CN104448447B - A kind of preparation method of environmental protection low-smoke and flame retardant powder styrene butadiene rubber - Google Patents
A kind of preparation method of environmental protection low-smoke and flame retardant powder styrene butadiene rubber Download PDFInfo
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Abstract
The invention provides the preparation method of a kind of maximum environmental protection low-smoke and flame retardant type powder styrene butadiene rubber that smoke density is less than 110, oxygen index (OI) is more than 40%.This invention uses styrene-butadiene latex and anhydride to carry out acylation reaction, then expansible graphite (EG) is carried out coating modification, finally by the method for direct condensation powdering after acylated styrene-butadiene latex and the mixing of functionalization expansible graphite with polarity latex.This method improves expansible graphite and the compatibility of elastomeric material and particle size stability significantly, solve the problem that expansible graphite dispersion in rubber matrix is uneven, impart the feature of environmental protection of powder styrene butadiene rubber fire resistance, low cigarette, the feature of high efficiency.
Description
Technical field
The present invention relates to the preparation method of a kind of fire-retardant powder styrene butadiene rubber, be specifically related to a kind of acylated styrene-butadiene latex and functionalization expansible graphite (EG) is directly blended, the then preparation method of the low-smoke and flame retardant powder styrene butadiene rubber of condensation powdering.
Background technology
It is known that, powder styrene butadiene rubber (PSBR) is a kind of hydrocarbon rubbers, the elements such as substantial amounts of carbon, hydrogen are all contained on its main chain, 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 is to produce a large amount of smog and toxicant during 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, mainly prepared by the method adding fire retardant and smoke suppressant about the low cigarette of elastomeric material, fire-retardant research.As: CN101121796A discloses a kind of by adding a small amount of expansible graphite, the production method of the Halogen thermoplastic flame-retardant rubber of LSZH when preparation good flame retardation effect, burning.ZL200810057092.1 discloses a kind of by adding APP, Firebrake ZB, nano-inorganic substance, white carbon etc., prepares a kind of oil resistant, heat-resisting expansion type flame-proof rubber.ZL96116942.7 discloses and a kind of is used in conjunction with each other with halogen-free flame retardants aluminium hydroxide (magnesium), antimony oxide and phosphorus flame retardant, 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 using organic phosphorus flame retardant triaryl phosphate and organic modified nano montmorillonite to compound preparation, and be applied in natural rubber system with 10～15wt% additions, prepare environment-friendly flame retardant rubber material.CN102040779A discloses a kind of containing EPDM rubber, isocyanate-terminated polybutadiene, vulcanizing agent, the mixture of hydroxide flame retardant, to obtain a kind of flame retardant rubber by mixing, sulfuration.
Summary of the invention
Present invention aim at providing the preparation method of a kind of maximum environmental protection low-smoke and flame retardant type powder styrene butadiene rubber that smoke density is less than 110, oxygen index (OI) is more than 40%.This invention uses styrene-butadiene latex and anhydride to carry out acylation reaction, then expansible graphite (EG) is carried out coating modification, finally by the method for direct condensation powdering after acylated styrene-butadiene latex and the mixing of functionalization expansible graphite with polarity latex.This method improves expansible graphite and the compatibility of elastomeric material and particle size stability significantly, solve the problem that expansible graphite dispersion in rubber matrix is uneven, impart the feature of environmental protection of powder styrene butadiene rubber fire resistance, low cigarette, the feature of high efficiency.
" part " of the present invention each means mass parts.
A kind of low cigarette of the present invention, the preparation method of fire-retardant powder styrene butadiene rubber, concrete preparation process is:
(1) preparation of acylated styrene-butadiene latex: be in terms of 100 parts by styrene-butadiene latex quality; 100 parts of styrene-butadiene latexes, 1～5 part of emulsifying agent, 5～10 parts of solvents it are initially charged in polymeric kettle; 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; after stirring reaction 1～4h; being subsequently adding the diluted hydrochloric acid aqueous solution that 10～15 parts of mass concentrations are 1.5%～5.0% and terminate reaction, sucking filtration, washing prepare acylated styrene-butadiene latex.
(2) functionalization expansible graphite: be in terms of 100 parts by expansible graphite quality, 1～5 part of titanate coupling agent and 50～100 parts of water, 5～10 parts of ethanol are joined in polymeric kettle and be uniformly mixed, it is 2～6 with acid regulation system pH value, it is subsequently adding 100 parts of expansible graphites, stirring mixing 10～30min；Add 5～15 parts of carboxylic styrene butadiene latex stirring mixing 30～60min；Dehydration, be dried, grind obtain functionalization expansible graphite.
(3) preparation of fire-retardant powder styrene butadiene rubber: be in terms of 100 parts by acylated styrene-butadiene latex quality; take 100 parts of acylated styrene-butadiene latexes and 2～12 parts of functionalization expansible graphites, 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, the most scrubbed, be dehydrated, be dried to 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, preferably phthalic anhydride, and its addition is 3～15 parts, preferably 7～12 parts.
Catalyst of the present invention is selected from aluminum trichloride (anhydrous) (AlCl3), boron trifluoride (BF3), butter of tin (SnCl4), zinc dichloride (ZnCl2One in), preferably AlCl3, its addition is 0.01～0.2 part, preferably 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, preferably CS2。
The particle diameter of expansible graphite of the present invention is 20 μm～200 μm, preferably 30 μm～100 μm.
Carboxylic styrene butadiene latex of the present invention is with butadiene, styrene as main monomer, and unsaturated carboxylic acid is that function monomer obtains through emulsion polymerization, and unsaturated carboxylic acid therein is acrylic acid, methacrylic acid or 2-ethylacrylic acid, preferably acrylic acid.The solids content 41%～55% of carboxylic styrene butadiene latex, latex particle size 100～175nm.
Titanate coupling agent of the present invention can be selected from the compounding of one or more in isopropyl two oleic acid acyloxy titanate esters (NDZ-101), dioctyl phosphoric acid acyloxy titanate esters (NDZ-102), isopropyl three oleic acid acyloxy titanate esters (NDZ-105), dodecyl benzenesulfonyl titanate esters (NDZ-109), dioctylphyrophosphoric acid acyloxy titanate esters (NDZ-201), dioctyl phosphito acyloxy titanate esters (NDZ-401).
Acid of the present invention can be selected from one or more in oxalic acid, hydrochloric acid, sulphuric acid, phosphoric acid, dust technology, preferably oxalic acid, and the mass concentration of its acid is 0.03%～0.1%.
Styrene-butadiene latex of the present invention is to be formed by emulsion polymerization copolymerization by conjugated diene hydrocarbon compound and aryl ethylene compounds.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 being used, interleaving agent, flocculating agent, buffer agent etc. are all not specially limited, all can use conven-tional adjuvants generally in the art, its addition is also those skilled in the art can be with calculated conventional amount used according to the consumption of latex, and the present invention does not the most do particular determination.
Emulsifying agent is known to those skilled in the art as described in the present invention, can be one or more in anion emulsifier and nonionic emulsifier.As: one or more in fatty acid soaps, RA rosin acid, dodecylbenzene sodium sulfonate, sodium lauryl sulphate, polyoxyethylene sorbitol acid anhydride list olein, preferably dodecylbenzene sodium sulfonate can be selected from.
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, preferably sodium hydroxide.
The present invention use expansible graphite (EG) under flame interaction, the H of interlayer2SO4Gas is discharged with graphite generation redox reaction, start to expand and form the porous densification layer of charcoal that heat conductivity is low, intercept flame heat regulating conduction, the oxidation reaction of the cigarette precursor formed in suppression burning, contribute to removing the living radical that flame is propagated, there is good smoke-inhibiting flame retardant effect.But EG is made up of carbon atom in layer, and interlayer is inserted with sulfate group, causing with nonpolar styrene-butadiene latex poor compatibility, interface is difficult to be formed good bonding；Graphite layers adhesion is weak simultaneously, and layer structure is easy to move from other structure being connected China and foreign countries, and particle size stability is poor, causes expansible graphite to be difficult to disperse well in styrene-butadiene latex substrate, have impact on smoke-inhibiting flame retardant effect.In order to solve this problem, first EG surface is carried out functional modification, use titanate coupling agent to process EG particle so that carboxylic styrene butadiene latex forms close clad at particle surface.Secondly styrene-butadiene latex is carried out acylated process.The most not only make expansible graphite particle surface with a certain amount of polar group carboxyl; can and acylated styrene-butadiene latex polar groups acyl group produce the mutual attractive force between molecule; improve the caking property between particle and styrene-butadiene latex matrix; improve the compatibility of expansible graphite and acylated styrene-butadiene latex significantly; it is capable of being evenly dispersed in styrene-butadiene latex substrate; but also it is possible to prevent the outer shifting of graphite layers; ensure that particle size is stable; contribute to expanding stablizing of carbon layers having thicknesses, improve the shield effectiveness of carbon-coating.Therefore, functionalization expansible graphite in powder styrene butadiene rubber press down cigarette and flame retardant effect and persistency can be manifested further, its maximum smoke density less than 110, oxygen index (OI) more than more than 40% higher than the requirement of high temperature flame-proof rubber national standard.It is low that the method has adding proportion, and smoke elimination efficiency is high, good flame retardation effect, the modified feature such as low cost, environment-protecting asepsis.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of styrene-butadiene latex and the acylated styrene-butadiene latex of embodiment 1 preparation.
Wherein, a-styrene-butadiene latex SBR1500；B-is acylated styrene-butadiene latex SBR1500.
Detailed description of the invention
The effect of the 1 explanation present invention below in conjunction with the accompanying drawings, in Fig. 1, a is the infrared spectrogram of styrene-butadiene latex SBR1500 sample, and b is the infrared spectrogram of the acylated styrene-butadiene latex SBR1500 sample of embodiment 1 preparation, the degree of acetylation 13.1% of b.As can be seen from Figure 1: the FTIR spectrogram of sample b is at 1670cm-1And 1280cm-1Two new absworption peaks occur.Wherein 1670cm-1The characteristic absorption peak that absworption peak is carbonyl at place, illustrates that styrene-butadiene latex SBR1500 occurs acetylization reaction, and the FTIR spectrogram of sample a does not has herein absworption peak to occur.Additionally, 1280cm-1Absworption peak can be attributed to C-O key out-of-plane vibration absorb, prove the existence of carbonyl (C=O) further.It addition, the FTIR spectrogram of sample b is at 840cm-1The absworption peak at place is remarkably reinforced, and it can be attributed to the characteristic absorption peak of para-position disubstituted benzenes ring, illustrates that acylated styrene-butadiene latex SBR1500 acylation reaction occurs mainly in the para-position of phenyl ring.
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:
Embodiment 1
(1) preparation of acylated styrene-butadiene latex: be initially charged 100 parts of styrene-butadiene latex SBR1500,2 parts of dodecylbenzene sodium sulfonate, 5.5 parts of CS in polymeric kettle2, then stir, heat, when still temperature rise to be polymerized is to 40 DEG C, rapidly join 0.05 part of AlCl3, until system adds 5 parts of phthalic anhydrides when becoming orange red, after then reacting 2h when 45 DEG C, it being eventually adding the diluted hydrochloric acid aqueous solution that 12 parts of mass fractions are 2.4% and terminate reaction, sucking filtration, washing prepare acylated styrene-butadiene latex a.Sample analysis: the degree of acetylation recording acylated styrene-butadiene latex is 13.1%.
(2) preparation of functionalization expansible graphite: 1.5 parts of NDZ-101 coupling agents and 60 parts of water, 6 parts of ethanol are joined in polymeric kettle and are uniformly mixed, with mass concentration be 0.05% oxalic acid solution regulation system pH value be 5, it is subsequently adding 100 parts of expansible graphites (45 μm), stirring mixing 10～30min；Add 7 parts of carboxylic styrene butadiene latex stirring mixing 60min；Dehydration, be dried, grind obtain functionalization expansible graphite a.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of acylated styrene-butadiene latex a and 2 parts of functionalization expansible graphite a, 50 parts of water join stirring mixing 30min 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, the most scrubbed, be dehydrated, be dried to obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown in Table 1 after tested.
Embodiment 2
(1) preparation of acylated styrene-butadiene latex: with embodiment 1.
(2) preparation of functionalization expansible graphite: with embodiment 1.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of acylated styrene-butadiene latex a and 4 parts of functionalization expansible graphite a, 50 parts of water join stirring mixing 30min 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, the most scrubbed, be dehydrated, be dried to obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown in Table 1 after tested.
Embodiment 3
(1) preparation of acylated styrene-butadiene latex: with embodiment 1.
(2) preparation of functionalization expansible graphite: with embodiment 1.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of acylated styrene-butadiene latex a and 6 parts of functionalization expansible graphite a, 50 parts of water join stirring mixing 30min 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, the most scrubbed, be dehydrated, be dried to obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown in Table 1 after tested.
Embodiment 4
(1) preparation of acylated styrene-butadiene latex: be initially charged 100 parts of styrene-butadiene latex SBR1500,3 parts of dodecylbenzene sodium sulfonate, 7.5 parts of CS in polymeric kettle2, then stir, heat, when still temperature rise to be polymerized is to 40 DEG C, rapidly join 0.07 part of AlCl3, until system adds 6.5 parts of phthalic anhydrides when becoming orange red, after then reacting 2h when 45 DEG C, it being eventually adding the diluted hydrochloric acid aqueous solution that 13 parts of mass fractions are 3.0% and terminate reaction, sucking filtration, washing prepare acylated styrene-butadiene latex b.Sample analysis: the degree of acetylation recording acylated styrene-butadiene latex is 14.8%.
(2) preparation of functionalization expansible graphite: 2.5 parts of NDZ-101 coupling agents and 60 parts of water, 7 parts of ethanol are joined in polymeric kettle and are uniformly mixed, with mass concentration be 0.05% oxalic acid solution regulation system pH value be 5, it is subsequently adding 100 parts of expansible graphites (70 μm), stirring mixing 10～30min；Add 10 parts of carboxylic styrene butadiene latex stirring mixing 60min；Dehydration, be dried, grind obtain functionalization expansible graphite b.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of acylated styrene-butadiene latex b and 8 parts of functionalization expansible graphite b, 70 parts of water join stirring mixing 30min in condensing field; when then heating to 55 DEG C; it is sequentially added into 3.5 parts of potassium oleates, 4 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, the most scrubbed, be dehydrated, be dried to obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown in Table 1 after tested.
Embodiment 5
(1) preparation of acylated styrene-butadiene latex: with embodiment 4.
(2) preparation of functionalization expansible graphite: with embodiment 4.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of acylated styrene-butadiene latex b and 9 parts of functionalization expansible graphite b, 70 parts of water join stirring mixing 30min in condensing field; when then heating to 55 DEG C; it is sequentially added into 3.5 parts of potassium oleates, 4 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, the most scrubbed, be dehydrated, be dried to obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown in Table 1 after tested.
Embodiment 6
(1) preparation of acylated styrene-butadiene latex: with embodiment 4.
(2) preparation of functionalization expansible graphite: with embodiment 4.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of acylated styrene-butadiene latex b and 10 parts of functionalization expansible graphite b, 70 parts of water join stirring mixing 30min in condensing field; when then heating to 55 DEG C; it is sequentially added into 3.5 parts of potassium oleates, 4 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, the most scrubbed, be dehydrated, be dried to obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown in Table 1 after tested.
Embodiment 7
(1) halogen is acylated the preparation of styrene-butadiene latex: be initially charged 100 parts of styrene-butadiene latex SBR1712,4 parts of dodecylbenzene sodium sulfonate, 8.5 parts of CS in polymeric kettle2, then stir, heat, when still temperature rise to be polymerized is to 40 DEG C, rapidly join 0.12 part of AlCl3, until system adds 8.5 parts of phthalic anhydrides when becoming orange red, after then reacting 2h when 45 DEG C, it being eventually adding the diluted hydrochloric acid aqueous solution that 13 parts of mass fractions are 4.5% and terminate reaction, sucking filtration, washing prepare acylated styrene-butadiene latex c.Sample analysis: the degree of acetylation recording acylated styrene-butadiene latex is 15.6%.
(2) preparation of functionalization expansible graphite: 2.5 parts of NDZ-401 coupling agents and 70 parts of water, 9 parts of ethanol are joined in polymeric kettle and are uniformly mixed, with mass concentration be 0.05% oxalic acid solution regulation system pH value be 5, it is subsequently adding 100 parts of expansible graphites (70 μm), stirring mixing 10～30min；Add 13 parts of carboxylic styrene butadiene latex stirring mixing 60min；Dehydration, be dried, grind obtain functionalization expansible graphite c.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of acylated styrene-butadiene latex c and 11 parts of functionalization expansible graphite c, 80 parts of water join stirring mixing 30min in condensing field; when then heating to 55 DEG C; it is sequentially added into 4 parts of potassium oleates, 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, the most scrubbed, be dehydrated, be dried to obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown in Table 1 after tested.
Comparative example 1
(1) preparation of acylated styrene-butadiene latex: with embodiment 1.
(2) preparation of functionalization expansible graphite: with embodiment 1.
(3) preparation of fire-retardant powder styrene butadiene rubber: other condition is same as in Example 1, difference is in the preparation process of fire-retardant powder styrene butadiene rubber that the addition of functionalization expansible graphite a is 1 part, that is: 100 parts of acylated styrene-butadiene latex a and 1 part of functionalization expansible graphite a are taken, 50 parts of water join stirring mixing 30min 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, the most scrubbed, dehydration, it is dried to obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown in Table 1 after tested.
Comparative example 2
(1) preparation of acylated styrene-butadiene latex: with embodiment 1.
(2) preparation of fire-retardant powder styrene butadiene rubber: other condition is same as in Example 2, difference is in the preparation process of fire-retardant powder styrene butadiene rubber to be not added with functionalization expansible graphite a, but it is directly added into expansible graphite (45 μm), its addition is 4 parts, that is: 100 parts of acylated styrene-butadiene latex a and 4 parts of expansible graphites are taken, 50 parts of water join stirring mixing 30min 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, the most scrubbed, dehydration, it is dried to obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown in Table 1 after tested.
Comparative example 3
(1) preparation of acylated styrene-butadiene latex: with embodiment 1.
(2) preparation of functionalization expansible graphite: other condition is same as in Example 1, difference is in the preparation process of expansible graphite to be added without carboxylic styrene butadiene latex, that is: 1.5 parts of NDZ-101 coupling agents and 60 parts of water, 6 parts of ethanol are joined in polymeric kettle and are uniformly mixed, with mass concentration be 0.05% oxalic acid solution regulation system pH value be 5, it is subsequently adding 100 parts of expansible graphites (45 μm), stirring mixing 10～30min；Dehydration, be dried, grind obtain functionalization expansible graphite (a-1).
(3) preparation of fire-retardant powder styrene butadiene rubber: other condition is same as in Example 3, difference be in compositions preparation process add functionalization expansible graphite without carboxylic styrene butadiene latex and containing only coupling agent, the addition of functionalization expansible graphite (a-1) 6 parts, that is: 100 parts of acylated styrene-butadiene latex a and 6 parts of functionalization expansible graphites (a-1) are taken, 50 parts of water join stirring mixing 30min 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, the most scrubbed, dehydration, it is dried to obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown in Table 1 after tested.
Comparative example 4
(1) preparation of acylated styrene-butadiene latex: with embodiment 1.
(2) preparation of functionalization expansible graphite: other condition is same as in Example 1, difference is in the preparation process of expansible graphite to be added without NDZ-101 coupling agent, that is: 60 parts of water, 7 parts of ethanol are joined in polymeric kettle and are uniformly mixed, with mass concentration be 0.05% oxalic acid solution regulation system pH value be 5, it is subsequently adding 100 parts of expansible graphites (70 μm), stirring mixing 10～30min；Add 10 parts of carboxylic styrene butadiene latex stirring mixing 60min；Dehydration, be dried, grind obtain functionalization expansible graphite (b-1).
(3) preparation of fire-retardant powder styrene butadiene rubber: other condition is same as in Example 3, difference be in compositions preparation process add functionalization expansible graphite without coupling agent and containing only carboxylic styrene butadiene latex, the addition of functionalization expansible graphite (b-1) 8 parts, that is: 100 parts of acylated styrene-butadiene latex b and 8 parts of functionalization expansible graphites (b-1) are taken, 70 parts of water join stirring mixing 30min in condensing field, when then heating to 55 DEG C, it is sequentially added into 3.5 parts of potassium oleates, 4 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, the most scrubbed, dehydration, it is dried to obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown in Table 1 after tested.
Comparative example 5
(1) preparation of functionalization expansible graphite: with embodiment 4.
(2) preparation of fire-retardant powder styrene butadiene rubber: other condition is same as in Example 5, difference is added without acylated styrene-butadiene latex b, but is directly added into functionalization expansible graphite b in styrene-butadiene latex SBR1500 and is condensed during being cohesion.That is: take 100 parts of styrene-butadiene latex SBR1500 and 9 parts of functionalization expansible graphite b, 70 parts of water join stirring mixing 30min in condensing field, when then heating to 55 DEG C, it is sequentially added into 3.5 parts of potassium oleates, 4 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, the most scrubbed, be dehydrated, be dried to obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown in Table 1 after tested.
Comparative example 6
(1) preparation of acylated styrene-butadiene latex: with embodiment 4.
(2) preparation of fire-retardant powder styrene butadiene rubber: other condition is same as in Example 6, difference is in the preparation process of fire-retardant powder styrene butadiene rubber to be not added with functionalization expansible graphite a, but it is directly added into expansible graphite (70 μm), its addition is 10 parts, that is: 100 parts of acylated styrene-butadiene latex b and 10 parts of expansible graphites are taken, 70 parts of water join stirring mixing 30min in condensing field, when then heating to 55 DEG C, it is sequentially added into 3.5 parts of potassium oleates, 4 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, the most scrubbed, dehydration, it is dried to obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown in Table 1 after tested.
Comparative example 7
(1) preparation of functionalization expansible graphite: with embodiment 7.
(2) preparation of fire-retardant powder styrene butadiene rubber: other condition is same as in Example 7, difference is added without acylated styrene-butadiene latex c during being cohesion, but in styrene-butadiene latex SBR1712, be directly added into functionalization expansible graphite c be condensed, that is: 100 parts of styrene-butadiene latex SBR1712 and 11 parts of functionalization expansible graphite c are taken, 80 parts of water join stirring mixing 30min in condensing field, when then heating to 55 DEG C, it is sequentially added into 4 parts of potassium oleates, 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, the most scrubbed, dehydration, it is dried to obtain low cigarette, fire-retardant powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown in Table 1 after tested.
The performance of table 1 flame retardant type powder styrene butadiene rubber
Claims (14)
1. low cigarette, a preparation method for fire-retardant powder styrene butadiene rubber, concrete preparation process is:
(1) preparation of acylated styrene-butadiene latex: be in terms of 100 parts by styrene-butadiene latex quality, is initially charged 100 parts in polymeric kettle
Styrene-butadiene latex, 1～5 part of emulsifying agent, 5～10 parts of solvents, stir, heat, 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,
After stirring reaction 1～4h, it is subsequently adding the diluted hydrochloric acid aqueous solution that 10～15 parts of mass concentrations are 1.5%～5.0% and terminates anti-
Should, sucking filtration, washing prepare acylated styrene-butadiene latex；
(2) functionalization expansible graphite: be in terms of 100 parts by expansible graphite quality, by 1～5 part of titanate coupling agent
Join in polymeric kettle be uniformly mixed with 50～100 parts of water, 5～10 parts of ethanol, with acid regulation system pH value be 2～
6, it is subsequently adding 100 parts of expansible graphites, stirring mixing 10～30min；Add 5～15 parts of carboxylic styrene butadiene latexs to stir
Mix mixing 30～60min；Dehydration, be dried, grind obtain functionalization expansible graphite；
(3) preparation of fire-retardant powder styrene butadiene rubber: be in terms of 100 parts by acylated styrene-butadiene latex quality, takes 100 parts of acylated fourths
Benzene latex and 2～12 parts of functionalization expansible graphites, 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, uses buffer agent regulation system
PH value is 8～11, stirs 10～30min and carry out ripening when being warming up to 70～90 DEG C, the most scrubbed, be dehydrated, be dried
Obtain low cigarette, fire-retardant powder styrene butadiene rubber product；
Described styrene-butadiene latex is to be formed by emulsion polymerization copolymerization by conjugated diene hydrocarbon compound and aryl ethylene compounds,
Described conjugated diene hydrocarbon compound is C4Class conjugated diene hydrocarbon compound, described aryl ethylene compounds selected from styrene,
α-methyl styrene or ethyl styrene.
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 is succinic anhydride, maleic anhydride, neighbour
One in phthalate anhydride.
4. preparation method as claimed in claim 1, it is characterised in that described anhydride addition is 7～12 parts.
5. preparation method as claimed in claim 1, it is characterised in that described catalyst selected from aluminum trichloride (anhydrous), boron trifluoride,
One in butter of tin, zinc dichloride.
6. preparation method as claimed in claim 1, it is characterised in that described catalyst is aluminum chloride.
7. preparation method as claimed in claim 1, it is characterised in that described catalyst be addition be 0.05～0.15 part.
8. preparation method as claimed in claim 1, it is characterised in that described solvent selected from Carbon bisulfide, Nitrobenzol, petroleum ether,
One in sym-tetrachloroethane, dichloroethanes.
9. preparation method as claimed in claim 1, it is characterised in that the particle diameter of described expansible graphite is 20 μm～200 μm.
10. preparation method as claimed in claim 1, it is characterised in that the particle diameter of described expansible graphite is 30 μm～100 μm.
11. preparation methoies as claimed in claim 1, it is characterised in that described carboxylic styrene butadiene latex is butadiene, styrene and not
Saturated carboxylic acid obtains through emulsion polymerization.
12. preparation methoies as claimed in claim 11, it is characterised in that described unsaturated carboxylic acid be acrylic acid, methacrylic acid or
2-ethylacrylic acid.
13. preparation methoies as claimed in claim 1, it is characterised in that described titanate coupling agent is selected from isopropyl two oleic acid acyl-oxygen
Base titanate esters, dioctyl phosphoric acid acyloxy titanate esters, isopropyl three oleic acid acyloxy titanate esters, dodecyl benzenesulfonyl
Answering of one or more in titanate esters, dioctylphyrophosphoric acid acyloxy titanate esters, dioctyl phosphito acyloxy titanate esters
Join.
14. preparation methoies as claimed in claim 1, it is characterised in that described acid is selected from oxalic acid, hydrochloric acid, sulphuric acid, phosphoric acid, dilute
One or more in nitric acid.
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