CN103333424A - Halogen-free environment-friendly polystyrene flame retardant and preparation method thereof - Google Patents
Halogen-free environment-friendly polystyrene flame retardant and preparation method thereof Download PDFInfo
- Publication number
- CN103333424A CN103333424A CN2013102368579A CN201310236857A CN103333424A CN 103333424 A CN103333424 A CN 103333424A CN 2013102368579 A CN2013102368579 A CN 2013102368579A CN 201310236857 A CN201310236857 A CN 201310236857A CN 103333424 A CN103333424 A CN 103333424A
- Authority
- CN
- China
- Prior art keywords
- halogen
- free environment
- agent
- calcium carbonate
- polystyrene
- 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.)
- Granted
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a halogen-free environment-friendly polystyrene flame retardant and a preparation method thereof. The preparation method comprises the steps of: adding II-type ammonium polyphosphate, expanded graphite, calcium carbonate, a carbon forming accelerator and a surfactant into a high-speed mixing machine, increasing the temperature, and mixing at a high speed to prepare a compound flame retardant, then adding a surfactant, and continuing high-speed mixing to obtain the halogen-free environment-friendly polystyrene flame retardant. The adhesive property of carbon residue can be improved by adopting reaction of low-cost calcium carbonate and ammonium polyphosphate, the usage amount of the expanded graphite can be effectively reduced, the smoke release quantity can be decreased, and the occurrence of molten drop phenomena can be prevented; and the synergetic flame retardant effect of the compound flame-retardant system can be greatly enhanced, and the flame retardance effect is good.
Description
Technical field
The present invention relates to a kind of polystyrene and fire retardant thereof, specifically a kind of halogen-free environment-friendly flame-proof agent that is applied to polystyrene.
Background technology
Polystyrene (PS) is one of resin of global output maximum, and is nontoxic because of it, density is little, resistance to chemical attack and electrical insulating property are good, is widely used in fields such as electronics/electrical equipment, automobile, building, toy, packing.But polystyrene very easily burns, and strong oxicracking causes during burning melts and drip phenomenon shortcomings such as release serious and toxic gas and seriously restricted it and promote the use of in the field that fire protection requirement is arranged.Along with people improve day by day for safe requirement, the exploitation of fire retardant polystyrene enjoys favor.
Add fire retardant in the polystyrene resin and can improve its flame retardant properties, its fire retardant commonly used is halogenated flame retardant, phosphorus flame retardant, inorganic combustion inhibitor and expansion type flame retardant.Use halogenated flame retardant can effectively improve its flame retardant resistance, but in its combustion processes, smoke release is big, and melting phenomenon is obvious, easily discharge poisonous or corrosive gases generation " secondary harm ", studies show that recently polybromodiphenyl ether class material can produce carcinogenic substance when burning.At present, propose or implemented the regulations of rules of forbidding or limiting the use of halogenated flame retardant both at home and abroad.And common halogen-free flame retardants exists flame retarding efficiency low, bad with the consistency of polystyrene problem.Cause the cost of manufacture height, addition is big, the problem that the polystyrene degradation is serious, and unfavorable big area is promoted.
CN102585375A discloses " the special-purpose halogen-free environment-friendly flame-proof agent of a kind of polypropylene ".With the covering property ammonium polyphosphate, efficient char-forming agent, the synergistic char-forming agent becomes charcoal promotor, and modified polypropenes such as anti-dripping agent obtain a kind of environmental protection fire retarding agent of Halogen.Though it has described the cooperative flame retardant effect of ammonium polyphosphate and expanded graphite, its matrix is polypropylene, and its application in polystyrene is not described, and is not applied to calcium carbonate, thereby might have the not enough problem of charcoal layer structural strength.
CN1850911A discloses a kind of " having concurrently fire-retardant and polymer-based carbon functional composite material conducting function ".With expanded graphite, expansible black lead is main flame retardant, and with red phosphorus, ammonium polyphosphate etc. are auxiliary flame retardant, obtains a kind of fire-retardant and polymer matrix composite conducting function of having concurrently.Its cost is higher, and finds that in test charcoal layer structure not enough problem in burning back is outstanding.
CN102277030A discloses " a kind of for the fire-retardant high-efficiency environment friendly fire retardant of coating ".With ammonium polyphosphate, tetramethylolmethane, a kind of material flame-retardant that is coated with of compositions such as tea saponin, thus obtain a kind of anti-flaming dope preferably.It is mainly used among the anti-flaming dope, and not mentioned application among resin.And do not add expanded graphite and calcium carbonate.
Summary of the invention
Problem of the present invention is to overcome simple use ammonium polyphosphate and expanded graphite cost height, and the not enough problem of structural strength of using its charcoal layer behind the expanded graphite in resin, and a kind of polystyrene halogen-free environment-friendly flame-proof agent and preparation method thereof is provided.
A kind of technical scheme of halogen-free environment-friendly flame-proof agent is as follows:
The composition of raw material and content by mass parts are: 30 ~ 70 parts of ammonium polyphosphates, 10 ~ 50 parts of expanded graphites, 10 ~ 25 parts in calcium carbonate, 3 ~ 5 parts of one-tenth charcoal promotor, 0.5 ~ 3 part in tensio-active agent.
Further, the composition of raw material and content by mass parts are: 55 parts of ammonium polyphosphates, 25 parts of expanded graphites, 15 parts in calcium carbonate, 5 parts of one-tenth charcoal promotor, 3 parts in tensio-active agent.
In such scheme, the polymerization degree of described ammonium polyphosphate is n 〉=1000, and grain size is 80 ~ 200 orders; Described expanded graphite is of a size of 80 ~ 200 orders, and expansion multiple is 0.15 ~ 0.25 m3/kg; Described calcium carbonate is light calcium carbonate; Described one-tenth charcoal promotor is zinc oxide, zinc borate, magnesian a kind of; Described tensio-active agent is a kind of of silane coupling agent KH550, KH570.
A kind of halogen-free environment-friendly flame-proof agent preparation method's technical scheme is as follows:
Take by weighing raw material by above-mentioned raw material composition and the mass fraction of content thereof, again with ammonium polyphosphate, expanded graphite, calcium carbonate becomes charcoal promotor to add high-speed mixer, be warming up to 90 ~ 130 ℃, at rotating speed high-speed mixing 3 ~ 5min of 800 ~ 1200r/min, be mixed into compound flame retardant after, add 1 ~ 3% tensio-active agent of compound flame retardant total mass again, continue high-speed mixing 5 ~ 8min, namely make the halogen-free environment-friendly flame-proof agent.
Realize a kind of halogen-free environment-friendly flame-proof agent provided by the present invention and preparation method thereof, its prepared halogen-free environment-friendly flame-proof agent has high flame retardant, high smoke-suppressing, the characteristics that can effectively suppress the fusion drip phenomenon in the polystyrene combustion processes, in this system, do not introduce simultaneously the halogen series elements, fire-retardant process pollution on the environment is little, and it is few to produce harmful material, and little to the mechanical property influence of matrix.With respect to the material of equal flame retardant properties, price is cheaper.Be a kind of flame retarding efficiency height and the little material of contaminative.
Description of drawings
The SEM scintigram of Fig. 1 residue: be the pure PS burning SEM scan image of residue afterwards among the figure.
The SEM scintigram of Fig. 2 residue: be the SEM scan image that adds residue after the PS burning of fire retardant among the figure.
Embodiment
Below the specific embodiment of the present invention is made further instruction.
Embodiment 1
Implement a kind of polystyrene halogen-free environment-friendly flame-proof provided by the present invention agent, the composition of this halogen-free environment-friendly flame-proof agent and content thereof are composed as follows by mass parts:
30 ~ 70 parts ammonium polyphosphate, described ammonium polyphosphate are II type ammonium polyphosphates, and its polymerization degree is n 〉=1000, and grain size is 80 ~ 200 orders.
10 ~ 50 parts expanded graphite, described expanded graphite are 80 ~ 200 orders, and expansion multiple is 0.15 ~ 0.25 m3/kg.
10 ~ 25 parts calcium carbonate, described calcium carbonate are light calcium carbonate.
3 ~ 5 parts one-tenth charcoal promotor, described one-tenth charcoal promotor is zinc oxide, zinc borate, a kind of among the magnesium oxide.
0.5 ~ 3 parts tensio-active agent, described tensio-active agent are a kind of among silane coupling agent KH550, the KH570.
Based on technique scheme, preferably be embodied as further: composition and the content thereof of halogen-free environment-friendly flame-proof agent are defined as by mass parts: ammonium polyphosphate: expanded graphite: calcium carbonate: become charcoal promotor: tensio-active agent=55:25:15:5:3.
Realize the agent of the above-mentioned a kind of polystyrene halogen-free environment-friendly flame-proof of the present invention, adopt among the APP/EG and introduce calcium carbonate, can greatly reduce the addition of expanded graphite, reduced the cost of manufacture of fire-retardant mixture; Under the high temperature; the reaction product of calcium carbonate and ammonium polyphosphate; improved the adhesive property of products of combustion, improved the structural strength of the dilator of combustion processes expanded graphite generation, the system that makes forms constitutionally stable protection charcoal layer; promoted provide protection; and the interpolation of this system can reduce the smoke release of PS in combustion processes, has prevented the generation of fusion drip phenomenon; have tangible flame retardant synergistic effect, the flame retardant effect that has is outstanding.
Embodiment 2
Implement the preparation method of the above-mentioned a kind of polystyrene halogen-free environment-friendly flame-proof of the present invention agent, this preparation method takes by weighing raw material by a kind of polystyrene halogen-free environment-friendly flame-proof agent weight part, and with ammonium polyphosphate, expanded graphite, calcium carbonate, become charcoal promotor to add high-speed mixer, be warming up to 90 ~ 130 ℃, rotating speed high-speed mixing 3 ~ 5min at 800 ~ 1200r/min, be mixed into compound flame retardant, after add 1 ~ 3% the tensio-active agent account for the compound flame retardant total mass again, continue high-speed mixing 5 ~ 8min, namely make the agent of polystyrene halogen-free environment-friendly flame-proof.
Realize the preparation method of above-mentioned a kind of polystyrene halogen-free environment-friendly flame-proof agent, this preparation method can effectively reduce the invalid expansion of expanded graphite that Yin Gaowen causes, improve the actual utilising efficiency of additive, and guaranteed under the short time, various components to be mixed, and promoted consistency in matrix PS, guaranteed the effect that the effect of various additives can be brought into play in actual applications greatly.
On the basis of above-mentioned enforcement a kind of compositional flame-retardant polyphenylacetylene combination of the present invention and preparation method thereof, further specify below by specific embodiment.
Embodiment 1
A kind of halogen-free environment-friendly flame-proof agent that is applied to polystyrene, this fire retardant is to be made by the raw material of following weight part: 55 parts of ammonium polyphosphates (APP), 25 parts of expanded graphites (EG), calcium carbonate (CaCO
3) 15 parts, 5 parts in magnesium oxide (MgO), 3 parts of silane coupling agents (KH570).
Above-mentioned a kind of preparation method who is applied to the halogen-free environment-friendly flame-proof agent of polystyrene, this method is to take by weighing raw material by above-mentioned weight part, ammonium polyphosphate, expanded graphite, calcium carbonate, magnesium oxide are added high-speed mixer, be warming up to 130 ℃, at the rotating speed high-speed mixing 5min of 800r/min, be mixed into compound flame retardant after, add 2% silane coupling agent KH570 of compound flame retardant total mass again, continue high-speed mixing 8min, make the halogen-free environment-friendly flame-proof agent of polystyrene.
Present embodiment is introduced calcium carbonate on the basis of APP/EG, has improved the intensity of carbon residue structure effectively, guarantees its lasting provide protection, and in the Actual combustion process, can increase speed and the quality of non-flammable gases, plays flame retardant effect in gas phase.And the proportioning that changes each component will obtain the consistent flame-retardant formulations of flame retardant properties.The product halogen-free environment-friendly flame-proof agent of gained is applied to polystyrene, tests its combustionproperty.Obtaining its UL-94 standard class is the V-0 level, and oxygen index is 30.2%.
Embodiment 2
A kind of halogen-free environment-friendly flame-proof agent that is applied to polystyrene, this fire retardant is to be made by the raw material of following weight part: 60 parts of ammonium polyphosphates (APP), 20 parts of expanded graphites (EG), calcium carbonate (CaCO
3) 15 parts, 5 parts in zinc oxide (ZnO), 3 parts of silane coupling agents (KH570).
Above-mentioned a kind of preparation method who is applied to the halogen-free environment-friendly flame-proof agent of polystyrene, this method is to take by weighing raw material by above-mentioned weight part, ammonium polyphosphate, expanded graphite, calcium carbonate, zinc oxide are added high-speed mixer, be warming up to 90 ℃, at the rotating speed high-speed mixing 5min of 1000r/min, be mixed into compound flame retardant after, add 1 ~ 3% silane coupling agent KH570 of compound flame retardant total mass again, continue high-speed mixing 5min, namely make the agent of a kind of polystyrene halogen-free environment-friendly flame-proof.
Embodiment 3
A kind of halogen-free environment-friendly flame-proof agent that is applied to polystyrene is made by the raw material of following weight part: ammonium polyphosphate (APP) 45, expanded graphite (EG) 35, calcium carbonate (CaCO
3) 15, zinc borate (ZB-2335) 5, silane coupling agent (KH550) 3.
Preparation method: take by weighing raw material by above-mentioned weight part, ammonium polyphosphate, expanded graphite, calcium carbonate, zinc borate are added high-speed mixer, be warming up to 100 ℃, rotating speed high-speed mixing 3min at 1200r/min, 2% the silane coupling agent KH550 that adds the compound flame retardant total mass, continue high-speed mixing 5min, namely obtain this product.
Accompanying drawing is the SEM image of residue behind pure PS and this prescription of the interpolation fire retardant PS composition burn afterwards.As we can see from the figure, behind the interpolation fire retardant, its carbon residue structure forms network, and expanding volume becomes big and structural strength improves, thereby the obstruction inner material has reduced the sustained combustion of PS significantly because of contact external flame or oxygen sustained combustion.
Claims (4)
1. polystyrene halogen-free environment-friendly flame-proof agent, the composition of its described halogen-free environment-friendly flame-proof agent and content thereof are as follows by mass parts:
30 ~ 70 parts of ammonium polyphosphates;
10 ~ 50 parts of expanded graphites;
10 ~ 25 parts in calcium carbonate;
Become 3 ~ 5 parts of charcoal promotor;
0.5 ~ 3 part in tensio-active agent.
2. polystyrene halogen-free environment-friendly flame-proof as claimed in claim 1 agent, the composition of its described fire retardant and content thereof by mass parts are: ammonium polyphosphate: expanded graphite: calcium carbonate: become charcoal promotor: tensio-active agent=55:25:15:5:3.
3. polystyrene halogen-free environment-friendly flame-proof as claimed in claim 1 or 2 agent, its described ammonium polyphosphate are II type ammonium polyphosphates, and its polymerization degree is n 〉=1000, and grain size is 80 ~ 200 orders; Described expanded graphite is 80 ~ 200 orders, and expansion multiple is 0.15 ~ 0.25 m3/kg; Described calcium carbonate is light calcium carbonate; Described one-tenth charcoal promotor is zinc oxide, zinc borate, a kind of among the magnesium oxide; Described tensio-active agent is a kind of among silane coupling agent KH550, the KH570.
4. the preparation method of a polystyrene halogen-free environment-friendly flame-proof as claimed in claim 1 agent, its described method is to take by weighing raw material by claim 1 or 2 described weight parts, with ammonium polyphosphate, expanded graphite, calcium carbonate, become charcoal promotor to add high-speed mixer, be warming up to 90 ~ 130 ℃, rotating speed high-speed mixing 3 ~ 5min at 800 ~ 1200r/min, be mixed into compound flame retardant, after add 1 ~ 3% the tensio-active agent account for the compound flame retardant total mass again, continue high-speed mixing 5 ~ 8min, namely make the agent of polystyrene halogen-free environment-friendly flame-proof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310236857.9A CN103333424B (en) | 2013-06-15 | 2013-06-15 | Halogen-free environment-friendly polystyrene flame retardant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310236857.9A CN103333424B (en) | 2013-06-15 | 2013-06-15 | Halogen-free environment-friendly polystyrene flame retardant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103333424A true CN103333424A (en) | 2013-10-02 |
| CN103333424B CN103333424B (en) | 2015-06-03 |
Family
ID=49241636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310236857.9A Active CN103333424B (en) | 2013-06-15 | 2013-06-15 | Halogen-free environment-friendly polystyrene flame retardant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103333424B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923405A (en) * | 2014-04-28 | 2014-07-16 | 郴州和利泡沫塑料有限公司 | Flame-retardant additive for expandable polystyrene material |
| CN105131449A (en) * | 2015-09-25 | 2015-12-09 | 太原理工大学 | Expanded antiflaming environment-friendly polystyrene |
| CN106118022A (en) * | 2016-06-29 | 2016-11-16 | 青岛科技大学 | A kind of thermoplastic fire retardant, flame retardant thermoplastic and preparation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731920A (en) * | 2012-07-04 | 2012-10-17 | 太原理工大学 | Compounding flame retardation polystyrene composition and preparation method thereof |
-
2013
- 2013-06-15 CN CN201310236857.9A patent/CN103333424B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731920A (en) * | 2012-07-04 | 2012-10-17 | 太原理工大学 | Compounding flame retardation polystyrene composition and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923405A (en) * | 2014-04-28 | 2014-07-16 | 郴州和利泡沫塑料有限公司 | Flame-retardant additive for expandable polystyrene material |
| CN103923405B (en) * | 2014-04-28 | 2016-04-13 | 郴州和利泡沫塑料有限公司 | A kind of flame-retardant additive for Expandable Polystyrene (EPS) material |
| CN105131449A (en) * | 2015-09-25 | 2015-12-09 | 太原理工大学 | Expanded antiflaming environment-friendly polystyrene |
| CN106118022A (en) * | 2016-06-29 | 2016-11-16 | 青岛科技大学 | A kind of thermoplastic fire retardant, flame retardant thermoplastic and preparation method |
| CN106118022B (en) * | 2016-06-29 | 2021-07-27 | 青岛科技大学 | Thermoplastic plastic flame retardant, flame-retardant thermoplastic plastic and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103333424B (en) | 2015-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102174223B (en) | Flame-retardant foamed polyethylene material and preparation method thereof | |
| CN102731888B (en) | Multilayer coated red phosphorus low-smoke halogen-free flame-retardant polyolefin cable sheath material and preparation method thereof | |
| CN101735514B (en) | Flame-retardant polypropylene material and preparation method | |
| CN102367306A (en) | High efficiency halogen-free flame retardant polypropylene composite material and its preparation method | |
| CN101402758B (en) | Non-halogen flame-proof polyvinyl composite and method of producing the same | |
| CN102134352A (en) | Expansion type flame-retardant polypropylene composite material and preparation method thereof | |
| CN103333423B (en) | Compound flame-retardant polystyrene composition and preparation method thereof | |
| CN103289290B (en) | A kind of phosphorus system synergistic flame-retardant ABS compound material and preparation method thereof | |
| CN105295101A (en) | Microencapsulated red phosphorus fire retardant and preparation method and application thereof | |
| CN103333457A (en) | High-smoke suppression and high-oxygen index phenolic aldehyde fire-proof heat-preserving board and preparation method thereof | |
| CN113583299A (en) | High-expansion fireproof low-smoke halogen-free flame retardant composition and thermoplastic resin composition | |
| CN101274987A (en) | Calcium hydroxide-based halogen-free flame-proof plastic masterbatch and preparation for special resin therefor | |
| CN103333424B (en) | Halogen-free environment-friendly polystyrene flame retardant and preparation method thereof | |
| CN102219958A (en) | Material of efficient inflaming-retarding composite plastic woven bag | |
| JPH0225381B2 (en) | ||
| CN114031850A (en) | Tin-phosphorus-nitrogen expansion type flame-retardant polypropylene composite material and preparation method thereof | |
| CN103881185A (en) | Fire-retardant modified polyethylene material and preparation method thereof | |
| CN104327474A (en) | Montmorillonite synergic flame-retardation PC/ABS alloy material and preparation method thereof | |
| CN100487036C (en) | Paligorskite-linear low density polyethylene composite flame-proof material | |
| CN103881186A (en) | Phosphor-nitrogen fire-retardant polyethylene composite material and preparation method thereof | |
| CN107286643A (en) | A kind of PA6 flame retardant plastics | |
| CN103724788B (en) | A kind of cable sheath and preparation method thereof | |
| CN102850677A (en) | High-toughness halogen-free flame-retardant PS material and preparation method thereof | |
| CN101161775A (en) | Novel halogen-free environment-friendly type flame-proof polypropylene material | |
| CN105111728A (en) | Preparation process for flame-retardant nylon resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210209 Address after: 030600 Xingye street, Yuci District Industrial Park, Jinzhong, Shanxi Patentee after: Feimusheng (Shanxi) material technology Co.,Ltd. Address before: 030024 No. 79 West Main Street, Wan Berlin District, Shanxi, Taiyuan, Yingze Patentee before: Taiyuan University of Technology |