CN104448663A - Method for preparing environment-friendly low-smoke flame-retardant powdered butadiene styrene rubber - Google Patents
Method for preparing environment-friendly low-smoke flame-retardant powdered butadiene styrene rubber Download PDFInfo
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Abstract
The invention provides a method for preparing an environment-friendly low-smoke flame-retardant powdered butadiene styrene rubber with the maximum smoke density less than 100 and the oxygen index more than 45%. In the present invention, expandable graphite (EG) is subjected to coating modification by adopting polar latex. Then, styrene-butadiene latex is respectively modified by allyltriphenylphosphorus bromide and a polar monomer through graft polymerization. Finally, the grafted styrene-butadiene latex is mixed with the functionalized EG to directly agglomerate into powder. According to the invention, compatibility between the EG and the butadiene styrene rubber and dimensional stability of rubber particles are significantly improved. The problem that EG is dispersed non-uniformly in a butadiene styrene rubber matrix is overcome and the flame-retardant powdered butadiene styrene rubber is environment-friendly, low-smoke and high-efficient.
Description
Technical field
The present invention relates to a kind of preparation method of fire-retardant powder styrene butadiene rubber, be specifically related to a kind of functionalization expansible black lead (EG) and the low cigarette of graft modification styrene-butadiene latex, the preparation method of high flame retardant powder styrene butadiene rubber.
Background technology
As everyone knows, powder styrene butadiene rubber (PSBR) is a kind of hydrocarbon rubbers, all containing elements such as a large amount of carbon, hydrogen on its main chain, easily inflammable gas is produced during melted by heat, when high temperature easily and oxygen effect burn, cause its oxygen index low, flame retardant properties is poor, bring potential fire hazard thus, limit the application of PSBR in the fields such as mine, electronics, electrical equipment industry, automobile, aircraft, steamer.At present, the industrial halogen containing flame-retardant that generally adopts of China prepares flame retardant rubber, its advantage is to have higher flame retardant resistance, shortcoming produces a large amount of smog and toxicant when being burning, make adult respiratory distress, the consequence that its hazardness often produces than burning is even more serious, is the primary Hazard Factor causing people's injures and deaths in fire.In recent years, along with the reinforcement day by day of global safety environmental consciousness, the requirement of people to the flame retardant properties of fire savety and goods is more and more higher, develops novel low cigarette, the combustion elastomeric material of high flame retardant becomes study hotspot.
In prior art, about the low cigarette of elastomeric material, fire-retardant research are mainly prepared by the method for adding fire retardant and smoke suppressant.As: CN101121796A discloses a kind of by adding a small amount of expansible black lead, 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 ammonium polyphosphate, zinc borate, nano-inorganic substance, white carbon black etc., prepares a kind of oil resistant, heat-resisting expansion type flame-proof rubber.ZL96116942.7 discloses and a kind of to be used in conjunction with each other with halogen-free flame retardants aluminium hydroxide (magnesium), antimonous oxide and phosphorus flame retardant, by mixing blending technology, prepares low cigarette, low toxicity, environment-friendly type flame-retardant rubber floor that flame retardant properties is good.ZL201010136235.5 discloses a kind of efficient, the environment friendly flame retardant that adopt organic phosphorus flame retardant triaryl phosphate and the composite preparation of organic modified nano polynite, and be applied in natural rubber system with 10 ~ 15wt% addition, prepare environment-friendly flame retardant rubber material.CN102040779A discloses a kind of with the mixture containing Ethylene Propylene Terpolymer rubber, isocyanate-terminated polyhutadiene, vulcanizing agent, hydroxide flame retardant, obtains a kind of flame retardant rubber by mixing, sulfuration.CN 1324885A discloses the unsaturated carboxylic acid-modified inorganic fire-retarded fillers such as a kind of employing methacrylic acid (MAA) or vinylformic acid (AA), the halogen-free fireproof rubber material of preparation excellent flame retardancy.After Tan Haisheng etc. adopt propenyl chloride and methyl methacrylate-grafted modified natural rubber latex, obtain the graftomer of flame retardant properties and good mechanical performance " the preparation and property research of AC/MMA graft modification natural rubber latex " (elastomerics, 2002,12 (6): 32 ~ 35).
Summary of the invention
The preparation method that the object of the invention is to provide a kind of maximum smoke density to be less than 100, oxygen index is greater than the environmental protection low-smoke and flame retardant type powder styrene butadiene rubber of 45%.This invention adopts polarity latex to carry out coating modification to expansible black lead (EG), then with allyl group tri-phenyl-phosphorus bromide and polar monomer, respectively modification of graft is carried out to styrene-butadiene latex, finally by the method for direct condensation powdering after the styrene-butadiene latex of graft modification and the mixing of functionalization expansible black lead.This method improves consistency and the particle size stability of expansible black lead and elastomeric material significantly, solve the problem of the dispersion inequality of expansible black lead in rubber matrix, impart the feature of the feature of environmental protection of powder styrene butadiene rubber flame retardant properties, low cigarette, high efficiency.
" part " of the present invention all refers to mass parts.
The preparation method of a kind of low cigarette of the present invention, fire-retardant powder styrene butadiene rubber, concrete preparation process is:
(1) functionalization expansible black lead: be 100 parts in expansible black lead 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, be 2 ~ 6 by sour regulation system pH value, then add 100 parts of expansible black leads, be uniformly mixed 10 ~ 30min; Add 5 ~ 15 parts of carboxylic styrene butadiene latexs again and be uniformly mixed 30 ~ 60min; Dehydration, drying, grinding obtain functionalization expansible black lead.
(2) preparation of flame retardant type graft latex: be 100 parts in styrene-butadiene latex quality, first 100 ~ 200 parts of deionized waters are added in polymeric kettle, then 100 parts of styrene-butadiene latexes are added successively, 1 ~ 10 part of emulsifying agent, 0.1 ~ 1.0 part of molecular weight regulator, after nitrogen replacement, and then the allyl group tri-phenyl-phosphorus bromide grafted monomer of 5 ~ 15 parts is first added, stir, heating, still temperature to be polymerized adds 0.1 ~ 0.5 part of initiator when reaching 40 ~ 60 DEG C, after reaction 5 ~ 10h, then at the polar monomer and 0.05 ~ 0.1 part of initiator that add 1 ~ 5 part, after continuing reaction 2 ~ 4h, add 0.1 ~ 0.5 part of terminator, obtained flame retardant type grafting styrene-butadiene latex.
(3) preparation of fire-retardant powder styrene butadiene rubber: be 100 parts in fire-retardant grafting styrene-butadiene latex quality, get 100 parts of flame retardant type graft latexes and 1 ~ 10 part of functionalization expansible black lead, 50 ~ 100 parts of water join in condensing field and are uniformly mixed 10 ~ 30min, when being then warming up to 40 ~ 60 DEG C, add 2 ~ 5 portions of separants, 2 ~ 6 parts of flocculation agent successively, be 8 ~ 11 by buffer reagent regulation system pH value, stir 10 ~ 30min when being warming up to 70 ~ 90 DEG C and carry out slaking, then obtain low cigarette, high flame retardant powder styrene butadiene rubber product through washing, dehydration, drying.
The particle diameter of expansible black lead of the present invention is 20 μm ~ 200 μm, preferably 30 μm ~ 100 μm.
Carboxylic styrene butadiene latex of the present invention is with divinyl, vinylbenzene for main monomer, and unsaturated carboxylic acid is that function monomer obtains through letex polymerization, and unsaturated carboxylic acid is wherein vinylformic acid, methacrylic acid or 2-ethylacrylic acid, preferred vinylformic 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 one or more composite in sec.-propyl two oleic acid acyloxy titanic acid ester (NDZ-101), dioctyl phosphoric acid acyloxy titanic acid ester (NDZ-102), sec.-propyl three oleic acid acyloxy titanic acid ester (NDZ-105), dodecyl benzenesulfonyl titanic acid ester (NDZ-109), dioctylphyrophosphoric acid acyloxy titanic acid ester (NDZ-201), dioctyl phosphito acyloxy titanic acid ester (NDZ-401).
Acid of the present invention can be selected from oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, dust technology one or more, preferred oxalic acid, the mass concentration of its acid is 0.03% ~ 0.1%.
Allyl group tri-phenyl-phosphorus bromide structural formula of the present invention is as follows:
Polar monomer of the present invention is selected from the one in vinyl acetate between to for plastic (VA), maleic anhydride (MAH), hydroxyethyl methylacrylate (HEMA), preferable methyl Hydroxyethyl acrylate (HEMA) grafting styrene-butadiene latex (SBR-g-HEMA), percentage of grafting 0.5% ~ 2.5%.
Initiator of the present invention is selected from Potassium Persulphate, di-tert-butyl hydrogen peroxide (TBHP), 2,5-dimethyl-2, one in 5-di-t-butyl hexane peroxide (BPDH), ditertiary butyl peroxide (DTBP), dicumyl peroxide (DCP), benzoyl peroxide (BPO), preferred BPO, its add-on is 0.05 ~ 0.5 part, preferably 0.05 ~ 0.2 part.
The conven-tional adjuvants that the present invention all can adopt this area general to adopted emulsifying agent, molecular weight regulator, terminator, separant, flocculation agent, buffer reagent etc., its add-on is also the conventional amount used that those skilled in the art can calculate according to the consumption of latex, and the present invention does not do particular determination.Emulsifying agent as described in the present invention is conventionally known to one of skill in the art, can be one or more in anionic emulsifier and nonionic emulsifying agent.As: can be selected from fatty acid soaps, RA rosin acid, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, polyoxyethylene sorbitol acid anhydride list olein one or more, preferred Sodium dodecylbenzene sulfonate.
Emulsifying agent of the present invention can be one or more in anionic emulsifier and nonionic emulsifying agent.As: can be selected from metal carboxylate, fatty acid soaps, RA rosin acid, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, polyoxyethylene sorbitol acid anhydride list olein one or more, preferred Sodium dodecylbenzene sulfonate.
Molecular weight regulator of the present invention can be selected from the one in uncle ten carbon mercaptan, tert-dodecyl mercaptan, uncle 14 carbon mercaptan, uncle 16 carbon mercaptan, preferred tertiary DDM dodecyl mercaptan.
Described terminator can be selected from diethyl hydroxylamine, oxammonium sulfate, Sodium Dimethyldithiocarbamate one or more.
Separant of the present invention can be selected from potassium stearate, sodium stearate, potassium oleate, sodium oleate, synthetic fatty acid potassium, sodium fat synthesis one or more.
Flocculation agent of the present invention can be selected from univalent metal salt, divalent metal salt, divalent metal salt one or more.Such as: one or more in sodium-chlor, magnesium chloride, iron(ic) chloride, calcium chloride, magnesium sulfate, Tai-Ace S 150, alum.
Buffer reagent of the present invention can be selected from the one in sodium carbonate, sodium bicarbonate, sodium hydroxide, ammoniacal liquor, bicarbonate of ammonia, preferred sodium hydroxide.
First the present invention carries out functional modification to EG surface, adopts titanate coupling agent process EG particle, makes carboxylic styrene butadiene latex form coating layer closely at particle surface, make expansible black lead particle surface with a certain amount of polar group carboxyl.In addition additionally by polar monomer hydroxyethyl methylacrylate (HEMA) graft modification styrene-butadiene latex, a certain amount of carboxyl and hydroxyl is formed on its surface, these groups can be strong with the polar group carboxyl of expansible black lead particle surface of process chemisorption, this effect can improve the cohesiveness between particle and styrene-butadiene latex matrix, improve the consistency of expansible black lead and acidylate styrene-butadiene latex significantly, can realize being evenly dispersed in styrene-butadiene latex matrix, but also can prevent the outer of graphite layers from moving, guarantee particle size is stablized, contribute to the stable of expansion carbon layers having thicknesses, improve the shield effectiveness of carbon-coating.Thus impelling the cigarette that presses down of functionalization expansible black lead to imitate fire-retardant fruit and further promoted, its maximum smoke density is less than 100.
Secondly, the present invention's a kind of flame-retardant monomer allyl group tri-phenyl-phosphorus bromide of grafting again in styrene-butadiene latex matrix, thus make fire-retardant group phosphorus and bromine to be effectively embedded on the main chain of powder styrene butadiene rubber polymeric, impart high efficiency and the persistence of powder styrene butadiene rubber flame retardant properties.Expansible black lead starts expansion and forms the fine and close layer of charcoal of the low porous of thermal conductivity when decomposes simultaneously, obstruct flame heat regulating conducts, remove the living radical of propagation of flame, there is good flame retardant effect, along with the improvement of expansible black lead and styrene-butadiene latex consistency, expansible black lead shows good flame retardant effect, in the flame retardant properties improving material, allyl group tri-phenyl-phosphorus bromide and expansible black lead can give play to synergistic effect definitely, the flame retardant effect contributing to powder styrene butadiene rubber material is improved significantly, can prepare oxygen index up to more than 45% fire-retardant powder styrene butadiene rubber.The features such as it is low that the method has adding proportion, and smoke elimination efficiency is high, and good flame retardation effect, modification cost are low.
Accompanying drawing explanation
Fig. 1 is the fire-retardant process schematic of expansible black lead.
Embodiment
Enumerate following examples and comparative example so that 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.Embodiment and " part " described in comparative example all refer to mass parts.
(1) raw material sources:
(2) analysis test method:
The mensuration of percentage of grafting: get the sample of about 4g in weighing bottle by pipette from three-necked bottle, add 2 ~ 3 quinol solution after weighing, dry to constant weight, then above-mentioned sample is placed in Soxhlet extractor, with toluene extractive distillation 24h in 90 DEG C of water-baths, be then dried to constant weight.Be calculated as follows monomer-grafted rate:
In formula: m
0-latex total mass (g); The sample quality (g) taken after m-reaction; m
mthe total mass (g) of monomer in-reactant; m
sNRthe quality (g) of natural rubber in-sample; m
1the quality (g) of sample after-extraction.
The mensuration of maximum smoke density: measure according to the method described in GB/T8323-1987.
The mensuration of oxygen index: measure according to the method described in GB10707-1989.
The mensuration of vertical combustion: measure according to the method described in GB/T13488-1992.
Self-extinguishing time measures: measure according to the method described in UL-94.
Embodiment 1
(1) functionalization expansible black lead: 2 parts of titanate coupling agent NDZ-101 and 60 part water, 6 parts of ethanol are joined in polymeric kettle and are uniformly mixed, be 0.05% oxalic acid solution regulation system pH value by mass concentration be 4, then add 100 parts of expansible black leads, be uniformly mixed 20min; Add 6 parts of carboxylic styrene butadiene latexs again and be uniformly mixed 50min; Dehydration, drying, grinding obtain functionalization expansible black lead a.
(2) preparation of flame retardant type graft latex: first add 150 parts of deionized waters in polymeric kettle, then add 100 parts of styrene-butadiene latex SBR1500,2.5 parts of Sodium dodecylbenzene sulfonatees, 0.3 part of DDM dodecyl mercaptan successively, after nitrogen replacement, and then the allyl group tri-phenyl-phosphorus bromide grafted monomer of 6 parts is first added, stir, heat, still temperature to be polymerized adds 0.15 part of BPO when reaching 50 DEG C, after reaction 8h, then at HEMA and the 0.05 part BPO adding 2 parts, after continuing reaction 3h, add 0.2 diethyl hydroxylamine, obtained flame retardant type grafting styrene-butadiene latex a.Sampling analysis: the percentage of grafting recording SBR-g-HEMA is 0.9%.
(3) preparation of fire-retardant powder styrene butadiene rubber: get 100 parts of flame retardant type graft latex a and 1.5 parts of functionalization expansible black lead a, 70 parts of water join in condensing field and are uniformly mixed 25min, when being then warming up to 50 DEG C, add 3 parts of potassium oleates successively, 2.5 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, add 3 parts of potassium oleates successively, 2.5 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out slaking, then through washing, dehydration, drying obtains low cigarette, high flame retardant powder styrene butadiene rubber product.Sampling analysis: make standard test specimen, performance is in table 1 after tested.
Embodiment 2
(1) preparation of functionalization expansible black lead: with embodiment 1.
(2) preparation of flame retardant type graft latex: with embodiment 1.
(3) preparation of fire-retardant powder styrene butadiene rubber: get 100 parts of flame retardant type graft latex a and 3 parts of functionalization expansible black lead a, 70 parts of water join in condensing field and are uniformly mixed 25min, when being then warming up to 50 DEG C, add 3 parts of potassium oleates successively, 2.5 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, add 3 parts of potassium oleates successively, 2.5 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out slaking, then through washing, dehydration, drying obtains low cigarette, high flame retardant powder styrene butadiene rubber product.Sampling analysis: make standard test specimen, performance is in table 1 after tested.
Embodiment 3
(1) preparation of functionalization expansible black lead: with embodiment 1.
(2) preparation of flame retardant type graft latex: with embodiment 1.
(3) preparation of flame retardant type powder styrene butadiene rubber: get 100 parts of flame retardant type graft latex a and 4 parts of functionalization expansible black lead a, 70 parts of water join in condensing field and are uniformly mixed 25min, when being then warming up to 50 DEG C, add 3 parts of potassium oleates successively, 2.5 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, add 3 parts of potassium oleates successively, 2.5 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out slaking, then through washing, dehydration, drying obtains low cigarette, high flame retardant powder styrene butadiene rubber product.Sampling analysis: make standard test specimen, performance is in table 1 after tested.
Embodiment 4
(1) functionalization expansible black lead: 3.5 parts of titanate coupling agent NDZ-101 and 60 part water, 6 parts of ethanol are joined in polymeric kettle and are uniformly mixed, be 0.05% oxalic acid solution regulation system pH value by mass concentration be 4, then add 100 parts of expansible black leads, be uniformly mixed 20min; Add 10 parts of carboxylic styrene butadiene latexs again and mix mixing 50min; Dehydration, drying, grinding obtain functionalization expansible black lead b.
(2) preparation of flame retardant type graft latex: first add 150 parts of deionized waters in polymeric kettle, then add 100 parts of styrene-butadiene latex SBR1500,3.0 dialkyl benzene sulfonic acids sodium, 0.4 part of DDM dodecyl mercaptan successively, after nitrogen replacement, and then the allyl group tri-phenyl-phosphorus bromide grafted monomer of 9 parts is first added, stir, heat, still temperature to be polymerized adds 0.21BPO when reaching 50 DEG C, after reaction 8h, then 3.2 parts of HEMA and 0.07 part BPO are being added, after continuing reaction 3h, add 0.3 diethyl hydroxylamine, obtained flame retardant type grafting styrene-butadiene latex b.Sampling analysis: the percentage of grafting recording SBR-g-HEMA is 1.4%.
(3) preparation of fire-retardant powder styrene butadiene rubber: get 100 parts of flame retardant type graft latex b and 6 parts of functionalization expansible black lead b, 70 parts of water join in condensing field and are uniformly mixed 25min, when being then warming up to 50 DEG C, add 3.5 sour potassium successively, 2.5 parts of magnesium chlorides, be 9.4 to condense by sodium hydroxide regulation system pH value, add 3.5 parts of potassium oleates successively, 3.0 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out slaking, then through washing, dehydration, drying obtains low cigarette, high flame retardant powder styrene butadiene rubber product.Sampling analysis: make standard test specimen, performance is in table 1 after tested.
Embodiment 5
(1) preparation of functionalization expansible black lead: with embodiment 4.
(2) preparation of flame retardant type graft latex: with embodiment 4.
(3) preparation of fire-retardant powder styrene butadiene rubber: get 100 parts of flame retardant type graft latex b and 7.5 parts of functionalization expansible black lead b, 70 parts of water join in condensing field and are uniformly mixed 25min, when being then warming up to 50 DEG C, add 3.5 sour potassium successively, 2.5 parts of magnesium chlorides, be 9.4 to condense by sodium hydroxide regulation system pH value, add 3.5 parts of potassium oleates successively, 3.0 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out slaking, then through washing, dehydration, drying obtains low cigarette, high flame retardant powder styrene butadiene rubber product.Sampling analysis: make standard test specimen, performance is in table 1 after tested.
Embodiment 6
(1) preparation of functionalization expansible black lead: with embodiment 4
(2) preparation of flame retardant type graft latex: with embodiment 4
(3) preparation of fire-retardant powder styrene butadiene rubber: get 100 parts of flame retardant type graft latex b and 8.0 parts of functionalization expansible black lead b, 70 parts of water join in condensing field and are uniformly mixed 25min, when being then warming up to 50 DEG C, add 3.5 sour potassium successively, 2.5 parts of magnesium chlorides, be 9.4 to condense by sodium hydroxide regulation system pH value, add 3.5 parts of potassium oleates successively, 3.0 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out slaking, then through washing, dehydration, drying obtains low cigarette, high flame retardant powder styrene butadiene rubber product.Sampling analysis: make standard test specimen, performance is in table 1 after tested.
Embodiment 7
(1) functionalization expansible black lead: 4.0 parts of titanate coupling agent NDZ-401 and 80 part water, 8 parts of ethanol are joined in polymeric kettle and are uniformly mixed, be 0.05% oxalic acid solution regulation system pH value by mass concentration be 4, then add 100 parts of expansible black leads, be uniformly mixed 20min; Add 14 parts of carboxylic styrene butadiene latexs again and mix mixing 50min; Dehydration, drying, grinding obtain functionalization expansible black lead c.
(2) preparation of flame retardant type graft latex: first add 180 parts of deionized waters in polymeric kettle, then add 100 parts of styrene-butadiene latex SBR1712,3.5 dialkyl benzene sulfonic acids sodium, 0.5 part of DDM dodecyl mercaptan successively, after nitrogen replacement, and then the allyl group tri-phenyl-phosphorus bromide grafted monomer of 13 parts is first added, stir, heat, still temperature to be polymerized adds 0.35BPO when reaching 50 DEG C, after reaction 8h, then 4.5 parts of HEMA and 0.08 part BPO are being added, after continuing reaction 3h, add 0.4 diethyl hydroxylamine, obtained flame retardant type grafting styrene-butadiene latex c.Sampling analysis: the percentage of grafting recording SBR-g-HEMA is 2.2%.
(3) preparation of fire-retardant powder styrene butadiene rubber: get 100 parts of flame retardant type graft latex c and 9.5 parts of functionalization expansible black lead c, 80 parts of water join in condensing field and are uniformly mixed 25min, when being then warming up to 50 DEG C, add 4 sour potassium successively, 3.5 parts of magnesium chlorides, be 9.4 to condense by sodium hydroxide regulation system pH value, add 4.0 parts of potassium oleates successively, 3.5 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out slaking, then through washing, dehydration, drying obtains low cigarette, high flame retardant powder styrene butadiene rubber product.Sampling analysis: make standard test specimen, performance is in table 1 after tested.
Comparative example 1
(1) functionalization expansible black lead: with embodiment 1.
(2) preparation of flame retardant type graft latex: with embodiment 1.
(3) preparation of fire-retardant powder styrene butadiene rubber: other condition is identical with embodiment 1, difference is that the add-on of functionalization expansible black lead a in the preparation process of fire-retardant powder styrene butadiene rubber is 0.7 part, that is: 100 parts of flame retardant type graft latex a and 0.7 parts of functionalization expansible black lead a are got, 70 parts of water join in condensing field and are uniformly mixed 25min, when being then warming up to 50 DEG C, add 3 parts of potassium oleates successively, 2.5 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, add 3 parts of potassium oleates successively, 2.5 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out slaking, then through washing, dehydration, drying obtains low cigarette, high flame retardant powder styrene butadiene rubber product.Sampling analysis: make standard test specimen, performance is in table 1 after tested.
Comparative example 2
(1) preparation of flame retardant type graft latex: with embodiment 1.
(2) preparation of fire-retardant powder styrene butadiene rubber: other condition is identical with embodiment 2, difference is not add functionalization expansible black lead a in the preparation process of fire-retardant powder styrene butadiene rubber, but directly add expansible black lead, its add-on is 3 parts, that is: 100 parts of flame retardant type graft latex a and 3 part expansible black leads are got, 70 parts of water join in condensing field and are uniformly mixed 25min, when being then warming up to 50 DEG C, add 3 parts of potassium oleates successively, 2.5 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, add 3 parts of potassium oleates successively, 2.5 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out slaking, then through washing, dehydration, drying obtains low cigarette, high flame retardant powder styrene butadiene rubber product.Sampling analysis: make standard test specimen, performance is in table 1 after tested.
Comparative example 3
(1) preparation of functionalization expansible black lead: with embodiment 1.
(2) preparation of flame retardant type graft latex: other condition is identical with embodiment 1, difference is not add hydroxyethyl methylacrylate (HEMA) in the preparation process of graft latex, that is: in polymeric kettle, 150 parts of deionized waters are first added, then 100 parts of styrene-butadiene latex SBR1500 are added successively, 2.5 parts of Sodium dodecylbenzene sulfonatees, 0.3 part of DDM dodecyl mercaptan, after nitrogen replacement, and then the allyl group tri-phenyl-phosphorus bromide grafted monomer of 6 parts is first added, stir, heating, still temperature to be polymerized adds 0.15 part of BPO when reaching 50 DEG C, after reaction 8h, finally add 0.2 diethyl hydroxylamine, obtained flame retardant type grafting styrene-butadiene latex (a-1).
(3) preparation of fire-retardant powder styrene butadiene rubber: other condition is identical with embodiment 3, difference is not add flame retardant type grafting styrene-butadiene latex a in the preparation process of fire-retardant powder styrene butadiene rubber, but add the flame retardant type grafting styrene-butadiene latex (a-1) of non-grafting HEMA, that is: 100 parts of flame retardant type graft latexes (a-1) and 4 parts of functionalization expansible black lead a are got, 70 parts of water join in condensing field and are uniformly mixed 25min, when being then warming up to 50 DEG C, add 3 parts of potassium oleates successively, 2.5 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, add 3 parts of potassium oleates successively, 2.5 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out slaking, then through washing, dehydration, drying obtains low cigarette, high flame retardant powder styrene butadiene rubber product.Sampling analysis: make standard test specimen, performance is in table 1 after tested.
Comparative example 4
(1) preparation of functionalization expansible black lead: with embodiment 4.
(2) preparation of flame retardant type powder styrene butadiene rubber: other condition is identical with embodiment 4, difference is not add flame retardant type grafting styrene-butadiene latex b in the process of condensing, but in styrene-butadiene latex SBR1500, directly adds functionalization expansible black lead b condense.That is: get 100 parts of styrene-butadiene latex SBR1500 and 6 parts of functionalization expansible black lead b, 70 parts of water to join in condensing field and be uniformly mixed 25min, when being then warming up to 50 DEG C, add 3.5 sour potassium, 2.5 parts of magnesium chlorides successively, be 9.4 to condense by sodium hydroxide regulation system pH value, add 3.5 parts of potassium oleates, 3.0 parts of magnesium chlorides successively, condense when being 9.3 by sodium hydroxide regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out slaking, then obtain low cigarette, high flame retardant powder styrene butadiene rubber product through washing, dehydration, drying.Sampling analysis: make standard test specimen, performance is in table 1 after tested.
Comparative example 5
(1) preparation of functionalization expansible black lead: with embodiment 4.
(2) preparation of flame retardant type graft latex: other condition is identical with embodiment 4, difference is not add allyl group tri-phenyl-phosphorus bromide in the preparation process of graft latex, that is: in polymeric kettle, 150 parts of deionized waters are first added, then 100 parts of styrene-butadiene latex SBR1500 are added successively, 3.0 dialkyl benzene sulfonic acids sodium, 0.4 part of DDM dodecyl mercaptan, after nitrogen replacement, and then 3.2 parts of HEMA and 0.07 part BPO are added, when still temperature to be polymerized reaches 50 DEG C, after reaction 3h, then 0.3 diethyl hydroxylamine is being added, obtained flame retardant type grafting styrene-butadiene latex (b-1).
(3) preparation of flame retardant type powder styrene butadiene rubber: other condition is identical with embodiment 3, difference is not add flame retardant type grafting styrene-butadiene latex b in the preparation process of fire-retardant powder styrene butadiene rubber, but add the flame retardant type grafting styrene-butadiene latex (b-1) of non-grafting allyl group tri-phenyl-phosphorus bromide, that is: 100 parts of flame retardant type graft latexes (b-1) and 7.5 parts of functionalization expansible black lead b are got, 70 parts of water join in condensing field and are uniformly mixed 25min, when being then warming up to 50 DEG C, add 3.5 sour potassium successively, 2.5 parts of magnesium chlorides, be 9.4 to condense by sodium hydroxide regulation system pH value, add 3.5 parts of potassium oleates successively, 3.0 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out slaking, then through washing, dehydration, drying obtains low cigarette, high flame retardant powder styrene butadiene rubber product.Sampling analysis: make standard test specimen, performance is in table 1 after tested.
Comparative example 6
(1) preparation of functionalization expansible black lead: other condition is identical with embodiment 4, difference is not add NDZ-101 coupling agent in the preparation process of expansible black lead, that is: 60 parts of water, 6 parts of ethanol are joined in polymeric kettle and are uniformly mixed, be 0.05% oxalic acid solution regulation system pH value by mass concentration be 4, then add 100 parts of expansible black leads, be uniformly mixed 20min; Add 10 parts of carboxylic styrene butadiene latexs again and mix mixing 50min; Dehydration, drying, grinding obtain functionalization expansible black lead (b-1).
(2) preparation of flame retardant type graft latex: with embodiment 4
(3) preparation of fire-retardant powder styrene butadiene rubber: other condition is identical with embodiment 6, difference is that the functionalization expansible black lead added in composition preparation process does not only contain carboxylic styrene butadiene latex containing coupling agent, the add-on of functionalization expansible black lead (b-1) 8.0 parts, that is: 100 parts of flame retardant type graft latex b and 8.0 parts of functionalization expansible black leads (b-1) are got, 70 parts of water join in condensing field and are uniformly mixed 25min, when being then warming up to 50 DEG C, add 3.5 sour potassium successively, 2.5 parts of magnesium chlorides, be 9.4 to condense by sodium hydroxide regulation system pH value, add 3.5 parts of potassium oleates successively, 3.0 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out slaking, then through washing, dehydration, drying obtains low cigarette, high flame retardant powder styrene butadiene rubber product.Sampling analysis: make standard test specimen, performance is in table 1 after tested.
Comparative example 7
(1) preparation of flame retardant type graft latex: with embodiment 7.
(2) preparation of fire-retardant powder styrene butadiene rubber: other condition is identical with embodiment 7, difference is not add functionalization expansible black lead c in the preparation process of fire-retardant powder styrene butadiene rubber, but directly add expansible black lead, its add-on is 9.5 parts, that is: 100 parts of flame retardant type graft latex c and 9.5 part expansible black leads are got, 80 parts of water join in condensing field and are uniformly mixed 25min, when being then warming up to 50 DEG C, add 4 sour potassium successively, 3.5 parts of magnesium chlorides, be 9.4 to condense by sodium hydroxide regulation system pH value, add 4.0 parts of potassium oleates successively, 3.5 parts of magnesium chlorides, condense when being 9.3 by sodium hydroxide regulation system pH value, stir 25min when being warming up to 80 DEG C and carry out slaking, then through washing, dehydration, drying obtains low cigarette, high flame retardant powder styrene butadiene rubber product.Sampling analysis: make standard test specimen, performance is in table 1 after tested.
The performance of table 1 flame retardant type powder styrene butadiene rubber
Claims (10)
1. a preparation method for powder styrene butadiene rubber, concrete preparation process is:
(1) functionalization expansible black lead: be 100 parts in expansible black lead 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, be 2 ~ 6 by sour regulation system pH value, then add 100 parts of expansible black leads, be uniformly mixed 10 ~ 30min; Add 5 ~ 15 parts of carboxylic styrene butadiene latexs again and be uniformly mixed 30 ~ 60min; Dehydration, drying, grinding obtain functionalization expansible black lead;
(2) preparation of flame retardant type graft latex: be 100 parts in styrene-butadiene latex quality, first 100 ~ 200 parts of deionized waters are added in polymeric kettle, then 100 parts of styrene-butadiene latexes are added successively, 1 ~ 10 part of emulsifying agent, 0.1 ~ 1.0 part of molecular weight regulator, after nitrogen replacement, and then the allyl group tri-phenyl-phosphorus bromide grafted monomer of 5 ~ 15 parts is first added, stir, heating, still temperature to be polymerized adds 0.1 ~ 0.5 part of initiator when reaching 40 ~ 60 DEG C, after reaction 5 ~ 10h, then at the polar monomer and 0.05 ~ 0.1 part of initiator that add 1 ~ 5 part, after continuing reaction 2 ~ 4h, add 0.1 ~ 0.5 part of terminator, obtained flame retardant type grafting styrene-butadiene latex,
(3) preparation of fire-retardant powder styrene butadiene rubber: be 100 parts in fire-retardant grafting styrene-butadiene latex quality, get 100 parts of flame retardant type graft latexes and 1 ~ 10 part of functionalization expansible black lead, 50 ~ 100 parts of water join in condensing field and are uniformly mixed 10 ~ 30min, when being then warming up to 40 ~ 60 DEG C, add 2 ~ 5 portions of separants, 2 ~ 6 parts of flocculation agent successively, be 8 ~ 11 by buffer reagent regulation system pH value, stir 10 ~ 30min when being warming up to 70 ~ 90 DEG C and carry out slaking, then obtain low cigarette, high flame retardant powder styrene butadiene rubber product through washing, dehydration, drying.
2. preparation method as claimed in claim 1, is characterized in that the particle diameter of described expansible black lead is 20 μm ~ 200 μm.
3. preparation method as claimed in claim 1, is characterized in that the particle diameter of described expansible black lead is 30 μm ~ 100 μm.
4. preparation method as claimed in claim 1, is characterized in that described carboxylic styrene butadiene latex is divinyl, vinylbenzene and unsaturated carboxylic acid obtains through letex polymerization.
5. preparation method as claimed in claim 1, is characterized in that described unsaturated carboxylic acid is vinylformic acid, methacrylic acid or 2-ethylacrylic acid.
6. preparation method as claimed in claim 1, is characterized in that described titanate coupling agent is selected from one or more composite in sec.-propyl two oleic acid acyloxy titanic acid ester, dioctyl phosphoric acid acyloxy titanic acid ester, sec.-propyl three oleic acid acyloxy titanic acid ester, dodecyl benzenesulfonyl titanic acid ester, dioctylphyrophosphoric acid acyloxy titanic acid ester, dioctyl phosphito acyloxy titanic acid ester.
7. preparation method as claimed in claim 1, it is characterized in that described described acid is selected from oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, dust technology one or more.
8. preparation method as claimed in claim 1, is characterized in that described polar monomer is selected from the one in vinyl acetate between to for plastic, maleic anhydride, hydroxyethyl methylacrylate.
9. preparation method as claimed in claim 1, it is characterized in that described initiator is selected from Potassium Persulphate, di-tert-butyl hydrogen peroxide, 2, one in 5-dimethyl-2,5-di-t-butyl hexane peroxide, ditertiary butyl peroxide, dicumyl peroxide, benzoyl peroxide.
10. the preparation method as described in claim 1 or 9, is characterized in that described initiator add-on is 0.05 ~ 0.2 part.
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| CN107274991A (en) * | 2015-11-10 | 2017-10-20 | 李聪 | A kind of waterproof layer of durable security cable |
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| CN108192166A (en) * | 2016-12-08 | 2018-06-22 | 中国石油天然气股份有限公司 | A kind of method of modifying of high dispersive gum filler carbon nanotube |
| CN110016234A (en) * | 2019-04-17 | 2019-07-16 | 山东显元化工研究院有限公司 | A kind of SBR styrene-butadiene latex and preparation method thereof for modified emulsifying asphalt |
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| CN113444334A (en) * | 2021-07-14 | 2021-09-28 | 上海迈瑞尔化学技术有限公司 | Preparation method of high-impact polystyrene modified by high-molecular composite flame retardant |
| CN113583374A (en) * | 2021-07-14 | 2021-11-02 | 上海迈瑞尔化学技术有限公司 | Preparation method of nanoscale ultra-dispersed environment-friendly flame-retardant low-smoke high-impact polystyrene |
| CN113444334B (en) * | 2021-07-14 | 2022-10-21 | 上海葛蓝化工科技有限公司 | Preparation method of high-impact polystyrene modified by high-molecular composite flame retardant |
| CN113583374B (en) * | 2021-07-14 | 2023-08-01 | 上海葛蓝化工科技有限公司 | Preparation method of nanoscale super-dispersed environment-friendly flame-retardant low-smoke high-impact polystyrene |
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