CN106496920B - low smoke density ABS resin and preparation method thereof - Google Patents
low smoke density ABS resin and preparation method thereof Download PDFInfo
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- CN106496920B CN106496920B CN201610911349.XA CN201610911349A CN106496920B CN 106496920 B CN106496920 B CN 106496920B CN 201610911349 A CN201610911349 A CN 201610911349A CN 106496920 B CN106496920 B CN 106496920B
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- abs resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The present invention discloses a kind of low smoke density ABS resin and preparation method thereof, which is prepared by each component of following weight percent：(1) ABS resin 40~80%, (2) smoke inhibition fire retardant 20~40%, (3) bulking agent 0~10%, (4) multifunctional assistant 0~10%, the sum of above-mentioned each component weight percent are 100%.The present invention, as smoke inhibition fire retardant, has lower smoke density using aluminium hydroxide, can more effectively reduce the flue gas release of material in a fire, better guarantee is provided for personnel safety in fire；Compared with common use nitrogen phosphorus system expanding fire retardant, silicon-series five-retardant, zinc stannate, ammonium octamolybdate etc., there is less expensive price；The effects that multifunctional assistant in the present invention has both increase-volume, coupling, toughening simultaneously, can keep the physical mechanical property of material itself when flame-retardant smoke inhibition agent content is high；Raw material of the present invention is prepared and processing method is simple and practicable and with obvious effects, is suitble to practical situations, there is the possibility of the fairly good marketization.
Description
Technical field
The present invention relates to the blending of polymer composite, increase-volume, Flame Retardancy energy technical field of measurement and test, and in particular to
A kind of low smoke density (smoke density 52) ABS resin and preparation method thereof.
Technical background
ABS resin be the 1940s exploitation a kind of novel universal thermoplastic engineering plastic, be acrylonitrile (A),
The terpolymer of butadiene (B), styrene (S).It has coordinated the superior function of three kinds of components, has higher shock resistance strong
Degree, good processing performance and chemical stability, are readily molded into type, product has both toughness and flexibility rich in gloss.ABS
Resin is widely used in the row such as auto industry, electronic apparatus industry, light industry household electrical appliances, weaving and building with its remarkable comprehensive performance
Industry has been increasingly becoming one of maximum thermoplastic of dosage.
But ABS resin is a kind of inflammable high molecular material, horizontal firing speed quickly, about 2.5-5.1cm/
Min, especially ABS resin will produce a large amount of black smokes in burning, and from continuing to burn after fire, flame is in yellow black smoke, burning
Afterwards plastics softening, burn, but dripped without melting, not only result in serious property loss, can also give people life security and
Living environment brings great threat.This disadvantage limits its scope of application, and therefore, how to have improved the anti-flammability of ABS resin
It is very paid close attention to as today's society and urgent problem to be solved.A lot of research work has been carried out in fire-retardant about ABS resin,
The flame-proof ABS resin being much commercialized also all is introduced to the market, still, at present to the flame-retardant modified main or concentration of ABS resin
On preventing burning, and to a certain extent ignore reduction burning when material smoke amount the problem of.
The lethal main reason of personnel is not to be scorched to death, but be smothered to death by smoke in a fire, is existed between ABS resin
The a large amount of of the fields such as electronic apparatus, auto industry use (it is emphasized that ABS resin is the main former material for manufacturing school bus
Material), from the perspective of protection people's life safety, reduce resistance of the smoke amount of ABS resin in combustion in ABS resin
It fires particularly important in study on the modification.
Invention content
The present invention is directed to the above-mentioned deficiency of the prior art, provides the low smoke density that smoke delivery is low in a kind of combustion process
ABS resin.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of low smoke density ABS resin, it is special
Sign is that the material is prepared by each component of following weight percent：
The sum of above-mentioned each component weight percent is 100%.
Preferably, the above-mentioned low smoke density ABS resin of the present invention, the material by following weight percent each component system
It is standby：
The sum of above-mentioned each component weight percent is 100%.
ABS resin of the present invention is acrylonitrile-butadiene-styrene copolymer.
Smoke inhibition fire retardant of the present invention is aluminium hydroxide, also referred to as hibbsite, abbreviation ATH, with chemical formula
Al(OH)3Or Al2O3·3H2O indicates that purity is more than 95%, granularity 600-10000 mesh.
Bulking agent of the present invention is copolymer (the phenylethylene-maleic anhydride graft copolymerization of maleic anhydride graft phenylethene
Object, SMA), the styrene segment in bulking agent is compatible with the styrene segment in matrix ABS, and maleic anhydride have polarity with
Inorganic smoke inhibition fire retardant is compatible, so as to the interface bridging as ABS and smoke inhibition fire retardant, improves the compatibility of system.
Multifunctional assistant of the present invention is organic phosphorus rare earth compound, refers to containing phenyl-phosphonic acid in molecule simultaneously
The compound of functional group and rare earth ion；The preparation method of the compound is as follows：The phenyl-phosphonic acid of 2x mol is dissolved in second
Alcohol/water mixed solvent, the commercially available hydrated rare-earth chloride or hydrated rare-earth nitrate of x mol are dissolved in deionized water, then will
The two mixes and pH is adjusted to 1-5 with NaOH solution, anti-using deionized water after 24 hours are stirred at reflux at 70-90 DEG C
Filtering is washed in after backwashing, is dried to constant weight at 80 DEG C to obtain the final product.
Preferably, rare earth ion is preferred with lanthanum and cerium ion, formula is ReH (O3PC6H5)2(wherein
Re refers to thulium), geometry is similar with clay, exists with laminar nano crystal form, and interlamellar spacing is about
1.5nm, the thickness 100-200nm of single crystalline lamellae have very high thermal stability and charcoal remaining, and initial decomposition temperature is more than
300 DEG C, 700 DEG C of charcoal remnants are higher than 65%.Rare earth ion in multifunctional assistant has strong coordination ability, to material combustion process
In the reactions such as dehydrogenation, oxidation, crosslinking have catalytic action, help to improve the physical mechanical property, flame retardant property and suppression of material
Smoke performance.
Rare earth ion in multifunctional assistant can be catalyzed smoke inhibition fire retardant and promote it at charcoal, to make material burn
The layer of charcoal of more complete densification, the significantly more efficient smoke delivery for reducing material can be formed in the process；And it is multi-functional
Auxiliary agent exists with laminar nano crystal form, and crystalline lamellae has higher intensity, can support suppression cigarette resistance in combustion
Fire dosage form at layer of charcoal, be not in phenomenon of caving in ensure layer of charcoal in combustion, by layer of charcoal suppress flue gas will not
Occur due to layer of charcoal cave in unexpected quick release come out the phenomenon that.
Rare earth ion in multifunctional assistant has stronger lewis acidity, and macromolecule material can be made by Friedel-Crafts reaction
Material forms carbonium ion, and the presence of carbonium ion can improve the polarity of macromolecule matrix, so as to improve itself and smoke inhibition fire retardant
Compatibility, improve bulking agent and matrix interface cohesive force, more effectively promote smoke inhibition fire retardant in macromolecule matrix
Dispersion, even if to which when smoke inhibition fire retardant additive amount is higher, material still can keep certain physical mechanical property.
Organophosphor functional group in multifunctional assistant decomposes or lamella as can pass through the organic group around lamella
Internal O-P-O keys fracture, forms PO free radicals, captures H the and OH free radicals in high molecular material combustion process, play
Condensed phase flame-retardant smoke inhibition acts on, and the phenyl ring in organophosphor functional group is compatible with the phenyl ring in matrix ABS, can also be further
The compatibility for improving material internal, improves the physical mechanical property of material.
The present invention also provides a kind of preparation method of above-mentioned low smoke density ABS resin, specific steps include：
(1) each raw material is weighed according to proportioning, and it is small that dry 7-9 is respectively put into air dry oven at 85-95 DEG C
When；
(2) dried later raw material is put into moderate-speed mixers and is premixed 2~10 minutes；Mixed raw material is put again
Enter and carry out melt blending in torque rheometer, time 5-15 point is blended in 170-200 DEG C of blending temperature, 50-80 revs/min of rotating speed
Low smoke density ABS resin is finally made in clock.
The advantages of the present invention：A kind of low smoke density ABS resin prepared by the present invention uses aluminium hydroxide
As smoke inhibition fire retardant, compared with common use nitrogen phosphorus system expanding fire retardant, silicon-series five-retardant, zinc stannate, ammonium octamolybdate etc.,
There is lower smoke density under conditions of identical proportioning, the flue gas release of material in a fire can be more effectively reduced, for fire
Personnel safety, which provides, in calamity preferably ensures；A kind of low smoke density ABS resin prepared by the present invention uses aluminium hydroxide conduct
Smoke inhibition fire retardant has compared with common use nitrogen phosphorus system expanding fire retardant, silicon-series five-retardant, zinc stannate, ammonium octamolybdate etc.
Less expensive price；The effects that multifunctional assistant in the present invention has both increase-volume, coupling, toughening simultaneously, can be in flame-retardant smoke inhibition
The physical mechanical property of material itself is kept when agent content is high；Raw material of the present invention is prepared and processing method is simple and practicable,
And it is with obvious effects, it is suitble to practical situations, there is the possibility of the fairly good marketization.
Specific implementation mode
The present invention is described in further detail below by specific embodiment, but the present invention is not limited solely to following reality
Apply example.The person skilled in the art in the field according to the content of present invention to some nonessential modifications and adaptations for making of the present invention still
It belongs to the scope of protection of the present invention.
Embodiment：
A kind of preparation method of low smoke density ABS resin described in the embodiment of the present invention is：Each raw material is weighed according to proportioning,
And drying 8 hours at 90 DEG C are respectively put into air dry oven, dried later raw material is then put into middling speed and is mixed
It is premixed 2~10 minutes in clutch, then mixed raw material is put into torque rheometer and carries out melt blending, blending temperature 170-
200 DEG C, time 5-15 minute is blended in 50-80 revs/min of rotating speed, and a kind of low smoke density ABS trees of the present invention are finally made
Fat.
The specific preparation method of multifunctional assistant of the present invention includes：It is 1 that 10mmol phenyl-phosphonic acids, which are dissolved in volume ratio,:1
The in the mixed solvent of 100ml ethanol/waters obtains phenyl-phosphonic acid solution, and then acquired solution is placed in reaction vessel；It will
5mmolReCl36H2O is added drop-wise to after being dissolved in 100ml deionized waters in the reaction vessel of the above-mentioned solution containing phenyl-phosphonic acid, stirring,
PH is adjusted to 2 with the NaOH solution of 0.1mol/L, is then stirred at reflux at 70-90 DEG C 24 hours, obtains white suspension；
The white suspension of gained filters, and is washed through deionized water, 80 DEG C of drying to constant weights obtain powdery solid granules i.e. Phenylphosphine
Acid rare earth salt.
The formula and smoke density of the embodiment of the present invention, and it is shown in Table 1 with the comparative situation for not adding multifunctional assistant, wherein
Smoke density is tested with reference to GB/T8627-2007, and limit oxygen index is tested with reference to GB/T2406-2009, and tensile strength refers to GB/T
1040-1992 is tested, and Izod notched impact strength is tested with reference to GB/T1043.
The formula and its smoke density of the low smoke density ABS resin of 1 embodiment and comparative example of table
From table 1 it can be seen that, multifunctional assistant have both increase-volume, coupling, toughening characteristic, make low smoke density ABS resin
While keeping relatively low smoke density, physical mechanical property will not be lost because of the addition higher anti-flaming smoke-inhibiting agent of content.This
Inventive embodiments 3 and the common ABS trees prepared using nitrogen phosphorus system expanding fire retardant, silicon-series five-retardant, zinc stannate, ammonium octamolybdate
The comparative situation of fat is shown in Table 2, and wherein the testing standard of property indices is the same as table 1.
Several ABS resins using different smoke inhibition fire retardants of table 2 compare
As can be seen from Table 2, the embodiment of the present invention is had using aluminium hydroxide as anti-flaming smoke-inhibiting agent very excellent
Flame-retardant smoke inhibition effect has good application prospect in electronic apparatus, body of a motor car material and part field.
Claims (7)
1. a kind of low smoke density ABS resin, it is characterised in that：The material is prepared by each component of following weight percent：
（1）ABS resin 55 ~ 67%,
（2）Smoke inhibition fire retardant 25 ~ 32%,
（3）Bulking agent 5 ~ 8%,
（4）Multifunctional assistant 3-5%
The sum of above-mentioned each component weight percent is 100%；
The multifunctional assistant is organic phosphorus rare earth compound, refers to containing phenyl-phosphonic acid functional group and dilute in molecule simultaneously
The compound of earthmetal cations exists with laminar nano crystal form, and interlamellar spacing is about 1.5 nm, the thickness of single crystalline lamellae
100-200 nm。
2. low smoke density ABS resin according to claim 1, it is characterised in that：The ABS resin is acrylic nitrile-butadiene
Diene-styrene copolymer.
3. low smoke density ABS resin according to claim 1, it is characterised in that：The smoke inhibition fire retardant is hydroxide
Aluminium, purity are more than 95%, granularity 600-10000 mesh.
4. low smoke density ABS resin according to claim 1, it is characterised in that：The bulking agent connects for maleic anhydride
Branch styrol copolymer.
5. low smoke density ABS resin according to claim 1, it is characterised in that：The rare earth ion be lanthanum or
Cerium ion.
6. low smoke density ABS resin according to claim 1, it is characterised in that：The multifunctional assistant is organophosphor
The preparation method for being rare earth compound includes：By 2xThe phenyl-phosphonic acid of mol is dissolved in ethanol/water mixed solvent,xThe city of mol
The hydrated rare-earth chloride or hydrated rare-earth nitrate sold are dissolved in deionized water, then mix the two and with NaOH solution by pH
It is adjusted to 1-5, in 70-90oAfter being stirred at reflux 24 hours under C, filtering is washed repeatedly using deionized water, 80oIt is dried extremely under C
Constant weight to obtain the final product.
7. the preparation method of low smoke density ABS resin according to claim 1, it is characterised in that：Specific steps include：
（1）Each raw material is weighed according to proportioning, and is respectively put into air dry oven in 85-95oIt is 7-9 hours dry under C；
（2）Dried later raw material is put into moderate-speed mixers and is premixed 2 ~ 10 minutes；Mixed raw material is put into again and is turned
Melt blending, blending temperature 170-200 are carried out in square rheometeroTime 5-15 minute is blended in C, 50-80 revs/min of rotating speed,
Low smoke density ABS resin is finally made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610911349.XA CN106496920B (en) | 2016-10-20 | 2016-10-20 | low smoke density ABS resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610911349.XA CN106496920B (en) | 2016-10-20 | 2016-10-20 | low smoke density ABS resin and preparation method thereof |
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| CN106496920A CN106496920A (en) | 2017-03-15 |
| CN106496920B true CN106496920B (en) | 2018-10-12 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017873A (en) * | 2017-12-27 | 2018-05-11 | 洛阳神佳窑业有限公司 | A kind of Auto Instrument desk special-purpose anti-flaming material |
| CN108623985B (en) * | 2018-04-11 | 2020-08-21 | 厦门稀土材料研究所 | Rare earth synergistic flame-retardant ABS material |
| CN110437577B (en) * | 2019-08-28 | 2022-04-22 | 东莞市华立实业股份有限公司 | Low-smoke halogen-free flame-retardant ABS material for edge banding and preparation method thereof |
| CN114953682A (en) * | 2022-05-09 | 2022-08-30 | 宁波瑞成包装材料有限公司 | High-barrier flame-retardant polypropylene film and preparation method thereof |
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| CN103073856A (en) * | 2012-12-26 | 2013-05-01 | 浙江大学宁波理工学院 | Phenyl phosphonic acid rare-earth salt compounded system flame-retardant glass fiber enhanced PET material and preparation method thereof |
| CN103265788A (en) * | 2013-06-03 | 2013-08-28 | 上海金发科技发展有限公司 | Halogen-free flame retardant low-smoke high-toughness ABS (acrylonitrile butadiene styrene) alloy and preparation method thereof |
| CN103289332A (en) * | 2013-05-27 | 2013-09-11 | 浙江大学宁波理工学院 | Glass fiber enhanced poly(ethylene terephthalate) nano flame-retardant composite material and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073856A (en) * | 2012-12-26 | 2013-05-01 | 浙江大学宁波理工学院 | Phenyl phosphonic acid rare-earth salt compounded system flame-retardant glass fiber enhanced PET material and preparation method thereof |
| CN103289332A (en) * | 2013-05-27 | 2013-09-11 | 浙江大学宁波理工学院 | Glass fiber enhanced poly(ethylene terephthalate) nano flame-retardant composite material and preparation method thereof |
| CN103265788A (en) * | 2013-06-03 | 2013-08-28 | 上海金发科技发展有限公司 | Halogen-free flame retardant low-smoke high-toughness ABS (acrylonitrile butadiene styrene) alloy and preparation method thereof |
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