CN108912444A - A kind of environment friendly halogen-free fireproof master batch and preparation method thereof - Google Patents
A kind of environment friendly halogen-free fireproof master batch and preparation method thereof Download PDFInfo
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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Abstract
The invention discloses a kind of environment friendly halogen-free fireproof master batch and preparation method thereof, the environment friendly halogen-free fireproof master batch includes the raw material of following parts by weight：Polypropylene or 80-110 parts of polyethylene；0.01-0.3 parts of antioxidant；75-100 parts of composite modified halogen-free flameproof pulvis；Polypropylene wax or 3-5 parts of polyethylene wax；Wherein, composite modified halogen-free flameproof pulvis includes the raw material of following parts by weight：1-2 parts of silane coupling agent；0.8-1.2 parts of stearic acid；50-60 parts of hydrotalcite powder；20-25 parts of aluminium hydrate powder；10-15 parts of talcum powder.By adding composite modified halogen-free flameproof pulvis in the formula to master batch, the flame retardant effect of master batch is improved.It is composite modified that composite modified halogen-free flameproof pulvis selects inorganic fire retardants to carry out, and by the combination and synergistic effect of each component, makes it have preferable flame retardant effect.
Description
Technical field
The invention belongs to Material Fields, and in particular to a kind of environment friendly halogen-free fireproof master batch and preparation method thereof.
Background technique
In recent years, with the promotion of environmental protection consciousness, the plastic flame master batch of environment-friendly type has become flame-retarded technology development
Trend.Traditional bromide fire retardant, the double S ethers of deca-BDE, tetrabromobisphenol A, eight bromo ether, eight bromines, TBC etc., because its is right
The harm of environmental protection and its own murder by poisoning to the nervous system and immune system of human body, completely inadaptable production and use
Needs.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of environment friendly halogen-free fireproof master batches and preparation method thereof.Pass through
Composite modified halogen-free flameproof pulvis is added into the formula of master batch, improves the flame retardant effect of master batch.Composite modified halogen-free flameproof powder
It is composite modified that agent selects inorganic fire retardants to carry out, and by the combination and synergistic effect of each component, makes it have preferable resistance
Fuel efficiency fruit.
The technical scheme adopted by the invention is as follows：
A kind of environment friendly halogen-free fireproof master batch, the raw material including following parts by weight：
Polypropylene or 80-110 parts of polyethylene；
0.01-0.3 parts of antioxidant；
75-100 parts of composite modified halogen-free flameproof pulvis；
Polypropylene wax or 3-5 parts of polyethylene wax.
The composite modified halogen-free flameproof pulvis includes the raw material of following parts by weight：
1-2 parts of silane coupling agent；
0.8-1.2 parts of stearic acid；
50-60 parts of hydrotalcite powder；
20-25 parts of aluminium hydrate powder；
10-15 parts of talcum powder.
The polypropylene, polyethylene MRF be respectively 3~4g/10min, 2~4g/10min.
The antioxidant is antioxidant 1076.
The silane coupling agent is KH550.
D97≤1 μm of the hydrotalcite powder.
D97≤10 μm of the aluminium hydrate powder.
D97≤0.5 μm of the talcum powder.
The present invention also provides the preparation methods of the environment friendly halogen-free fireproof master batch, include the following steps：
S1, hydrotalcite powder is added in powder composition modification machine, then is separately added into aluminium hydrate powder, talcum powder and tristearin
Acid, high-speed stirred are simultaneously warming up to 100-110 DEG C, heat preservation 8-10min；Then silane coupling agent is added, is warming up to 150-165 DEG C,
6-8min is kept the temperature, the composite modified halogen-free flameproof pulvis can be obtained；
S2, the raw material of each environment friendly halogen-free fireproof master batch of formula ratio is mixed, is stirred 5 minutes in 80-95 DEG C of temperature range
The material mixed, the material mixed is added in parallel equidirectional two-screw extruder, and extruding pelletization obtains ring
Protect halogen-free flame-retardant master batch.
Each inorganic particle soilless sticking tendency, has excellent in the composite modified halogen-free flameproof pulvis that such preparation process obtains
Processing fluidity and dispersibility.And it is good with base resin compatibility, so that its additional amount in resin is when larger
Layering is not allowed to be also easy to produce, the problems such as frosting, decorative pattern.
The mixing speed of the high-speed stirred is 1200 revs/min.
In the environment friendly halogen-free fireproof master batch raw material, the determination of composite modified halogen-free flameproof wp formula is fully considered
The factor of three aspects below：
1., select Halogen, be nontoxic, low cigarette, efficient environmentally friendly inorganic fire retardants are as primary raw material, prevent halogen system
Fire retardant can generate a large amount of cigarette and toxic and acrid gas in combustion, so as to cause merely by fire cannot
The caused corrosion to circuit switch and other metal objects and the pollution to environment.
2., inorganic fire retardants two or more in formula system be used cooperatively, strengthen fire retardant " cooling effect ",
" dilution effect " and " partition effect ".
A, cooling effect：The use of aluminium hydrate powder (ATH) is exactly that the thermal capacitance of polymer can be improved by it in formula,
It is decomposed when heated, this kind of decomposition reaction can absorb a large amount of latent heat, thus can reduce the actual temperature of material surface and make to gather
Conjunction object is degraded to low molecular rate and slows down, and the generation of combustible is reduced, to improve its flame retardant property.
B, dilution effect：Aluminium hydrate powder (ATH) can release H under ignition temperature2O、CO2、N2Equal non-combustibles gas
Body, these gases can dilute simultaneously the concentration of imflammable gas and surface oxygen and burning not can be carried out, and play gas phase resistance
Fuel efficiency fruit.Hydrotalcite powder is aqueous hydrotalcite compound, it is a kind of inorganic compound with special construction,
The existing low-temperature zone of hydrotalcite powder decomposition temperature section has high temperature section again, has had both aluminium hydrate powder (ATH) and Mg (OH)2Fire retardant
Advantage further enhances fire-retardant dilution effect.
C, separate effect：First, due to the unique layer structure of hydrotalcite powder and laminate composition and interlayer anion can
Modulation, thermal degradation products promote polymer surfaces rapid dehydration to carbonize, and then form charring layer, and simple substance charcoal will not evaporate
Burning and decomposition combustion, therefore there is flame retardant effect.Second, talcum powder and aluminium hydrate powder (ATH) can divide under ignition temperature
Solution generates nonvolatile glassy mass and is coated on polymer surfaces, and the glassy state protective layer of this densification also plays isolation
Film.
3., the fire-retardant powder body materials of ultra-fine inorganic of three kinds of hydrotalcite powder, aluminium hydrate powder, talcum powder different crystal forms structures matches
It closes and uses, reach the crystal form complementary effect of powder, the difference of different chemical compositions can effectively make up single ultra-fine nonmetallic
The intrinsic performance deficiency of powder, the ultrafine inorganic powder complex that forming properties have complementary advantages, and less than the hydrotalcite of 1 μm of partial size
Powder and talcum powder help to play " small-size effect ", by reach in flame-retardant system after modification polymer with it is inorganic fire-retarded
Excellent compatibility and dispersibility between agent, to guarantee that product has the physical properties such as good stretching, impact.
In the halogen-free flame-retardant master batch formula provided by the invention, limited by the cooperation of each raw material and amount ranges, institute
Halogen-free flame-retardant master batch have very excellent processing heat stability, no precipitation performance, water-fast, light aging resisting, it is nontoxic, not with
Other additives generate the characteristics such as side reaction, have very strong economic and social benefit.
Specific embodiment
The following describes the present invention in detail with reference to examples.
Talcum powder and hydrotalcite powder in the present invention are Wuhu Tongda New Materials Technology Co., Ltd.'s production, remaining raw material
It is commercially available.
Embodiment 1
A kind of environment friendly halogen-free fireproof master batch, the raw material including following parts by weight：
108 parts of polyethylene；
0.12 part of antioxidant 1076；
94 parts of composite modified halogen-free flameproof pulvis；
4.5 parts of polyethylene wax H110；
Composite modified halogen-free flameproof pulvis, the raw material including following parts by weight：
1.8 parts of Silane coupling agent KH550；
1,801 1.2 parts of stearic acid Indonesia；
57 parts of hydrotalcite powder；
24 parts of aluminium hydrate powder；
15 parts of talcum powder.
The MRF of the polyethylene is 2~4g/10min.
D97≤1 μm of the hydrotalcite powder；D97≤10 μm of the aluminium hydrate powder；D97≤0.5 of the talcum powder
μm。
The preparation method of the environment friendly halogen-free fireproof master batch is：
S1, hydrotalcite powder is added in powder composition modification machine, then is separately added into aluminium hydrate powder, talcum powder and stearic acid
Indonesia 1801, high-speed stirred are simultaneously warming up to 102 DEG C, heat preservation 9min；Then silane coupling agent is added, is warming up to 155 DEG C, heat preservation
The composite modified halogen-free flameproof pulvis can be obtained in 7min；
S2, be added into composite modified halogen-free flameproof pulvis polyethylene wax H110 and antioxidant 1076, polyvinyl resin after
Continue and stirs 5 minutes materials mixed in 82 DEG C of temperature ranges；The material mixed is added to parallel equidirectional two-screw
In extruder, extruding pelletization is carried out, environment-friendly halogen-free flame-proof master batch is obtained；The technological parameter of the extruding pelletization is：It squeezes out
The control of the temperature range that each section of machine is 150 DEG C -180 DEG C, melt temperature control at 160 DEG C, melt pressure control 5.0Mpa with
Inside it is granulated.
The performance for the environment-friendly halogen-free flame-proof master batch that the present embodiment obtains is tested, the results are shown in Table 1.It will be environmentally friendly
HDPE and PP product is not made for type halogen-free flame-retardant master batch, and the surface of both products is asked without quality such as decorative pattern, layering, frostings
Topic, and its mechanical property and flame retardant property are tested, as a result as shown in table 2, table 3.
Table 1
Note：Density is detected according to the standard of GB1033-2008；Melt index according to GB3682-2000 standard into
Row detection；Content of beary metal is according to IEC 62321:2015 standard is detected.
Table 2
Note：Flame retardant property is detected according to the standard of UL94；Tensile strength is examined according to GB/T1040-2006 standard
It surveys；Impact property is detected according to standard ASTM D256-2010.
Table 3
Note：Flame retardant property is detected according to the standard of UL94；Tensile strength is examined according to GB/T1040-2006 standard
It surveys；Impact property is detected according to standard ASTM D256-2010.
Embodiment 2
A kind of environment friendly halogen-free fireproof master batch, the raw material including following parts by weight：
95 parts of polypropylene；
0.22 part of antioxidant 1076；
80 parts of composite modified halogen-free flameproof pulvis
4.1 parts of polypropylene wax；
The composite modified halogen-free flameproof pulvis, the raw material including following parts by weight：
1.6 parts of Silane coupling agent KH550；
1,801 1.0 parts of stearic acid Indonesia；
52 parts of hydrotalcite powder；
25 parts of aluminium hydrate powder；
12 parts of talcum powder.
The polyacrylic MRF is 3~4g/10min.
D97≤1 μm of the hydrotalcite powder；D97≤10 μm of the aluminium hydrate powder；D97≤0.5 of the talcum powder
μm。
The preparation method of the environment friendly halogen-free fireproof master batch is：
S1, hydrotalcite powder is added in powder composition modification machine, then is separately added into aluminium hydrate powder, talcum powder and stearic acid
Indonesia 1801, high-speed stirred are simultaneously warming up to 109 DEG C, heat preservation 10min；Then Silane coupling agent KH550 is added, is warming up to 160 DEG C,
6min is kept the temperature, the composite modified halogen-free flameproof pulvis can be obtained.
S2, into composite modified halogen-free flameproof pulvis, addition polypropylene wax and antioxidant 1076, acrylic resin continue to exist
95 DEG C of temperature ranges stir 5 minutes materials mixed；The material mixed is added to parallel equidirectional two-screw to squeeze out
In machine, extruding pelletization is carried out, environment-friendly halogen-free flame-proof master batch is obtained；The technological parameter of the extruding pelletization is：Extruder is each
The temperature range control of section is 150 DEG C -180 DEG C, melt temperature control at 175 DEG C, melt pressure control within 5.0Mpa into
Row is granulated.
The performance for the environment-friendly halogen-free flame-proof master batch that the present embodiment obtains is tested, the results are shown in Table 1.It will be environmentally friendly
HDPE and PP product is not made for type halogen-free flame-retardant master batch, and the surface of both products is asked without quality such as decorative pattern, layering, frostings
Topic, and its mechanical property and flame retardant property are tested, as a result as shown in table 2, table 3.
Comparative example 1
A kind of fire-retardant master granule, the raw material including following parts by weight：
The MRF of the polyethylene is 2~4g/10min；D97≤5 μm of the brucite powder；The D97 of the carbide slag
≤10μm；D97≤0.5 μm of the talcum powder.
Comparative example 2
A kind of fire-retardant master granule, the raw material including following parts by weight：
The polyacrylic MRF is 3~4g/10min；D97≤5 μm of the brucite powder；The D97 of the carbide slag
≤10μm；D97≤0.5 μm of the talcum powder.
HDPE and PP product is made in the obtained halogen-free flame-retardant master batch of above-mentioned comparative example 1 and the formula production of comparative example 2, this
There are the apparent masses problems such as frosting, surface water wave on the surface of two kinds of products, and tests its mechanical property and flame retardant property, such as table
1, shown in 2, change flame retardant constituent of the invention if can be seen that from table 1 and 2, and the non-modified rear directly work of fire retardant
For the raw material of master batch, then the anti-flammability and mechanical property of HDPE the and PP product obtained are poor.
The above-mentioned detailed description carried out referring to embodiment to a kind of environment friendly halogen-free fireproof master batch and preparation method thereof, is explanation
Property without being restrictive, several embodiments can be enumerated according to limited range, therefore of the invention overall not departing from
Change and modification under design, should belong within protection scope of the present invention.
Claims (10)
1. a kind of environment friendly halogen-free fireproof master batch, which is characterized in that the raw material including following parts by weight：
2. environment friendly halogen-free fireproof master batch according to claim 1, which is characterized in that the composite modified halogen-free flameproof pulvis
Raw material including following parts by weight：
3. environment friendly halogen-free fireproof master batch according to claim 1 or 2, which is characterized in that the polypropylene, polyethylene
MRF is respectively 3~4g/10min, 2~4g/10min.
4. environment friendly halogen-free fireproof master batch according to claim 1 or 2, which is characterized in that the antioxidant is antioxidant
1076。
5. environment friendly halogen-free fireproof master batch according to claim 2, which is characterized in that the silane coupling agent is KH550.
6. environment friendly halogen-free fireproof master batch according to claim 2, which is characterized in that D97≤1 μm of the hydrotalcite powder.
7. according to environment friendly halogen-free fireproof master batch described in claim 2 or 5 or 6, which is characterized in that the aluminium hydrate powder
D97≤10μm。
8. according to environment friendly halogen-free fireproof master batch described in claim 2 or 5 or 6, which is characterized in that the D97 of the talcum powder≤
0.5μm。
9. the preparation method of environment friendly halogen-free fireproof master batch according to claim 1, which is characterized in that include the following steps：
S1, hydrotalcite powder is added in powder composition modification machine, then is separately added into aluminium hydrate powder, talcum powder and stearic acid, it is high
Speed stirs and is warming up to 100-110 DEG C, heat preservation 8-10min；Then silane coupling agent is added, is warming up to 150-165 DEG C, keeps the temperature 6-
The composite modified halogen-free flameproof pulvis can be obtained in 8min；
S2, the raw material of each environment friendly halogen-free fireproof master batch of formula ratio is mixed, stirs 5 minutes and obtains in 80-95 DEG C of temperature range
The material mixed is added in parallel equidirectional two-screw extruder, extruding pelletization by the material mixed, obtains environmentally friendly nothing
Halogen fire-retardant master granule.
10. preparation method according to claim 9, which is characterized in that the technological parameter of the extruding pelletization is：Extruder
Each section of temperature range control is 150 DEG C -180 DEG C, and at 155 DEG C -175 DEG C, melt pressure control exists for melt temperature control
It is granulated within 5.0Mpa.
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| CN110483895A (en) * | 2019-09-09 | 2019-11-22 | 王良仁 | A kind of fire retardant plastic mastre batch and preparation method for cable filling rope |
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| CN116218077A (en) * | 2022-12-28 | 2023-06-06 | 上海金发科技发展有限公司 | Halogen-free flame-retardant master batch, halogen-free flame-retardant composite material, and preparation methods and applications thereof |
| CN116218077B (en) * | 2022-12-28 | 2024-03-15 | 上海金发科技发展有限公司 | Halogen-free flame-retardant master batch, halogen-free flame-retardant composite material, and preparation methods and applications thereof |
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Application publication date: 20181130 |