CN112266532A - Polypropylene reinforced composite material with good appearance and capable of being sprayed and preparation method thereof - Google Patents
Polypropylene reinforced composite material with good appearance and capable of being sprayed and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a good-appearance sprayable polypropylene reinforced composite material, which comprises the following components in parts by weight: 55-82 parts of polypropylene, 15-35 parts of glass fiber, 3-10 parts of special compatilizer, 0-0.3 part of lubricant, 0-0.3 part of light stabilizer and 0.2-0.6 part of antioxidant. The special compatilizer is used for preparing the sprayable high-performance polypropylene reinforced composite material with good appearance, and the composite material has good tensile strength, bending modulus and cantilever beam notch impact strength, and can meet the development trends of light weight, olefination, high performance and the like required by the automobile industry at the present stage.
Description
Technical Field
The invention relates to a good-appearance sprayable polypropylene reinforced composite material and a preparation method thereof, belonging to the technical field of modification of high polymer materials.
Background
The glass fiber reinforced polypropylene (GFRPP) has the advantages of high rigidity, high impact, good fatigue creep resistance, short molding period, cyclic utilization and the like, solves a series of defects of low rigidity, fatigue creep variation and the like of pure PP to a great extent, and is widely applied to various fields of household appliances, electronic and electric appliances, building industry, aerospace, ships, automobiles and the like after being put into use in the 70 s. However, in the aspect of engineering application, the phenomenon of glass fiber exposure limits the use of GFRPP materials to a great extent, and in addition, the spraying effect of the glass fiber materials is poor, so that the glass fiber materials are limited in the application in various aspects such as automobile functional parts and the like.
In recent years, with the increasing demands for the use environment and the appearance of polymer materials, higher demands have been made on the surface fiber floating condition of GFRPP composites. In many studies at present, some scholars add the anti-floating fiber master batch into a finished product by using the glass fiber and PB-1 as the anti-floating fiber master batch, so that the retention length of the glass fiber in the master batch is reduced after secondary machine passing, and the mechanical property of the product is influenced; or the zinc oxide is used as the anti-floating fiber master batch which is white and can not be applied to dark products. Other scholars add anti-floating agents to the product, and the types of anti-floating agents are various, such as using high-melt-index PP (MFR > 500g/10min), ethylene bis stearamide dispersant and TAF lubricant to compound, but the ethylene bis stearamide dispersant and TAF are small molecules and have the risk of sticking. In addition, the appearance spraying performance of the glass fiber reinforced polypropylene material cannot be better solved.
Poly-1-butene (poly-1-butene, also known as PB-1 or iBu) is a thermoplastic resin polymerized from 1-butene, is a translucent, colorless and odorless solid, has a regular molecular structure, and has chemical resistance, aging resistance and electrical insulation similar to those of polypropylene. But it has a unique property that after being cooled and crystallized from a melt state, the crystal can be changed into a more stable crystal form I (melting point 124 ℃) after being placed at room temperature for three or four days, and the strength and the rigidity are improved along with the change. Poly-1-butene has outstanding advantages of excellent creep resistance, environmental stress cracking resistance and impact resistance, and is superior to polyethylene, and therefore, it is mainly used as pipes, such as water supply pipes, hot water pipes, industrial pipes, and building pipes. The application of the film and the packaging is expanding day by day. Because of excellent heat resistance, boiling water boiling resistance, transparency, non-toxicity and other characteristics, the material can be widely used as medical instruments, such as syringes, three-way valves, blood separation tanks, tube tanks for ultraviolet blood analysis, and quartz glass and the like; physicochemical appliances such as measuring cylinder, vessel, beaker, etc. It can also be used for medicine and food packaging, such as milk container, tableware, electronic oven, food packaging film, transparent packaging material, instead of thermosetting resin and optical plastic. And can be used for producing release paper, heat-resistant lens, etc., and has wide application in aviation and aerospace.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a good-appearance sprayable polypropylene reinforced composite material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a good-appearance, sprayable polypropylene reinforced composite comprising the following components in parts by weight: 55-82 parts of polypropylene, 15-35 parts of glass fiber, 3-10 parts of special compatilizer, 0-0.3 part of lubricant, 0-0.3 part of light stabilizer and 0.2-0.6 part of antioxidant.
As a preferred embodiment of the composite material, the composite material comprises the following components in parts by weight: 62-76 parts of polypropylene, 20-35 parts of glass fiber, 4-8 parts of special compatilizer, 0.1-0.2 part of lubricant, 0.1-0.2 part of light stabilizer and 0.3-0.5 part of antioxidant. When the composite material comprises the components in parts by weight, the composite material has higher appearance anti-floating fiber grade, longer glass fiber retention length and higher surface tension.
As a preferred embodiment of the composite material according to the invention, the polypropylene has a melt flow rate of 60 to 1500g/10min, measured according to ISO 1133 using a weight of 2.16kg and at a temperature of 230 ℃.
In a preferred embodiment of the composite material of the present invention, the glass fibers are alkali-free chopped glass fibers, and the filament diameter of the glass fibers is 10 to 13 μm.
As a preferred embodiment of the composite material of the present invention, the lubricant is at least one of an amide lubricant and a stearate lubricant, the antioxidant is at least one of a hindered phenol antioxidant and a phosphite antioxidant, and the light stabilizer is a hindered amine light stabilizer.
As a preferred embodiment of the composite material, the special compatilizer is poly-1-butylene grafted sodium maleate.
As a preferred embodiment of the composite material, the raw materials for preparing the special compatilizer comprise the following components in parts by weight: 100 parts of poly-1-butene and 1.5-4.5 parts of sodium maleate.
As a preferred embodiment of the composite material, the raw materials for preparing the special compatilizer also comprise the following components in parts by weight: 0.2-0.4 part of antioxidant, 0.2-0.4 part of initiator, 2-3 parts of comonomer alpha-methyl styrene and 1-1.5 parts of comonomer 1-octene.
The invention uses the self-made poly-1-butylene grafted sodium maleate (PB-1-g-sodium maleate) purified product, and applies the characteristic that the melting point (124 ℃) of PB-1 is lower than the melting point (167 ℃) of PP, so that the PB-1 melt viscosity is low at the same temperature, the glass fiber surface can be better infiltrated, the sodium maleate in the PB-1-g-sodium maleate purified product can be well combined with the glass fiber, and the PB-1 and PP have better compatibility, therefore, the PB-1-g-sodium maleate purified product not only plays a role in resisting floating fiber, but also plays a role in a compatilizer, and the sprayability of the polypropylene can be obviously improved.
As a preferred embodiment of the composite material, the preparation method of the special compatilizer comprises the following steps:
(1) uniformly mixing poly-1-butene, sodium maleate and an antioxidant by a high-speed mixer to obtain a mixture;
(2) dissolving an initiator, a comonomer alpha-methylstyrene and a comonomer 1-octene in acetone to obtain a mixed solution A for later use;
(3) adding the mixed solution A obtained in the step (2) into the mixture obtained in the step (1), uniformly mixing by using a high-speed mixer, adding the mixture into a double-screw extruder after acetone is completely volatilized, and carrying out melt extrusion grafting reaction to obtain a poly-1-butylene grafted sodium maleate crude product;
(4) adding the crude product of the poly-1-butylene grafted sodium maleate obtained in the step (3) into xylene, stirring until the crude product is completely dissolved to obtain a mixed solution B, then pouring the mixed solution B into an acetone solution while the mixed solution B is hot to generate a flocculent precipitate product, washing with acetone to obtain a first purified product, and then drying the flocculent precipitate to constant weight; and repeating the steps for the second and third purification, and finally, drying the obtained poly-1-butylene grafted sodium maleate purified product in vacuum to constant weight for later use, thus obtaining the special compatilizer.
In the step (1), the rotating speed of the high-speed mixer is 650-750 rpm, and the antioxidant is at least one of antioxidant 1010 and antioxidant 168; in the step (2), the mass ratio of the initiator to the acetone is (0.2-0.4): (35-45), wherein the initiator is di-tert-butyl peroxide, and the dissolving temperature is 35-45 ℃; in the step (3), the temperature of the double-screw extruder is 135-150 ℃; in the step (4), the mass ratio of the poly-1-butylene grafted sodium maleate crude product to the xylene to the acetone is 1: (35-45): (60-70), the dissolving temperature is 70-80 ℃, the washing times with acetone are 3-5 times, and the vacuum drying time is 24 hours.
In a second aspect, the present invention provides a method for preparing the above composite material, comprising the steps of: mixing polypropylene, a special compatilizer, a light stabilizer, a lubricant and an antioxidant in a high-speed mixer; and adding the mixed particles into a double-screw extruder for melt extrusion and granulation, adding glass fiber from a side feed for extrusion molding, drying, cooling and packaging to obtain the polypropylene reinforced composite material with good appearance and spraying capability.
As a preferred embodiment of the preparation method, the mixing time of the high-speed mixer is 3-5 minutes, and the rotating speed is 200-300 revolutions per minute; the temperature of the double-screw extruder is 230 ℃, 250 ℃, 260 ℃, 270 ℃, 265 ℃, 260 ℃ and 250 ℃ from the feeding section to the head in sequence.
The extrusion process of the polypropylene reinforced composite material with good appearance and sprayable performance is also very critical, the extrusion temperature of the common glass fiber reinforced PP is generally 200-230 ℃, the extrusion temperature of the invention is 230-270 ℃, the glass fiber can be better infiltrated and the shear can be reduced due to low melt viscosity at high temperature, so that the composite material has good anti-floating fiber effect, long glass fiber retention length and high mechanical property, and better coating performance is realized due to better coating.
Compared with the prior art, the invention has the beneficial effects that:
(1) the special compatilizer is used for preparing the sprayable high-performance polypropylene reinforced composite material with good appearance, good tensile strength, bending modulus and cantilever beam notch impact strength, and can meet the development trends of light weight, olefination, high performance and the like required by the automobile industry at the present stage.
(2) The glass fiber can be better wrapped and infiltrated by using the specific polypropylene, so that the appearance anti-floating fiber effect is good; the invention uses the self-made PB-1-g-sodium maleate purified product, and applies the characteristic that the melting point (124 ℃) of PB-1 is lower than the melting point (167 ℃) of PP, the PB-1 melt viscosity is low at the same temperature, so that the glass fiber surface can be better infiltrated, the sodium maleate in the PB-1-g-sodium maleate purified product can be well combined with the glass fiber, and the PB-1 and the PP have good compatibility, so that the PB-1-g-sodium maleate purified product has the functions of resisting floating fiber and a compatilizer, and the spraying performance can be obviously improved.
(3) The extrusion process of the polypropylene reinforced composite material with good appearance and sprayable performance is also very critical, the extrusion temperature of the common glass fiber reinforced PP is generally 200-230 ℃, the extrusion temperature of the invention is 230-270 ℃, the glass fiber can be better infiltrated and the shear can be reduced due to low melt viscosity at high temperature, so that the composite material has good floating fiber resistant effect, long glass fiber retention length and high mechanical property, and better coating performance is realized due to better coating. The invention has simple production process and is suitable for mass production.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
The following examples and comparative examples were tested for density according to ISO 1183-1-2019, tensile properties according to ISO 527-2-2016 at a tensile rate of 10mm/min, bending properties according to ISO 178-. The method for testing the retention length of the glass fiber comprises the following steps: the extruded particles are fully combusted in a muffle furnace at 650 ℃ for 4 hours, the retention length of the burnt glass fiber residues is tested, and 500 pieces of the glass fiber residues are analyzed to obtain the average retention length in unit mm. The sprayability was characterized by using surface tension, the larger the surface tension, the better the sprayability, the surface tension was in accordance with Ford BO 116-03-2018 standard in mN/m, and the comparative table of the surface tension solution formulation is shown in Table 1.
TABLE 1
The appearance anti-floating fiber is evaluated according to the existence degree of the floating fiber and is divided into 1-5 grades, and the specific evaluation grade is shown in table 2.
TABLE 2
The main representative materials used in the examples of the present invention and the comparative examples are as follows:
polypropylene: the model is as follows: p1000(MFR 1000g/10min), manufacturer: shanghai Huahe Co., Ltd; the model is as follows: p1200(MFR 1200g/10min), manufacturer: shanghai Huahe Co., Ltd; the model is as follows: p1500(MFR 1500g/10min), manufacturer: shanghai Huahe Co., Ltd; the model is as follows: M60T (MFR 60g/10min), manufacturer: refining in the sea; the model is as follows: MH7900(MFR 150g/10min), manufacturer: LG chemistry; the model is as follows: EP548R (MFR 26g/10min), manufacturer: zhonghai shell brand.
PB-1: the model is as follows: PB0800M (MFR 200g/10min, 190 ℃/2.16kg), manufacturer: linadebo basel; the model is as follows: PB0401M (MFR 15g/10min, 190 ℃/2.16kg), manufacturer: linadebo basel; .
Alkali-free chopped glass fiber: the model is as follows: e7CS13-03-508A (monofilament diameter 13 μm), manufacturer: a boulder group; the model is as follows: e7CS10-03-508A (monofilament diameter 10 μm), manufacturer: a boulder group.
Sodium maleate: the model is as follows: sodium maleate, manufacturer: shanghai Kyokups chemical Co., Ltd.
Di-tert-butyl peroxide: the model is as follows: DTBP, manufacturer: togying City, Haiying chemical Co., Ltd.
α -methylstyrene: the model is as follows: AMS, manufacturer: japan mitsui chemical.
1-octene: the model is as follows: 1-Octene, manufacturer: the Nanjing Hui Jing petrochemical.
Xylene: xylene, manufacturer: dongguan city qi feng chemical company Limited.
Acetone: acetone, manufacturer: shanghai Xinwei chemical Co., Ltd.
Antioxidant: hindered phenol type: 1010, manufacturer: shandong Sanfeng; phosphite type: 168, manufacturer: shandong san Feng.
Light stabilizer: the model is as follows: UV-3808PP5, manufacturer: belgium solvay.
Lubricant: amide type number: TR016, manufacturer: STRUTTOL, USA; calcium stearate type: BS-3818, manufacturer: chemical industry of Huaming Tai; the zinc stearate model: BS-2818, manufacturer: chemical industry of Huaming Tai.
Example 1
The preparation method of the specially prepared compatilizer in the embodiment is as follows:
(a) firstly, weighing 100 parts of poly-1-butene PB0800M, 1.5 parts of sodium maleate, 0.1 part of antioxidant 1010 and 0.1 part of antioxidant 168, and uniformly mixing by a high-speed mixer at the rotating speed of 650rpm to obtain a mixture;
(b) dissolving 0.2 part of initiator di-tert-butyl peroxide (DTBP), 2 parts of comonomer alpha-methyl styrene (AMS) and 1 part of comonomer 1-Octene (1-Octene) in 35 ℃ of acetone to obtain a mixed solution A for later use;
(c) adding the mixed solution A obtained in the step (b) into the mixture obtained in the step (a), uniformly mixing by using a high-speed mixer, adding the mixture into a double-screw extruder after acetone is completely volatilized, and carrying out melt extrusion grafting reaction to obtain a PB-1-g-sodium maleate crude product; wherein the temperature of the double-screw extruder is 135 ℃;
(d) adding 1 part of the PB-1-g-sodium maleate crude product into 35 parts of dimethylbenzene, stirring at 70 ℃ until the crude product is completely dissolved to obtain a mixed solution B, then pouring the mixed solution B into 60 parts of acetone solution while the mixed solution B is hot to generate a flocculent precipitate product, washing the flocculent precipitate for 3 times by using acetone to obtain a first purified product, and then putting the flocculent precipitate into a ventilated kitchen and drying to constant weight; and repeating the steps for the second and third purification, and finally putting the purified product of the PB-1-g-sodium maleate into a vacuum drying oven to be dried for 24 hours until the weight is constant for later use, thereby obtaining the special compatilizer.
A good-appearance, sprayable polypropylene reinforced composite comprising the following components in parts by weight: 55 parts of polypropylene, 35 parts of glass fiber, 10 parts of special compatilizer, 0.3 part of lubricant, 0.3 part of light stabilizer and 0.2 part of antioxidant.
The preparation method of the composite material comprises the following steps: 55 parts of polypropylene PP M60T, 10 parts of the specially-made compatilizer PB-1-g-sodium maleate purified product, 0.3 part of light stabilizer, 0.3 part of lubricant BS-2818, 0.1 part of antioxidant 1010 and 0.1 part of antioxidant 168 are weighed and mixed in a high-speed mixer for 3 minutes, wherein the rotating speed of the high-speed mixer is 200 revolutions per minute. And adding the mixed particles into a double-screw extruder for melt extrusion, granulation, drying, cooling and packaging, wherein 35 parts of glass fiber E7CS10-03-508A is added into the extrusion molding material from a side feed. The temperature of the twin-screw extruder is 230 ℃, 250 ℃, 260 ℃, 270 ℃, 265 ℃, 260 ℃ and 250 ℃ from the feeding section to the head in sequence.
Specific properties of the polypropylene composite material prepared in this example are shown in table 3.
Comparative example 1
The melt flow rate of the polypropylene used in this comparative example is outside the scope of the present invention, and the comparative example differs from example 1 only in the polypropylene used, and the other components in the composite and the method of preparation are the same as in example 1.
The raw materials and the preparation method of the specially prepared compatilizer in the comparative example are the same as those in example 1.
A polypropylene reinforced composite material comprises the following components in parts by weight: 55 parts of polypropylene, 35 parts of glass fiber, 10 parts of special compatilizer, 0.3 part of lubricant, 0.3 part of light stabilizer and 0.2 part of antioxidant.
The preparation method of the composite material of the comparative example comprises the following steps: firstly, 55 parts of polypropylene PP 548R, 10 parts of a special compatilizer PB-1-g-sodium maleate purified product, 0.3 part of a light stabilizer, 0.3 part of a lubricant BS-2818, 0.1 part of an antioxidant 1010 and 0.1 part of an antioxidant 168 are weighed and mixed in a high-speed mixer for 3 minutes, wherein the rotating speed of the high-speed mixer is 200 revolutions per minute. And adding the mixed particles into a double-screw extruder for melt extrusion, granulation, drying, cooling and packaging, wherein 35 parts of glass fiber E7CS10-03-508A is added into the extrusion molding material from a side feed. The temperature of the twin-screw extruder is 230 ℃, 250 ℃, 260 ℃, 270 ℃, 265 ℃, 260 ℃ and 250 ℃ from the feeding section to the head in sequence.
The specific properties of the polypropylene composite prepared in this comparative example are shown in table 3.
Comparative example 2
This comparative example differs from example 1 only in that no tailored compatibilizer is included, and the other components in the composite and the method of preparation are the same as in example 1.
A polypropylene reinforced composite material comprises the following components in parts by weight: 55 parts of polypropylene, 35 parts of glass fiber, 0.3 part of lubricant, 0.3 part of light stabilizer and 0.2 part of antioxidant.
The preparation method of the composite material of the comparative example comprises the following steps: firstly, 55 parts of polypropylene PP M60T, 0.3 part of a light stabilizer, 0.3 part of lubricant BS-2818, 0.1 part of antioxidant 1010 and 0.1 part of antioxidant 168 are weighed and mixed in a high-speed mixer for 3 minutes, wherein the rotating speed of the high-speed mixer is 200 revolutions per minute. And adding the mixed particles into a double-screw extruder for melt extrusion, granulation, drying, cooling and packaging, wherein 35 parts of glass fiber E7CS10-03-508A is added into the extrusion molding material from a side feed. The temperature of the twin-screw extruder is 230 ℃, 250 ℃, 260 ℃, 270 ℃, 265 ℃, 260 ℃ and 250 ℃ from the feeding section to the head in sequence.
The specific properties of the polypropylene composite prepared in this comparative example are shown in table 3.
Comparative example 3
The comparative example is different from example 1 only in the preparation method of the composite material, the temperature of extrusion granulation is different, and other components in the composite material and the preparation method are the same as example 1.
The raw materials and the preparation method of the specially prepared compatilizer in the comparative example are the same as those in example 1.
A good-appearance, sprayable polypropylene reinforced composite comprising the following components in parts by weight: 55 parts of polypropylene, 35 parts of glass fiber, 10 parts of special compatilizer, 0.3 part of lubricant, 0.3 part of light stabilizer and 0.2 part of antioxidant.
The preparation method of the composite material of the comparative example comprises the following steps: 55 parts of polypropylene PP M60T, 10 parts of the specially-made compatilizer PB-1-g-sodium maleate purified product, 0.3 part of light stabilizer, 0.3 part of lubricant BS-2818, 0.1 part of antioxidant 1010 and 0.1 part of antioxidant 168 are weighed and mixed in a high-speed mixer for 3 minutes, wherein the rotating speed of the high-speed mixer is 200 revolutions per minute. And adding the mixed particles into a double-screw extruder for melt extrusion, granulation, drying, cooling and packaging, wherein 35 parts of glass fiber E7CS10-03-508A is added into the extrusion molding material from a side feed. The temperature of the twin-screw extruder is 200 ℃, 210 ℃, 220 ℃, 210 ℃, 205 ℃, 200 ℃ from the feeding section to the head in sequence.
The specific properties of the polypropylene composite prepared in this comparative example are shown in table 3.
Example 2
The preparation method of the specially prepared compatilizer in the embodiment is as follows:
(a) firstly, weighing 100 parts of poly-1 butene PB0401M, 4.5 parts of sodium maleate, 0.2 part of antioxidant 1010 and 0.2 part of antioxidant 168, and uniformly mixing by a high-speed mixer at the rotating speed of 750rpm to obtain a mixture;
(b) dissolving 0.4 part of initiator di-tert-butyl peroxide (DTBP), 3 parts of comonomer alpha-methyl styrene (AMS) and 1.5 parts of comonomer 1-Octene (1-Octene) in 45 parts of acetone at 45 ℃ to obtain a mixed solution A for later use;
(c) adding the mixed solution A obtained in the step (b) into the mixture obtained in the step (a), uniformly mixing by using a high-speed mixer, adding the mixture into a double-screw extruder after acetone is completely volatilized, and carrying out melt extrusion grafting reaction to obtain a PB-1-g-sodium maleate crude product; wherein the temperature of the double-screw extruder is 150 ℃;
(d) adding 1 part of the PB-1-g-sodium maleate crude product into 45 parts of dimethylbenzene, stirring at the temperature of 80 ℃ until the crude product is completely dissolved to obtain a mixed solution B, then pouring the mixed solution B into 70 parts of acetone solution while the mixed solution B is hot to generate a flocculent precipitate product, washing the flocculent precipitate product for 5 times by using acetone to obtain a first purified product, and then putting the flocculent precipitate into a ventilated kitchen and drying the flocculent precipitate to constant weight; and repeating the steps for the second and third purification, and finally putting the purified product of the PB-1-g-sodium maleate into a vacuum drying oven to be dried for 24 hours until the weight is constant for later use, thereby obtaining the special compatilizer.
A good-appearance, sprayable polypropylene reinforced composite comprising the following components in parts by weight: 82 parts of polypropylene, 15 parts of glass fiber, 3 parts of special compatilizer and 0.6 part of antioxidant.
The preparation method of the composite material comprises the following steps: 82 parts of polypropylene PP MH7900, 3 parts of the specially-prepared compatilizer PB-1-g-sodium maleate purified product, 0.3 part of antioxidant 1010 and 0.3 part of antioxidant 168 are weighed and mixed with a high-speed mixer for 5 minutes, wherein the rotating speed of the high-speed mixer is 300 revolutions per minute. And adding the mixed particles into a double-screw extruder for melt extrusion, granulation, drying, cooling and packaging, wherein 15 parts of glass fiber E7CS13-03-508A is added into the extrusion molding material from a side feed. The temperature of the twin-screw extruder is 230 ℃, 250 ℃, 260 ℃, 270 ℃, 265 ℃, 260 ℃ and 250 ℃ from the feeding section to the head in sequence.
Specific properties of the polypropylene composite material prepared in this example are shown in table 3.
Example 3
The raw materials and the preparation method of the specially prepared compatilizer in this example are the same as those in example 2.
A good-appearance, sprayable polypropylene reinforced composite comprising the following components in parts by weight: 64 parts of polypropylene, 30 parts of glass fiber, 6 parts of special compatilizer and 0.6 part of antioxidant.
The preparation method of the composite material comprises the following steps: 64 parts of polypropylene PP MH7900, 6 parts of the specially-prepared compatilizer PB-1-g-sodium maleate purified product, 0.3 part of antioxidant 1010 and 0.3 part of antioxidant 168 are weighed and mixed with a high-speed mixer for 5 minutes, wherein the rotating speed of the high-speed mixer is 300 revolutions per minute. And adding the mixed particles into a double-screw extruder for melt extrusion, granulation, drying, cooling and packaging, wherein 30 parts of glass fiber E7CS13-03-508A is added into the extrusion molding material from a side feed. The temperature of the twin-screw extruder is 230 ℃, 250 ℃, 260 ℃, 270 ℃, 265 ℃, 260 ℃ and 250 ℃ from the feeding section to the head in sequence.
Specific properties of the polypropylene composite material prepared in this example are shown in table 3.
Example 4
The preparation method of the specially prepared compatilizer in the embodiment is as follows:
(a) firstly, weighing 100 parts of poly-1 butene PB0401M, 3.2 parts of sodium maleate, 0.16 part of antioxidant 1010 and 0.22 part of antioxidant 168, and uniformly mixing the components by a high-speed mixer at the rotating speed of 695rpm to obtain a mixture;
(b) dissolving 0.31 part of initiator di-tert-butyl peroxide (DTBP), 2.7 parts of comonomer alpha-methyl styrene (AMS) and 1.4 parts of comonomer 1-Octene (1-Octene) in 40 parts of acetone at 40 ℃ to obtain a mixed solution A for later use;
(c) and (c) adding the mixed solution A obtained in the step (b) into the mixture obtained in the step (a), uniformly mixing by using a high-speed mixer, adding into a double-screw extruder after acetone is completely volatilized, and carrying out melt extrusion grafting reaction to obtain a PB-1-g-sodium maleate crude product. Wherein the temperature of the double-screw extruder is 142 ℃;
(d) adding 1 part of the PB-1-g-sodium maleate crude product into 37.9 parts of dimethylbenzene, stirring at the temperature of 77 ℃ until the crude product is completely dissolved to obtain a mixed solution B, then pouring the mixed solution B into 68 parts of acetone solution while the mixed solution B is hot to generate a flocculent precipitate product, washing the flocculent precipitate product for 5 times by using acetone to obtain a first purified product, and then putting the flocculent precipitate into a ventilated kitchen and drying the flocculent precipitate to constant weight; and repeating the steps for the second and third purification, and finally putting the purified product of the PB-1-g-sodium maleate into a vacuum drying oven to be dried for 24 hours until the weight is constant for later use, thereby obtaining the special compatilizer.
A good-appearance, sprayable polypropylene reinforced composite comprising the following components in parts by weight: 65 parts of polypropylene, 30 parts of glass fiber, 5 parts of special compatilizer, 0.22 part of lubricant, 0.18 part of light stabilizer and 0.49 part of antioxidant.
The preparation method of the composite material comprises the following steps: weighing 65 parts of polypropylene PP P1000, 5 parts of the specially-produced compatilizer PB-1-g-sodium maleate purified product, 0.18 part of light stabilizer, 0.22 part of lubricant TR016, 0.22 part of antioxidant 1010 and 0.27 part of antioxidant 168, and mixing in a high-speed mixer for 3.8 minutes, wherein the rotating speed of the high-speed mixer is 269 revolutions per minute. And adding the mixed particles into a double-screw extruder for melt extrusion, granulation, drying, cooling and packaging, wherein 30 parts of glass fiber E7CS13-03-508A is added into the extrusion molding material from a side feed. The temperature of the twin-screw extruder is 230 ℃, 250 ℃, 260 ℃, 270 ℃, 265 ℃, 260 ℃ and 250 ℃ from the feeding section to the head in sequence.
Specific properties of the polypropylene composite material prepared in this example are shown in table 3.
Example 5
The preparation method of the specially prepared compatilizer in the embodiment is as follows:
(a) firstly, weighing 100 parts of poly-1 butene PB0401M, 4.2 parts of sodium maleate, 0.16 part of antioxidant 1010 and 0.22 part of antioxidant 168, and uniformly mixing by a high-speed mixer at the rotating speed of 725rpm to obtain a mixture;
(b) 0.37 part of initiator di-tert-butyl peroxide (DTBP), 2.8 parts of comonomer alpha-methyl styrene (AMS) and 1.5 parts of comonomer 1-Octene (1-Octene) are dissolved in 43 parts of acetone at 42 ℃ to obtain a mixed solution A for later use.
(c) And (c) adding the mixed solution A obtained in the step (b) into the mixture obtained in the step (a), uniformly mixing by using a high-speed mixer, adding into a double-screw extruder after acetone is completely volatilized, and carrying out melt extrusion grafting reaction to obtain a PB-1-g-sodium maleate crude product. Wherein the temperature of the twin-screw extruder is 147 ℃.
(d) Adding 1 part of PB-1-g-sodium maleate crude product into 43.8 parts of dimethylbenzene, stirring at 79 ℃ until the crude product is completely dissolved to obtain a mixed solution B, pouring the mixed solution B into 62 parts of acetone solution while the mixed solution B is hot to generate a flocculent precipitate product, washing the flocculent precipitate with acetone for 5 times to obtain a first purified product, and then putting the flocculent precipitate into a ventilated kitchen and drying to constant weight; and repeating the steps for the second and third purification, and finally putting the purified product of the PB-1-g-sodium maleate into a vacuum drying oven to be dried for 24 hours until the weight is constant for later use, thereby obtaining the special compatilizer.
A good-appearance, sprayable polypropylene reinforced composite comprising the following components in parts by weight: 68 parts of polypropylene, 25 parts of glass fiber, 7 parts of special compatilizer, 0.26 part of lubricant, 0.23 part of light stabilizer and 0.46 part of antioxidant.
The preparation method of the composite material comprises the following steps: 68 parts of polypropylene PP 1200, 7 parts of the special compatilizer PB-1-g-sodium maleate purified product, 0.23 part of light stabilizer, 0.26 part of lubricant TR016, 0.22 part of antioxidant 1010 and 0.24 part of antioxidant 168 are weighed and mixed in a high-speed mixer for 4.7 minutes, wherein the rotating speed of the high-speed mixer is 288 revolutions per minute. And adding the mixed particles into a double-screw extruder for melt extrusion, granulation, drying, cooling and packaging, wherein 25 parts of glass fiber E7CS10-03-508A is added into the extrusion molding material from a side feed. The temperature of the twin-screw extruder is 230 ℃, 250 ℃, 260 ℃, 270 ℃, 265 ℃, 260 ℃ and 250 ℃ from the feeding section to the head in sequence.
Specific properties of the polypropylene composite material prepared in this example are shown in table 3.
Example 6
In this example, the raw materials and the preparation method of the specially prepared compatibilizer are the same as those in example 1.
A good-appearance, sprayable polypropylene reinforced composite comprising the following components in parts by weight: polypropylene PP 60T 62 parts, glass fiber E7CS10-03-508A 35 parts, special compatilizer 4 parts, lubricant BS-28180.1 parts, light stabilizer UV-3808PP 50.1 parts and antioxidant 10100.3 parts.
The preparation method of the polypropylene reinforced composite material of this example is the same as that of example 1. Specific properties of the polypropylene composite material prepared in this example are shown in table 3.
Example 7
In this example, the raw materials and the preparation method of the specially prepared compatibilizer are the same as those in example 1.
A good-appearance, sprayable polypropylene reinforced composite comprising the following components in parts by weight: polypropylene PP 60T 76 parts, glass fiber E7CS10-03-508A 20 parts, special compatilizer 8 parts, lubricant BS-28180.2 parts, light stabilizer UV-3808PP 50.2 parts and antioxidant 10100.5 parts.
The preparation method of the polypropylene reinforced composite material of this example is the same as that of example 1. Specific properties of the polypropylene composite material prepared in this example are shown in table 3.
TABLE 3
As can be seen from Table 3, the combination of properties of the polypropylene reinforced composite material with any of the main components replaced by others did not achieve the desired effect. The invention prepares the high-performance polypropylene reinforced composite material with good appearance, floating fiber resistance and spraying performance by using special polypropylene and a special compatilizer, when the content of the glass fiber is 35 parts, the tensile strength can reach 120MPa, the bending strength can reach 180MPa, the bending modulus can reach 9000MPa, and the notched impact of a cantilever beam can reach 15kJ/m2And the development trends of light weight, olefination, high performance and the like required by the automobile industry at the present stage can be met.
And when the composite material comprises the following components in parts by weight: 62-76 parts of polypropylene, 20-35 parts of glass fiber, 4-8 parts of special compatilizer, 0.1-0.2 part of lubricant, 0.1-0.2 part of light stabilizer and 0.3-0.5 part of antioxidant, so that the prepared polypropylene reinforced composite material has the advantages of higher level of appearance anti-floating fiber, longer glass fiber retention length and higher surface tension.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A good-appearance sprayable polypropylene reinforced composite material is characterized by comprising the following components in parts by weight: 55-82 parts of polypropylene, 15-35 parts of glass fiber, 3-10 parts of special compatilizer, 0-0.3 part of lubricant, 0-0.3 part of light stabilizer and 0.2-0.6 part of antioxidant.
2. The composite material of claim 1, wherein the composite material comprises the following components in parts by weight: 62-76 parts of polypropylene, 20-35 parts of glass fiber, 4-8 parts of special compatilizer, 0.1-0.2 part of lubricant, 0.1-0.2 part of light stabilizer and 0.3-0.5 part of antioxidant.
3. The composite material according to claim 1 or 2, wherein the polypropylene has a melt flow rate of 60 to 1500g/10min, as measured according to ISO 1133 & 2011 using a weight of 2.16kg and a temperature of 230 ℃; the glass fiber is alkali-free chopped glass fiber, and the monofilament diameter of the glass fiber is 10-13 mu m; the lubricant is at least one of an amide lubricant and a stearate lubricant; the antioxidant is at least one of hindered phenol antioxidant and phosphite antioxidant; the light stabilizer is hindered amine light stabilizer.
4. The composite of claim 1 or 2, wherein the tailored compatibilizer is poly-1-butene grafted sodium maleate.
5. The composite material of claim 4, wherein the raw materials for preparing the tailor-made compatibilizer comprise the following components in parts by weight: 100 parts of poly-1-butene and 1.5-4.5 parts of sodium maleate.
6. The composite material of claim 5, wherein the raw materials for preparing the tailor-made compatibilizer further comprise the following components in parts by weight: 0.2-0.4 part of antioxidant, 0.2-0.4 part of initiator, 2-3 parts of comonomer alpha-methyl styrene and 1-1.5 parts of comonomer 1-octene.
7. The composite material of claim 6, wherein the tailored compatibilizer is prepared by a method comprising the steps of:
(1) uniformly mixing poly-1-butene, sodium maleate and an antioxidant by a high-speed mixer to obtain a mixture;
(2) dissolving an initiator, a comonomer alpha-methylstyrene and a comonomer 1-octene in acetone to obtain a mixed solution A for later use;
(3) adding the mixed solution A obtained in the step (2) into the mixture obtained in the step (1), uniformly mixing by using a high-speed mixer, adding the mixture into a double-screw extruder after acetone is completely volatilized, and carrying out melt extrusion grafting reaction to obtain a poly-1-butylene grafted sodium maleate crude product;
(4) adding the crude product of the poly-1-butylene grafted sodium maleate obtained in the step (3) into xylene, stirring until the crude product is completely dissolved to obtain a mixed solution B, then pouring the mixed solution B into an acetone solution while the mixed solution B is hot to generate a flocculent precipitate product, washing with acetone to obtain a first purified product, and then drying the flocculent precipitate to constant weight; and repeating the steps for the second and third purification, and finally, drying the obtained poly-1-butylene grafted sodium maleate purified product in vacuum to constant weight for later use, thus obtaining the special compatilizer.
8. The composite material of claim 7, wherein in the step (1), the rotation speed of the high-speed mixer is 650-750 rpm, and the antioxidant is at least one of antioxidant 1010 and antioxidant 168; in the step (2), the mass ratio of the initiator to the acetone is (0.2-0.4): (35-45), wherein the initiator is di-tert-butyl peroxide, and the dissolving temperature is 35-45 ℃; in the step (3), the temperature of the double-screw extruder is 135-150 ℃; in the step (4), the mass ratio of the poly-1-butylene grafted sodium maleate crude product to the xylene to the acetone is 1: (35-45): (60-70), the dissolving temperature is 70-80 ℃, the washing times with acetone are 3-5 times, and the vacuum drying time is 24 hours.
9. A method of preparing a composite material according to any one of claims 1 to 8, comprising the steps of: mixing polypropylene, a special compatilizer, a light stabilizer, a lubricant and an antioxidant in a high-speed mixer; and adding the mixed particles into a double-screw extruder for melt extrusion and granulation, adding glass fiber from a side feed for extrusion molding, drying, cooling and packaging to obtain the polypropylene reinforced composite material with good appearance and spraying capability.
10. The method according to claim 9, wherein the mixing time of the high-speed mixer is 3 to 5 minutes, and the rotation speed is 200 to 300 rpm; the temperature of the twin-screw extruder is H1-230 ℃, H2-250 ℃, H3-260 ℃, H4-260 ℃, H5-270 ℃, H6-270 ℃, H7-270 ℃, H8-265 ℃, H9-260 ℃ and H10-250 ℃ from the feeding section to the head.
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| WO2022077864A1 (en) * | 2020-10-12 | 2022-04-21 | 金发科技股份有限公司 | Sprayable polypropylene reinforced composite material with good appearance and preparation method therefor |
| CN115368680A (en) * | 2022-09-30 | 2022-11-22 | 金发科技股份有限公司 | Polypropylene micro-foaming material and preparation method and application thereof |
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| CN114874551B (en) * | 2022-06-22 | 2022-12-13 | 广东安拓普聚合物科技有限公司 | Color master batch based on waste polypropylene and preparation method thereof |
| CN116640382A (en) * | 2023-06-06 | 2023-08-25 | 成都金发科技新材料有限公司 | Spraying-free material and preparation method and application thereof |
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