CN106496920A - 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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- CN106496920A CN106496920A CN201610911349.XA CN201610911349A CN106496920A CN 106496920 A CN106496920 A CN 106496920A CN 201610911349 A CN201610911349 A CN 201610911349A CN 106496920 A CN106496920 A CN 106496920A
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- abs resin
- smoke density
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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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The present invention discloses a kind of low smoke density ABS resin and preparation method thereof, and the material is prepared by each component of following percentage by weight：(1) ABS resin 40～80%, (2) smoke inhibition fire retardant 20～40%, (3) bulking agent 0～10%, (4) multifunctional assistant 0～10%, above-mentioned each component percentage by weight sum are 100%.The present invention as smoke inhibition fire retardant, with lower smoke density, can more effectively be reduced material flue gas release in a fire, provide preferably guarantee for personal security in fire using aluminium hydroxide；With common using nitrogen phosphorus system expanding fire retardant, silicon-series five-retardant, zinc, ammonium octamolybdate etc. compared with, with less expensive price；Multifunctional assistant in the present invention has the effect such as increase-volume, coupling, toughness reinforcing simultaneously concurrently, can keep the physical and mechanical propertiess of material itself when flame-retardant smoke inhibition agent content is high；Preparation of raw material of the present invention and processing method are simple, and effect is substantially, is suitable for practical situations, have the probability of the goodish 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 forties in 20th century exploitation a kind of novel universal thermoplastic engineering plastic, be acrylonitrile (A),
Butadiene (B), the terpolymer of styrene (S).It has coordinated the superior function of three kinds of components, strong with higher shock resistance
Degree, good processing characteristics and chemical stability, it is easy to which molded, product is rich in gloss, and has toughness and flexibility concurrently.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 combination property
Industry, has been increasingly becoming one of maximum thermoplastic of consumption.
But, ABS resin is a kind of inflammable macromolecular material, its horizontal firing speed quickly, about 2.5-5.1cm/
Min, particularly ABS resin can produce a large amount of black smokes in burning, continue to burn after fire, and flame burns in yellow black smoke
Plastics soften, burn afterwards, but without melting drippage, not only result in serious property loss, the life security that can also give people and
Living environment brings great threat.This shortcoming limits its range of application, therefore, how to have improved the anti-flammability of ABS resin
Become today's society extremely to pay close attention to and problem demanding prompt solution.Fire-retardant with regard to ABS resin has been carried out numerous studies work,
The flame-proof ABS resin of a lot of commercializations is also all introduced to the market, but, at present the flame-retardant modified main of ABS resin is still concentrated
On burning is prevented, and ignore the problem of material smoke amount when reducing burning to a certain extent.
The lethal main reason of personnel is not to be scorched to death in a fire, but is smothered to death by smoke, and exists between ABS resin
A large amount of uses in the fields such as electronic apparatus, auto industry are (it is emphasized that ABS resin is the main former material for manufacturing school bus
Material), from for the angle of protection people's life safety, reduce resistance of the ABS resin smoke amount in combustion in ABS resin
Particularly important in combustion study on the modification.
Content of the invention
A kind of above-mentioned deficiency of the present invention for prior art, there is provided the low low smoke density of smoke delivery in combustion process
ABS resin.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is：A kind of low smoke density ABS resin, its are special
Levy and be, the material is prepared by each component of following percentage by weight：
Above-mentioned each component percentage by weight sum is 100%.
Preferably, the above-mentioned low smoke density ABS resin of the present invention, each component system of the material by following percentage by weight
Standby：
Above-mentioned each component percentage by weight sum 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 Alumina hydrate, and abbreviation ATH, with chemical formula
Al(OH)3Or Al2O3·3H2O represents that purity is more than 95%, granularity 600-10000 mesh.
Bulking agent of the present invention is maleic anhydride graft phenylethene copolymer (phenylethylene-maleic anhydride graft copolymerization
Thing, 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, such that it is able to as ABS and the interface bridging of smoke inhibition fire retardant, improve the compatibility of system.
Multifunctional assistant of the present invention is organophosphors system rare earth compound, refers in molecule while containing phenyl-phosphonic acid
Functional group and the compound of 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 of x mol or hydrated rare-earth nitrate are dissolved in deionized water, then will
Both mixing and with NaOH solution by pH regulator to 1-5, after being stirred at reflux 24 hours at 70-90 DEG C, anti-using deionized water
Multiple washing and filtering, dries at 80 DEG C and obtains final product to constant weight.
Preferably, rare earth ion is preferred with lanthanum and cerium ion, its formula is ReH (O3PC6H5)2(wherein
Re refers to thulium), its 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, remaining with very high heat stability and charcoal, initial decomposition temperature is more than
300 DEG C, 700 DEG C of charcoals are remaining higher than 65%.Rare earth ion in multifunctional assistant has strong coordination ability, to material combustion process
In dehydrogenation, oxidation, the reaction such as crosslinking have catalytic action, be favorably improved physical and mechanical propertiess, fire resistance and the suppression of material
Smoke performance.
Rare earth ion in multifunctional assistant can be catalyzed smoke inhibition fire retardant and promote which into charcoal, so that material is in burning
During can form more complete fine and close layer of charcoal, the significantly more efficient smoke delivery for reducing material；And it is multi-functional
Auxiliary agent is present with laminar nano crystal form, and crystalline lamellae has higher intensity, can support suppression cigarette resistance in combustion
Combustion dosage form into layer of charcoal, so as to ensure that layer of charcoal is not in phenomenon of caving in combustion, the flue gas that is suppressed by layer of charcoal will not
Occur as layer of charcoal is caved in unexpected quick release phenomenon out.
Rare earth ion in multifunctional assistant has stronger lewis acidity, can make macromolecule material 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
The compatibility, improve the interface cohesive force of bulking agent and matrix, more effectively promote smoke inhibition fire retardant in macromolecule matrix
Dispersion, even if so as to when smoke inhibition fire retardant addition is higher, material still can keep certain physical and mechanical propertiess.
Organophosphors functional group in multifunctional assistant decomposes or lamella as passing through the organic group around lamella
Internal O-P-O bond fissions, form PO free radicals, capture H the and OH free radicals in macromolecular material combustion process, play
Condensed phase flame-retardant smoke inhibition is acted on, and the phenyl ring in organophosphors functional group is compatible with the phenyl ring in matrix ABS, it is also possible to further
Improve the compatibility of material internal, improve the physical and mechanical propertiess of material.
The present invention also provides a kind of preparation method of above-mentioned low smoke density ABS resin, and concrete steps include：
(1) each raw material is weighed according to proportioning, and be respectively put in air dry oven that at 85-95 DEG C to dry 7-9 little
When；
(2) dried later raw material is put in moderate-speed mixers and is premixed 2～10 minutes；Again mixed raw material is put
Enter, 170-200 DEG C of blending temperature, 50-80 rev/min of rotating speed, blending time 5-15 point
Clock, is finally obtained low smoke density ABS resin.
The advantages of the present invention：A kind of low smoke density ABS resin prepared by the present invention adopts aluminium hydroxide
As smoke inhibition fire retardant, with common using nitrogen phosphorus system expanding fire retardant, silicon-series five-retardant, zinc, ammonium octamolybdate etc. compared with,
There is under conditions of identical proportioning lower smoke density, can more effectively reduce material flue gas release in a fire, be fire
In calamity, personal security is provided and is preferably ensured；A kind of low smoke density ABS resin prepared by the present invention adopts aluminium hydroxide conduct
Smoke inhibition fire retardant, with common using nitrogen phosphorus system expanding fire retardant, silicon-series five-retardant, zinc, ammonium octamolybdate etc. compared with, have
Less expensive price；Multifunctional assistant in the present invention has the effect such as increase-volume, coupling, toughness reinforcing simultaneously concurrently, can be in flame-retardant smoke inhibition
The physical and mechanical propertiess of material itself are kept when agent content is high；Preparation of raw material of the present invention and processing method are simple,
And effect is substantially, is suitable for practical situations, there is the probability of the goodish marketization.
Specific embodiment
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 some nonessential modifications and adaptations that present invention is made to the present invention still
Belong to protection scope of the present invention.
Embodiment：
The preparation method of a kind 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 in air dry oven, dried later raw material is put into middling speed then and is mixed
Premix 2～10 minutes in clutch, then mixed raw material is put in torque rheometer carries out melt blending, blending temperature 170-
200 DEG C, 50-80 rev/min of rotating speed is blended minute time 5-15, and a kind of low smoke density ABS trees of the present invention are finally obtained
Fat.
The specific preparation method of multifunctional assistant of the present invention includes：10mmol phenyl-phosphonic acids are dissolved in volume ratio for 1:1
Phenyl-phosphonic acid solution is obtained in the mixed solvent of 100ml ethanol/waters, and then resulting solution is placed in reaction vessel；Will
5mmolReCl3 6H2O are added drop-wise to after being dissolved in 100ml deionized waters in the above-mentioned reaction vessel containing phenyl-phosphonic acid solution, stirring,
Then pH regulator to 2 is stirred at reflux at 70-90 DEG C 24 hours, obtains white suspension by the NaOH solution with 0.1mol/L；
The white suspension sucking filtration of gained, through deionized water wash, 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 1 is shown in Table with the contrast situation without multifunctional assistant, wherein
Smoke density is tested with reference to GB/T8627-2007, and limited 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 of table and comparative example
Can see from table 1, multifunctional assistant has the characteristic of increase-volume, coupling, toughness reinforcing concurrently, make low smoke density ABS resin
While relatively low smoke density is kept, physical and mechanical propertiess will not be lost because the higher anti-flaming smoke-inhibiting agent of content is added.This
The ABS trees that inventive embodiments 3 are prepared with common employing nitrogen phosphorus system expanding fire retardant, silicon-series five-retardant, zinc, ammonium octamolybdate
The contrast situation of fat is shown in Table 2, and wherein the testing standard of property indices is with table 1.
Several ABS resin contrasts using different smoke inhibition fire retardants of table 2
As can be seen from Table 2, the embodiment of the present invention is had very excellent using aluminium hydroxide as anti-flaming smoke-inhibiting agent
Flame-retardant smoke inhibition effect, has good application prospect in electronic apparatus, body of a motor car material and part field.
Claims (9)
1. a kind of low smoke density ABS resin, it is characterised in that：The material is prepared by each component of following percentage by weight：
Above-mentioned each component percentage by weight sum is 100%.
2. low smoke density ABS resin according to claim 1, it is characterised in that：The material is by following percentage by weight
Prepared by each component：
Above-mentioned each component percentage by weight sum is 100%.
3. low smoke density ABS resin according to claim 1, it is characterised in that：Described ABS resin is acrylic nitrile-butadiene
Diene-styrene copolymer.
4. low smoke density ABS resin according to claim 1, it is characterised in that：Described smoke inhibition fire retardant is hydroxide
Aluminum, purity are more than 95%, granularity 600-10000 mesh.
5. low smoke density ABS resin according to claim 1, it is characterised in that：Described bulking agent is connect for maleic anhydride
Branch styrol copolymer.
6. low smoke density ABS resin according to claim 1, it is characterised in that：Described multifunctional assistant is organophosphors
It is rare earth compound, refers in molecule while the compound containing phenyl-phosphonic acid functional group and rare earth ion, is received with stratiform
Rice crystal form is present, and interlamellar spacing is about 1.5nm, the thickness 100-200nm of single crystalline lamellae.
7. low smoke density ABS resin according to claim 6, it is characterised in that：Described rare earth ion be lanthanum or
Cerium ion.
8. low smoke density ABS resin according to claim 1, it is characterised in that：Described multifunctional assistant is organophosphors
It is that the preparation method of rare earth compound includes：The phenyl-phosphonic acid of 2x mol is dissolved in ethanol/water mixed solvent, the city of x mol
The hydrated rare-earth chloride or hydrated rare-earth nitrate that sells is dissolved in deionized water, then mixes and with NaOH solution both by pH
Adjust to 1-5, after 24 hours are stirred at reflux at 70-90 DEG C, filtered using deionized water cyclic washing, dried to perseverance at 80 DEG C
Obtain final product again.
9. the preparation method of the low smoke density ABS resin described in a kind of claim 1, it is characterised in that：Concrete steps include：
(1) each raw material is weighed according to proportioning, and be respectively put in air dry oven and dry 7-9 hours at 85-95 DEG C；
(2) dried later raw material is put in moderate-speed mixers and is premixed 2～10 minutes；Again mixed raw material is put into and is turned
Melt blending is carried out in square flow graph, and 170-200 DEG C of blending temperature, 50-80 rev/min of rotating speed are blended minute time 5-15, most
Low smoke density ABS resin is obtained eventually.
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 |
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| 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 true CN106496920A (en) | 2017-03-15 |
| CN106496920B CN106496920B (en) | 2018-10-12 |
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Cited By (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 |
| CN108623985A (en) * | 2018-04-11 | 2018-10-09 | 厦门稀土材料研究所 | A kind of rare earth cooperative flame retardant ABS material |
| CN110437577A (en) * | 2019-08-28 | 2019-11-12 | 东莞市华立实业股份有限公司 | A kind of edge band low smoke halogen-free flame retardant ABS material 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 |
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 |
| 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 |
-
2016
- 2016-10-20 CN CN201610911349.XA patent/CN106496920B/en active Active
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 |
Cited By (5)
| 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 |
| CN108623985A (en) * | 2018-04-11 | 2018-10-09 | 厦门稀土材料研究所 | A kind of rare earth cooperative flame retardant ABS 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 |
| CN110437577A (en) * | 2019-08-28 | 2019-11-12 | 东莞市华立实业股份有限公司 | A kind of edge band low smoke halogen-free flame retardant ABS material 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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