CN107513222A - Glass fiber reinforced halogen-free flame-retardant polypropylene resin composite and its products formed - Google Patents
Glass fiber reinforced halogen-free flame-retardant polypropylene resin composite and its products formed Download PDFInfo
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- CN107513222A CN107513222A CN201610422500.3A CN201610422500A CN107513222A CN 107513222 A CN107513222 A CN 107513222A CN 201610422500 A CN201610422500 A CN 201610422500A CN 107513222 A CN107513222 A CN 107513222A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The present invention relates to technical field of polymer materials, is specifically related to a kind of glass fiber reinforced halogen-free flame-retardant polypropylene resin composite and its products formed.The glass fiber reinforced halogen-free flame-retardant polypropylene resin composite includes acrylic resin, glass fibre and halogen-free flame retardants.The glass fiber reinforced halogen-free flame-retardant acrylic resin products formed is made up of the glass fiber reinforced halogen-free flame-retardant polypropylene resin composite.The glass fiber reinforced halogen-free flame-retardant polypropylene resin composite and its products formed of the present invention, the comprehensive mechanical property of composition can be improved, and good flame retardation effect, and environmental protection, so as to expand polyacrylic application, polypropylene is set to apply on to the higher automobile of mechanical property and environmental requirement, electric equipment products.
Description
【Technical field】
The present invention relates to technical field of polymer materials, is specifically related to a kind of glass fiber reinforced halogen-free flame-retardant
Polypropylene resin composite and its products formed.
【Background technology】
Polypropylene (abbreviation PP) has the advantages that proportion is small, source is wide, using the widest in general-purpose plastics
It is general, but polyacrylic limited oxygen index is low, is easily dripped in burning, especially glass fiber reinforced polypropylene
In burning, due to the candle wick effect of glass fibre, glass fiber reinforced polypropylene composite material is than pure poly- third
Alkene more easy firing.
Not only addition is big when in use for traditional halogenated flame retardant and metal hydroxide combustion inhibitor, influences material
The subjectivity property of material, and halogenated flame retardant smoke amount when resin burns is big, generation has hypertoxic gaseous state halogen
Based compound, not environmentally, due to the raising to environmental requirement, have a strong impact on that polypropylene produces in electron and electrician
Application in product.
In view of this, it is necessary to develop a kind of glass fiber reinforced halogen-free flame-retardant polypropylene resin composite in fact,
With overcome the above-mentioned flame retardant effect of glass fiber reinforced polypropylene in the prior art bad and fire retardant not environmentally lack
Fall into.
【The content of the invention】
It is therefore an object of the present invention to a kind of glass fiber reinforced halogen-free flame-retardant polypropylene resin composite is provided,
Said composition is on the basis of comprehensive mechanical property is good, not only good flame retardation effect, and environmental protection.
In order to achieve the above object, glass fiber reinforced halogen-free flame-retardant polypropylene resin composite of the invention,
It represents to include in parts by weight：
Acrylic resin 1-80 parts；
Glass fibre 5-45 parts；
Halogen-free flame retardants 10-40 parts；
Wherein halogen-free flame retardants forms for two or more halogen-free flame retardants compounding.
Alternatively, the acrylic resin be impact resistance atactic copolymerized polypropene, block copolymerization polypropylene,
At least one of poly- polypropylene.
Alternatively, it is 230 DEG C in environment temperature, when load is 2.6Kg, the melting of the acrylic resin refers to
Number is 2-45g/10min.
Alternatively, the glass fibre is be chopped virgin glass fibre or chopped flat glass fiber, the glass
The length of fiber is 1-5mm.
Alternatively, the halogen-free flame retardants is ammonium phosphate salt, APP class, organophosphor salt, phosphonic acids
It is esters, phosphorous acid esters, phosphoric acid ester, phosphonium salts class, phosphorus heterocycle and its derivative species, cyanamide class, double
Cyanamide class, melamine class, guanidinesalt class and its derivative, melamine polyphosphate class, melamine are more
Polyphosphoric acid salt, phosphate and its derivative, red phosphorus, magnesium hydroxide, aluminium hydroxide, expansiveness graphite
In two or more compounding.
Alternatively, in the halogen-free flame retardants phosphorus mass fraction be halogen-free flame retardants 4-40%, the Halogen
The mass fraction of nitrogen is the 0-20% of halogen-free flame retardants in fire retardant.
Alternatively, 0.1-20 weights are also included in the glass fiber reinforced halogen-free flame-retardant polypropylene resin composite
Measure the synergistic flame retardant of part
Alternatively, the synergistic flame retardant is montmorillonite, antimony oxide, magnesia, ammonium octamolybdate, boron
At least one of sour zinc, piece barium borate, Nano-class zinc oxide, molybdenum oxide.
Alternatively, in the glass fiber reinforced halogen-free flame-retardant polypropylene resin composite also include anti-dripping agent,
At least one of antioxidant, ultra-violet absorber, releasing agent, lubricant.
In addition, the present invention a kind of glass fiber reinforced halogen-free flame-retardant acrylic resin products formed is also provided, its by
The glass fiber reinforced halogen-free flame-retardant polypropylene resin composite is formed.
Compared to prior art, glass fiber reinforced halogen-free flame-retardant polypropylene resin composite of the invention, lead to
Cross and glass fibre, the halogen-free flame retardants of compounding are added in acrylic resin, it is possible to increase the synthesis of composition
Mechanical property, and good flame retardation effect, and environmental protection, so as to expand polyacrylic application, make polypropylene should
With on to the higher automobile of mechanical property and environmental requirement, electric equipment products.
【Embodiment】
The glass fiber reinforced halogen-free flame-retardant polypropylene resin composite of the present invention, it represents to wrap in parts by weight
Include：
Acrylic resin 1-80 parts, the acrylic resin are impact resistance atactic copolymerized polypropene, block copolymerization
One or more compoundings in polypropylene, HOPP, it is 230 DEG C in environment temperature, load 2.6Kg
When, the melt index of the acrylic resin is 2-45g/10min, it is ensured that obtained composition has excellent
Processing characteristics.
Glass fibre 5-45 parts, the glass fibre are virgin glass fibre or the chopped flat glass fiber of being chopped,
The length of the glass fibre is 1-5mm.By adding glass fibre in the composition, a kind of height can be obtained
The products formed of intensity, high load capacity deformation temperature (HDT), glass fibre 5-45 parts are added, shaping can be made
The load deformation temperature of product reaches more than 132 DEG C.
Halogen-free flame retardants 10-40 parts, the halogen-free flame retardants are that two or more halogen-free flame retardants is answered
With into.Wherein, the halogen-free flame retardants is ammonium phosphate salt, APP class, organophosphor salt, phosphine
Esters of gallic acid, phosphorous acid esters, phosphoric acid ester, phosphonium salts class, phosphorus heterocycle and its derivative species, cyanamide class,
Dicyandiamide class, melamine class, guanidinesalt class and its derivative, melamine polyphosphate class, melamine
Polyphosphoric acids salt, phosphate and its derivative, red phosphorus, magnesium hydroxide, aluminium hydroxide, expansiveness stone
Two or more compounding in ink, it is ensured that the flame retardant rating of products formed can reach UL-94 1.0mmV-0
Grade.Wherein, in the halogen-free flame retardants phosphorus mass fraction be halogen-free flame retardants 4-40%, the Halogen
The mass fraction of nitrogen is the 0-20% of halogen-free flame retardants in fire retardant.
Wherein, in order to strengthen flame retardant effect, the glass fiber reinforced halogen-free flame-retardant polypropylene resin composite
In may also include the synergistic flame retardants of 0.1-20 parts by weight, the synergistic flame retardant is montmorillonite, three oxidations two
At least one of antimony, magnesia, ammonium octamolybdate, Firebrake ZB, piece barium borate, zinc oxide, molybdenum oxide.
Certainly, the species of the synergistic flame retardant and addition are determined by the species and addition of halogen-free flame retardants.
Wherein, in the range of the effect of the present invention is not damaged, the glass fiber reinforced halogen-free flame-retardant poly- third
Also include in olefine resin composition in anti-dripping agent, antioxidant, ultra-violet absorber, releasing agent, lubricant
At least one, so as to obtain other functional composite materials.
To have further understanding to the purpose of the present invention, effect and technological means, in conjunction with specific embodiment
It is described as follows.
Embodiment 1
Wherein, the halogen-free flame retardants described in embodiment 1 is APP class and melamine polyphosphate class
The compounding of fire retardant.
Weigh each component of corresponding weight；Then, each component is stirred using single shaft agitator；Will be above-mentioned mixed
Compound is added separately to melting extrusion in double screw extruder and is granulated.Processing when in order to prevent fire retardant heat point
Solution, highest processing temperature are controlled below 230 DEG C.
Embodiment 2
Wherein, the halogen-free flame retardants described in embodiment 2 is APP class and melamine polyphosphate class
The compounding of fire retardant.
Weigh each component of corresponding weight；Then, each component is stirred using single shaft agitator；Will be above-mentioned mixed
Compound is added separately to melting extrusion in double screw extruder and is granulated.Processing when in order to prevent fire retardant heat point
Solution, highest processing temperature are controlled below 230 DEG C.
Embodiment 3
Wherein, the halogen-free flame retardants described in embodiment 3 is phosphoric acid ester and Melamine Polyphosphate class
The compounding of fire retardant.
Weigh each component of corresponding weight；Then, each component is stirred using single shaft agitator；Will be above-mentioned mixed
Compound is added separately to melting extrusion in double screw extruder and is granulated.Processing when in order to prevent fire retardant heat point
Solution, highest processing temperature are controlled below 230 DEG C.
Embodiment 4
Wherein, the halogen-free flame retardants described in embodiment 4 is phosphoric acid ester and Melamine Polyphosphate class
The compounding of fire retardant, synergistic flame retardant are Nano-class zinc oxide.
Weigh each component of corresponding weight；Then, each component is stirred using single shaft agitator；Will be above-mentioned mixed
Compound is added separately to melting extrusion in double screw extruder and is granulated.Processing when in order to prevent fire retardant heat point
Solution, highest processing temperature are controlled below 230 DEG C.
After various embodiments above melting extrusion is granulated, then the particle in each embodiment is molded on injection machine
GB standard testing battens are molded, are marked by the mechanical performance of GB standard testing resulting materials, and according to UL-94
Quasi- test fire resistance, test result are as shown in table 1：
Table 1：The test result of each embodiment
| Test event | Testing standard | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Tensile strength (MPa) | ISO1183 | 39.86 | 42.96 | 42.51 | 45.80 |
| Elongation at break (%) | ISO527-1,-2 | 1.97 | 2.46 | 1.42 | 1.45 |
| Bending strength (MPa) | ISO 178 | 63.4 | 67.8 | 70.0 | 75.2 |
| Bending modulus (MPa) | ISO 178 | 4699 | 4076 | 4752 | 4700 |
| Impact strength (KJ/m2) | ISO 180 | 4.3 | 5.1 | 4.7 | 5.1 |
| Load deformation temperature (DEG C) | ISO75-2 | 132.0 | 136.2 | 135.0 | 136.5 |
| Flame retardant rating | UL-94 | 1.2mm V-0 | 1.6mm V-1 | 1.2mm V-0 | 1.0mm V-0 |
| Proportion | ISO 1133 | 1.17 | 1.15 | 1.20 | 1.20 |
| Content of halogen | —— | Do not detect | Do not detect | Do not detect | Do not detect |
It can be learnt by table 1：Embodiment 1 and embodiment 3 are made comparisons, can be learnt using different
Halogen-free flame retardants is compounded, can reach preferable flame retardant effect, embodiment 3 and embodiment 4 are compared,
Can learn can reach more preferably flame retardant effect by adding synergistic flame retardant.Therefore, by polypropylene
Glass fibre and halogen-free flame retardants are added in resin, on the basis of halogen-free environment-friendly flame-proof is polyacrylic, is improved
The comprehensive mechanical property of resulting materials, and good flame retardation effect, thus expand polyacrylic application.
In addition, the present invention a kind of glass fiber reinforced halogen-free flame-retardant acrylic resin products formed is also provided, its by
The glass fiber reinforced halogen-free flame-retardant polypropylene resin composite is formed, i.e., by the glass fiber reinforcement without
Halogen Flam-retardant polypropylene resin composition obtains glass fiber reinforced halogen-free flame-retardant polypropylene tree after injection molding
Fat products formed.The products formed can be used in the automobile higher to mechanical property and environmental requirement, electronics electricity
On device product, polyacrylic application is thus expanded.
Claims (10)
1. a kind of glass fiber reinforced halogen-free flame-retardant polypropylene resin composite, it is characterised in that by weight
Number expression includes：
Acrylic resin 1-80 parts；
Glass fibre 5-45 parts；
Halogen-free flame retardants 10-40 parts；
Wherein halogen-free flame retardants forms for two or more halogen-free flame retardants compounding.
2. glass fiber reinforced halogen-free flame-retardant polypropylene resin composite as claimed in claim 1, its feature
It is, the acrylic resin is impact resistance atactic copolymerized polypropene, block copolymerization polypropylene, homopolymerization poly- third
At least one of alkene.
3. glass fiber reinforced halogen-free flame-retardant polypropylene resin composite as claimed in claim 1 or 2, its
It is characterised by, is 230 DEG C in environment temperature, when load is 2.6Kg, the melt index of the acrylic resin
For 2-45g/10min.
4. glass fiber reinforced halogen-free flame-retardant polypropylene resin composite as claimed in claim 1, its feature
It is, the glass fibre is virgin glass fibre or the chopped flat glass fiber of being chopped, the glass fibre
Length is 1-5mm.
5. glass fiber reinforced halogen-free flame-retardant polypropylene resin composite as claimed in claim 1, its feature
Be, the halogen-free flame retardants be ammonium phosphate salt, APP class, organophosphor salt, phosphonic acid ester,
Phosphorous acid esters, phosphoric acid ester, phosphonium salts class, phosphorus heterocycle and its derivative species, cyanamide class, dicyandiamide class,
Melamine class, guanidinesalt class and its derivative, melamine polyphosphate class, Melamine Polyphosphate
Two kinds in class, phosphate and its derivative, red phosphorus, magnesium hydroxide, aluminium hydroxide, expansiveness graphite
Or two or more compoundings.
6. the glass fiber reinforced halogen-free flame-retardant polypropylene resin composite as described in claim 1 or 5, its
It is characterised by, the mass fraction of phosphorus is the 4-40% of halogen-free flame retardants in the halogen-free flame retardants, the Halogen resistance
The mass fraction for firing nitrogen in agent is the 0-20% of halogen-free flame retardants.
7. glass fiber reinforced halogen-free flame-retardant polypropylene resin composite as claimed in claim 1, its feature
It is, also including 0.1-20 parts by weight in the glass fiber reinforced halogen-free flame-retardant polypropylene resin composite
Synergistic flame retardant.
8. glass fiber reinforced halogen-free flame-retardant polypropylene resin composite as claimed in claim 7, its feature
Be, the synergistic flame retardant be montmorillonite, antimony oxide, magnesia, ammonium octamolybdate, Firebrake ZB,
At least one of piece barium borate, Nano-class zinc oxide, molybdenum oxide.
9. glass fiber reinforced halogen-free flame-retardant polypropylene resin composite as claimed in claim 1, its feature
It is, anti-dripping agent, antioxygen is also included in the glass fiber reinforced halogen-free flame-retardant polypropylene resin composite
At least one of agent, ultra-violet absorber, releasing agent, lubricant.
A kind of 10. glass fiber reinforced halogen-free flame-retardant acrylic resin products formed, it is characterised in that the glass
Glass fiber reinforcement halogen-free polypropylene flame redardant synthetic resin is as the glass described in any one in claim 1 to 9
Glass fiber reinforcement halogen-free polypropylene flame redardant resin combination is formed.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610422500.3A CN107513222A (en) | 2016-06-16 | 2016-06-16 | Glass fiber reinforced halogen-free flame-retardant polypropylene resin composite and its products formed |
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| CN201610422500.3A CN107513222A (en) | 2016-06-16 | 2016-06-16 | Glass fiber reinforced halogen-free flame-retardant polypropylene resin composite and its products formed |
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Cited By (2)
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| CN110819010A (en) * | 2019-11-14 | 2020-02-21 | 四川长虹电器股份有限公司 | Halogen-free flame-retardant polypropylene material with ultrahigh specific gravity and preparation method thereof |
| CN110964247A (en) * | 2019-11-21 | 2020-04-07 | 浙江大学宁波理工学院 | Halogen-free flame-retardant reinforced polypropylene and preparation method thereof |
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Cited By (3)
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|---|---|---|---|---|
| CN110819010A (en) * | 2019-11-14 | 2020-02-21 | 四川长虹电器股份有限公司 | Halogen-free flame-retardant polypropylene material with ultrahigh specific gravity and preparation method thereof |
| CN110964247A (en) * | 2019-11-21 | 2020-04-07 | 浙江大学宁波理工学院 | Halogen-free flame-retardant reinforced polypropylene and preparation method thereof |
| CN110964247B (en) * | 2019-11-21 | 2022-08-23 | 浙江大学宁波理工学院 | Halogen-free flame-retardant reinforced polypropylene and preparation method thereof |
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Application publication date: 20171226 |