CN109370043B - Low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing UL94-5VA and preparation method thereof - Google Patents
Low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing UL94-5VA and preparation method thereof Download PDFInfo
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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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- 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
- C08K3/18—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
- 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
- C08K2201/003—Additives being defined by their diameter
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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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- C—CHEMISTRY; METALLURGY
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention discloses a short glass fiber reinforced halogen-free flame-retardant polypropylene material with low cost and capable of passing UL94-5VA and a preparation method thereof. The chopped glass fiber reinforced halogen-free flame-retardant polypropylene material is prepared from the following raw materials in parts by mass: 40-70 parts of polypropylene; 5-30 parts of chopped glass fiber; 24-35 parts of a P-N intumescent flame retardant; 0.3-1 part of flame retardant synergist; 2-10 parts of a compatilizer; 0.3-0.5 part of a lubricant; 0.2-0.4 part of antioxidant; 0.1-0.2 part of emulsion anti-dripping agent. Meanwhile, the preparation method of the short glass fiber reinforced halogen-free flame retardant polypropylene material with low cost and capable of passing UL94-5VA is also disclosed. The polypropylene material prepared by the invention has the advantages of low cost, low density, high glow wire, stable molding shrinkage and high yield, and the flame retardance can reach UL-945 VA level.
Description
Technical Field
The invention relates to a short glass fiber reinforced halogen-free flame-retardant polypropylene material with low cost and capable of passing UL94-5VA and a preparation method thereof, belonging to the field of flame-retardant modified materials.
Background
The polypropylene has the characteristics of low cost and no moisture absorption, and has good electrical property, corrosion resistance, high insulating property and the like, so that the polypropylene becomes a favored substitute material in the household appliance industry. However, polypropylene materials are easy to burn and easily cause fire, and the size of the product is unstable due to large molding shrinkage. In particular, in recent years, the requirements of the new energy battery industry and the household appliance industry on the product size and the fire-proof grade are getting tighter and tighter, and the development of the flame-retardant polypropylene with high flame-retardant grade and low shrinkage is a future development trend, in particular to the glass fiber reinforced halogen-free flame-retardant polypropylene material. Compared with the traditional bromine-antimony system reinforced polypropylene, the halogen-free flame-retardant reinforced polypropylene is environment-friendly and low in density, and can replace partial flame-retardant ABS, flame-retardant PPO and other products in the future.
The existing halogen-free flame retardant polypropylene mainly uses an intumescent phosphorus-nitrogen flame retardant, which comprises an ammonium polyphosphate system and a piperazine pyrophosphate system, and the piperazine pyrophosphate system has higher temperature resistance, so the halogen-free flame retardant polypropylene is more suitable for producing glass fiber reinforced flame retardant polypropylene.
The halogen-free flame retardants adopted by the glass fiber reinforced halogen-free flame retardant polypropylene materials reported in CN106995559A and CN103827197A are expensive piperazine pyrophosphate flame retardants, and although the flame retardant grade can achieve 5VA, the material cost is high and even higher than that of the traditional flame retardant ABS, so that the popularization and application are difficult.
Because the shearing heat of the glass fiber can cause the decomposition of the ammonium polyphosphate, the flame retardant efficiency can be greatly reduced, and therefore, in a glass fiber reinforced flame retardant system, the ammonium polyphosphate is difficult to achieve the flame retardant 5VA grade, and no related literature report exists.
Disclosure of Invention
The invention aims to solve the technical problem of greatly improving the flame retardant efficiency of ammonium polyphosphate in a glass fiber reinforced system, thereby providing a short glass fiber reinforced halogen-free flame retardant polypropylene material which has low cost and can pass UL94-5VA and a preparation method thereof, and further widening the application of the glass fiber reinforced flame retardant polypropylene material in the new energy industry and the household appliance industry.
The technical scheme adopted by the invention is as follows:
the low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing through UL94-5VA is prepared from the following raw materials in parts by mass:
in the low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material which can pass through UL94-5VA, the melt index of polypropylene is more than or equal to 25g/10min at 230 ℃ and 2.16 kg.
In the low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing through UL94-5VA, the short glass fiber is alkali-free short glass fiber subjected to surface treatment by a silane coupling agent, the length is 2-4mm, and the diameter is 11-14 μm.
In the low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing UL94-5VA, the P-N intumescent flame retardant consists of ammonium polyphosphate and a carbon source.
In the low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing UL94-5VA, the flame-retardant synergist is at least one of active nano zinc oxide, 4A molecular sieve, zirconium phosphate, manganese phosphate, zinc borate, lanthanum oxide and colemanite.
In the low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material which can pass through UL94-5VA, the compatilizer is maleic anhydride grafted polypropylene.
In the low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material which can pass through UL94-5VA, the emulsion anti-dripping agent is an aqueous dispersion type anti-dripping agent.
In the low-cost chopped glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing through UL94-5VA, the lubricant is at least one of erucamide, oleamide, stearic acid, magnesium stearate, calcium stearate, zinc stearate, silicone powder, polyethylene wax and ethylene bisstearamide.
In the low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing through UL94-5VA, the antioxidant is at least one of antioxidants 168, 245, 626, 1010, 1075, 1076, 1098 and A330.
The preparation method of the low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing through UL94-5VA comprises the following steps:
1) weighing the raw materials according to the composition;
2) the preparation method comprises the following steps of preparing by adopting a double-screw extruder with double-stage side feeding: uniformly mixing polypropylene, a compatilizer, an antioxidant, a lubricant and an emulsion anti-dripping agent, and putting into a main feeding port; uniformly mixing the P-N intumescent flame retardant and the flame retardant synergist, and putting the mixture into a first-stage feeding port; putting the chopped glass fiber into a second-stage side feeding port; extruding the materials by a double-screw extruder, and granulating to obtain the short glass fiber reinforced halogen-free flame-retardant polypropylene material with low cost and capable of passing UL94-5 VA.
In the preparation method, the double-screw extruder is designed with a screw combination of a shearing block and a toothed disc.
The invention has the beneficial effects that:
the polypropylene material prepared by the invention has the advantages of low cost, low density, high glow wire, stable molding shrinkage and high yield, and the flame retardance can reach UL-945 VA level.
The method comprises the following specific steps:
1. the ammonium polyphosphate with low cost is adopted as a flame retardant to replace the traditional expensive piperazine pyrophosphate flame retardant, the flame retardant grade can reach 5VA, and the cost is reduced by 6000-9000 yuan/ton.
2. In order to achieve the purposes, the material is improved from three aspects of raw material formula, machine equipment and screw combination:
from the raw material formula, the synergist nano zinc oxide and the emulsion type anti-dripping agent are adopted, and the short glass fiber is adopted for reinforcement. The nano zinc oxide accelerates the carbon formation of the flame retardant, and the flame retardant efficiency is greatly improved; compared with the traditional powder anti-dripping agent, the emulsion anti-dripping agent has excellent dispersion performance, the addition amount of 0.1 percent can ensure that a sample strip does not drip in a 5VA test, and the sample strip cannot break due to expansion during processing, so that the production efficiency is greatly improved. Compared with continuous long glass fibers, the short glass fibers have the length of about 2-4mm, the glass fibers are chopped without strong shearing of screws, and the glass fibers can be dispersed only by the combination of the strongly dispersed screws, so that the shearing heat generated by the short glass fibers is smaller, and the flame retardant ammonium polyphosphate is not decomposed to reduce the flame retardant efficiency.
The production equipment is also greatly improved. The traditional short glass fiber reinforced flame retardant material adopts a first-order side feeding mode, namely, the flame retardant is fed with polypropylene and an auxiliary agent from the main side, and the short glass fiber is fed from the side, so that the traditional decabromodiphenylethane system has low processing efficiency, but the decabromodiphenylethane has high temperature resistance and cannot be decomposed, and the flame retardant efficiency cannot be reduced. In the case of a halogen-free system, the flame retardant enters the screw too early, so that the shearing action time of the screw is long, the flame retardant efficiency is reduced if the screw is light, the color is yellow, and the flame retardant is completely decomposed if the screw is heavy, so that the production cannot be carried out. Aiming at the defect, the invention designs double-stage side feeding, the flame retardant is fed from the fifth area, and the glass fiber is fed from the seventh area, thereby not only ensuring the flame retardant efficiency of the flame retardant, but also keeping the length of the glass fiber, and greatly improving the comprehensive performance and the production efficiency of finished particles.
After the raw material formula and processing equipment are optimized, a key effect of UL 945 VA and screw combination cannot be achieved by an ammonium polyphosphate system, the screw combination must be suitable for the system, the combination is weak, glass fibers cannot be dispersed, strip breakage is serious during grain extraction, the combination is strong, the flame retardant efficiency is greatly reduced, and the grade of 5VA cannot be achieved. Therefore, the toothed disc and the shearing block are combined together, the dispersion of the glass fibers is improved by utilizing the toothed disc, and meanwhile, the flame retardant is not decomposed, so that the halogen-free flame retardant glass fiber reinforced flame retardant system is more suitable.
Detailed Description
The low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing through UL94-5VA is prepared from the following raw materials in parts by mass:
preferably, in the low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing through UL94-5VA, the melt index of polypropylene is more than or equal to 25g/10min at 230 ℃ and 2.16 kg; it is further preferred that the polypropylene has a melt index of 25g/10min to 100g/10min at 230 ℃ and 2.16 kg.
Preferably, in the low-cost chopped glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing through UL94-5VA, the chopped glass fiber is alkali-free chopped glass fiber subjected to surface treatment by a silane coupling agent, the length of the chopped glass fiber is 2-4mm, and the diameter of the chopped glass fiber is 11-14 μm.
Preferably, in the low-cost chopped glass fiber reinforced halogen-free flame retardant polypropylene material capable of passing UL94-5VA, the P-N intumescent flame retardant consists of ammonium polyphosphate (APP) and a carbon source; further, in the P-N intumescent flame retardant, the mass ratio of ammonium polyphosphate to a carbon source is (3-5): 1.
more preferably, in the P-N intumescent flame retardant, the carbon source is a triazine charring agent.
Furthermore, in the P-N intumescent flame retardant, the mass content of P is 18-22%, and the mass content of N is 17-19%; still more preferably, in the P-N intumescent flame retardant, the mass content of P is 20% and the mass content of N is 18%.
Compared with a piperazine pyrophosphate system, the P-N intumescent flame retardant used in the invention has a price of 20-30 yuan/Kg, and the addition amount of the flame retardant in a 5VA product is 30%, so compared with the above, the cost of one ton of glass fiber reinforced flame retardant polypropylene material can be reduced by 6000-9000 yuan, and the price advantage is very obvious.
Preferably, in the low-cost chopped glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing UL94-5VA, the flame-retardant synergist is at least one of active nano zinc oxide, 4A molecular sieve, zirconium phosphate, manganese phosphate, zinc borate, lanthanum oxide and colemanite; further preferably, the flame retardant synergist is active nano zinc oxide, the effective content of the nano zinc oxide in the active nano zinc oxide can reach 99.5%, and the carbon forming efficiency of the flame retardant can be improved.
Preferably, in the low-cost glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing through UL94-5VA, the compatilizer is maleic anhydride grafted polypropylene (PP-g-MAH); further, the grafting rate of the maleic anhydride grafted polypropylene is 1.4-1.6%, and the preferred grafting rate is 1.5%; the melt index of the maleic anhydride grafted polypropylene is more than or equal to 100g/10min at 190 ℃ and 2.16 kg. The high grafting ratio can reduce the addition amount of the compatilizer, reduce the odor of the material and greatly improve the aging performance of the material.
Preferably, in the low-cost chopped glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing UL94-5VA, the emulsion-shaped anti-dripping agent is an aqueous dispersion type anti-dripping agent; further, the emulsion-like anti-dripping agent is a PTFE aqueous dispersion type anti-dripping agent, and the specific type can be selected from INOFLON AD 9300. Compared with the common powdery anti-dripping agent, the aqueous dispersion type anti-dripping agent has very good dispersibility and processing performance, can not cause agglomeration and expansion to cause strip breakage during grain extraction, and can meet the requirement that a sample strip does not drip in a UL-945 VA test by 0.1wt percent of addition amount.
Preferably, in the low-cost chopped glass fiber reinforced halogen-free flame retardant polypropylene material capable of passing UL94-5VA, the lubricant is at least one of erucamide, oleamide, stearic acid, magnesium stearate, calcium stearate, zinc stearate, silicone powder, polyethylene wax and ethylene bis stearamide; more preferably, the lubricant is at least one of magnesium stearate, calcium stearate, silicone powder, polyethylene wax and ethylene bis stearamide; still more preferably, the lubricant is at least one of calcium stearate, polyethylene wax and ethylene bis stearamide.
Preferably, in the low-cost chopped glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing UL94-5VA, the antioxidant is at least one of antioxidant 168, 245, 626, 1010, 1075, 1076, 1098 and A330; more preferably, the antioxidant is at least one of antioxidants 168, 626, 1010 and 1075.
The preparation method of the low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing through UL94-5VA comprises the following steps:
1) weighing the raw materials according to the composition;
2) the preparation method comprises the following steps of preparing by adopting a double-screw extruder with double-stage side feeding: uniformly mixing polypropylene, a compatilizer, an antioxidant, a lubricant and an emulsion anti-dripping agent, and putting into a main feeding port; uniformly mixing the P-N intumescent flame retardant and the flame retardant synergist, and putting the mixture into a first-stage feeding port; putting the chopped glass fiber into a second-stage side feeding port; extruding the materials by a double-screw extruder, and granulating to obtain the short glass fiber reinforced halogen-free flame-retardant polypropylene material with low cost and capable of passing UL94-5 VA.
Preferably, in the preparation method, the length-diameter ratio of the double-screw extruder is 48: 1, divided into 12 segments.
Preferably, in the preparation method, the 5 th stage of the double-screw extruder is provided with a first stage side feeding port, and the 7 th stage is provided with a second stage side feeding port. The first-stage side feeding of the flame retardant and the flame-retardant synergist and the second-stage side feeding of the short glass fiber have the advantage of avoiding the flame retardant from being decomposed due to the shearing of a screw rod too early, thereby keeping the flame-retardant efficiency of the flame retardant to the maximum extent.
Preferably, in the preparation method, the 4 th section of the double-screw extruder is provided with a natural exhaust port, and the 11 th section of the double-screw extruder is provided with a vacuum exhaust port.
Preferably, in the preparation method, the processing vacuum degree of the double-screw extruder is more than or equal to 0.08MPa, and the rotating speed of the screw is controlled to be 300r/min to 400 r/min.
Preferably, in the preparation method, the double-screw extruder is designed with a screw combination of the shearing block and the toothed disc; further explanation is as follows: the screw combination is designed with weak shearing and strong dispersion, so that the uniform dispersion of the glass fibers and the flame retardant is ensured, the high flame retardant efficiency of the flame retardant is also maintained, the dispersion of the flame retardant mainly takes the thin shear block as the main part, and the dispersion of the glass fibers mainly takes the tooth-shaped disc as the main part. For example, take 75 machines as an example: the screw combination design from the 5 th zone to the vacuum port is as follows: 96/96, 96/96, 96/96, 72/72, 72/72, 56/56, 45 °/5/36, 45 °/5/36, 96/96, 96/96, 96/96, 72/72, 72/72, 72/72, 56/56, 56/56, 45 °/5/36, 8/8, 18/18, 18/18, 18/18, 8/8, 72/72, 56/56, 45 °/5/36, 8/8, 18/18, 18/18, 18/18, 8/8, 56/56, 56/56, 56/56, 56/28L; wherein 96/96, 72/72 and 56/56 are forward conveying blocks, 56/28L is a reverse conveying block, 45 DEG/5/36 is a forward shearing block, 8/8 is a transition block, and 18/18 is a tooth-shaped disc.
The present invention will be described in further detail with reference to specific examples. These examples are merely representative descriptions of the present invention, but the present invention is not limited thereto.
The starting materials used in the following examples are illustrated below: the antioxidant is prepared by mixing a Pasteur antioxidant 1010 and a Pasteur antioxidant 168 according to a mass ratio of 2: 1; the lubricant is PE wax, and the specific model is Bunni BN 500; the PP raw material is EP548R produced by Zhonghai shell brand; ammonium polyphosphate and triazine charring agents are all produced by Puseofur chemical Co. All others are, unless otherwise specified, commercially available starting materials.
Example 1 (10% glass fiber reinforced flame retardant polypropylene):
(1) the raw material ratio is as follows: the short glass fiber reinforced halogen-free flame-retardant polypropylene material with low cost and capable of passing through UL-945 VA comprises the following raw material components in parts by mass: 60.7 parts of polypropylene EP548R, 21.7 parts of ammonium polyphosphate, 4.3 parts of a char forming agent, 0.5 part of nano zinc oxide, 10 parts of alkali-free short glass fiber, 2 parts of PP-g-MAH, 0.3 part of an antioxidant, 0.3 part of a lubricant and 0.2 part of an emulsion type anti-dripping agent.
(2) The preparation method comprises the following steps: feeding 60.7 parts of EP548R, 2 parts of PP-g-MAH, 0.3 part of antioxidant, 0.3 part of lubricant and 0.2 part of emulsion anti-dripping agent from a main feed after uniformly stirring; uniformly stirring 21.7 parts of ammonium polyphosphate, 4.3 parts of charring agent and 0.5 part of nano zinc oxide, and feeding from a first-stage side feed; feeding 10 parts of short glass fiber from the second-stage side, and performing twin-screw extrusion granulation to obtain finished particles, wherein the rotating speed of a screw is 350r/min, the processing temperature is 190-.
(3) Screw combination: taking a 75 machine as an example, the screw combination from the first stage side feeding (zone 5) to the vacuum port (zone 11) is as follows: 96/96, 96/96, 96/96, 72/72, 72/72, 56/56, 45 °/5/36, 45 °/5/36, 96/96, 96/96, 96/96, 72/72, 72/72, 72/72, 56/56, 56/56, 45 °/5/36, 45 °/5/36, 72/72, 72/72, 45 °/5/36, 8/8, 18/18, 18/18, 18/18, 8/8, 56/56, 56/56, 56/56, 56/28L. Wherein 96/96, 72/72 and 56/56 are forward conveying blocks, 56/28L is a reverse conveying block, 45 DEG/5/36 is a forward shearing block, 8/8 is a transition block, and 18/18 is a tooth-shaped disc.
Example 2 (15% glass fiber reinforced flame retardant polypropylene):
(1) the raw material ratio is as follows: the short glass fiber reinforced halogen-free flame-retardant polypropylene material with low cost and capable of passing through UL-945 VA comprises the following raw material components in parts by mass: 52.1 parts of polypropylene EP548R, 23.2 parts of ammonium polyphosphate, 5.8 parts of a char forming agent, 0.7 part of nano zinc oxide, 15 parts of alkali-free short glass fiber, 2.5 parts of PP-g-MAH, 0.3 part of an antioxidant, 0.3 part of a lubricant and 0.1 part of an emulsion type anti-dripping agent.
(2) The preparation method comprises the following steps: uniformly stirring 52.1 parts of EP548R, 2.5 parts of PP-g-MAH, 0.3 part of antioxidant, 0.3 part of lubricant and 0.1 part of emulsion anti-dripping agent, and feeding from a main feed; uniformly stirring 23.2 parts of ammonium polyphosphate, 5.8 parts of charring agent and 0.7 part of nano zinc oxide, and feeding from a first-stage side feed; feeding 15 parts of short glass fiber from the second-stage side, and performing twin-screw extrusion granulation to obtain finished particles, wherein the rotating speed of a screw is 350r/min, the processing temperature is 190-.
(3) Screw combination: taking a 75 machine as an example, the screw combination from the first stage side feeding (zone 5) to the vacuum port (zone 11) is as follows: 96/96, 96/96, 96/96, 72/72, 72/72, 56/56, 45 °/5/36, 45 °/5/36, 96/96, 96/96, 96/96, 72/72, 72/72, 72/72, 56/56, 56/56, 45 °/5/36, 8/8, 18/18, 18/18, 18/18, 8/8, 72/72, 56/56, 45 °/5/36, 8/8, 18/18, 18/18, 18/18, 8/8, 56/56, 56/56, 56/56, 56/28L. Wherein 96/96, 72/72 and 56/56 are forward conveying blocks, 56/28L is a reverse conveying block, 45 DEG/5/36 is a forward shearing block, 8/8 is a transition block, and 18/18 is a tooth-shaped disc. Compared with the embodiment 1, the content of the glass fiber and the flame retardant are increased, and the set of toothed discs are added on the design of the screw, so that the dispersion of the flame retardant and the glass fiber is enhanced, and the problem of strip breakage during production can be effectively solved.
Example 3 (25% glass fiber reinforced flame retardant polypropylene):
(1) the raw material ratio is as follows: the short glass fiber reinforced halogen-free flame-retardant polypropylene material with low cost and capable of passing through UL-945 VA comprises the following raw material components in parts by mass: 40.5 parts of polypropylene EP548R, 24 parts of ammonium polyphosphate, 6 parts of carbon forming agent, 0.8 part of nano zinc oxide, 25 parts of alkali-free short glass fiber, 3 parts of PP-g-MAH, 0.3 part of antioxidant, 0.3 part of lubricant and 0.1 part of emulsion type anti-dripping agent.
(2) The preparation method comprises the following steps: feeding 40.5 parts of EP548R, 3 parts of PP-g-MAH, 0.3 part of antioxidant, 0.3 part of lubricant and 0.1 part of emulsion anti-dripping agent from a main feed after uniformly stirring; uniformly stirring 24 parts of ammonium polyphosphate, 6 parts of charring agent and 0.8 part of nano zinc oxide, and feeding from a first-stage side feed; feeding 25 parts of short glass fiber from the second-stage side, and performing twin-screw extrusion granulation to obtain finished particles, wherein the rotating speed of a screw is 350r/min, the processing temperature is 190-.
(3) Screw combination: taking a 75 machine as an example, the screw combination from the first stage side feeding (zone 5) to the vacuum port (zone 11) is as follows: 96/96, 96/96, 96/96, 72/72, 72/72, 56/56, 45 °/5/36, 45 °/5/36, 96/96, 96/96, 96/96, 72/72, 72/72, 72/72, 56/56, 56/56, 45 °/5/36, 8/8, 18/18, 18/18, 18/18, 8/8, 45 °/5/36, 45 °/5/36L, 56/56, 56/56, 56/56, 56/56, 8/8, 18/18, 18/18, 18/18, 8/8, 56/28L. Wherein 96/96, 72/72 and 56/56 are forward conveying blocks, 56/28L is a reverse conveying block, 45 °/5/36 is a forward cutting block, 45 °/5/36L is a reverse cutting block, 8/8 is a transition block, and 18/18 is a tooth-shaped disc. Compared with the embodiment 2, the content of the glass fiber is increased to 25%, in order to strengthen the distribution of the glass fiber, a reverse shearing block of 45 degrees/5/36L is added behind the first set of toothed discs, and simultaneously, the second set of toothed discs are moved towards the direction of a vacuum port and matched with a reverse conveying block of 56/28L, so that the glass fiber is better dispersed.
Comparative example 1:
the process differs from example 1 in that conventional zinc oxide is used in the formulation and the particle size (D50) is only 10 μm. Comparative example 2:
the only difference between the process and example 1 is that the anti-drip agent used is a powdered anti-drip agent.
Comparative example 3:
the only difference between the process and example 1 is that the glass fibers used are continuous long glass fibers, which are fed from the first vent (zone 4).
Comparative example 4:
the only difference between the process and example 1 is that the first order side feed production is used and both the flame retardant and the polypropylene are fed from the main feed.
Comparative example 5:
the main difference between the method and the embodiment 2 is that the screw combination does not use a toothed disc, a forward shear block is used for enhancing dispersion, and the screw combination from the fifth area to the vacuum port is as follows: 96/96, 96/96, 96/96, 72/72, 72/72, 56/56, 45 °/5/36, 45 °/5/36, 96/96, 96/96, 96/96, 72/72, 72/72, 72/72, 56/56, 56/56, 45 °/5/36, 45 °/5/36, 72/72, 72/72, 45 °/5/36, 45 °/5/56, 56/56, 56/56, 56/56, 56/28L, the design of the combination is mainly focused on protecting the flame retardant from decomposition, with moderate shear, but weak dispersion.
Comparative example 6:
the main difference between the method and the embodiment 2 is that a screw combination does not use a toothed disc, a forward shearing block and a reverse conveying block are used for enhancing dispersion, and the screw combination from the fifth area to a vacuum port is as follows: 96/96, 96/96, 96/96, 72/72, 72/72, 56/56, 45 °/5/36, 45 °/5/36, 96/96, 96/96, 96/96, 72/72, 72/72, 72/72, 56/56, 45 °/5/56, 45 °/5/36, 56/28L, 72/72, 72/72, 45 °/5/56, 45 °/5/56, 45 °/5/36, 56/56, 56/56 and 56/28L, and the combination is mainly designed to emphasize dispersion of glass fibers and has stronger shearing.
Table 1 shows the performance test results of the polypropylene materials of examples 1-3 and comparative examples 1-6.
The detection methods of the test items in table 1 are described below:
5VA flame retardant test: testing according to the detection standard of UL-94;
tensile strength: testing according to ASTM D638;
bending property: testing was performed according to ASTM D790;
glow wire test: the test was carried out according to IEC 60695-2-13 standard.
TABLE 1 comparison of the Main Properties of the examples with those of the comparative examples
The above tests are combined to show that all the examples meet the requirement of 5 VA.
The results of comparative example 1 show that nano-zinc oxide must be selected to exert synergistic effect, and the flame retardant level can reach 5VA level.
The results of comparative example 2 show that although the conventional powder type anti-dripping agent can achieve the anti-dripping effect and the flame retardant level can reach 5VA level, the strip breakage phenomenon in production is serious and the production efficiency is low.
Comparative example 3 in the production process, because continuous long glass fiber can be normally granulated only by screw shearing, a large amount of shearing heat can be brought, the ammonium polyphosphate can be decomposed, the flame retardant efficiency is rapidly reduced to UL94V2 level, and meanwhile, the particles are yellowed, foamed and seriously broken in the production process.
The results of comparative example 4 show that the flame retardant and the polypropylene are fed together from the main feed, the flame retardant grade can only reach V0 grade, and the flame retardant is frequently broken during production, mainly because the time of the flame retardant passing through the screw extruder is prolonged due to the feeding of the flame retardant from the main feed, and the flame retardant efficiency is greatly reduced due to the shearing action of the glass fibers, and meanwhile, the main feed is fed with the flame retardant and the polypropylene simultaneously, so that the blanking of the main feed is unstable, the pressure of a machine head is unstable, and finally the phenomenon of broken strips occurs in the production process.
The results of comparative example 5 show that the toothed discs are replaced by the shear blocks of 45 °/5/36 and 45 °/5/56, and although the shear is enhanced, the glass fiber dispersion effect is poor due to the lack of the toothed discs, so that the production process is unstable and the strip breaking phenomenon is serious. Meanwhile, the shearing strength of the shearing block is much stronger than that of the tooth-shaped disc, and the flame retardant grade can only reach V0 grade.
Comparative example 6 is for solving the production disconnected strip problem, for letting the fine dispersion of glass, has increased reverse transportation piece 56/28L, and the purpose is firstly for the fine broken glass of better shearing, secondly strengthens the fine dispersion of glass, but final effect is not good, because strong shearing can let glass fine dispersion better, but fire retardant ammonium polyphosphate is not temperature resistant, leads to the fire retardant just foaming decomposition in process of production, can not take out the grain production smoothly.
The above detailed description of the present invention is only a preferred embodiment of the present invention, and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the protection and coverage of the present invention.
Claims (6)
1. A low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing UL94-5VA is characterized in that: the composite material is prepared from the following raw materials in parts by mass:
the chopped glass fiber is alkali-free short glass fiber subjected to surface treatment by a silane coupling agent, the length of the chopped glass fiber is 2-4mm, and the diameter of the chopped glass fiber is 11-14 mu m;
the P-N intumescent flame retardant consists of ammonium polyphosphate and a carbon source;
the flame retardant synergist is active nano zinc oxide;
the preparation method of the low-cost short glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing UL94-5VA comprises the following steps:
1) weighing raw materials according to the composition of the short glass fiber reinforced halogen-free flame-retardant polypropylene material with low cost and capable of passing UL94-5 VA;
2) the preparation method comprises the following steps of preparing by adopting a double-screw extruder with double-stage side feeding: uniformly mixing polypropylene, a compatilizer, an antioxidant, a lubricant and an emulsion anti-dripping agent, and putting into a main feeding port; uniformly mixing the P-N intumescent flame retardant and the flame retardant synergist, and putting the mixture into a first-stage feeding port; putting the chopped glass fiber into a second-stage side feeding port; extruding the materials by a double-screw extruder, and granulating to obtain the short glass fiber reinforced halogen-free flame-retardant polypropylene material with low cost capable of passing UL94-5 VA;
the twin-screw extruder is designed with a screw combination of a shear block and a toothed disc.
2. The low-cost chopped glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing UL94-5VA of claim 1, wherein: the melt index of the polypropylene is more than or equal to 25g/10min at 230 ℃ and 2.16 kg.
3. The low-cost chopped glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing UL94-5VA of claim 1, wherein: the compatilizer is maleic anhydride grafted polypropylene.
4. The low-cost chopped glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing UL94-5VA of claim 1, wherein: the emulsion-like anti-dripping agent is an aqueous dispersion type anti-dripping agent.
5. The low-cost chopped glass fiber reinforced halogen-free flame-retardant polypropylene material capable of passing UL94-5VA of claim 1, wherein: the lubricant is at least one of erucamide, oleamide, stearic acid, magnesium stearate, calcium stearate, zinc stearate, silicone powder, polyethylene wax and ethylene bisstearamide; the antioxidant is at least one of antioxidants 168, 245, 626, 1010, 1075, 1076, 1098 and A330.
6. A preparation method of a short glass fiber reinforced halogen-free flame retardant polypropylene material with low cost capable of passing UL94-5VA is characterized by comprising the following steps: the method comprises the following steps:
1) weighing raw materials according to the composition of any one of claims 1 to 5;
2) the preparation method comprises the following steps of preparing by adopting a double-screw extruder with double-stage side feeding: uniformly mixing polypropylene, a compatilizer, an antioxidant, a lubricant and an emulsion anti-dripping agent, and putting into a main feeding port; uniformly mixing the P-N intumescent flame retardant and the flame retardant synergist, and putting the mixture into a first-stage feeding port; putting the chopped glass fiber into a second-stage side feeding port; extruding the materials by a double-screw extruder, and granulating to obtain the short glass fiber reinforced halogen-free flame-retardant polypropylene material with low cost capable of passing UL94-5 VA;
the twin-screw extruder is designed with a screw combination of a shear block and a toothed disc.
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| CN110079009B (en) * | 2019-04-03 | 2021-08-17 | 广东聚石化学股份有限公司 | Halogen-free flame-retardant polypropylene composite material with ultrahigh fluidity and preparation method thereof |
| CN111484670A (en) * | 2019-12-20 | 2020-08-04 | 四川鑫达企业集团有限公司 | Halogen-free flame-retardant low-floating-fiber reinforced polypropylene composite material and preparation method thereof |
| CN110982177A (en) * | 2019-12-25 | 2020-04-10 | 苏州和塑美科技有限公司 | Flame-retardant heat-conducting nano composite material and preparation method and application thereof |
| CN113773647A (en) * | 2021-09-30 | 2021-12-10 | 盐城市科恒达材料有限公司 | Cable flame-retardant fire-resistant base material and preparation process thereof |
| CN114213758A (en) * | 2021-12-30 | 2022-03-22 | 苏州禾昌聚合材料股份有限公司 | Engineering plastic material with special functional groups and preparation method thereof |
| CN115505207B (en) * | 2022-09-29 | 2023-11-10 | 宁波公牛光电科技有限公司 | Short glass fiber reinforced flame-retardant polypropylene material, application and preparation method |
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