CN102453324A - Halogen-free flame-retardant nylon 66 masterbatch - Google Patents
Halogen-free flame-retardant nylon 66 masterbatch Download PDFInfo
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- CN102453324A CN102453324A CN2010105205550A CN201010520555A CN102453324A CN 102453324 A CN102453324 A CN 102453324A CN 2010105205550 A CN2010105205550 A CN 2010105205550A CN 201010520555 A CN201010520555 A CN 201010520555A CN 102453324 A CN102453324 A CN 102453324A
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Abstract
The invention discloses a halogen-free flame-retardant nylon 66 masterbatch, which comprises the following components in percentage by weight: 20 to 90 percent of polyhexamethylene adipamide, 5 to 60 percent of flame retardant A, 5 to 60 percent of flame retardant B, 0.1 to 2 percent of antioxidant and 0.1 to 2 percent of light stabilizer. The invention has the advantages that: different from a method of directly adding the flame retardants, the method comprises the following steps of: preparing a halogen-free flame-retardant masterbatch taking nylon 66 as a matrix and blending with nylon 66 to obtain halogen-free flame-retardant nylon 66 masterbatch; and the halogen-free flame-retardant nylon 66 masterbatch is more convenient to store and use and has better operability and higher mechanical properties and flame retardancy.
Description
Technical field
The present invention relates to a kind of halogen-free flame-proof nylon 66 having master batch, relate in particular to a kind of halogen-free flame-proof nylon 66 having master batch of suitable manufacturing environmental protection nylon product.
Background technology
As everyone knows, nylon is one of the most frequently used engineering plastics, and wear resistance is good, and erosion resistance is strong, and processing characteristics is excellent, is widely used in fields such as automobile, electronics, living utensil, packing.But the shortcoming that it is inflammable has limited it and has further applied.Because according to the theory of " phosphorus-halogen cooperative flame retardant ", the used fire retardant nearly 70% of fire-retardant Nylon 66 master batch in the market is a halogen containing flame-retardant, mainly is with polybromodiphenyl ether and polybrominated biphenyl; This type material flame retarding efficiency is high; Consumption is few, and little to the influence of material physics and chemistry property, has very high cost performance; Therefore its market competitiveness is very strong; Forbid containing the sale that gathers dibromodiphenyl ether and gather the electronic and electrical equipment of bromo biphenyl but played the ROHS of European Union instruction on July 1st, 2006, reason is that this series products burning produces volume of smoke and corrosive gases, and generates Dioxins.The application of this type Halogen fire-retardant nylon has received very big restriction, loses its market competitiveness just gradually.
The fire-retardant main of nylon 66 realized through two kinds of approach: use additive flame retardant and use reactive flame retardant.Use the reactive flame retardant complete processing complicated, cost is also than higher, so additive flame retardant still in existing market still in the highest flight.The addition type halogen-free flame retardants mainly contains: phosphorus flame retardant, nitrogen flame retardant, expansion type flame retardant, silicon-series five-retardant, nano level metal oxynitride etc.
The paper that people such as Wang Aimin deliver on " plastics " 2004 the 33rd volumes the 6th phase 37-40 page or leaf shows that micro encapsulation red phosphorus is applied in the glass fiber enhanced nylon 66, not only has good flame retardant property and mechanical property and increases than using red phosphorus separately.In addition, red phosphorus and boron oxide or inorganic combustion inhibitor Mg (OH)
2, Al (OH)
3Composite is a kind of effective fire retardant of glass fiber reinforced nylon 66.
People such as Wang Jianrong " are reporting the expandable flame retardant effect of MPP to glass fiber enhanced nylon 66 on 004 year the 32nd volume of engineering plastics application 2 the 2nd phase 52-54 page or leaf; When find adding massfraction and be 25% MPP; Can make its oxygen index bring up to 38; Reach the UL94V-0 level, in combustion processes, can observe marked inflation and become the charcoal phenomenon.
Li Shujuan etc. are in that " publish thesis on Chinese plastics 2005 the 19th volume the 1st phase 6-9 page or leaf nylon 66 compositional flame-retardant systems are studied, they find to adopt, and 35% phosphorus-bromine antimony compositional flame-retardant system LOI can reach 33.6%, but mechanical property can descend.Adopt the collaborative magnesium hydroxide flame retardant nylon 66 of triphenylphosphate and MMT, obtained good flame-retardant effect.
Can both play fire-retardant effect to a certain extent though have the flame-retardant system of dissimilar additive flame retardants now, its flame retardant properties improves limited.The present invention is that flame-retardant system carries out compounded combination to phosphorus system and nitrogen, has reached the fire retardant usage quantity and has reduced and the better effect of flame retardant properties.
Summary of the invention
Technical problem to be solved of the present invention is, has the not good problem of flame retardant effect to existing fire-retardant Nylon 66 master batch, provides a kind of flame retardant effect better halogen-free flame-proof nylon 66 having master batch.
The present invention solves the problems of the technologies described above through following technical proposal:
A kind of halogen-free flame-proof nylon 66 having master batch, by weight percentage, its composition is:
Polyhexamethylene adipamide 20-90%
Fire retardant A 5-60%
Fire retardant B 5-60%
Inhibitor 0.1-2%
Photostabilizer 0.1-2%.
Wherein, polyhexamethylene adipamide specifically can be 20%, 30%, 40%, 50%, 60%, 70%0% or 90%.Fire retardant A specifically can be 5%, 10%, 20%, 30%, 40%, 50% or 60%.Fire retardant B specifically can be 5%, 10%, 20%, 30%, 40%, 50% or 60%.Inhibitor specifically can be 0.1%, 0.3%, 0.6%, 0.8%, 1.0%, 1.2%, 1.5%, 1.8%, 2.0%.Photostabilizer specifically can be 0.1%, 0.3%, 0.6%, 0.8%, 1.0%, 1.2%, 1.5%, 1.8%, 2.0%.
Said fire retardant A is a phosphorus flame retardant, and has a kind of tetraphenyl resorcinol diphosphate or its verivate of being selected from least.
Said fire retardant B is the melamine based flame retardant, and has a kind of melamine cyanurate or its verivate of being selected from least.
Said inhibitor is phenol antioxidant, ester class inhibitor, metal passivator or its mixture.Oxidation inhibitor makes nylon 66 in the course of processing, keep chemicalstability, avoids oxidized and makes performance impaired.
Said phenol antioxidant is an antioxidant 1010.
Said photostabilizer is titanium oxide, carbon black, benzotriazole category, hindered amines or its mixture.Photostabilizer can prevent nylon 66 in processing and in storing because illumination and deterioration by oxidation.
Fire-retardant principle: fire retardant A and fire retardant B are respectively phosphorus system and melamine compounds, all belong to the expansion additive flame retardant, and compound is scattered in the base material with physics mode and gives base material with flame retardant resistance.The effect of fire retardant is to suppress the generation of one or more component of combustion to reach prevention or to slow down the incendiary purpose; It is fire-retardant that fire retardant mechanism of the present invention belongs to condensed phase; The surface generates the porous charcoal layer when burning; The difficult combustion of this charcoal layer, heat insulation, oxygen barrier can stop combustible gas to get into the burning gas phase again, cause burning and interrupt.And the melamine compounds can also play the effect of delustring.
The present invention is a fire retardant with non-halogen compound, is matrix resin with nylon 66, makes a kind of halogen-free flame-proof nylon 66 having master batch, has solved the flame retardant properties of nylon 66 and the problem of environmental-protecting performance.
A kind of preparation method of halogen-free flame-proof nylon 66 having master batch, with said components mixed number minute in high-speed mixer in proportion, the back adds granulation in the screw extrusion press, and processing temperature 200-300 ℃, the screw rod revolution is at 200-580 rev/min.
Compared with prior art, the present invention has following beneficial effect:
Different with direct interpolation fire retardant, it is the halogen-free flameproof master batch of matrix that the present invention at first makes with nylon 66, and then is blended into halogen-free flame-proof nylon 66 having with nylon 66, the depositing and use more conveniently of halogen-free flameproof master batch, and operability is better.
Through the phosphorus addition type of selection high-efficiency environment friendly and the halogen-free flame retardants combined system of nitrogen addition type; Only use little additive; Just can obtain all splendid nylon 66 master batches of flame retardant properties and environmental requirement performance, can satisfy the request for utilization of industries such as automobile and electronic apparatus.
Embodiment
Embodiment 1
A kind of halogen-free flame-proof nylon 66 having master batch, by weight percentage, its composition is:
Polyhexamethylene adipamide 86.3
Melamine cyanurate 12
Tetraphenyl resorcinol diphosphate 1
3,5-di-t-butyl-4 hydroxy phenyl propionic acid octadecanol ester 0.5
Sebacic acid is two 2,2,6,6-tetramethyl piperidine alcohol ester 0.2
A kind of preparation method of halogen-free flame-proof nylon 66 having master batch, with said components mixed number minute in high-speed mixer in proportion, the back adds granulation in the screw extrusion press, and processing temperature 200-300 ℃, the screw rod revolution is at 200-580 rev/min.
Embodiment 2
A kind of halogen-free flame-proof nylon 66 having master batch, by weight percentage, its composition is:
Polyhexamethylene adipamide 88.5
Melamine cyanurate 10
Tetraphenyl resorcinol diphosphate 1
3,5-di-t-butyl-4 hydroxy phenyl propionic acid octadecanol ester 0.3
Sebacic acid is two 2,2,6,6-tetramethyl piperidine alcohol ester 0.2
Other are identical with embodiment 1.
Embodiment 3
A kind of halogen-free flame-proof nylon 66 having master batch, by weight percentage, its composition is:
Polyhexamethylene adipamide 85
Melamine cyanurate 12.5
Tetraphenyl resorcinol diphosphate 2
3,5-di-t-butyl-4 hydroxy phenyl propionic acid octadecanol ester 0.3
Sebacic acid is two 2,2,6,6-tetramethyl piperidine alcohol ester 0.2
Other are identical with embodiment 1.
Embodiment 4
A kind of halogen-free flame-proof nylon 66 having master batch, by weight percentage, its composition is:
Polyhexamethylene adipamide 86
Melamine cyanurate 11.5
Tetraphenyl resorcinol diphosphate 2
3,5-di-t-butyl-4 hydroxy phenyl propionic acid octadecanol ester 0.3
Sebacic acid is two 2,2,6,6-tetramethyl piperidine alcohol ester 0.2
Other are identical with embodiment 1.
Embodiment 5
A kind of halogen-free flame-proof nylon 66 having master batch, by weight percentage, its composition is:
Polyhexamethylene adipamide 30
Melamine cyanurate 60
Tetraphenyl resorcinol diphosphate 9
3,5-di-t-butyl-4 hydroxy phenyl propionic acid octadecanol ester 0.8
Sebacic acid is two 2,2,6,6-tetramethyl piperidine alcohol ester 0.2
Other are identical with embodiment 1.
Embodiment 6
A kind of halogen-free flame-proof nylon 66 having master batch, by weight percentage, its composition is:
Polyhexamethylene adipamide 20
Melamine cyanurate 18
Tetraphenyl resorcinol diphosphate 60
3,5-di-t-butyl-4 hydroxy phenyl propionic acid octadecanol ester 0.8
Sebacic acid is two 2,2,6,6-tetramethyl piperidine alcohol ester 1.2
Other are identical with embodiment 1.
Embodiment 7
A kind of halogen-free flame-proof nylon 66 having master batch, by weight percentage, its composition is:
Polyhexamethylene adipamide 40
Melamine cyanurate 18
Tetraphenyl resorcinol diphosphate 50
3,5-di-t-butyl-4 hydroxy phenyl propionic acid octadecanol ester 1.0
Sebacic acid is two 2,2,6,6-tetramethyl piperidine alcohol ester 1.0
Other are identical with embodiment 1.
Embodiment 8
A kind of halogen-free flame-proof nylon 66 having master batch, by weight percentage, its composition is:
Polyhexamethylene adipamide 50
Melamine cyanurate 30
Tetraphenyl resorcinol diphosphate 18.3
3,5-di-t-butyl-4 hydroxy phenyl propionic acid octadecanol ester 0.6
Sebacic acid is two 2,2,6,6-tetramethyl piperidine alcohol ester 1.1
Other are identical with embodiment 1.
Comparative Examples
A kind of halogen-free flame-proof nylon 66 having master batch, by weight percentage, its composition is:
Polyhexamethylene adipamide 99.5
Fire retardant A 0
Fire retardant B 0
3,5-di-t-butyl-4 hydroxy phenyl propionic acid octadecanol ester 0.3
Sebacic acid is two 2,2,6,6-tetramethyl piperidine alcohol ester 0.2
Physical mechanics of the foregoing description and flame retardant properties comparison sheet
The physical mechanics of embodiment 5, embodiment 6, embodiment 7 and embodiment 8 and flame retardant properties also in the above table scope, are no longer specifically repeated at this.
Claims (7)
1. halogen-free flame-proof nylon 66 having master batch, by weight percentage, its composition is:
Polyhexamethylene adipamide 20-90%
Fire retardant A 5-60%
Fire retardant B 5-60%
Inhibitor 0.1-2%
Photostabilizer 0.1-2%.
2. halogen-free flame-proof nylon 66 having master batch according to claim 1 is characterized in that, said fire retardant A is a phosphorus flame retardant, and has a kind of tetraphenyl resorcinol diphosphate or its verivate of being selected from least.
3. halogen-free flame-proof nylon 66 having master batch according to claim 1 is characterized in that, said fire retardant B is the melamine based flame retardant, and has a kind of melamine cyanurate or its verivate of being selected from least.
4. halogen-free flame-proof nylon 66 having master batch according to claim 1 is characterized in that, said inhibitor is phenol antioxidant, ester class inhibitor, metal passivator or its mixture.
5. halogen-free flame-proof nylon 66 having master batch according to claim 1 is characterized in that, said phenol antioxidant is an antioxidant 1010.
6. halogen-free flame-proof nylon 66 having master batch according to claim 5 is characterized in that, said photostabilizer is titanium oxide, carbon black, benzotriazole category, hindered amines or its mixture.
7. the preparation method of the described halogen-free flame-proof nylon 66 having master batch of one of claim 1 to 6; With the described component of claim 1 mixed number minute in high-speed mixer in proportion; Add granulation in the screw extrusion press, processing temperature 200-300 ℃, the screw rod revolution is at 200-580 rev/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105205550A CN102453324A (en) | 2010-10-27 | 2010-10-27 | Halogen-free flame-retardant nylon 66 masterbatch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105205550A CN102453324A (en) | 2010-10-27 | 2010-10-27 | Halogen-free flame-retardant nylon 66 masterbatch |
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| CN102453324A true CN102453324A (en) | 2012-05-16 |
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| CN2010105205550A Pending CN102453324A (en) | 2010-10-27 | 2010-10-27 | Halogen-free flame-retardant nylon 66 masterbatch |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665830A (en) * | 2012-08-31 | 2014-03-26 | 东丽纤维研究所（中国）有限公司 | Polyamide composition and preparation method thereof |
| CN106065176A (en) * | 2016-08-12 | 2016-11-02 | 上海安凸塑料添加剂有限公司 | A kind of halogen-free flame-retardant polyamide composition |
| CN112538261A (en) * | 2020-11-12 | 2021-03-23 | 江苏伯纳德生物科技发展有限公司 | Method for preparing functional master batch with high solid content and good interface compatibility |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789335A (en) * | 2005-12-16 | 2006-06-21 | 攀钢集团攀枝花钢铁研究院 | Dedicated nano compound agglomerate for outdoors lamp and its preparation method |
| CN101456962A (en) * | 2008-12-29 | 2009-06-17 | 黄华昌 | High-content red phosphorus flame-retardant master batch |
| CN101798460A (en) * | 2010-02-08 | 2010-08-11 | 佛山市南海易乐工程塑料有限公司 | Composite flame retardant glass fibre reinforced nylon 66 insulating strip and preparation method thereof |
-
2010
- 2010-10-27 CN CN2010105205550A patent/CN102453324A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789335A (en) * | 2005-12-16 | 2006-06-21 | 攀钢集团攀枝花钢铁研究院 | Dedicated nano compound agglomerate for outdoors lamp and its preparation method |
| CN101456962A (en) * | 2008-12-29 | 2009-06-17 | 黄华昌 | High-content red phosphorus flame-retardant master batch |
| CN101798460A (en) * | 2010-02-08 | 2010-08-11 | 佛山市南海易乐工程塑料有限公司 | Composite flame retardant glass fibre reinforced nylon 66 insulating strip and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665830A (en) * | 2012-08-31 | 2014-03-26 | 东丽纤维研究所（中国）有限公司 | Polyamide composition and preparation method thereof |
| CN106065176A (en) * | 2016-08-12 | 2016-11-02 | 上海安凸塑料添加剂有限公司 | A kind of halogen-free flame-retardant polyamide composition |
| CN106065176B (en) * | 2016-08-12 | 2018-10-12 | 上海安凸塑料添加剂有限公司 | A kind of halogen-free flame-retardant polyamide composition |
| CN112538261A (en) * | 2020-11-12 | 2021-03-23 | 江苏伯纳德生物科技发展有限公司 | Method for preparing functional master batch with high solid content and good interface compatibility |
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Application publication date: 20120516 |