3.5 parts of magnesium chlorides; it is 9 with NaOH regulation system pH value; stir 25min when being warming up to 80 DEG C and carry out ripening, finally scrubbed, dehydration, dry obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is in Table 1 after tested.
Embodiment 3
(1) preparation of halogen acidylate styrene-butadiene latex: with embodiment 1.
(2) preparation of functionalization smoke suppressant: with embodiment 1.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of bromine acidylate styrene-butadiene latex a and 14 parts of functionalization aluminium hydroxide a, 90 parts of water join stirring mixing 25min in condensing field; when then heating to 55 DEG C; it is sequentially added into 2.5 parts of potassium oleates, 3.5 parts of magnesium chlorides; it is 9 with NaOH regulation system pH value; stir 25min when being warming up to 80 DEG C and carry out ripening, finally scrubbed, dehydration, dry obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is in Table 1 after tested.
Embodiment 4
(1) preparation of halogen acidylate styrene-butadiene latex: be initially charged 100 parts of styrene-butadiene latex SBR1500,3 parts of dodecylbenzene sodium sulfonate, 7.0 parts of CS in polymeric kettle2, then stirring, heating, when still temperature rise to be polymerized is to 45 DEG C, rapidly join 0.15 part of AlCl3, until adding 11 parts of phthalic anhydrides, stirring reaction 3h when system becomes orange red, then adding 7 parts of bromines, and dripping 0.35 part of HCl-CH3(molar concentration of HCl is OH solution: 0.5mol/L) as catalyst, reacts 20h when 50 DEG C, is eventually adding the diluted hydrochloric acid aqueous solution that 13 parts of mass concentrations are 2.5% and terminates reaction, and sucking filtration, washing prepare bromine acidylate styrene-butadiene latex b.Sample analysis: the acylation degree recording bromine acidylate styrene-butadiene latex b is 16.8%；Bromine content is 20.5mol%.
(2) preparation of functionalization smoke suppressant: 3.5 parts of KH-550 and 80 parts of water, 8 parts of ethanol are joined in polymeric kettle and are uniformly mixed, is 9 with NaOH regulation system pH value, it is subsequently adding 100 parts of aluminium hydroxide, stirring mixing 30min；Add 15 parts of lauric acid glycol ester stirring mixing 50min；Dehydration, dry obtain functionalization aluminium hydroxide b.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of bromine acidylate styrene-butadiene latex b and 17 parts of functionalization aluminium hydroxide b, 90 parts of water join stirring mixing 25min in condensing field; when then heating to 55 DEG C; it is sequentially added into 3 parts of potassium oleates, 4 parts of magnesium chlorides; it is 10 with NaOH regulation system pH value; stir 25min when being warming up to 80 DEG C and carry out ripening, finally scrubbed, dehydration, dry obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is in Table 1 after tested.
Embodiment 5
(1) preparation of halogen acidylate styrene-butadiene latex: with embodiment 4.
(2) preparation of functionalization smoke suppressant: with embodiment 4.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of bromine acidylate styrene-butadiene latex b and 19 parts of functionalization aluminium hydroxide a, 90 parts of water join stirring mixing 25min in condensing field; when then heating to 55 DEG C; it is sequentially added into 3 parts of potassium oleates, 4 parts of magnesium chlorides; it is 10 with NaOH regulation system pH value; stir 25min when being warming up to 80 DEG C and carry out ripening, finally scrubbed, dehydration, dry obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is in Table 1 after tested.
Embodiment 6
(1) preparation of halogen acidylate styrene-butadiene latex: with embodiment 4.
(2) preparation of functionalization smoke suppressant: with embodiment 4.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of bromine acidylate styrene-butadiene latex b and 21 parts of functionalization aluminium hydroxide b, 90 parts of water join stirring mixing 25min in condensing field; when then heating to 55 DEG C; it is sequentially added into 3 parts of potassium oleates, 4 parts of magnesium chlorides; it is 10 with NaOH regulation system pH value; stir 25min when being warming up to 80 DEG C and carry out ripening, finally scrubbed, dehydration, dry obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is in Table 1 after tested.
Embodiment 7
(1) preparation of halogen acidylate styrene-butadiene latex: be initially charged 100 parts of styrene-butadiene latex SBR1712,4 parts of dodecylbenzene sodium sulfonate, 8.0 parts of CS in polymeric kettle2, then stirring, heating, when still temperature rise to be polymerized is to 45 DEG C, rapidly join 0.17 part of AlCl3, until adding 14 parts of phthalic anhydrides, stirring reaction 3h when system becomes orange red, then adding 9 parts of bromines, and dripping 0.4 part of HCl-CH3(molar concentration of HCl is OH solution: 0.6mol/L) as catalyst, reacts 20h when 50 DEG C, is eventually adding the diluted hydrochloric acid aqueous solution that 13 parts of mass concentrations are 2.5% and terminates reaction, and sucking filtration, washing prepare bromine acidylate styrene-butadiene latex c.Sample analysis: the acylation degree recording bromine acidylate styrene-butadiene latex c is 19.1%；Bromine content is 23.4mol%.
(2) preparation of functionalization smoke suppressant: 4.0 parts of A-151 and 90 parts of water, 9 parts of ethanol are joined in polymeric kettle and are uniformly mixed, with being 9 with NaOH regulation system pH value, is subsequently adding 100 parts of magnesium hydroxide, stirring mixing 30min；Add 23 parts of lauric acid butanediol ester stirring mixing 50min；Dehydration, dry obtain functionalization magnesium hydroxide c.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of bromine acidylate styrene-butadiene latex c and 23 parts of functionalization magnesium hydroxide c, 90 parts of water join stirring mixing 25min in condensing field; when then heating to 55 DEG C; it is sequentially added into 3.5 parts of potassium oleates, 4.5 parts of magnesium chlorides; it is 10 with NaOH regulation system pH value; stir 25min when being warming up to 80 DEG C and carry out ripening, finally scrubbed, dehydration, dry obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is in Table 1 after tested.
Embodiment 8
(1) preparation of halogen acidylate styrene-butadiene latex: with embodiment 7.
(2) preparation of functionalization smoke suppressant: 2.0 parts of A-151 and 2.5 parts of KH-550,90 parts of water, 9 parts of ethanol are joined in polymeric kettle and are uniformly mixed, with being 9 with NaOH regulation system pH value, is subsequently adding 100 parts of magnesium hydroxide, stirring mixing 30min；Add 23 parts of lauric acid butanediol ester stirring mixing 50min；Dehydration, dry obtain functionalization magnesium hydroxide d.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of bromine acidylate styrene-butadiene latex c and 24.5 parts of functionalization magnesium hydroxide d, 90 parts of water join stirring mixing 25min in condensing field; when then heating to 55 DEG C; it is sequentially added into 3.5 parts of potassium oleates, 4.5 parts of magnesium chlorides; it is 10 with NaOH regulation system pH value; stir 25min when being warming up to 80 DEG C and carry out ripening, finally scrubbed, dehydration, dry obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is in Table 1 after tested.
Comparative example 1
(1) preparation of halogen acidylate styrene-butadiene latex: with embodiment 1.
(2) preparation of functionalization smoke suppressant: with embodiment 1.
(3) preparation of fire-retardant powder styrene butadiene rubber: other condition is identical with embodiment 1, the addition being different in that in the preparation process of fire-retardant powder styrene butadiene rubber functionalization magnesium hydroxide a is 7 parts, that is: 100 parts of bromine acidylate styrene-butadiene latex a and 7 parts of functionalization aluminium hydroxide a are taken, 90 parts of water join stirring mixing 25min in condensing field, when then heating to 55 DEG C, it is sequentially added into 2.5 parts of potassium oleates, 3.5 parts of magnesium chlorides, it is 9 with NaOH regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out ripening, finally scrubbed, dehydration, dry and obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is in Table 1 after tested.
Comparative example 2
(1) preparation of halogen acidylate styrene-butadiene latex: with embodiment 1.
(2) preparation of fire-retardant powder styrene butadiene rubber: other condition is identical with embodiment 2, it is different in that in the preparation process of fire-retardant powder styrene butadiene rubber and is not added with functionalization aluminium hydroxide a, but it is directly added into aluminium hydroxide, its addition is 12 parts, that is: 100 parts of bromine acidylate styrene-butadiene latex a and 12 parts of functionalization aluminium hydroxide are taken, 90 parts of water join stirring mixing 25min in condensing field, when then heating to 55 DEG C, it is sequentially added into 2.5 parts of potassium oleates, 3.5 parts of magnesium chlorides, it is 9 with NaOH regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out ripening, finally scrubbed, dehydration, dry and obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is in Table 1 after tested.
Comparative example 3
(1) preparation of halogen acidylate styrene-butadiene latex: with embodiment 1.
(2) preparation of functionalization smoke suppressant: other condition is identical with embodiment 1, it is different in that in the preparation process of functionalization smoke suppressant and is added without lauric acid glycol ester, that is: 2.0 parts of KH-550 and 70 parts of water, 6 parts of ethanol are joined in polymeric kettle and are uniformly mixed, it is 8.5 with NaOH regulation system pH value, it is subsequently adding 100 parts of aluminium hydroxide, stirring mixing 30min；Dehydration, dry obtain functionalization aluminium hydroxide (a-1).
(3) preparation of fire-retardant powder styrene butadiene rubber: other condition is identical with embodiment 3, be different in that in compositions preparation process add functionalization aluminium hydroxide without lauric acid glycol ester containing only coupling agent, the addition of functionalization aluminium hydroxide (a-1) 14 parts, that is: 100 parts of bromine acidylate styrene-butadiene latex a and 14 parts of functionalization aluminium hydroxide (a-1) are taken, 90 parts of water join stirring mixing 25min in condensing field, when then heating to 55 DEG C, it is sequentially added into 2.5 parts of potassium oleates, 3.5 parts of magnesium chlorides, it is 9 with NaOH regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out ripening, finally scrubbed, dehydration, dry and obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is in Table 1 after tested.
Comparative example 4
(1) preparation of halogen acidylate styrene-butadiene latex: other condition is identical with embodiment 4; it is different in that in the preparation process of halogen acidylate styrene-butadiene latex and is added without bromine, it may be assumed that in polymeric kettle, be initially charged 100 parts of styrene-butadiene latex SBR1500,3 parts of dodecylbenzene sodium sulfonate, 7.0 parts of CS2, then stirring, heating, when still temperature rise to be polymerized is to 45 DEG C, rapidly join 0.15 part of AlCl3, until system adds 11 parts of phthalic anhydrides, stirring reaction 3h when becoming orange red, it being subsequently adding the diluted hydrochloric acid aqueous solution that 13 parts of mass concentrations are 2.5% and terminate reaction, sucking filtration, washing prepare acidylate styrene-butadiene latex (b-1).
(2) preparation of functionalization smoke suppressant: with embodiment 4.
(3) preparation of fire-retardant powder styrene butadiene rubber: other condition is identical with embodiment 4; it is different in that in the preparation process of fire-retardant powder styrene butadiene rubber and is added without bromine acidylate styrene-butadiene latex b, but in acidylate styrene-butadiene latex (b-1), add functionalization aluminium hydroxide b be condensed.That is: take 100 parts of acidylate styrene-butadiene latexes (b-1) and 17 parts of functionalization aluminium hydroxide b, 90 parts of water join stirring mixing 25min in condensing field; when then heating to 55 DEG C; it is sequentially added into 3 parts of potassium oleates, 4 parts of magnesium chlorides; it is 10 with NaOH regulation system pH value; stir 25min when being warming up to 80 DEG C and carry out ripening, finally scrubbed, dehydration, dry obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is in Table 1 after tested.
Comparative example 5
(1) preparation of functionalization smoke suppressant: with embodiment 4.
(2) preparation of fire-retardant powder styrene butadiene rubber: other condition is identical with embodiment 5, is different in that in the process of cohesion and is added without bromine acidylate styrene-butadiene latex b, but is directly added into functionalization aluminium hydroxide b in styrene-butadiene latex SBR1500 and is condensed.That is: take 100 parts of styrene-butadiene latex SBR1500 and 19 parts of functionalization aluminium hydroxide b, 90 parts of water join stirring mixing 25min in condensing field, when then heating to 55 DEG C, it is sequentially added into 3 parts of potassium oleates, 4 parts of magnesium chlorides, it is 10 with NaOH regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out ripening, finally scrubbed, dehydration, dry obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is in Table 1 after tested.
Comparative example 6
(1) preparation of halogen acidylate styrene-butadiene latex: with embodiment 4.
(2) preparation of functionalization smoke suppressant: other condition is identical with embodiment 4, it is different in that in the preparation process of functionalization smoke suppressant and is added without KH-550, that is: 80 parts of water, 8 parts of ethanol are joined in polymeric kettle and are uniformly mixed, it is 9 with NaOH regulation system pH value, it is subsequently adding 100 parts of aluminium hydroxide, stirring mixing 30min；Add 15 parts of lauric acid glycol ester stirring mixing 50min；Dehydration, dry obtain functionalization aluminium hydroxide (b-1).
(3) preparation of fire-retardant powder styrene butadiene rubber: other condition is identical with embodiment 6, be different in that in the preparation process of fire-retardant powder styrene butadiene rubber add functionalization aluminium hydroxide without silane resin acceptor kh-550, the addition of functionalization aluminium hydroxide (b-1) 21 parts, that is: 100 parts of bromine acidylate styrene-butadiene latex b and 21 parts of functionalization aluminium hydroxide (b-1) are taken, 90 parts of water join stirring mixing 25min in condensing field, when then heating to 55 DEG C, it is sequentially added into 3 parts of potassium oleates, 4 parts of magnesium chlorides, it is 10 with NaOH regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out ripening, finally scrubbed, dehydration, dry and obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is in Table 1 after tested.
Comparative example 7
(1) preparation of halogen acidylate styrene-butadiene latex: with embodiment 7.
(2) preparation of fire-retardant powder styrene butadiene rubber: other condition is identical with embodiment 7, it is different in that in the preparation process of fire-retardant powder styrene butadiene rubber and is not added with functionalization magnesium hydroxide c, but it is directly added into magnesium hydroxide, its addition is 23 parts, that is: 100 parts of bromine acidylate styrene-butadiene latex c and 23 parts of magnesium hydroxide are taken, 90 parts of water join stirring mixing 25min in condensing field, when then heating to 55 DEG C, it is sequentially added into 3.5 parts of potassium oleates, 4.5 parts of magnesium chlorides, it is 10 with NaOH regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out ripening, finally scrubbed, dehydration, dry and obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is in Table 1 after tested.
Comparative example 8
(1) preparation of functionalization smoke suppressant: with embodiment 8.
(2) preparation of fire-retardant powder styrene butadiene rubber: other condition is identical with embodiment 8, is different in that in the process of cohesion and is added without bromine acidylate styrene-butadiene latex c, but is directly added into functionalization magnesium hydroxide d in styrene-butadiene latex SBR1712 and is condensed.That is: take 100 parts of bromine acidylate styrene-butadiene latex c and 24.5 parts of functionalization magnesium hydroxide d, 90 parts of water join stirring mixing 25min in condensing field; when then heating to 55 DEG C; it is sequentially added into 3.5 parts of potassium oleates, 4.5 parts of magnesium chlorides; it is 10 with NaOH regulation system pH value; stir 25min when being warming up to 80 DEG C and carry out ripening, finally scrubbed, dehydration, dry obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is in Table 1 after tested.
The performance of table 1 flame retardant type powder styrene butadiene rubber
Claims (15)
1. a preparation method for low cigarette, fire-retardant powder styrene butadiene rubber, concrete preparation process is:
(1) preparation of halogen acidylate styrene-butadiene latex: count for 100 parts with styrene-butadiene latex quality, polymeric kettle is initially charged 100 parts of styrene-butadiene latexes, 1～5 part of emulsifying agent, 5～10 parts of solvents, stirring, heating, when still temperature to be polymerized reaches 25～50 DEG C, it is rapidly added 0.01～0.2 part of catalyst under agitation, until adding 3～15 parts of anhydride when system becomes orange red, stirring reaction 1～4h, then 4～10 portions of halogenating agents are added, and drip the methanol solution of 0.1～0.5 part of HCl, after reacting 15～30h when 30～60 DEG C, add the diluted hydrochloric acid aqueous solution that 10～15 parts of mass concentrations are 1.5%～5.0% and terminate reaction, sucking filtration, washing prepares halogen acidylate styrene-butadiene latex；
(2) preparation of functionalization smoke suppressant: count for 100 parts with smoke suppressant quality, 1～5 part of silane coupler and 50～100 parts of water, 5～10 parts of ethanol are joined in polymeric kettle and be uniformly mixed, it is 8～10 with buffer agent regulation system pH value, it is subsequently adding 100 parts of smoke suppressants, stirs mixing 10～30min；Add 10～20 parts of lauric acid polyol ester stirring mixing 30～60min；Dehydration, dry, grind and obtain functionalization smoke suppressant；
(3) preparation of fire-retardant powder styrene butadiene rubber: count for 100 parts with halogen acidylate styrene-butadiene latex quality; take 100 parts of halogen acidylate styrene-butadiene latexes and 10～25 parts of functionalization smoke suppressants, 50～100 parts of water join stirring mixing 10～30min in condensing field; when then heating to 50～60 DEG C; it is sequentially added into 2～5 portions of interleaving agents, 2～6 parts of flocculating agents; it is 8～11 with buffer agent regulation system pH value; stir 10～30min when being warming up to 70～90 DEG C and carry out ripening, finally scrubbed, dehydration, dry obtain low cigarette, fire-retardant powder styrene butadiene rubber product.
2. preparation method as claimed in claim 1, it is characterised in that described anhydride is dibasic acid anhydride compound.
3. preparation method as claimed in claim 1, it is characterised in that described anhydride one in succinic anhydride, maleic anhydride, phthalic anhydride.
4. preparation method as claimed in claim 1, it is characterised in that the addition of described anhydride is 7～12 parts.
5. preparation method as claimed in claim 1, it is characterised in that described halogenating agent is liquid chlorine, the one in bromine.
6. preparation method as claimed in claim 1, it is characterised in that described catalyst one in aluminum trichloride (anhydrous), boron trifluoride, butter of tin, zinc dichloride.
7. preparation method as claimed in claim 1, it is characterised in that described catalyst charge is 0.05～0.15 part.
8. preparation method as claimed in claim 1, it is characterised in that described solvent one in Carbon bisulfide, Nitrobenzol, petroleum ether, sym-tetrachloroethane, dichloroethanes.
9. preparation method as claimed in claim 1, it is characterised in that described smoke suppressant is at least one in magnesium hydroxide, aluminium hydroxide, calcium hydroxide, brucite, calcium aluminate, calcium carbonate.
10. preparation method as claimed in claim 1, it is characterised in that described lauric acid polyol ester compounds is selected from one or more in lauric acid glycol ester, lauric acid propylene glycol ester, lauric acid glycerine ester, lauric acid butanediol ester, lauric acid pentaerythritol ester.
11. preparation method as claimed in claim 1, it is characterised in that in the methanol solution of described HCl, the molar concentration of HCl is 0.1～0.7mol/L.
12. preparation method as claimed in claim 1, it is characterised in that described silane coupler is selected from one or more in gamma-aminopropyl-triethoxy-silane, 3-glycydoxy trimethoxy silane, VTES, N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, γ-methacryloxypropyl trimethoxy silane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, vinyltrimethoxy silane.
13. preparation method as claimed in claim 1, it is characterised in that described interleaving agent is selected from one or more in potassium stearate, sodium stearate, potassium oleate, enuatrol.
14. preparation method as claimed in claim 1, it is characterised in that described flocculating agent is selected from one or more in sodium chloride, magnesium chloride, iron chloride, calcium chloride, magnesium sulfate, aluminum sulfate, Alumen.
15. preparation method as claimed in claim 1, it is characterised in that described buffer agent one in sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonia, ammonium hydrogen carbonate.
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| CN113402835B (en) * | 2021-07-14 | 2022-10-21 | 上海葛蓝化工科技有限公司 | Preparation method of high-flame-retardant, low-smoke and high-impact polystyrene |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6433064B1 (en) * | 1998-12-18 | 2002-08-13 | Pku Pulverkautschuk Union Gmbh | Rubber powder compositions and process for the production 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 |
| CN103159867A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Preparation method for flame-retardant powdered rubber |
-
2013
- 2013-09-18 CN CN201310426586.3A patent/CN104448452B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6433064B1 (en) * | 1998-12-18 | 2002-08-13 | Pku Pulverkautschuk Union Gmbh | Rubber powder compositions and process for the production 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 |
| CN103159867A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Preparation method for flame-retardant powdered rubber |
Non-Patent Citations (1)
| Title |
|---|
| 纳米级粉末橡胶协同阻燃HIPS;彭晓玲等;《合成树脂及塑料》;20091231;第26卷(第2期);1-3 * |
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