CN101205309B - Antimony trioxide synergist - Google Patents
Antimony trioxide synergist Download PDFInfo
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- CN101205309B CN101205309B CN2007101715800A CN200710171580A CN101205309B CN 101205309 B CN101205309 B CN 101205309B CN 2007101715800 A CN2007101715800 A CN 2007101715800A CN 200710171580 A CN200710171580 A CN 200710171580A CN 101205309 B CN101205309 B CN 101205309B
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- antimony trioxide
- synergist
- trioxide synergist
- polyester
- flame retardant
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Abstract
The invention relates to the technical field of inorganic flame retardants, in particular to an antimony trioxide synergist and a flame-retardant polyester or a polyester alloy containing the antimony trioxide synergist. The antimony trioxide synergist is characterized in that the antimony trioxide synergist comprises the magnesium oxide or mixtures containing the magneisium oxide. The antimony trioxide synergist provided by the invention can effectively lower the addition amount of the antimony trioxide in the flame-retardant polyester and the polyester alloy, lower the risk that the antimony trioxide can drive the polyester materials to be degraded, maintian the excellent flame-retardancy of the materials, and simultaneously lower the flame-retardant cost of the materials due to the low price of the synergist.
Description
Technical field
The present invention relates to the inorganic combustion inhibitor technical field, be specifically related to a kind of antimony trioxide synergist and contain the flame retardant polyester or the polyester alloy of this antimony trioxide synergist.
Background technology
For many years, weisspiessglanz (Sb
2O
3) usually with halogen flame and in order to the enhancing latter's flame retardant efficiency (perhaps be used for containing the superpolymer of halogen separately, as clorafin, PVC etc.).Work as Sb
2O
3With halogen flame and time spent, the mol ratio of halogen/antimony generally should be 3: 1, and the effect of halogen/antimony flame-retardant system is not only relevant with both ratios, and with halogen flame and relevant by the resolution model of fire-retardant Properties of Polymer and superpolymer.With Sb
2O
3To prepare the way of flame retardant plastics commonplace though be used for polyester and alloy thereof, has Sb always
2O
3Can make the problem of polyester degraded.
One of developing direction of inorganic fire-retarded synergist is the compound synergist that development antimony and other metals are formed, and some kind in this class synergist is excellent performance not only, and cheap.For example, the trade mark is the synergist of Thermoguard CPA, is the mixture based on antimony, though its antimony content compares Sb
2O
3Low, but other metals that it contains have promoted its synergistic function greatly, thus its efficient can with Sb
2O
3Be equal to, but price is far below Sb
2O
3
The compound synergist of antimony-silicon of and for example a series of trade mark Oncor only contains 50% Sb
2O
3, its efficient is than Sb
2O
3Inferior, but because of its price is low, so by this index of efficient/price, they may be higher than Sb
2O
3
The overview based on the compound synergist of antimony of external exploitation
| Trade names | Form | Purposes |
| Oncor 23A Oncor 75A DTA | Sb 2O 3/SiO 2＝50/50 Sb 2O 3/SiO 2=25/75 antimony/zirconium composite | PVC, ABS, PP, coating coating PVC, rubber |
| FCP 100，FCP300 Thermoguard CPA XLD-1053-FR | Sb 2O 3Mixture antimony/multi-metal mixture Sb for main body 2O 3/ halogenide | PVC, ABS, PP, PS ABS, electric wire, cable coat material LDPE |
In addition, Sb2O3 also can be composite with aluminium hydroxide, zinc borate, fluoroborate etc., not only can reduce the consumption of Sb2O3, and the amount of being fuming also greatly reduces; The somebody has carried out the composite research of ZnO or MoO3 and Sb2O3 in addition, and the compound that obtains has good fire-retardant, smoke-suppressing, and has static resistance concurrently.
For a long time, people are seeking the synergistic agent that can match in excellence or beauty with weisspiessglanz always, even to this day, do not find complete ideal weisspiessglanz surrogate as yet.
Therefore, find a kind of synergistic agent of antimonous oxide cheaply to reduce the consumption of antimonous oxide in flame retardant polyester and the alloy thereof, improving still from material property, cost control all has sizable meaning.
Summary of the invention
Purpose of the present invention is intended to disclose a kind of antimony trioxide synergist, replaces Sb2O3 to be used for flame retardant polyester plastics and alloy thereof with part, when keeping its excellent flame, reduces its side effect and fire-retardant cost in polyester processing.
A kind of antimony trioxide synergist is characterized in that by magnesium oxide or contains magnesian mixture forming.
But magnesian mixture MgO and the SiO of containing of the present invention
2Binary mixture, its weight ratio is 1: 2-2: 3; Also MgO, SiO2 and Fe
2O
3Tertiary mixture, its weight ratio are 1: 2: 0.006.
In embodiment of the present invention, described antimony trioxide synergist can partly replace antimonous oxide commonly used in flame retardant polyester and the alloy thereof, keeps identical flame retardant rating, and the replacement amount can be 5-75%, preferred 20-60%, best 35-50%.
In embodiment of the present invention, the whiteness of described antimony trioxide synergist is greater than 95%, fineness 6000-25000 order, median size 0.80-2.5 micron.
On the one hand, the present invention also provides a kind of flame retardant polyester or polyester alloy that contains antimony trioxide synergist of the present invention.
Described polyester comprises PBT and PET, and wherein the relative viscosity of PBT is 0.8-1.5PaS, and melt temperature is 225-240 ℃, and the relative viscosity of PET is 0.8-1.0PaS, and melt temperature is 250-260 ℃.
Described polyester alloy comprises the PBT/ABS alloy, PET/ABS alloy, PBT/PET alloy.
Described ABS is vinyl cyanide, divinyl and styrene copolymer, and its rubber content is 35%-70%, and relative density is 1.0-1.04, and melt temperature is 190-220 ℃.
In embodiment of the present invention, described polyester alloy is formed by the feedstock production of following weight part:
PBT 0～90
PET 0～90
ABS 0～50
Nucleator 1～7
Sb
2O
3 1～6
Sb
2O
3Synergistic agent 0.5～4
Fire retardant 1～20
Oxidation inhibitor 0.1～1
Filler 0～35.
Used fire retardant is a halogenated flame retardant, comprises TDE, tribromophenol, dibromophenol, tetrabromo-bisphenol, tetrabromobisphenol A carbonic ester oligopolymer, brominated epoxy resin, poly-bromostyrene, Brominated Polystyrene and multipolymer thereof.
The flame retardant polyester and the alloy plastic thereof of the present invention's preparation have following premium properties:
1. good processing stability
Because antimonous oxide causes the polyester material degraded to a certain extent, molten finger becomes big; As the standard of weighing stability, survey melting index with melting index through several minutes extruding pelletizations; Reaching under the situation of identical flame retardant effect, the melting index of not using antimony trioxide synergist is obviously than having used the big of this synergistic agent, this explanation antimony trioxide synergist can effectively reduce the addition of antimonous oxide, keep identical flame retardant effect, played preventing the purpose of degrading to a certain extent again.
2. flame retardant resistance
The flame retardant resistance of this flame retardant plastics adopts the test of UL94 combustion experiment method.The antimony trioxide synergist that the present invention finds is under the situation that replaces the 0-60% antimonous oxide, still keep the V-0 level, the secondary after flame time of every sample all is no more than 5 seconds, is not with sample and burns the standard lines place, the dropping that does not cause absorbent cotton to catch fire.
3. excellent comprehensive performances
Flame retardant polyester plastics of the present invention and alloy thereof, because antimony trioxide synergist partly replaces antimonous oxide, reduced the risk that antimonous oxide makes polyester degrade in the course of processing, be in a ratio of the flame retardant polyester plastic agent alloy that uses this synergistic agent, tensile strength, flexural strength, shock strength all improves.
4. low-cost
Because this antimony trioxide synergist price is low, generally has only 1/3 to 1/2 of antimonous oxide, substituting antimonous oxide with its part has no small cost advantage.
The synergistic agent of antimonous oxide provided by the present invention can effectively reduce the addition of antimonous oxide in flame retardant polyester and alloy thereof, reduce the risk that antimonous oxide may make the polyester material degraded, the excellent flame retardancy that keeps material, owing to this synergistic agent low price, can reduce the fire-retardant cost of material simultaneously.
Embodiment
Below in conjunction with specific embodiment, further illustrate the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.Ratio and per-cent are based on weight, unless stated otherwise.Embodiment 1-4 contains the flame retardant polyester or the polyester alloy of the synergistic agent of antimonous oxide.
Proportioning 1-4
| Material name | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| PBT (part) | 100 | 52 | 0 | 70 |
| PET (part) | 0 | 0 | 89 | 13 |
| ABS (part) | 0 | 48 | 0 | 0 |
| Sb 2O 3(part) | 1.5 | 2 | 1.5 | 1.5 |
| Sb 2O 3Synergistic agent (part) | 1.5 | 3 | 1.5 | 1.5 |
| Nucleator (part) | 3 | 2 | 3 | 3 |
| Halogenated flame retardant (part) | 8.5 | 10 | 8.5 | 8 |
| Oxidation inhibitor (part) | 0.3 | 0.3 | 0.3 | 0.3 |
| Filler (part) | 0 | 0 | 20 | 25 |
Annotate: Sb
2O
3Synergistic agent: embodiment 1 is MgO; Embodiment 2 is MgO and SiO
2Binary mixture (1: 2); Embodiment 3 and embodiment 4 are MgO, SiO2 and Fe
2O
3Tertiary mixture
Whole components were put into high-speed mixer and mixing 3 minutes in proportion, use the screw extrusion press extruding pelletization then, the processing temperature of embodiment 1 and embodiment 2 is at 220-240 ℃, and the processing temperature of embodiment 3 and embodiment 4 is at 230-265 ℃, screw speed is 450rpm, and vacuum tightness is 0.06Mpa.
With the particle thorough drying, preparation standard mechanical property batten and fire-retardant batten on injection moulding machine, the batten mechanical property is pressed the ASTM standard testing, and incendivity is pressed the test of UL94 laboratory method.
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Tensile strength Mpa | 57 | 45 | 95 | 102 |
| Flexural strength Mpa | 92 | 62 | 135 | 140 |
| Modulus in flexure Mpa | 2970 | 2230 | 7460 | 7776 |
| Shock strength J/M | 51 | 198 | 57 | 67 |
| Melting index | 108 | 30 | 96 | 102 |
| 1.6mm it is fire-retardant | V0 | V0 | V0 | V0 |
Comparative Examples
| Material name | Comparative Examples 1-1 | Comparative Examples 1-2 | Comparative Examples 2 | Comparative Examples 3-1 | Comparative Examples 3-2 | Comparative Examples 4 |
| PBT (part) | 100 | 100 | 48 | 0 | 0 | 70 |
| PET (part) | 0 | 0 | 0 | 89 | 89 | 13 |
| ABS (part) | 0 | 0 | 30 | 0 | 0 | 0 |
| Sb 2O 3(part) | 1.5 | 3 | 2 | 1.5 | 3 | 3 |
| Sb 2O 3Synergistic agent (part) | 0 | 0 | 0 | 0 | 0 | 0 |
| Nucleator (part) | 3 | 3 | 2 | 3 | 3 | 3 |
| Halogenated flame retardant (part) | 8.5 | 8.5 | 10 | 8.5 | 8.5 | 8 |
| Material name | Comparative Examples 1-1 | Comparative Examples 1-2 | Comparative Examples 2 | Comparative Examples 3-1 | Comparative Examples 3-2 | Comparative Examples 4 |
| Oxidation inhibitor (part) | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Filler (part) | 0 | 0 | 0 | 20 | 20 | 25 |
| Material property | ||||||
| Tensile strength Mpa | 57 | 52 | 44.5 | 95 | 91 | 98 |
| Flexural strength Mpa | 91 | 85 | 61 | 135 | 126 | 132 |
| Modulus in flexure Mpa | 2975 | 2670 | 2200 | 7460 | 7230 | 7653 |
| Shock strength J/M | 51 | 43 | 200 | 57 | 52 | 61 |
| Melting index g/10min | 108 | 125 | 30 | 96 | 109 | 128 |
| 1.6mm it is fire-retardant | V1 | V-0 | V1 | V1 | V0 | V0 |
Scope of the present invention is not subjected to the restriction of described specific embodiments, and described embodiment is only desired also to comprise the method and the component of functional equivalent in the scope of the invention as the single example of illustrating all respects of the present invention.In fact, except content as herein described, those skilled in the art can easily grasp multiple improvement of the present invention with reference to above description and accompanying drawing.Described improvement also falls within the scope of appended claims.
Claims (9)
1. an antimony trioxide synergist is characterized in that by magnesium oxide or contains magnesian mixture forming, but described to contain magnesian mixture weight ratio be 1: 2-2: 3 MgO and SiO
2Binary mixture or weight ratio are 1: 2: 0.006 MgO, SiO
2And Fe
2O
3Tertiary mixture.
2. antimony trioxide synergist according to claim 1 is characterized in that it is 5-75% that described antimony trioxide synergist replaces the replacement amount of antimonous oxide.
3. antimony trioxide synergist according to claim 2 is characterized in that it is 20-60% that described antimony trioxide synergist replaces the replacement amount of antimonous oxide.
4. antimony trioxide synergist according to claim 2 is characterized in that it is 35-50% that described antimony trioxide synergist replaces the replacement amount of antimonous oxide.
5. antimony trioxide synergist according to claim 1, the whiteness that it is characterized in that described antimony trioxide synergist be greater than 95%, fineness 6000-25000 order.
6. antimony trioxide synergist according to claim 1 is characterized in that the fineness 6000-25000 order of described antimony trioxide synergist.
7. one kind contains the flame retardant polyester or the polyester alloy of antimony trioxide synergist according to claim 1.
8. flame retardant polyester according to claim 7 or polyester alloy are formed by the feedstock production of following weight part:
PBT 0～90
PET 0～90
ABS 0～50
Nucleator 1～7
Sb
2O
3 1～6
Sb
2O
3Synergistic agent 0.5～4
Fire retardant 1～20
Oxidation inhibitor 0.1～1
Filler 0～35,
Wherein, the consumption of PBT, PET, ABS is not zero simultaneously.
9. flame retardant polyester according to claim 8 or polyester alloy, it is characterized in that described fire retardant is a halogenated flame retardant, one of be selected from TDE, tribromophenol, dibromophenol, tetrabromo-bisphenol, tetrabromobisphenol A carbonic ester oligopolymer, brominated epoxy resin, poly-bromostyrene, Brominated Polystyrene and the multipolymer thereof or their any combinations.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101715800A CN101205309B (en) | 2007-11-30 | 2007-11-30 | Antimony trioxide synergist |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101715800A CN101205309B (en) | 2007-11-30 | 2007-11-30 | Antimony trioxide synergist |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101205309A CN101205309A (en) | 2008-06-25 |
| CN101205309B true CN101205309B (en) | 2010-10-27 |
Family
ID=39565801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101715800A Expired - Fee Related CN101205309B (en) | 2007-11-30 | 2007-11-30 | Antimony trioxide synergist |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101205309B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2008362986B2 (en) * | 2008-10-17 | 2012-09-27 | Kingfa Science & Technology Co., Ltd. | Flame retarding thermoplastic alloy and its preparation method |
| CN102675811A (en) * | 2012-05-11 | 2012-09-19 | 江苏安格特科技发展有限公司 | Low-smoke flame-retardant acrylonitrile butadiene styrene (ABS) alloy material |
| CN103451923A (en) * | 2012-05-31 | 2013-12-18 | 上海日多高分子材料有限公司 | Method for manufacturing artificial leather base fabric fire retardant from decabromodiphenylethane and antimonous oxide as raw materials |
| CN104231622B (en) * | 2014-10-09 | 2017-12-08 | 江苏晋伦塑料科技有限公司 | A kind of low precipitation flame-retardant polyamide composition and preparation method thereof |
| CN110028766A (en) * | 2019-03-25 | 2019-07-19 | 广东顺德顺炎新材料股份有限公司 | It is a kind of fire-retardant not drip modified PBT material and preparation method thereof without fine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067252A (en) * | 1991-05-27 | 1992-12-23 | 孙绍宜 | Modified version universal fire-retarding master particles with high concentration and method for making thereof |
| WO1999029776A1 (en) * | 1997-12-05 | 1999-06-17 | Minnesota Mining And Manufacturing Company | Flame retardant compositions |
| CN1570262A (en) * | 2003-07-14 | 2005-01-26 | 贾剑珉 | Flame-proof industrial canvas impregnating glue and process for making same |
| CN101020825A (en) * | 2006-02-16 | 2007-08-22 | 贾劲松 | Nanometer composite Sb-base fire retarding synergist and its prepn |
-
2007
- 2007-11-30 CN CN2007101715800A patent/CN101205309B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067252A (en) * | 1991-05-27 | 1992-12-23 | 孙绍宜 | Modified version universal fire-retarding master particles with high concentration and method for making thereof |
| WO1999029776A1 (en) * | 1997-12-05 | 1999-06-17 | Minnesota Mining And Manufacturing Company | Flame retardant compositions |
| CN1570262A (en) * | 2003-07-14 | 2005-01-26 | 贾剑珉 | Flame-proof industrial canvas impregnating glue and process for making same |
| CN101020825A (en) * | 2006-02-16 | 2007-08-22 | 贾劲松 | Nanometer composite Sb-base fire retarding synergist and its prepn |
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| Publication number | Publication date |
|---|---|
| CN101205309A (en) | 2008-06-25 |
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