CN110713656B - Polypropylene composite material and preparation method thereof - Google Patents
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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
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention belongs to the technical field of plastics, and particularly relates to a polypropylene composite material and a preparation method thereof. The invention provides a polypropylene composite material, which comprises: 10-60 parts of polypropylene; 1-10 parts of low-modulus polypropylene; 1-5 parts of a compatilizer; 15-40 parts of continuous long glass fiber; 0-5 parts of glass beads; 0.1-3 parts of a lubricant; 0.1-1.5 parts of antioxidant; 10-30 parts of a flame retardant. The polypropylene composite material has good mechanical property and appearance property, so that floating fibers are not easy to appear on the surface of an injection molding product, and the polypropylene composite material has excellent flame retardant property, processability and mechanical property, and meets the requirements of high-strength automobile parts and the industry of electronic and electric appliances.
Description
Technical Field
The invention belongs to the technical field of plastics, and particularly relates to a polypropylene composite material and a preparation method thereof.
Background
Polypropylene (PP), as a general plastic material, has excellent comprehensive properties, good chemical stability, good moldability and relatively low price, and has been widely used in the fields of household appliances and vehicles. However, PP has the disadvantages of low strength, modulus, hardness, poor low temperature impact resistance, large molding shrinkage, and easy aging, and it is often modified to meet the requirements of products in practical production applications.
Long Glass Fiber Reinforced Polypropylene (LGFPP) is often applied as an automobile module carrier material, so that the rigidity, the impact strength, the creep resistance and the dimensional stability of an automobile module product can be effectively improved, and a complex automobile module product can be made. However, the material is easy to have appearance problems of fiber floating, agglomeration and the like on the surface of a product after injection molding; meanwhile, since PP is a flammable material, the flame retardant property of LGFPP still needs to be further improved.
Disclosure of Invention
The invention mainly aims to provide a polypropylene composite material and a preparation method thereof, and aims to solve the problems that the surface of the existing long glass fiber reinforced polypropylene material is easy to float after injection molding and has low flame retardant property.
In order to achieve the purpose, the invention adopts the following technical scheme:
the polypropylene composite material comprises the following components in parts by weight based on 100 parts by weight of the polypropylene composite material:
the polypropylene composite material provided by the invention comprises polypropylene, low-modulus polypropylene, a compatilizer, continuous long glass fiber, glass beads, a lubricant, an antioxidant and a flame retardant which have specific weight part ratios, and under the synergistic action of the components, the polypropylene composite material provided by the invention has good mechanical properties and appearance properties, and has the advantages that floating fibers are not easy to appear on the surface of an injection molding product, and the polypropylene composite material has excellent flame retardant property, processability and mechanical properties, so that the requirements of high-strength automobile parts and the industry of electronic and electrical appliances are met.
Compared with the existing long glass fiber reinforced polypropylene material, the polypropylene composite material provided by the invention is introduced with low-modulus polypropylene (LMPP) and a flame retardant, so that the polypropylene composite material is endowed with good appearance performance and flame retardant performance. The LMPP has good compatibility with a PP matrix, the flow property of a material system is improved, the crystal structure of the PP is damaged due to the addition of the LMPP, the crystallinity of the material is reduced, the cooling speed of the material system is slowed down, the processability of the polypropylene composite material is improved, and the problem of fiber floating on the surface of an injection molding part of the polypropylene composite material is effectively solved. According to the invention, 1-10 parts by weight of LMPP, 10-40 parts by weight of PP, 0-5 parts by weight of glass beads and 15-40 parts by weight of continuous long glass fiber (LFT) are compounded, so that the problem of fiber floating on the surface of a polypropylene composite material product and the flame retardant property are obviously improved.
Correspondingly, the preparation method of the polypropylene composite material comprises the following steps:
weighing raw materials according to the polypropylene composite material;
mixing the polypropylene, the compatibilizer, the antioxidant, the low modulus polypropylene, the lubricant, the flame retardant and the glass beads to obtain a mixture;
and compounding the mixture and the continuous long glass fiber by adopting a melting impregnation process to obtain the polypropylene composite material.
According to the preparation method of the polypropylene composite material, the polypropylene composite material can be prepared by adopting a melt impregnation process, and the preparation method is simple, is simple and convenient to operate, and is easy for large-scale mass production.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The parts by weight of each component mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the mass between each component, and therefore, it is within the scope of the disclosure of the description of the embodiments of the present invention to scale up or down the content of each component of the composition according to the description of the embodiments of the present invention. Specifically, the mass described in the description of the embodiment of the present invention may be a unit of weight known in the chemical field such as μ g, mg, g, kg, etc.
The polypropylene composite material comprises the following components in parts by weight based on 100 parts by weight of the polypropylene composite material:
specifically, the polypropylene (PP) is a matrix of the polypropylene composite material, and the polypropylene is 10 to 60 parts by weight based on 100 parts by weight of the polypropylene composite material. In some embodiments, the polypropylene 10, 12, 15, 20, 23, 26, 29, 31, 33, 35, 38, 40, 41, 43, 46, 49, 53, 55, 58, 60 parts by weight based on 100 parts by weight of the polypropylene composite.
In one embodiment, the polypropylene is a co-polypropylene and/or a homo-polypropylene, and the polypropylene has a melt index of 50 to 120g/10min at 230 ℃ under 2.16 kg. In some embodiments, the polypropylene is a co-polypropylene. In some embodiments, the polypropylene is a homopolypropylene. In some embodiments, the polypropylene has a melt index of 50, 55, 60, 64, 71, 77, 80, 85, 90, 96, 100, 107, 111, 116, 120g/10 min.
The continuous long glass fiber (LFT) is compounded with the polypropylene to form a long glass fiber reinforced polypropylene system which is used for enhancing the mechanical strength of the polypropylene composite material, so that the polypropylene composite material has good mechanical properties. And 15-40 parts of the continuous long glass fiber based on 100 parts by weight of the polypropylene composite material. In some embodiments, the continuous long glass fiber 15, 17, 20, 22, 25, 27, 30, 32, 34, 35, 37, 38, 40 parts by weight based on 100 parts by weight of the polypropylene composite.
In one embodiment, the length of the continuous long glass fiber is 17-20 mm. In some embodiments, the continuous long glass fiber is selected from the group consisting of taishan T838LP type, chongqing composite international ER4305PM type, and owenshun SE4805 type.
The low modulus polypropylene (L-MODU)TMPP, LMPP) refers to a group using a special C2Polypropylene materials of low modulus, low molecular weight and narrow molecular weight distribution produced by symmetrical metallocene hybrid catalytic systems were originally sourced from Idemitsu Kosan corporation of japan. LMPP is introduced into the polypropylene composite material, so that the appearance performance and the processing performance of the polypropylene composite material are improved. On one hand, the LMPP has good compatibility with the PP matrix, and the flow property of a material system can be improved; on the other hand, due to the fact that the LMPP damages the crystal structure of the PP, the crystallinity of the material is reduced, the cooling speed of a material system is slowed down, the processability of the polypropylene composite material is improved, and meanwhile, the problem of fiber floating on the surface of a polypropylene composite material part is effectively solved.
And 1-10 parts of LMPP (LMPP) by weight based on 100 parts of the polypropylene composite material. In some specific embodiments, the LMPP is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts based on 100 parts by weight of the polypropylene composite. The LMPP in the weight portion range and other components such as PP, LFT and the like have synergistic effect, and the problem of fiber floating on the surface of an injection molding product of the existing polypropylene material can be effectively solved.
As an embodiment, the low-modulus polypropylene has a melt index of 300-900g/10min at 230 ℃ and 2.16 kg. In some embodiments, the low modulus polypropylene has a melt index of 600g/10 min.
As an embodiment, the low modulus polypropylene has a density of 0.91 to 0.95g/cm3。
As an embodiment, the low modulus polypropylene has a molecular weight (Mw) of 104-105。
The glass bead, also called cavity glass bead, is a hollow ball with small size, belonging to inorganic non-metal material, and has hard outer shell in which N is placed2Or CO2An inert gas. Incorporating the glass particles in the polypropylene compositeThe beads can further improve the apparent performance and the mechanical property of the polypropylene composite material, and have the advantages of light weight, high and low temperature resistance, good electrical insulation and thermal stability, corrosion resistance and the like. And 0-5 parts of glass beads by 100 parts of the polypropylene composite material. In some embodiments, the glass microspheres are 0.2, 0.5, 0.7, 1.0, 1.3, 1.5, 1.8, 2.1, 2.5, 2.8, 3.0, 3.3, 3.6, 3.9, 4.2, 4.5, 4.7, 4.9, 5.0 parts based on 100 parts by weight of the polypropylene composite. The glass beads in the weight part range, the LMPP and other components have synergistic effect, so that the apparent performance of the polypropylene composite material can be further improved, and the apparent performance of the polypropylene composite material is obviously improved compared with a scheme of only adding the LMPP.
In one embodiment, the glass beads have a particle size of 10 to 100 μm. The glass beads can be uniformly dispersed in the polypropylene composite material, so that the polypropylene composite material has excellent mechanical property and stable size.
The compatilizer is used for promoting the components in the polypropylene composite material to be uniformly mixed so as to ensure that the polypropylene composite material has good mechanical properties. And 1-5 parts of a compatilizer, based on 100 parts by weight of the polypropylene composite material. In some embodiments, the compatibilizer is 1, 2, 3, 4, 5 parts based on 100 parts by weight of the polypropylene composite.
The compatibilizer may refer to materials that are conventional in the art, and in some embodiments, the compatibilizer is selected from polypropylene-maleic anhydride graft (PP-g-MAH) and/or ethylene-ethyl acrylate copolymer (EEA), which may serve as a reactive toughener to increase the bonding force between the glass fiber and the PP matrix, and improve the mechanical strength. And the lubricant is used for reducing the friction between the polypropylene composite material and equipment and the friction between the components so as to reduce the processing energy consumption and further improve the processing performance of the polypropylene composite material. 0.1-3 parts of the lubricant by 100 parts of the polypropylene composite material. In some embodiments, the lubricant is 0.1, 0.3, 0.5, 0.8, 1.0, 1.2, 1.5, 1.7, 1.9, 2.1, 2.5, 2.6, 2.9, 3 parts based on 100 parts by weight of the polypropylene composite.
The lubricant may be referred to lubricant materials conventional in the art, such as in some embodiments, the lubricant is selected from at least one of calcium stearate, erucamide, and silicone masterbatches.
And the antioxidant is used for protecting the polypropylene composite material from being thermally degraded in the processing process and prolonging the service life of the polypropylene composite material. And 0.1-1.5 parts of antioxidant by 100 parts of the polypropylene composite material. In some embodiments, the antioxidant is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5 parts based on 100 parts by weight of the polypropylene composite.
The antioxidant may be referred to antioxidant materials conventional in the art, such as in some embodiments, the antioxidant comprises a primary antioxidant selected from hindered phenolic antioxidants; the secondary antioxidant is selected from phosphite and/or thioester antioxidants.
And the flame retardant is used for improving the flame retardant property of the polypropylene composite material. And 15-30 parts of a flame retardant based on 100 parts by weight of the polypropylene composite material. In some embodiments, the flame retardant 15, 17, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 parts by weight of the polypropylene composite is used as 100 parts by weight of the flame retardant, and the flame retardant in the range of the parts by weight is cooperated with other components, so that the flame retardant property of the polypropylene composite is remarkably improved.
The flame retardant may be made by referring to conventional flame retardant materials in the art, such as in some embodiments, the flame retardant is a mixture of decabromodiphenylethane and antimony trioxide, belongs to a composite flame retardant system of a halogen-antimony system, takes a halogen-containing organic compound as a main component, and takes Sb as Sb2O3Is a synergistic agent. The flame retardant has the flame retardant effect mainly of gas phase flame retardant and also has a certain condensed phase flame retardant effect, wherein decabromodiphenylethane is decomposed into HBr in the combustion process, and the HBr can be combusted with polymers to generate high-activity free radicals such as HO, O, OH and the likeReacting to generate halogen free radical with lower activity, thereby slowing or stopping combustion. In further embodiments, the mass ratio of the decabromodiphenylethane to the antimony trioxide is (2-4): 1. In some specific embodiments, the mass ratio of the decabromodiphenylethane to the antimony trioxide is 2:1, 3:1 and 4:1, so that the flame retardant property of the polypropylene composite material can be optimized.
In order to make the appearance performance, the processing performance and the flame retardant performance of the polypropylene composite material more excellent, the applicant further optimizes the using amount of each component in the polypropylene composite material.
As an embodiment, the polypropylene composite material comprises the following components in parts by weight based on 100 parts by weight of the polypropylene composite material:
as an embodiment, the polypropylene composite material comprises the following components in parts by weight based on 100 parts by weight of the polypropylene composite material:
in summary, the polypropylene composite material provided by the embodiment of the invention comprises polypropylene, low-modulus polypropylene, a compatilizer, continuous long glass fibers, glass microspheres, a lubricant, an antioxidant and a flame retardant in a specific weight part ratio, and under the synergistic action of the components, the polypropylene composite material provided by the embodiment of the invention has good mechanical properties and appearance properties, so that floating fibers are not easy to appear on the surface of an injection molding product, and the polypropylene composite material has excellent flame retardant properties, mechanical properties and processability, and meets the requirements of high-strength automobile parts and electronic communication industries.
Compared with the existing long glass fiber reinforced polypropylene material, the polypropylene composite material provided by the invention is introduced with low-modulus polypropylene (LMPP) and a flame retardant, so that the polypropylene composite material is endowed with good appearance performance and flame retardant performance. The LMPP has good compatibility with a PP matrix, the flow property of a material system is improved, the crystal structure of the PP is damaged due to the addition of the LMPP, the crystallinity of the material is reduced, the cooling speed of the material system is slowed down, and the problem of surface fiber floating of a polypropylene composite material part is effectively improved while the processability of the polypropylene composite material is improved. According to the invention, 1-10 parts by weight of LMPP, 10-60 parts by weight of PP, 0-5 parts by weight of glass beads and 15-40 parts by weight of continuous long glass fiber (LFT) are compounded, so that the problem of fiber floating on the surface of a polypropylene composite material product and the flame retardant property are obviously improved.
Based on the technical scheme, the preparation process of the polypropylene composite material is as follows.
Correspondingly, the preparation method of the polypropylene composite material comprises the following steps:
s01, weighing the raw materials according to the polypropylene composite material;
s02, mixing the polypropylene, the compatilizer, the antioxidant, the low-modulus polypropylene, the lubricant, the flame retardant and the glass beads to obtain a mixture;
and S03, compounding the mixture and the continuous long glass fiber by adopting a melting and dipping process to obtain the polypropylene composite material.
Specifically, in step S02, the polypropylene, the compatibilizer, the antioxidant, the low modulus polypropylene, the lubricant, the flame retardant, and the glass beads are mixed to achieve a pre-mixing among the polypropylene, the compatibilizer, the antioxidant, the low modulus polypropylene, the lubricant, the flame retardant, and the glass beads. In some embodiments, the mixing is in a high speed blender at 100rpm for 3 min.
In step S03, the mixture is compounded with the continuous long glass fiber using a melt impregnation process to prepare the polypropylene composite material. The melt impregnation process can refer to the conventional melt impregnation process in the field, and the polypropylene composite material with no surface emergence and good flame retardant performance can be obtained by adopting the melt impregnation process and combining the formula of the polypropylene composite material.
As an embodiment, the melt impregnation process comprises:
s031, the mixture is discharged and extruded from a feed port of a double-screw extruder of a long fiber device to obtain a melt;
s032, introducing the continuous long glass fiber into a dipping die head through a glass fiber frame of a long fiber device, carrying out dipping coating, water cooling, drawing and grain cutting on the melt, and obtaining the polypropylene composite material with the length meeting the requirements of the automobile module product process or the household product process.
In some embodiments, in step S031, the mixture is fed out from the feed port of the twin-screw extruder of the filament apparatus at a temperature of 200-. In a further embodiment, the temperature for blanking and extruding the mixture from the feed port of the double-screw extruder of the long fiber device is set to be 250-285 ℃.
In some embodiments, the polypropylene composite obtained in step S032 is a long glass fiber reinforced polypropylene composite with a length of 6-9mm, low fiber floating on the surface, and flame retardancy.
In summary, the preparation method of the polypropylene composite material provided by the embodiment of the invention can prepare the polypropylene composite material by adopting a melt impregnation process, and has the advantages of simple method, simple and convenient operation and easy large-scale mass production.
In order that the details of the above-described practice and operation of the present invention will be clearly understood by those skilled in the art, and the advanced properties of the polypropylene composite material and the method of making the same according to the embodiments of the present invention will be apparent, the practice of the present invention will be illustrated by the following examples.
The formulations of the polypropylene composites provided in examples 1-6 and comparative examples 1-2 are shown in Table 1:
TABLE 1
When in preparation, the following steps are adopted:
1) weighing raw materials according to the formula shown in Table 1;
2) mixing PP, a compatilizer, an antioxidant, LMPP, a lubricant, a flame retardant and glass beads in a high-speed mixer at a rotating speed of 100rpm for 3min to obtain a mixture;
3) feeding the mixture from a feed port of a double-screw extruder of long fiber equipment and extruding at the temperature of 250-285 ℃ to obtain a melt; and then, introducing the LFT into a dipping die head through a glass fiber frame of long fiber equipment, carrying out dipping and coating on the melt, carrying out water cooling, traction and grain cutting to obtain the long glass fiber reinforced polypropylene composite material with the length of 6-9mm, low floating fiber and flame retardance.
The polypropylene composites prepared in examples 1 to 6 and comparative examples 1 to 2 were subjected to mechanical property test and appearance evaluation, respectively, table 2 shows test items and test conditions, and table 3 shows test results.
As shown by the results, the polypropylene composite materials provided by examples 1-6 all have good appearance performance and flame retardant property, and simultaneously keep higher comprehensive mechanical property. The comparison between the example 1, the example 6 and the comparative example 2 shows that the problem that the surface of the existing long glass fiber reinforced polypropylene material is easy to float after injection molding can be solved by adding the LMPP. When the LMPP and the glass beads are added simultaneously, the polypropylene composite material has a more obvious effect of improving the appearance performance. And the method can be widely applied to the industries of automobile parts and electronic appliances.
TABLE 2
TABLE 3
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. The polypropylene composite material is characterized by comprising the following components in parts by weight based on 100 parts by weight of the polypropylene composite material:
10-60 parts of polypropylene;
1-10 parts of low-modulus polypropylene;
1-5 parts of a compatilizer;
15-40 parts of continuous long glass fiber;
0.2-5 parts of glass beads;
0.1-3 parts of a lubricant;
0.1-1.5 parts of antioxidant;
15-30 parts of a flame retardant;
the melt index of the low-modulus polypropylene is 300-900g/10min, and the density of the low-modulus polypropylene is 0.91-0.95g/cm3The low modulus polypropylene has a molecular weight of 104-105The low modulus polypropylene is a type using a special C2The polypropylene material with low modulus, low molecular weight and narrow molecular weight distribution is produced by the symmetrical metallocene composite catalytic system.
2. The polypropylene composite of claim 1, comprising the following components in parts by weight, based on 100 parts by weight of the polypropylene composite:
20-40 parts of polypropylene;
1-5 parts of low-modulus polypropylene;
2-4 parts of a compatilizer;
15-35 parts of continuous long glass fiber;
0.2-5 parts of glass beads;
0.1-3 parts of a lubricant;
0.1-1.5 parts of antioxidant;
15-30 parts of a flame retardant.
3. The polypropylene composite of claim 1, comprising the following components in parts by weight, based on 100 parts by weight of the polypropylene composite:
33 parts of polypropylene;
3 parts of low-modulus polypropylene;
3 parts of a compatilizer;
30 parts of continuous long glass fiber;
5 parts of glass beads;
1 part of a lubricant;
1 part of an antioxidant;
and 24 parts of a flame retardant.
4. The polypropylene composite according to any one of claims 1 to 3, wherein the polypropylene is a co-polypropylene and/or a homo-polypropylene and the polypropylene has a melt index of 50-120g/10 min.
5. The polypropylene composite according to any one of claims 1 to 3, wherein the glass microspheres have a particle size of 10-100 μm.
6. The polypropylene composite according to any one of claims 1 to 3, wherein the flame retardant is selected from a mixture of decabromodiphenylethane and antimony trioxide.
7. The polypropylene composite according to claim 6, wherein the mass ratio of decabromodiphenylethane to antimony trioxide is (2-4): 1.
8. The preparation method of the polypropylene composite material is characterized by comprising the following steps:
weighing raw materials according to the polypropylene composite material of any one of claims 1 to 7;
mixing the polypropylene, the compatibilizer, the antioxidant, the low modulus polypropylene, the lubricant, the flame retardant and the glass beads to obtain a mixture;
and compounding the mixture and the continuous long glass fiber by adopting a melting impregnation process to obtain the polypropylene composite material.
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| CN106967250B (en) * | 2017-03-16 | 2020-05-12 | 湖州艾历克工业材料有限公司 | Composition of long fiber reinforced thermoplastic molding material and use method thereof |
| CN106987051A (en) * | 2017-04-28 | 2017-07-28 | 安徽科聚新材料有限公司 | Fiber glass reinforced polypropylene material and preparation method thereof |
| CN110041609A (en) * | 2019-04-28 | 2019-07-23 | 东风汽车集团有限公司 | A kind of low floating fine continuously Long Glass Fiber Reinforced PP Composite and the preparation method and application thereof |
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