CN105754327A - Antimony trioxide compound flame retardant masterbatch for polycaprolactam and preparation method thereof - Google Patents
Antimony trioxide compound flame retardant masterbatch for polycaprolactam and preparation method thereof Download PDFInfo
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- CN105754327A CN105754327A CN201610124013.9A CN201610124013A CN105754327A CN 105754327 A CN105754327 A CN 105754327A CN 201610124013 A CN201610124013 A CN 201610124013A CN 105754327 A CN105754327 A CN 105754327A
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- polycaprolactam
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses an antimony trioxide compound flame retardant masterbatch for polycaprolactam (PA6) and a preparation method thereof. The flame retardant masterbatch comprises the following raw materials by weight: 40-65 parts of antimony trioxide; 10-30 parts of a flame retardant A; 8-25 parts of a flame retardant B; 2-5 parts of a coupling agent; 2-6 parts of a lubricant; and 10-25 parts of polycaprolactam resin. The flame retardant masterbatch is prepared by drying, surface modification, high speed thermal mixing, granulation and other steps. The antimony trioxide compound flame retardant masterbatch for polycaprolactam provided by the invention has the characteristics of high flame retardant efficiency and good processability, etc., is prepared from halogen-free and non-toxic environment-friendly raw materials and assistants, and can reach a high flame retardant effect without additional adding of halogenated flame retardants for collaboration, and has small influence on the mechanical properties of composite materials.
Description
Technical field
The invention belongs to fire proofing technical field, be specifically related to a kind of polycaprolactam antimony oxide compositional flame-retardant master batch and preparation method thereof.
Background technology
Polycaprolactam is the linear polyamide generated through ring-opening polymerization by monomer caprolactam, because having NH (CH2) 5CO repeat unit structure, tensile strength and excellent in abrasion resistance, flexible, mainly for the manufacture of synthetic fibers, it is also possible to make engineering plastics.Owing to nylon 6 (PA6) is containing amino, discharging a small amount of noble gas during combustion decomposition, therefore its combustion process is comparatively slow, has certain fire resistance, but to reach V-0 level or oxygen index (OI) to reach more than 30% must must carry out flame-retardant modified.But currently antimony oxide flame retardant PA6 generally adopts the mode directly adding stibium oxide powder to carry out fire-retardant, flame retardant effect is poor, the amount of being fuming is big, and due to disperse uneven and interface welding is bad cause the inorganic particles such as stibium oxide to add after the mechanical impact of PA6 composite is relatively big, seriously govern stibium oxide application in PA6 polymer.For inorganic particle difficult dispersion and difficult problem merged in resin, in industry, the mode frequently with composite modified or female granulated processed is improved.
At present, domestic have been developed for some flame-retardant master batch containing stibium oxide, but these fire-retardant master granule majorities are need to add halogen flame to carry out the fire-retardant master granule of Synergistic, or add merely the master batch that stibium oxide is fabricated to, as: patent " manufacture method of a kind of antimony trioxide parent particle " (patent No.: CN200710000830.4) discloses a kind of with antimony oxide powder body, carrier, dispersant and coupling agent for raw material, it is modified, extrudes, method that pelletize, screening, the process such as dry prepare antimony trioxide parent particle；And patent " a kind of antimony trioxide parent particle and preparation method thereof " (patent No.: CN201110429778.0) discloses a kind of antimony trioxide parent particle being raw material with nanmeter antimong trioxide, carrier, modified ethylene bis-fatty acid amides.Additionally, the patent of the domestic fire-retardant master granule also having part Halogen polycaprolactam to be correlated with, as patent " nylon 6 Composite environmental-friendflame flame retardant and nylon 6 flame retardant plastics " (patent No. 201210411329.8) discloses a kind of nylon 6 flame retardant plastics being main flame-retardant composition with trimethylsilyl dimethyl phosphonate, melamine cyanurate, antimony oxide, barium metaborate, though the patented product has good fire resistance, and it is not halogen-containing, but formula components introduces poisonous and harmful element, after combustion decomposition, air and water quality is caused certain pollution.
Through inquiry; with antimony oxide be main fire retardant nylon fire-retardant master granule or the research and development of antimony system compositional flame-retardant masterbatch less; optimize design by tradition antimony oxide product is refined, modifiies, composite etc., be a trend of Sb system fire retardant future development.And the individual character of fire-retardant master granule, specific aim are stronger, different resins need to adopt corresponding or that physical property is close base material to make fire-retardant master granule, it is difficult to accomplish general, and existing high-load (more than 70%) the antimony oxide fire-retardant master granule for PA6 resin finds no Patents.
Summary of the invention
Present invention aims to fire-retardant master granule majority in prior art is need to add after halogen flame carries out Synergistic or combustion decomposition air and water quality are caused the deficiencies such as certain pollution, provide a kind of polycaprolactam antimony oxide compositional flame-retardant master batch and preparation method thereof, carry out collaborative just to reach higher flame retardant effect without additionally adding halogenated flame retardant when described fire-retardant master granule uses, and environmentally friendly.
To achieve these goals, present invention employs techniques below scheme:
A kind of polycaprolactam antimony oxide compositional flame-retardant master batch, including the raw material of following weight portion:
(1) antimony oxide, 40～65 parts；
(2) fire retardant A, 10～30 parts；
(3) fire retardant B, 8～25 parts；
(4) coupling agent, 2～5 parts；
(5) lubricant, 2～6 parts；
(6) polycaprolactam, 10～25 parts.
Preferably, described antimony oxide particle diameter is 0.2～1.0 μm.
Preferably, described fire retardant A includes inorganic combustion inhibitor, including any one in magnesium hydroxide, montmorillonite, Firebrake ZB or two kinds.
Preferably, described fire retardant B includes halogenated aromatic, including brominated Polystyrene (BPS) or Chloropolystyrene any one.
Preferably, described coupling agent include silane coupler or Aluminate any one.
Preferably, described lubricant include zinc stearate or stearic acid stannum any one.
Preferably, described polycaprolactam is the good rounded grain shape resin of toughness.
The preparation method that the present invention also provides for a kind of polycaprolactam antimony oxide compositional flame-retardant master batch, comprises the steps of
S1, dry: to adopt hot air circulation that polycaprolactam is dried, temperature 90～110 DEG C, drying time 15h；
S2, surface modification: adopt coupling agent to antimony oxide and fire retardant A modifying surface, modification temperature 90～130 DEG C, stir speed (S.S.) 600～900rpm/min, time 2.0～4.0h, prepare modified antimony oxide, fire retardant A；
S3, at a high speed heat mixing: the modified antimony oxide, the fire retardant A that are prepared by step S2 are positioned in frequency-conversion agitator with polycaprolactam, fire retardant B, lubricant and carry out heat at a high speed mix, rotating speed 600～900rpm/min, temperature controls at 80～110 DEG C, incorporation time 5～10min, obtains mixture；
S4, pelletize: to extruder, the vertical blanking of mixture that step S3 prepares is carried out pelletize, and processing temperature is 200 DEG C～280 DEG C.
Processing temperature described in step S4 is nine sections of temperature control scopes, presents negative sense arc from first paragraph to the 6th section temperature in principle and lays, first increases by 3～8 DEG C subtract afterwards for jump, the six to eight section of equality of temperature, and a little higher than 8th section of temperature of die temperature 5～8 DEG C.
Advantages of the present invention:
1, have employed cheap and there is the magnesium hydroxide of good flame-retardant smoke inhibition function, montmorillonite and antimony oxide carry out composite, the advantage of comprehensive each component, optimum complementation can be formed in fire resistance, smoke suppressing and price three, reduce fire retardant cost, improve fire-retardant, the smoke suppressing of compound product.
2, the polycaprolactam antimony oxide compositional flame-retardant master batch of the present invention is not chosen halogenide and antimony oxide and is carried out cooperative flame retardant; but make full use of halogenated aromatic thermal degradation or the little molecule such as scattered halogen radical and unconverted monomer carries out cooperative flame retardant, not only environmental protection but also fire-retardant master granule mechanical performance can be improved.
3, adopt silane coupler or Aluminate that the inorganic particle such as antimony oxide, magnesium hydroxide is organised and carry out composite mixing again after coating modification, organic modification can be passed through and improve the compatibility of compound flame retardant and resin, reduce antimony oxide surface charge and surface tension, reduce the generation of agglomeration, improve dispersibility.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described, but is not intended to protection scope of the present invention.
Embodiment 1:
A kind of polycaprolactam antimony oxide compositional flame-retardant master batch, raw material including following weight portion: polycaprolactam 10kg, antimony oxide 65kg (main content more than 99.6%, particle diameter 0.5 μm), magnesium hydroxide 10kg, brominated Polystyrene 9kg, zinc stearate 3.5kg, Aluminate 2.5kg.
The preparation method of above-mentioned polycaprolactam antimony oxide compositional flame-retardant master batch, comprises the following steps:
S1, dry: to adopt hot air circulation that polycaprolactam is dried, temperature 100 DEG C, drying time 15h.
S2, surface modification: weigh antimony oxide by above-mentioned amount, magnesium hydroxide and Aluminate put into homogenizer and be modified, modification temperature 110 DEG C, stir speed (S.S.) 800rpm/min, mixing time 3.0h, prepare modified antimony oxide, magnesium hydroxide.
S3, at a high speed heat mixing: the modified antimony oxide, magnesium hydroxide and other components that are prepared by step S2 are put into and carried out mixed at high speed in variable ratio frequency changer high-speed mixer, rotating speed 700rpm/min, temperature controls at 100～110 DEG C, and incorporation time 5min obtains mixture.
S4, pelletize: by the step S3 vertical blanking of mixture prepared to extruder pelletize, processing temperature is 200 DEG C～280 DEG C.The conventional method that control mode produces by master batch is operated.
Embodiment 2:
A kind of polycaprolactam antimony oxide compositional flame-retardant master batch, raw material including following weight portion: polycaprolactam 25kg, antimony oxide 40kg (main content more than 99.6%, particle diameter 0.5 μm), montmorillonite 18kg, Chloropolystyrene 12kg, stearic acid stannum 3kg, silane coupler 2kg.
The preparation method of above-mentioned polycaprolactam antimony oxide compositional flame-retardant master batch, comprises the following steps:
S1, dry: to adopt hot air circulation that polycaprolactam is dried, temperature 90 DEG C, drying time 15h.
S2, surface modification: weigh antimony oxide by above-mentioned amount, montmorillonite and silane coupler put into homogenizer and be modified, modification temperature 90 DEG C, stir speed (S.S.) 600rpm/min, mixing time 2.0h, prepare modified antimony oxide, montmorillonite.
S3, at a high speed heat mixing: the modified antimony oxide, montmorillonite and other components that are prepared by step S2 are put into and carried out mixed at high speed in variable ratio frequency changer high-speed mixer, rotating speed 600rpm/min, temperature controls at 80～100 DEG C, and incorporation time 10min obtains mixture.
S4, pelletize: by the step S3 vertical blanking of mixture prepared to extruder pelletize, processing temperature is 200 DEG C～280 DEG C.The conventional method that control mode produces by master batch is operated.
Execute example 3:
A kind of polycaprolactam antimony oxide compositional flame-retardant master batch, raw material including following weight portion: polycaprolactam 20kg, antimony oxide 38kg (main content more than 99.6%, particle diameter 0.5 μm), Firebrake ZB 22kg, brominated Polystyrene 15kg, zinc stearate 3kg, Aluminate 2kg.
The preparation method of above-mentioned polycaprolactam antimony oxide compositional flame-retardant master batch, comprises the following steps:
S1, dry: to adopt hot air circulation that polycaprolactam is dried, temperature 110 DEG C, drying time 15h.
S2, surface modification: weigh antimony oxide by above-mentioned amount, Firebrake ZB and Aluminate put into homogenizer and be modified, modification temperature 130 DEG C, stir speed (S.S.) 900rpm/min, mixing time 4.0h, prepare modified antimony oxide, magnesium hydroxide.
S3, at a high speed heat mixing: the modified antimony oxide, Firebrake ZB and other components that are prepared by step S2 are put into and carried out mixed at high speed in variable ratio frequency changer high-speed mixer, rotating speed 900rpm/min, temperature controls at 100～110 DEG C, and incorporation time 5min obtains mixture.
S4, pelletize: by the step S3 vertical blanking of mixture prepared to extruder pelletize, processing temperature is 200 DEG C～280 DEG C.The conventional method that control mode produces by master batch is operated.
Application example
Being respectively applied in polycaprolactam composite flame-proof material by the master batch product obtained by above example 1～3, test the performance of material according to national standard, formula composition and the performance test results are as follows:
Table 1: formula composition and the performance test results formula unit: part
Can being drawn by upper table, being respectively applied in polycaprolactam composite flame-proof material by the master batch product obtained by above example 1～3, the material obtained has the characteristics such as flame retarding and smoke suppressing properties is good and environmentally friendly.
Above content is it cannot be assumed that specific embodiment of the invention is confined to these explanations; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; some simple deduction or replace can also be made, all should be considered as belonging to the scope of patent protection that the present invention is determined by submitted claims.
Claims (6)
1. a polycaprolactam antimony oxide compositional flame-retardant master batch, it is characterised in that: include the raw material of following weight portion:
(1) antimony oxide, 40～65 parts；
(2) fire retardant A, 10～30 parts；
(3) fire retardant B, 8～25 parts；
(4) coupling agent, 2～5 parts；
(5) lubricant, 2～6 parts；
(6) polycaprolactam, 10～25 parts.
2. polycaprolactam antimony oxide compositional flame-retardant master batch according to claim 1, it is characterised in that: described fire retardant A includes inorganic combustion inhibitor, including any one in magnesium hydroxide, montmorillonite, Firebrake ZB or two kinds.
3. polycaprolactam antimony oxide compositional flame-retardant master batch according to claim 1, it is characterised in that: described fire retardant B includes halogenated aromatic, including any one in brominated Polystyrene (BPS) or Chloropolystyrene.
4. polycaprolactam antimony oxide compositional flame-retardant master batch according to claim 1, it is characterised in that: described coupling agent includes any one in silane coupler or Aluminate.
5. polycaprolactam antimony oxide compositional flame-retardant master batch according to claim 1, it is characterised in that: described lubricant includes any one in zinc stearate or stearic acid stannum.
6. the preparation method of antimony oxide compositional flame-retardant master batch of the polycaprolactam according to any one of claim 1-5, it is characterised in that: comprise the following steps:
S1, dry: to adopt hot air circulation that polycaprolactam is dried, temperature 90～110 DEG C, drying time 15h；
S2, surface modification: adopt coupling agent to antimony oxide and fire retardant A modifying surface, modification temperature 90～130 DEG C, stir speed (S.S.) 600～900rpm/min, time 2.0～4.0h, prepare modified antimony oxide, fire retardant A；
S3, at a high speed heat mixing: the modified antimony oxide, the fire retardant A that are prepared by step S2 are positioned in frequency-conversion agitator with polycaprolactam, fire retardant B, lubricant and carry out heat at a high speed mix, rotating speed 600～900rpm/min, temperature controls at 80～110 DEG C, incorporation time 5～10min, obtains mixture；
S4, pelletize: to extruder, the vertical blanking of mixture that step S3 prepares is carried out pelletize, and temperature is 200 DEG C～280 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610124013.9A CN105754327A (en) | 2016-03-04 | 2016-03-04 | Antimony trioxide compound flame retardant masterbatch for polycaprolactam and preparation method thereof |
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| CN201610124013.9A CN105754327A (en) | 2016-03-04 | 2016-03-04 | Antimony trioxide compound flame retardant masterbatch for polycaprolactam and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108587133A (en) * | 2018-05-02 | 2018-09-28 | 合肥卡洛塑业科技有限公司 | A kind of anti-electrostatic fire retardant PA Masterbatch and preparation method thereof |
| CN113214542A (en) * | 2021-05-18 | 2021-08-06 | 湖南娄底华星锑业有限公司 | Composite antimony trioxide flame retardant and preparation method thereof |
| CN114196196A (en) * | 2021-12-27 | 2022-03-18 | 北京普利宏斌化工材料有限责任公司 | Flame-retardant polyamide resin composition |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108587133A (en) * | 2018-05-02 | 2018-09-28 | 合肥卡洛塑业科技有限公司 | A kind of anti-electrostatic fire retardant PA Masterbatch and preparation method thereof |
| CN113214542A (en) * | 2021-05-18 | 2021-08-06 | 湖南娄底华星锑业有限公司 | Composite antimony trioxide flame retardant and preparation method thereof |
| CN113214542B (en) * | 2021-05-18 | 2022-05-20 | 湖南娄底华星锑业有限公司 | Composite antimony trioxide flame retardant and preparation method thereof |
| CN114196196A (en) * | 2021-12-27 | 2022-03-18 | 北京普利宏斌化工材料有限责任公司 | Flame-retardant polyamide resin composition |
| CN114196196B (en) * | 2021-12-27 | 2024-03-15 | 安徽星贝达新材料科技有限公司 | Flame-retardant polyamide resin composition |
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Application publication date: 20160713 |