CN102643478A - Halogen-free flame-retarding long glass fiber reinforced polypropylene material and preparation method thereof - Google Patents

Abstract

The invention discloses a halogen-free flame-retardant long glass fiber reinforced polypropylene material and a preparation method thereof. The halogen-free flame-retardant ordinary glass fiber reinforced polypropylene material consists of 49-88.8wt% polypropylene, 0.1-0.5wt% heat stabilizer, 0.1-0.5wt% processing aid, 5-20wt% halogen-free flame retardant, The compatibilizer consists of 1-5wt% and long glass fiber 5-25wt%. The preparation method is as follows: a part of polypropylene and compatibilizer are plasticized by a single-screw extruder and then transported to a high-temperature melt tank; the remaining polypropylene, heat stabilizer, processing aid, and halogen-free flame retardant are After being plasticized by the extruder, it is transported to the low-temperature melt tank; the long glass fibers are sequentially input into the above-mentioned high-temperature melt tank and low-temperature melt tank, and then dragged and infiltrated, and pelletized. The invention has ultra-high fluidity, excellent flame retardant effect, high mechanical strength, low shrinkage rate, high dimensional stability, creep resistance and good thermo-oxidative aging performance.

Description

A kind of halogen-free flame-retardant long glass fiber reinforced polypropylene material and preparation method thereof

technical field

The invention relates to a halogen-free flame-retardant long glass fiber reinforced polypropylene material and a preparation method thereof, which belong to the field of polymer materials and their molding and processing.

Background technique

The main function of the lower guard plate of the engine is to protect the engine oil pan and related parts from the impact and bump of gravel. The requirements for impact performance are very high. Performance has certain requirements. Traditionally, they are made of metal sheet materials. However, the metal material has a high density, the parts weigh up to 10 kg, and the processing technology is cumbersome, the degree of design freedom is seriously insufficient, the degree of manufacturing integration is low, and it does not meet the modular requirements of automotive parts. There will be noise.

With the development of the automobile industry, long glass fiber reinforced polypropylene has gradually replaced SMC, BMC, GMT and metal materials in the engine bottom guard due to its excellent creep resistance, dynamic fatigue resistance, high rigidity and advantages of one-step injection molding production, but the engine bottom guard plate has higher and higher requirements for flame retardant grades. For example, the C4 grade in the Shenlong D45 1333 standard stipulates the requirements for automatic extinguishing, and with the development of the world's environmental protection industry, flame retardants have been halogen-free It is the general trend.

At present, the halogen-free flame retardant of long-wave fiber polypropylene mainly uses long-wave fiber polypropylene masterbatch and halogen-free flame retardant masterbatch for simple blending. Uneven distribution, resulting in uneven flame retardant properties. Therefore, it is imperative to develop a uniform long-wave fiber polypropylene material that integrates functionality and flame retardancy.

Contents of the invention

The object of the present invention is to provide a polymer material for engine bottom guard plate and its preparation method, so as to overcome the defects in the prior art and meet the needs of the development of automobile engine bottom guard plate materials.

In order to achieve the above object, the present invention provides a halogen-free flame-retardant long glass fiber reinforced polypropylene material, which is characterized in that it consists of the following components in weight percentage:

Polypropylene 49-88.8%;

Heat stabilizer 0.1-0.5%;

Processing aids 0.1-0.5%;

Halogen-free flame retardant 5-20%;

Compatibilizer 1-5%;

Long glass fibers 5-25%.

Preferably, the melt flow rate of the polypropylene is 50-1000 g/10 min.

Preferably, the heat stabilizer is any one or a mixture of phenols, amines, phosphites, semi-hindered phenols, complexes of acryloyl functional groups and thioesters, and calixarene .

Preferably, the processing aid is any one or a mixture of low molecular weight esters, metal soaps, stearic acid complex esters and amides.

Preferably, the halogen-free flame retardant is a phosphorus-nitrogen halogen-free environment-friendly intumescent flame retardant.

Preferably, the compatibilizer is a polar monomer graft polymer, and its polymer matrix is polyethylene, polypropylene, ethylene-α-ethylene-octene copolymer, copolymer of styrene and butadiene , polyethylene-polystyrene-polypropylene terpolymer, ethylene-propylene-butadiene terpolymer, ethylene-acrylate copolymer and ethylene-acrylate-glycidyl methacrylate copolymer A mixture of one or two, the polar monomer is any one or a mixture of maleic anhydride and its analogs and acrylic acid and its ester derivatives.

Preferably, the long glass fibers are alkali-free continuous glass fibers.

The present invention also provides a preparation method for the above-mentioned halogen-free flame-retardant long glass fiber reinforced polypropylene material, which is characterized in that the specific steps are as follows:

Step 1: Plasticize 4-40% by weight of polypropylene and compatibilizer through a single-screw extruder, then transport it to a high-temperature melt tank through a die, and the temperature in the tank is 280-380°C;

Step 2: Plasticize the remaining polypropylene, heat stabilizer, processing aid, and halogen-free flame retardant through a single-screw extruder, then transport it to a low-temperature melt tank through a die, and the temperature in the tank is 180-220°C;

Step 3: Input the long glass fibers into the high-temperature melt tank in the first step and the low-temperature melt tank in the second step in sequence at a speed of 20-100m/min, then drag and infiltrate, and then pelletize.

Preferably, the lengths of the high temperature melt tank and the low temperature melt tank are 1-4m.

Further, the length of the high-temperature melt tank is 2 m, and the length of the low-temperature melt tank is 1 m.

The raw material of the present invention adopts polypropylene resin with ultra-high melt flow rate, which is suitable for injection molding thin-walled large-scale auto parts products. At the same time, because the material uses a halogen-free phosphorus-nitrogen series expansion flame retardant, it meets the requirements of Rochs regulations and is New environmentally friendly materials, you can rest assured to make export products. In addition, the function of the heat stabilizer in the present invention is to inhibit the degradation during processing; the function of the processing aid is to improve its processing performance; the function of the compatibilizer is to increase the compatibility between the glass fiber and the polymer matrix.

The invention solves the disadvantages of easy delamination and unstable flame retardancy of traditional color-mixed products by improving the existing manufacturing process. Therefore, the material provided by the present invention has ultra-high fluidity, excellent flame retardant effect, high mechanical strength, low shrinkage rate, high dimensional stability, creep resistance and good thermo-oxidative aging performance, which meets the requirements of engine lower guard plate products. The design requirements of high-temperature rigidity, gravel impact toughness and flatness have realized the application of halogen-free flame-retardant long glass fiber reinforced polypropylene materials on thin-walled large flat parts in high-temperature installation environments. After testing, the helical flow length of the material provided by the invention is ≥1000mm, the flame retardant performance can reach the C4 (automatic extinguishing) flame retardant grade of Shenlong Automobile D45 1333, the tensile strength is ≥100MPa, the flexural modulus is ≥6500MPa, and the notched impact strength is ≥ 35KJ/m ² , heat distortion temperature ≥ 150°C, tensile strength retention rate ≥ 90% after thermo-oxidative aging (150°C, 1000hr).

Detailed ways

The present invention is further illustrated below by way of examples.

Example 1

The first step: 4 kg of polypropylene with a melt flow rate of 50 g/10 min and 1 kg of compatibilizer (CA-100, ExxonMobil) are plasticized by a single-screw extruder and then transported to a high-temperature melt through a die. Body tank, the temperature in the tank is set at 320°C;

The second step: 84.8 kg of polypropylene with a melt flow rate of 50g/10min, 0.1 kg of heat stabilizer (Irganox1010, CIBA company), 0.1 kg of processing aid (EB-FF, Japan Kao), 5 kg of halogen-free resistor The fuel (FP-2200, manufacturer) is plasticized by the single-screw extruder and transported to the low-temperature melt tank through the die, and the temperature in the tank is set at 185°C;

Step 3: Pass 5 kg of alkali-free continuous glass fibers through the high-temperature melt tank in the first step and the low-temperature melt tank in the second step in sequence at a speed of 25mm/min, and the long glass fibers are drawn and infiltrated from the melt tank Finally, cut into 12 mm long uniform particles with a pelletizer. The length of the high-temperature melt tank is 2m, and the length of the low-temperature melt tank is 1m.

Test its performance according to the corresponding standards, the list is as follows:

performance unit standard test Test Results Flame retardant performance / D45 1333 C4 (automatically extinguish) Spiral flow length mm / 1100 HDT(1.80MPa) ℃ ISO75/1-93 155 Tensile Strength MPa ISO527/2-93 102 Flexural modulus MPa ISO178/2-93 6800 Notched impact strength KJ/ ^m2 ISO179/2-93 38 Tensile Strength Retention (150℃, 1000hr) % ISO527/2-93 92

Example 2

Step 1: Plasticize 8 kg of polypropylene with a melt flow rate of 100g/10min and 2 kg of compatibilizer (Bondyram1001) through a single-screw extruder, then transport them to a high-temperature melt tank through a die, and set the temperature in the tank at 350°C;

The second step: 69.6 kg of polypropylene with a melt flow rate of 100g/10min, 0.2 kg of heat stabilizer (Irganox 1010, CIBA company), 0.2 kg of processing aid (EB-FF, Japan Kao), 10 kg of halogen-free The flame retardant FP-2200 is plasticized by the single-screw extruder and then transported to the low-temperature melt tank through the die, and the temperature in the tank is set at 190°C;

Step 3: Pass 10 kg of alkali-free continuous glass fibers through the high-temperature melt tank in the first step and the low-temperature melt tank in the second step in sequence at a speed of 40mm/min. After the long glass fibers are pulled and infiltrated from the melt tank , Cut into 12mm long uniform particles with a special granulator. The length of the high-temperature melt tank is 2m, and the length of the low-temperature melt tank is 1m.

Test its performance according to the corresponding standards, the list is as follows:

performance unit standard test Test Results Flame retardant performance / D45 1333 C4 (automatically extinguish) Spiral flow length mm / 1200 HDT(1.80MPa) ℃ ISO75/1-93 156 Tensile Strength MPa ISO527/2-93 105 Flexural modulus MPa ISO178/2-93 6700 Notched impact strength KJ/ ^m2 ISO179/2-93 39 Tensile Strength Retention (150℃, 1000hr) % ISO527/2-93 95

Example 3

Step 1: Plasticize 12kg of polypropylene with a melt flow rate of 180g/10min and 3kg of compatibilizer (Bondyram1001) through a single-screw extruder and transport them to a high-temperature melt tank through a die. The temperature in the tank is set at 360°C;

The second step: 54.4 kg of polypropylene with a melt flow rate of 180g/10min, 0.3 kg of heat stabilizer (Irganox 1010, CIBA company), 0.3 kg of processing aid (EB-FF, Japan Kao), 15 kg of halogen-free The flame retardant FP-2200 is plasticized by the single-screw extruder and then transported to the low-temperature melt tank through the die, and the temperature in the tank is set at 200°C;

Step 3: Pass 15 kg of alkali-free continuous glass fibers through the high-temperature melt tank in the first step and the low-temperature melt tank in the second step in sequence at a speed of 60 m/min. After the long glass fibers are pulled and infiltrated from the melt tank , Cut into 12mm long uniform particles with a special granulator. The length of the high-temperature melt tank is 2m, and the length of the low-temperature melt tank is 1m.

Test its performance according to the corresponding standards, the list is as follows:

performance unit standard test Test Results Flame retardant performance / D45 1333 C4 (automatically extinguish) Spiral flow length mm / 1180

HDT(1.80MPa) ℃ ISO75/1-93 158 Tensile Strength MPa ISO527/2-93 111 Flexural modulus MPa ISO178/2-93 6900 Notched impact strength KJ/ ^m2 ISO179/2-93 38 Tensile Strength Retention (150℃, 1000hr) % ISO527/2-93 97

Example 4

Step 1: Plasticize 16kg of polypropylene with a melt flow rate of 300g/10min and 4kg of compatibilizer (Bondyram1001) through a single-screw extruder and transport them to a high-temperature melt tank through a die. The temperature in the tank is set at 370°C;

The second step: 39.2 kilograms of polypropylene with a melt flow rate of 300g/10min, 0.4 kilograms of heat stabilizer (Irganox 1010, CIBA company), 0.4 kilograms of processing aids (EB-FF, Japan Kao), 20 kilograms of halogen-free The flame retardant FP-2200 is plasticized by the single-screw extruder and then transported to the low-temperature melt tank through the die, and the temperature in the tank is set at 210°C;

Step 3: Pass 20 kg of alkali-free continuous glass fibers through the high-temperature melt tank in the first step and the low-temperature melt tank in the second step in sequence at a speed of 70m/min. After the long glass fibers are drawn and infiltrated from the melt tank , Cut into 12mm long uniform particles with a special granulator. The length of the high-temperature melt tank is 2m, and the length of the low-temperature melt tank is 1m.

Test its performance according to the corresponding standards, the list is as follows:

performance unit standard test Test Results Flame retardant performance / D45 1333 C4 (automatically extinguish) Spiral flow length mm / 1400 HDT(1.80MPa) ℃ ISO75/1-93 158 Tensile Strength MPa ISO527/2-93 108 Flexural modulus MPa ISO178/2-93 6700 Notched impact strength KJ/ ^m2 ISO179/2-93 39 Tensile Strength Retention (150℃, 1000hr) % ISO527/2-93 96

Example 5

The first step: 20 kg of polypropylene with a melt flow rate of 1000g/10min and 5 kg of compatibilizer (CA-100, ExxonMobil) are plasticized by a single-screw extruder and then transported to a high-temperature melt through a die. Body tank, the temperature in the tank is set at 380°C;

The second step: 29 kg of polypropylene with a melt flow rate of 1000g/10min, 0.5 kg of heat stabilizer (Irganox1010, CIBA company), 0.5 kg of processing aid (EB-FF, Japan Kao), 20 kg of halogen-free resistor The fuel FP-2200 is plasticized by the single-screw extruder and then transported to the low-temperature melt tank through the die, and the temperature in the tank is set at 220°C;

Step 3: Pass 25 kg of alkali-free continuous glass fibers through the high-temperature melt tank in the first step and the low-temperature melt tank in the second step in sequence at a speed of 80 m/min. After the long glass fibers are drawn and infiltrated from the melt tank , Cut into 12mm long uniform particles with a special granulator. The length of the high-temperature melt tank is 2m, and the length of the low-temperature melt tank is 1m.

Test its performance according to the corresponding standards, the list is as follows:

performance unit standard test Test Results Flame retardant performance / D45 1333 C4 (automatically extinguish) Spiral flow length mm / 1700 HDT(1.80MPa) ℃ ISO75/1-93 159 Tensile Strength MPa ISO527/2-93 115 Flexural modulus MPa ISO178/2-93 6900 Notched impact strength KJ/ ^m2 ISO179/2-93 41 Tensile Strength Retention (150℃, 1000hr) % ISO527/2-93 95

Claims (10)

1. A halogen-free flame-retardant long glass fiber reinforced polypropylene material, characterized in that it consists of the following components in weight percentage: Polypropylene 49-88.8%; Heat stabilizer 0.1-0.5%; Processing aids 0.1-0.5%; Halogen-free flame retardant 5-20%; Compatibilizer 1-5%; Long glass fibers 5-25%. 2 . The non-halogen flame retardant long glass fiber reinforced polypropylene material according to claim 1 , wherein the melt flow rate of the polypropylene is 50-1000 g/10 min. 3. a kind of halogen-free flame-retardant long glass fiber reinforced polypropylene material as claimed in claim 1, is characterized in that, described thermal stabilizer is phenols, amines, phosphite, semi-hindered phenols, Any one or a mixture of complexes of acryloyl functional groups and thioesters and calixarene. 4. a kind of halogen-free flame-retardant long glass fiber reinforced polypropylene material as claimed in claim 1, is characterized in that, described processing aid is low molecular weight esters, metal soaps, stearic acid compound esters and Any one or a mixture of several amides. 5. A halogen-free flame-retardant long glass fiber reinforced polypropylene material as claimed in claim 1, wherein said halogen-free flame retardant is a phosphorus-nitrogen halogen-free environment-friendly expansion flame retardant. 6. A halogen-free flame-retardant long glass fiber reinforced polypropylene material as claimed in claim 1, wherein the compatibilizer is a polar monomer graft polymer, and its polymer matrix is polyethylene , polypropylene, ethylene-α-ethylene-octene copolymer, copolymer of styrene and butadiene, polyethylene-polystyrene-polypropylene terpolymer, ethylene-propylene-butadiene terpolymer , ethylene-acrylate copolymer and ethylene-acrylate-glycidyl methacrylate copolymer or a mixture of both, the polar monomers are maleic anhydride and its analogs and acrylic acid and its esters Any one or a mixture of several derivatives. 7. A halogen-free flame-retardant long glass fiber reinforced polypropylene material as claimed in claim 1, wherein the long glass fiber is an alkali-free continuous glass fiber. 8. The preparation method of a kind of halogen-free flame-retardant long glass fiber reinforced polypropylene material according to claim 1, characterized in that, the specific steps are as follows: Step 1: Plasticize 4-40% by weight of polypropylene and compatibilizer through a single-screw extruder, then transport it to a high-temperature melt tank through a die, and the temperature in the tank is 280-380°C; Step 2: Plasticize the remaining polypropylene, heat stabilizer, processing aid, and halogen-free flame retardant through a single-screw extruder, then transport it to a low-temperature melt tank through a die, and the temperature in the tank is 180-220°C; Step 3: Input the long glass fiber into the high-temperature melt tank in the first step and the low-temperature melt tank in the second step successively at a speed of 20-100m/min, then drag and infiltrate, and then pelletize. 9 . The method for preparing a halogen-free flame-retardant long glass fiber reinforced polypropylene material according to claim 8 , wherein the lengths of the high-temperature melt tank and the low-temperature melt tank are 1-4 m. 10. the preparation method of a kind of halogen-free flame-retardant long glass fiber reinforced polypropylene material as claimed in claim 9, is characterized in that, the length of described high-temperature melt tank is 2m, and the length of described low-temperature melt tank is 1m.