CN104448663B - 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
- Publication number
- CN104448663B CN104448663B CN201310428393.1A CN201310428393A CN104448663B CN 104448663 B CN104448663 B CN 104448663B CN 201310428393 A CN201310428393 A CN 201310428393A CN 104448663 B CN104448663 B CN 104448663B
- Authority
- CN
- China
- Prior art keywords
- parts
- preparation
- acid
- latex
- styrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
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 the preparation method of a kind of fire-retardant powder styrene butadiene rubber, be specifically related to a kind of functionalization expansible graphite
And the low cigarette of graft modification styrene-butadiene latex, the preparation method of high fire-retardance powder styrene butadiene rubber (EG).
Background technology
It is known that powder styrene butadiene rubber (PSBR) is a kind of hydrocarbon rubbers, its main chain all contains substantial amounts of carbon, hydrogen etc.
Element, is easily generated fuel gas during melted by heat, easily burn with oxygen effect when high temperature, cause its oxygen index (OI) low, fire-retardant
Poor-performing, thus brings potential fire hazard, limit PSBR mine, electronics, electrical equipment industry, automobile, aircraft,
Application in the fields such as steamer.At present, the industrial commonly used halogen containing flame-retardant of China prepares flame retardant rubber, has an advantage in that tool
Having higher anti-flammability, shortcoming is to produce a large amount of smog and toxicant during burning, makes adult respiratory distress, and its hazardness is often
Even more serious than the consequence that burning produces, it is the primary risk factor causing people's injures and deaths in fire.In recent years, along with global safety ring
Protecting the reinforcement day by day of 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 have become study hotspot.
In prior art, about the low cigarette of elastomeric material, fire-retardant research mainly by adding fire retardant and smoke suppressant
Prepared by method.As: CN101121796A discloses a kind of by adding a small amount of expansible graphite, prepares good flame retardation effect, combustion
The production method of the Halogen thermoplastic flame-retardant rubber of LSZH during burning.ZL200810057092.1 discloses a kind of by adding
APP, Firebrake ZB, nano-inorganic substance, white carbon etc., prepare a kind of oil resistant, heat-resisting expansion type flame-proof rubber.
ZL96116942.7 discloses one and cooperates with halogen-free flame retardants aluminium hydroxide (magnesium), antimony oxide and phosphorus flame retardant
Use, by mixing blending technology, prepare low cigarette, low toxicity, environment-friendly type flame-retardant rubber floor that fire resistance is good.
ZL201010136235.5 discloses a kind of employing organic phosphorus flame retardant triaryl phosphate and organic modified nano montmorillonite
Efficient, the environment friendly flame retardant of compounding preparation, and be applied in natural rubber system with 10～15wt% additions, preparation green
Environmental protection flame retardant elastomeric material.CN102040779A discloses a kind of with containing EPDM rubber, isocyanate-terminated poly-fourth
Diene, vulcanizing agent, the mixture of hydroxide flame retardant, obtain a kind of flame retardant rubber by mixing, sulfuration.CN 1324885A
Disclose a kind of unsaturated carboxylic acid-modified inorganic fire-retarded fillers such as methacrylic acid (MAA) or acrylic acid (AA) that use, preparation resistance
The halogen-free fireproof rubber material of combustion function admirable.Tan Haisheng etc. use propenyl chloride and methyl methacrylate-grafted modified natural
After latex, prepare the graft polymers " preparation of AC/MMA graft modification Heveatex of fire resistance and good mechanical performance
And performance study " (elastomer, 2002,12 (6): 32～35).
Summary of the invention
Present invention aim at providing a kind of maximum environmental protection low-smoke and flame retardant that smoke density is less than 100, oxygen index (OI) is more than 45%
The preparation method of type powder styrene butadiene rubber.This invention uses polarity latex expansible graphite (EG) to be carried out coating modification, then
Styrene-butadiene latex is carried out modification of graft respectively, finally by graft modification with pi-allyl tri-phenyl-phosphorus bromide and polar monomer
The method of direct condensation powdering after styrene-butadiene latex and the mixing of functionalization expansible graphite.This method improves inflatable stone significantly
Ink and the compatibility of elastomeric material and particle size stability, solve expansible graphite dispersion in rubber matrix uneven
Problem, imparts 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) functionalization expansible graphite: be in terms of 100 parts by expansible graphite quality, by 1～5 part of titanate coupling agent and
50～100 parts of water, 5～10 parts of ethanol join in polymeric kettle and are uniformly mixed, and are 2～6 with acid regulation system pH value, then
Add 100 parts of expansible graphites, stirring mixing 10～30min；Add 5～15 parts of carboxylic styrene butadiene latexs stirring mixing 30～
60min；Dehydration, be dried, grind obtain functionalization expansible graphite.
(2) preparation of flame retardant type graft latex: be in terms of 100 parts by styrene-butadiene latex quality, is firstly added 100 in polymeric kettle
～200 parts of deionized waters, then it is sequentially added into 100 parts of styrene-butadiene latexes, 1～10 part of emulsifying agent, 0.1～1.0 part of molecular-weight adjusting
Agent, after replacing with nitrogen, is and then initially charged the pi-allyl tri-phenyl-phosphorus bromide grafted monomers of 5～15 parts, stirs, heats, treat
Polymeric kettle temperature reaches to add 0.1～0.5 part of initiator when 40～60 DEG C, after reaction 5～10h, is then adding 1～5 part
Polar monomer and 0.05～0.1 part of initiator, after continuing reaction 2～4h, adds 0.1～0.5 part of terminator, prepared flame retardant type
Grafting styrene-butadiene latex.
(3) preparation of fire-retardant powder styrene butadiene rubber: be in terms of 100 parts by fire-retardant grafting styrene-butadiene latex quality, take 100 parts fire-retardant
Type graft latex and 1～10 part of functionalization expansible graphite, 50～100 parts of water join in condensing field stirring mixing 10～
30min, when then heating to 40～60 DEG C, 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 to obtain low
Cigarette, high fire-retardance powder styrene butadiene rubber product.
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 function list
Body obtains through emulsion polymerization, and unsaturated carboxylic acid therein is acrylic acid, methacrylic acid or 2-ethylacrylic acid, preferably propylene
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 isopropyl two oleic acid acyloxy titanate esters (NDZ-101), two
Octylphosphonic acid acyloxy titanate esters (NDZ-102), isopropyl three oleic acid acyloxy titanate esters (NDZ-105), detergent alkylate sulphur
Acyl titanate (NDZ-109), dioctylphyrophosphoric acid acyloxy titanate esters (NDZ-201), dioctyl phosphito acyloxy metatitanic acid
Compounding of one or more in ester (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 grass
Acid, the mass concentration of its acid is 0.03%～0.1%.
Pi-allyl tri-phenyl-phosphorus bromide structural formula of the present invention is as follows:
Polar monomer of the present invention is selected from vinyl acetate (VA), maleic anhydride (MAH), hydroxyethyl methylacrylate
(HEMA) one in, preferably hydroxyethyl methylacrylate (HEMA) grafting styrene-butadiene latex (SBR-g-HEMA), percent grafting 0.5%
～2.5%.
Initiator of the present invention is selected from potassium peroxydisulfate, di-tert-butyl hydrogen peroxide (TBHP), 2,5-dimethyl-2,5-
Di-t-butyl hexane peroxide (BPDH), di-tert-butyl peroxide (DTBP), cumyl peroxide (DCP), benzoyl peroxide
One in formyl (BPO), preferably BPO, its addition is 0.05～0.5 part, preferably 0.05～0.2 part.
The present invention emulsifying agent to being used, molecular weight regulator, terminator, interleaving agent, flocculating agent, buffer agent etc.
To use conven-tional adjuvants generally in the art, its addition is also that those skilled in the art can calculate according to the consumption of latex
The conventional amount used arrived, the present invention does not do particular determination.Emulsifying agent is known to those skilled in the art as described in the present invention, can
To be one or more in anion emulsifier and nonionic emulsifier.As: can be selected from fatty acid soaps, RA rosin acid, ten
One or more in dialkyl benzene sulfonic acids sodium, sodium lauryl sulphate, polyoxyethylene sorbitol acid anhydride list olein, preferably 12
Sodium alkyl benzene sulfonate.
Emulsifying agent of the present invention can be one or more in anion emulsifier and nonionic emulsifier.As:
Metal carboxylate, fatty acid soaps, RA rosin acid, dodecylbenzene sodium sulfonate, sodium lauryl sulphate, polyoxyethylene mountain can be selected from
One or more in pears alcohol acid anhydride list olein, preferably dodecylbenzene sodium sulfonate.
Molecular weight regulator of the present invention can be selected from uncle ten carbon mercaptan, tert-dodecyl mercaptan, uncle 14 carbon mercaptan,
One in uncle 16 carbon mercaptan, preferably tert-dodecyl mercaptan.
Described terminator can be selected from one or more in diethyl hydroxylamine, oxammonium sulfate., Sodium Dimethyldithiocarbamate.
Interleaving agent of the present invention can be selected from potassium stearate, sodium stearate, potassium oleate, enuatrol, synthetic fatty acid
One or more in potassium, sodium fat synthesis.
Flocculating agent of the present invention can be selected from the one in univalent metal salt, divalent metal salt, divalent metal salt or
Multiple.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 sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonia, ammonium hydrogen carbonate
One, preferably sodium hydroxide.
First the present invention carries out functional modification to EG surface, uses titanate coupling agent to process EG particle so that carboxyl
Styrene-butadiene latex forms close clad at particle surface so that expansible graphite particle surface is with a certain amount of polar group
Carboxyl.Additionally additionally by polar monomer hydroxyethyl methylacrylate (HEMA) graft modification styrene-butadiene latex, formed on its surface
A certain amount of carboxyl and hydroxyl, these groups can be strong with the polar group carboxyl of the expansible graphite particle surface processed
Chemisorption, this effect can improve the caking property between particle and styrene-butadiene latex matrix, it will be apparent that improves inflatable
Graphite and the compatibility of acylated styrene-butadiene latex, it is possible to realize being evenly dispersed in styrene-butadiene latex substrate, but also be possible to prevent
The outer shifting of graphite layers, it is ensured that particle size is stable, contributes to expanding stablizing of carbon layers having thicknesses, improves the shielding effect of carbon-coating
Really.Thus promoting the cigarette fire-retardant fruit of effect that presses down of functionalization expansible graphite further to be promoted, its maximum smoke density is less than
100。
Secondly, the present invention has been grafted again a kind of flame-retardant monomer pi-allyl tri-phenyl-phosphorus bromide in styrene-butadiene latex substrate, from
And fire-retardant group phosphorus and bromine can be effectively embedding on the main chain of powder styrene butadiene rubber polymeric, impart powder butylbenzene
The high efficiency of rubber flame-retarded performance and persistency.Simultaneously expansible graphite start when decomposes expand formed heat conductivity low
Porous densification layer of charcoal, intercept flame heat regulating conduction, remove flame propagate living radical, there is good flame retardant effect,
Along with the improvement of expansible graphite Yu the styrene-butadiene latex compatibility, expansible graphite shows good flame retardant effect, is improving material
Fire resistance aspect pi-allyl tri-phenyl-phosphorus bromide and the expansible graphite of material can give play to cooperative effect definitely, contribute to powder
The flame retardant effect of end styrene-butadiene rubber is improved significantly, it is possible to prepares oxygen index (OI) and is up to the fire-retardant powder of more than 45%
Butadiene-styrene rubber.It is low that the method has adding proportion, and smoke elimination efficiency is high, the feature such as good flame retardation effect, modified low cost.
Accompanying drawing explanation
Fig. 1 is the fire-retardant process schematic of expansible graphite.
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
It is only limitted 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 percent grafting: take the sample of about 4g in weighing botle by pipette from three-necked bottle, adds 2～3 after weighing
Drip quinol solution, dry to constant weight, then above-mentioned sample is placed in Soxhlet extractor, with toluene 90 DEG C of water-baths
Upper extractive distillation 24h, is then being dried to constant weight.It is calculated as follows monomer percent grafting:
In formula: m0-latex gross mass (g)；The sample quality (g) weighed after m-reaction；mmTotal matter of monomer in-reactant
Amount (g)；mSNRThe quality (g) of natural rubber in-sample；m1The quality (g) of sample after-extraction.
The mensuration of maximum smoke density: be measured according to the method described in GB/T8323-1987.
The mensuration of oxygen index (OI): be measured according to the method described in GB10707-1989.
The mensuration of vertical combustion: be measured according to the method described in GB/T13488-1992.
Self-extinguishing time measures: be measured according to the method described in UL-94.
Embodiment 1
(1) functionalization expansible graphite: 2 parts of titanate coupling agent NDZ-101 and 60 parts of water, 6 parts of ethanol are joined poly-
Close in still and be uniformly mixed, with mass concentration be 0.05% oxalic acid solution regulation system pH value be 4, being subsequently adding 100 parts can be swollen
Swollen graphite, stirring mixing 20min；Add 6 parts of carboxylic styrene butadiene latex stirring mixing 50min；Dehydration, be dried, grind obtain merit
Expansible graphite a can be changed.
(2) preparation of flame retardant type graft latex: be firstly added 150 parts of deionized waters in polymeric kettle, be then sequentially added into
100 parts of styrene-butadiene latex SBR1500,2.5 parts of dodecylbenzene sodium sulfonate, 0.3 part of DDM dodecyl mercaptan, after replacing with nitrogen, immediately
The pi-allyl tri-phenyl-phosphorus bromide grafted monomers being initially charged 6 parts, stir, heat, still temperature to be polymerized reaches to add when 50 DEG C
0.15 part of BPO, after reaction 8h, then at the HEMA and 0.05 part of BPO addition 2 parts, after continuing reaction 3h, adds 0.2 diethyl
Base azanol, prepares flame retardant type grafting styrene-butadiene latex a.Sample analysis: the percent grafting recording SBR-g-HEMA is 0.9%.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of flame retardant type graft latex a and 1.5 parts of functionalization are inflatable
Graphite a, 70 parts of water join stirring mixing 25min in condensing field, when then heating to 50 DEG C, be sequentially added into 3 parts of potassium oleates,
2.5 parts of magnesium chlorides, are condensed when being 9.3 with sodium hydroxide regulation system pH value, are sequentially added into 3 parts of potassium oleates, 2.5 parts of chlorinations
Magnesium, is condensed when being 9.3 with sodium hydroxide regulation system pH value, stirs 25min and carry out ripening, then warp when being warming up to 80 DEG C
Wash, be dehydrated, be dried to obtain low cigarette, high fire-retardance powder styrene butadiene rubber product.Sample analysis: make standard specimen, after tested property
1 can be shown in Table.
Embodiment 2
(1) preparation of functionalization expansible graphite: with embodiment 1.
(2) preparation of flame retardant type graft latex: with embodiment 1.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of flame retardant type graft latex a and 3 parts of inflatable stones of functionalization
Ink a, 70 parts of water join stirring mixing 25min in condensing field, when then heating to 50 DEG C, be sequentially added into 3 parts of potassium oleates, 2.5
Part magnesium chloride, is condensed when being 9.3 with sodium hydroxide regulation system pH value, is sequentially added into 3 parts of potassium oleates, 2.5 parts of magnesium chlorides,
It is condensed when being 9.3 with sodium hydroxide regulation system pH value, stirs 25min when being warming up to 80 DEG C and carry out ripening, then through washing
Wash, be dehydrated, be dried to obtain low cigarette, high fire-retardance powder styrene butadiene rubber product.Sample analysis: make standard specimen, after tested performance
It is shown in Table 1.
Embodiment 3
(1) preparation of functionalization expansible graphite: with embodiment 1.
(2) preparation of flame retardant type graft latex: with embodiment 1.
(3) preparation of flame retardant type powder styrene butadiene rubber: take 100 parts of flame retardant type graft latex a and 4 parts of functionalization are inflatable
Graphite a, 70 parts of water join stirring mixing 25min in condensing field, when then heating to 50 DEG C, be sequentially added into 3 parts of potassium oleates,
2.5 parts of magnesium chlorides, are condensed when being 9.3 with sodium hydroxide regulation system pH value, are sequentially added into 3 parts of potassium oleates, 2.5 parts of chlorinations
Magnesium, is condensed when being 9.3 with sodium hydroxide regulation system pH value, stirs 25min and carry out ripening, then warp when being warming up to 80 DEG C
Wash, be dehydrated, be dried to obtain low cigarette, high fire-retardance powder styrene butadiene rubber product.Sample analysis: make standard specimen, after tested property
1 can be shown in Table.
Embodiment 4
(1) functionalization expansible graphite: 3.5 parts of titanate coupling agent NDZ-101 and 60 parts of water, 6 parts of ethanol are joined
Polymeric kettle is uniformly mixed, with mass concentration be 0.05% oxalic acid solution regulation system pH value be 4, being subsequently adding 100 parts can
Expanded graphite, stirring mixing 20min；Add 10 parts of carboxylic styrene butadiene latexs and mix mixing 50min；Dehydration, be dried, grind obtain merit
Expansible graphite b can be changed.
(2) preparation of flame retardant type graft latex: be firstly added 150 parts of deionized waters in polymeric kettle, be then sequentially added into
100 parts of styrene-butadiene latex SBR1500,3.0 dialkyl benzene sulfonic acids sodium, 0.4 part of DDM dodecyl mercaptan, after replacing with nitrogen, and then first
Adding the pi-allyl tri-phenyl-phosphorus bromide grafted monomers of 9 parts, stir, heat, still temperature to be polymerized reaches to add when 50 DEG C
0.21BPO, after reaction 8h, is then adding 3.2 parts of HEMA and 0.07 part of BPO, after continuing reaction 3h, is adding 0.3 diethyl
Azanol, prepares flame retardant type grafting styrene-butadiene latex b.Sample analysis: the percent grafting recording SBR-g-HEMA is 1.4%.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of flame retardant type graft latex b and 6 parts of inflatable stones of functionalization
Ink b, 70 parts of water join stirring mixing 25min in condensing field, when then heating to 50 DEG C, be sequentially added into 3.5 acid potassium, 2.5 parts
Magnesium chloride, is 9.4 to be condensed with sodium hydroxide regulation system pH value, is sequentially added into 3.5 parts of potassium oleates, 3.0 parts of magnesium chlorides, use
Sodium hydroxide regulation system pH value is to be condensed when 9.3, stirs 25min and carry out ripening when being warming up to 80 DEG C, the most scrubbed,
It is dehydrated, is dried to obtain low cigarette, high fire-retardance powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown in Table after tested
1。
Embodiment 5
(1) preparation of functionalization expansible graphite: with embodiment 4.
(2) preparation of flame retardant type graft latex: with embodiment 4.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of flame retardant type graft latex b and 7.5 parts of functionalization are inflatable
Graphite b, 70 parts of water join stirring mixing 25min in condensing field, when then heating to 50 DEG C, be sequentially added into 3.5 acid potassium, 2.5
Part magnesium chloride, is 9.4 to be condensed with sodium hydroxide regulation system pH value, is sequentially added into 3.5 parts of potassium oleates, 3.0 parts of magnesium chlorides,
It is condensed when being 9.3 with sodium hydroxide regulation system pH value, stirs 25min when being warming up to 80 DEG C and carry out ripening, then through washing
Wash, be dehydrated, be dried to obtain low cigarette, high fire-retardance powder styrene butadiene rubber product.Sample analysis: make standard specimen, after tested performance
It is shown in Table 1.
Embodiment 6
(1) preparation of functionalization expansible graphite: with embodiment 4
(2) preparation of flame retardant type graft latex: with embodiment 4
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of flame retardant type graft latex b and 8.0 parts of functionalization are inflatable
Graphite b, 70 parts of water join stirring mixing 25min in condensing field, when then heating to 50 DEG C, be sequentially added into 3.5 acid potassium, 2.5
Part magnesium chloride, is 9.4 to be condensed with sodium hydroxide regulation system pH value, is sequentially added into 3.5 parts of potassium oleates, 3.0 parts of magnesium chlorides,
It is condensed when being 9.3 with sodium hydroxide regulation system pH value, stirs 25min when being warming up to 80 DEG C and carry out ripening, then through washing
Wash, be dehydrated, be dried to obtain low cigarette, high fire-retardance powder styrene butadiene rubber product.Sample analysis: make standard specimen, after tested performance
It is shown in Table 1.
Embodiment 7
(1) functionalization expansible graphite: 4.0 parts of titanate coupling agent NDZ-401 and 80 parts of water, 8 parts of ethanol are joined
Polymeric kettle is uniformly mixed, with mass concentration be 0.05% oxalic acid solution regulation system pH value be 4, being subsequently adding 100 parts can
Expanded graphite, stirring mixing 20min；Add 14 parts of carboxylic styrene butadiene latexs and mix mixing 50min；Dehydration, be dried, grind obtain merit
Expansible graphite c can be changed.
(2) preparation of flame retardant type graft latex: be firstly added 180 parts of deionized waters in polymeric kettle, be then sequentially added into
100 parts of styrene-butadiene latex SBR1712,3.5 dialkyl benzene sulfonic acids sodium, 0.5 part of DDM dodecyl mercaptan, after replacing with nitrogen, and then first
Adding the pi-allyl tri-phenyl-phosphorus bromide grafted monomers of 13 parts, stir, heat, still temperature to be polymerized reaches to add when 50 DEG C
0.35BPO, after reaction 8h, is then adding 4.5 parts of HEMA and 0.08 part of BPO, after continuing reaction 3h, is adding 0.4 diethyl
Azanol, prepares flame retardant type grafting styrene-butadiene latex c.Sample analysis: the percent grafting recording SBR-g-HEMA is 2.2%.
(3) preparation of fire-retardant powder styrene butadiene rubber: take 100 parts of flame retardant type graft latex c and 9.5 parts of functionalization are inflatable
Graphite c, 80 parts of water join stirring mixing 25min in condensing field, when then heating to 50 DEG C, be sequentially added into 4 acid potassium, 3.5 parts
Magnesium chloride, is 9.4 to be condensed with sodium hydroxide regulation system pH value, is sequentially added into 4.0 parts of potassium oleates, 3.5 parts of magnesium chlorides, use
Sodium hydroxide regulation system pH value is to be condensed when 9.3, stirs 25min and carry out ripening when being warming up to 80 DEG C, the most scrubbed,
It is dehydrated, is dried to obtain low cigarette, high fire-retardance powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown in Table after tested
1。
Comparative example 1
(1) functionalization expansible graphite: 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 same as in Example 1, difference is fire-retardant powder
In the preparation process of butadiene-styrene rubber, the addition of functionalization expansible graphite a is 0.7 part, it may be assumed that take 100 parts of flame retardant type graft latexes
A and 0.7 part of functionalization expansible graphite a, 70 parts of water join stirring mixing 25min in condensing field, when then heating to 50 DEG C,
It is sequentially added into 3 parts of potassium oleates, 2.5 parts of magnesium chlorides, is condensed when being 9.3 with sodium hydroxide regulation system pH value, is sequentially added into 3
Part potassium oleate, 2.5 parts of magnesium chlorides, be condensed when being 9.3 with sodium hydroxide regulation system pH value, is warming up to stirring when 80 DEG C
25min carries out ripening, the most scrubbed, be dehydrated, be dried to obtain low cigarette, high fire-retardance powder styrene butadiene rubber product.Sample analysis: system
Becoming standard specimen, performance is shown 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 same as in Example 2, difference is fire-retardant powder
Being not added with functionalization expansible graphite a in the preparation process of butadiene-styrene rubber, but be directly added into expansible graphite, its addition is 3
Part, it may be assumed that take 100 parts of flame retardant type graft latex a and 3 parts of expansible graphites, 70 parts of water join stirring mixing in condensing field
25min, when then heating to 50 DEG C, is sequentially added into 3 parts of potassium oleates, 2.5 parts of magnesium chlorides, with sodium hydroxide regulation system pH value is
It is condensed when 9.3, is sequentially added into 3 parts of potassium oleates, 2.5 parts of magnesium chlorides, carries out when being 9.3 with sodium hydroxide regulation system pH value
Cohesion, stirs 25min and carries out ripening when being warming up to 80 DEG C, the most scrubbed, be dehydrated, be dried to obtain low cigarette, high fire-retardance powder fourth
Benzene rubber product.Sample analysis: make standard specimen, performance is shown in Table 1 after tested.
Comparative example 3
(1) preparation of functionalization expansible graphite: with embodiment 1.
(2) preparation of flame retardant type graft latex: other condition is same as in Example 1, and difference is graft latex
Preparation process is added without hydroxyethyl methylacrylate (HEMA), it may be assumed that in polymeric kettle, be firstly added 150 parts of deionized waters, so
After be sequentially added into 100 parts of styrene-butadiene latex SBR1500,2.5 parts of dodecylbenzene sodium sulfonate, 0.3 part of DDM dodecyl mercaptan, put with nitrogen
After changing, being and then initially charged the pi-allyl tri-phenyl-phosphorus bromide grafted monomers of 6 parts, stir, heat, still temperature to be polymerized reaches 50
DEG C time add 0.15 part of BPO, reaction 8h after, be eventually adding 0.2 diethyl hydroxylamine, prepare flame retardant type grafting styrene-butadiene latex (a-1).
(3) preparation of fire-retardant powder styrene butadiene rubber: other condition is same as in Example 3, difference is fire-retardant powder
The preparation process of butadiene-styrene rubber is not added with flame retardant type grafting styrene-butadiene latex a, but adds the flame retardant type grafting fourth of non-grafted HEMA
Benzene latex (a-1), it may be assumed that take 100 parts of flame retardant type graft latexes (a-1) and 4 parts of functionalization expansible graphite a, 70 parts of water join
In condensing field, stirring mixing 25min, when then heating to 50 DEG C, is sequentially added into 3 parts of potassium oleates, 2.5 parts of magnesium chlorides, uses hydroxide
Sodium regulation system pH value is to be condensed when 9.3, is sequentially added into 3 parts of potassium oleates, 2.5 parts of magnesium chlorides, regulates body with sodium hydroxide
Be pH value be to be condensed when 9.3, 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, high fire-retardance powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown in Table 1 after tested.
Comparative example 4
(1) preparation of functionalization expansible graphite: with embodiment 4.
(2) preparation of flame retardant type powder styrene butadiene rubber: other condition is the same as in Example 4, difference is cohesion
During be added without flame retardant type grafting styrene-butadiene latex b, but in styrene-butadiene latex SBR1500, be directly added into the inflatable stone of functionalization
Ink b is condensed.That is: take 100 parts of styrene-butadiene latex SBR1500 and 6 parts of functionalization expansible graphite b, 70 parts of water join cohesion
Stirring mixing 25min in still, when then heating to 50 DEG C, is sequentially added into 3.5 acid potassium, 2.5 parts of magnesium chlorides, regulates with sodium hydroxide
System pH is 9.4 to be condensed, and is sequentially added into 3.5 parts of potassium oleates, 3.0 parts of magnesium chlorides, with sodium hydroxide regulation system pH value
It is to be condensed when 9.3, stirs 25min when being warming up to 80 DEG C and carry out ripening, the most scrubbed, be dehydrated, be dried to obtain low cigarette, height
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 flame retardant type graft latex: other condition is the same as in Example 4, and difference is graft latex
Preparation process is added without pi-allyl tri-phenyl-phosphorus bromide, it may be assumed that in polymeric kettle, be firstly added 150 parts of deionized waters, then depend on
100 parts of styrene-butadiene latex SBR1500 of secondary addition, 3.0 dialkyl benzene sulfonic acids sodium, 0.4 part of DDM dodecyl mercaptan, after replacing with nitrogen, tightly
It is subsequently added into 3.2 parts of HEMA and 0.07 part of BPO, when still temperature to be polymerized reaches 50 DEG C, after reaction 3h, then adds 0.3
Diethyl hydroxylamine, prepares flame retardant type grafting styrene-butadiene latex (b-1).
(3) preparation of flame retardant type powder styrene butadiene rubber: other condition is same as in Example 3, and difference is fireproof powder
The preparation process of end butadiene-styrene rubber is not added with flame retardant type grafting styrene-butadiene latex b, but adds non-grafted pi-allyl triphenyl phosphonium bromide
Flame retardant type grafting styrene-butadiene latex (b-1) of phosphorus, it may be assumed that take 100 parts of flame retardant type graft latexes (b-1) and 7.5 parts of functionalization are inflatable
Graphite b, 70 parts of water join stirring mixing 25min in condensing field, when then heating to 50 DEG C, be sequentially added into 3.5 acid potassium, 2.5
Part magnesium chloride, is 9.4 to be condensed with sodium hydroxide regulation system pH value, is sequentially added into 3.5 parts of potassium oleates, 3.0 parts of magnesium chlorides,
It is condensed when being 9.3 with sodium hydroxide regulation system pH value, stirs 25min when being warming up to 80 DEG C and carry out ripening, then through washing
Wash, be dehydrated, be dried to obtain low cigarette, high fire-retardance powder styrene butadiene rubber product.Sample analysis: make standard specimen, after tested performance
It is shown in Table 1.
Comparative example 6
(1) preparation of functionalization expansible graphite: other condition is the same as in Example 4, difference is inflatable stone
The preparation process of ink is added without NDZ-101 coupling agent, it may be assumed that 60 parts of water, 6 parts of ethanol are joined stirring in polymeric kettle and mix all
Even, with mass concentration be 0.05% oxalic acid solution regulation system pH value be 4, be subsequently adding 100 parts of expansible graphites, stirring mixing
20min；Add 10 parts of carboxylic styrene butadiene latexs and mix mixing 50min；Dehydration, be dried, grind obtain functionalization expansible graphite (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 same as in Example 6, and difference is compositions system
During Bei add functionalization expansible graphite without coupling agent and containing only carboxylic styrene butadiene latex, functionalization expansible graphite
(b-1) addition 8.0 parts, it may be assumed that take 100 parts of flame retardant type graft latex b and 8.0 parts of functionalization expansible graphites (b-1), 70 parts
Water joins stirring mixing 25min in condensing field, when then heating to 50 DEG C, is sequentially added into 3.5 acid potassium, 2.5 parts of magnesium chlorides, uses
Sodium hydroxide regulation system pH value is 9.4 to be condensed, and is sequentially added into 3.5 parts of potassium oleates, 3.0 parts of magnesium chlorides, uses sodium hydroxide
Regulation system pH value is to be condensed when 9.3, stirs 25min and carry out ripening when being warming up to 80 DEG C, the most scrubbed, be dehydrated, dry
Dry obtain low cigarette, high fire-retardance powder styrene butadiene rubber product.Sample analysis: make standard specimen, performance is shown 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 same as in Example 7, difference is fire-retardant powder
Being not added with functionalization expansible graphite c in the preparation process of butadiene-styrene rubber, but be directly added into expansible graphite, its addition is
9.5 parts, it may be assumed that take 100 parts of flame retardant type graft latex c and 9.5 parts of expansible graphites, 80 parts of water join stirring mixing in condensing field
25min, when then heating to 50 DEG C, is sequentially added into 4 acid potassium, 3.5 parts of magnesium chlorides, is 9.4 with sodium hydroxide regulation system pH value
It is condensed, is sequentially added into 4.0 parts of potassium oleates, 3.5 parts of magnesium chlorides, coagulates when being 9.3 with sodium hydroxide regulation system pH value
Poly-, 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, high fire-retardance powder butylbenzene
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 (9)
1. a preparation method for powder styrene butadiene rubber, concrete preparation process is:
(1) functionalization expansible graphite: be in terms of 100 parts by expansible graphite quality, by 1～5 part of titanate coupling agent and 50～
100 parts of water, 5～10 parts of ethanol join in polymeric kettle and are uniformly mixed, and are 2～6 with acid regulation system pH value, are 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；
(2) preparation of flame retardant type graft latex: be in terms of 100 parts by styrene-butadiene latex quality, be firstly added in polymeric kettle 100～
200 parts of deionized waters, then it is sequentially added into 100 parts of styrene-butadiene latexes, 1～10 part of emulsifying agent, 0.1～1.0 part of molecular weight regulator,
After replacing with nitrogen, and then it is initially charged the pi-allyl tri-phenyl-phosphorus bromide grafted monomers of 5～15 parts, stirs, heat, to be polymerized
Still temperature reaches to add 0.1～0.5 part of initiator when 40～60 DEG C, after reaction 5～10h, is subsequently adding the polarity list of 1～5 part
Body and 0.05～0.1 part of initiator, after continuing reaction 2～4h, add 0.1～0.5 part of terminator, prepares flame retardant type grafting butylbenzene
Latex；
(3) preparation of fire-retardant powder styrene butadiene rubber: be in terms of 100 parts by fire-retardant grafting styrene-butadiene latex quality, takes 100 parts of flame retardant types and connects
Branch latex and 1～10 part of functionalization expansible graphite, 50～100 parts of water join stirring mixing 10～30min in condensing field, so
After when being warming up to 40～60 DEG C, be sequentially added into 2～5 portions of interleaving agents, 2～6 parts of flocculating agents, be 8 with buffer agent regulation system pH value
～11, 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, high resistant
Combustion powder styrene butadiene rubber product.
2. preparation method as claimed in claim 1, it is characterised in that the particle diameter of described expansible graphite is 20 μm～200 μ
m。
3. preparation method as claimed in claim 1, it is characterised in that the particle diameter of described expansible graphite is 30 μm～100 μ
m。
4. preparation method as claimed in claim 1, it is characterised in that described carboxylic styrene butadiene latex be butadiene, styrene and
Unsaturated carboxylic acid obtains through emulsion polymerization.
5. preparation method as claimed in claim 4, it is characterised in that described unsaturated carboxylic acid is acrylic acid, methacrylic acid
Or 2-ethylacrylic acid.
6. preparation method as claimed in claim 1, it is characterised in that described titanate coupling agent is selected from isopropyl two oleic acid
Acyloxy titanate esters, dioctyl phosphoric acid acyloxy titanate esters, isopropyl three oleic acid acyloxy titanate esters, dodecyl benzenesulfonyl
Compounding of one or more in titanate esters, dioctylphyrophosphoric acid acyloxy titanate esters, dioctyl phosphito acyloxy titanate esters.
7. preparation method 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.
8. preparation method as claimed in claim 1, it is characterised in that described polar monomer is selected from vinyl acetate, maleic acid
One in acid anhydride, hydroxyethyl methylacrylate.
9. preparation method as claimed in claim 1, it is characterised in that described initiator selected from potassium peroxydisulfate, 2,5-diformazan
In base-2,5-di-t-butyl hexane peroxide, di-tert-butyl peroxide, cumyl peroxide, benzoyl peroxide one
Kind.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310428393.1A CN104448663B (en) | 2013-09-18 | 2013-09-18 | Method for preparing environment-friendly low-smoke flame-retardant powdered butadiene styrene rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310428393.1A CN104448663B (en) | 2013-09-18 | 2013-09-18 | Method for preparing environment-friendly low-smoke flame-retardant powdered butadiene styrene rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104448663A CN104448663A (en) | 2015-03-25 |
| CN104448663B true CN104448663B (en) | 2017-01-11 |
Family
ID=52895454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310428393.1A Active CN104448663B (en) | 2013-09-18 | 2013-09-18 | Method for preparing environment-friendly low-smoke flame-retardant powdered butadiene styrene rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104448663B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107274991A (en) * | 2015-11-10 | 2017-10-20 | 李聪 | A kind of waterproof layer of durable security cable |
| CN108192166B (en) * | 2016-12-08 | 2021-03-30 | 中国石油天然气股份有限公司 | Modification method of high-dispersion rubber filler carbon nano tube |
| CN108192138B (en) * | 2016-12-08 | 2020-08-07 | 中国石油天然气股份有限公司 | Modification method of carbon nano tube used as rubber filler |
| CN110016234B (en) * | 2019-04-17 | 2021-06-04 | 山东显元化工研究院有限公司 | SBR (styrene butadiene rubber) latex for modified emulsified asphalt and preparation method thereof |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649025A (en) * | 2009-06-06 | 2010-02-17 | 中国石油兰州石油化工公司 | Preparation method of carboxylic styrene butadiene latex |
| 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 CN201310428393.1A patent/CN104448663B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649025A (en) * | 2009-06-06 | 2010-02-17 | 中国石油兰州石油化工公司 | Preparation method of carboxylic styrene butadiene latex |
| 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 |
|---|
| "AC/MMA接枝改性天然胶乳的制备及性能研究";谭海生 等;《弹性体》;20021225;第12卷(第6期);32-35 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104448663A (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104448663B (en) | Method for preparing environment-friendly low-smoke flame-retardant powdered butadiene styrene rubber | |
| CN104448661B (en) | Low cigarette, the preparation method of high fire-retardance powder styrene butadiene rubber | |
| Xiao et al. | Flame retardant and its influence on the performance of asphalt–A review | |
| CN104448662B (en) | Method for preparing low-smoke and high flame retardant powdered butadiene styrene rubber | |
| CN103159867B (en) | Preparation method for flame-retardant powdered rubber | |
| CN104448446B (en) | A kind of preparation method of environmental-protection flame-retardant powder styrene butadiene rubber | |
| CN104448453B (en) | The preparation method of the low cigarette of a kind of halogen acidylate, fire-retardant powder styrene butadiene rubber | |
| CN104448150B (en) | Fire retardation powder styrene butadiene rubber preparation method | |
| KR102361451B1 (en) | Method for preparing large particle sized rubber latex, and method for preparing abs graft copolymer | |
| JP2016533406A (en) | Polymer particle having core-shell structure and rubber composition containing the same | |
| KR100832518B1 (en) | Flameproof phosphorous-containing copolymer and flameproof thermoplastic resin composition using the same | |
| CN104448447A (en) | Method for preparing environment-friendly low-smoke flame retardant powdered butadiene styrene rubber | |
| CN105348578A (en) | Preparation method of novel nanoscale fire retardant | |
| CN113402835B (en) | Preparation method of high-flame-retardant, low-smoke and high-impact polystyrene | |
| CN104448452B (en) | The low cigarette of halogen acidylate, fire-retardant powder styrene butadiene rubber preparation method | |
| CN104140557B (en) | Preparation and application of zinc hydroxystannate-palygorskite-mercaptan composite flame retardant | |
| CN105086025B (en) | Low-smoke and flame retardant powdered styrene butadiene rubber and preparation method thereof | |
| US3546160A (en) | Self-extinguishing styrene/acrylonitrile-copolymers | |
| CN105086030B (en) | Low-smoke and flame retardant powder styrene butadiene rubber and preparation method thereof | |
| CN105733054B (en) | The preparation technology of fire-retardant powder styrene butadiene rubber | |
| CN102453215B (en) | Inflaming retarding copolymer latex and preparation method thereof | |
| CN105733157A (en) | Preparation method of flame-retarding powder butadiene styrene rubber | |
| US3645926A (en) | Stabilized self-extinguishing latex foam rubber | |
| JP2007269863A (en) | Latex composition for wet masterbatch | |
| CN112126107A (en) | Expandable polystyrene and carbon black composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |