CN112480536A - Polypropylene composition and preparation and application thereof - Google Patents
Polypropylene composition and preparation and application thereof Download PDFInfo
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- CN112480536A CN112480536A CN202011356622.XA CN202011356622A CN112480536A CN 112480536 A CN112480536 A CN 112480536A CN 202011356622 A CN202011356622 A CN 202011356622A CN 112480536 A CN112480536 A CN 112480536A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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Abstract
The invention relates to a polypropylene composition and preparation and application thereof. The composite material obtained by the invention has excellent mechanical properties, the glass fiber glass length is obviously improved, and the composite material is suitable for the fields of automobile industry and household electrical appliances with higher requirements on material strength and toughness.
Description
Technical Field
The invention belongs to the field of modified plastics and preparation and application thereof, and particularly relates to a polypropylene composition and preparation and application thereof.
Background
The polypropylene (PP) resin has the advantages of small density, excellent chemical stability, easy processing and forming and the like, so the polypropylene resin has wide application in the fields of automobile industry, household appliances, electronic appliances and the like, and the glass fiber reinforced modification is an important means for improving the properties of polypropylene such as strength, heat resistance and the like in the modification of the polypropylene, so that the polypropylene can expand more application environments and fields.
In the field of modified plastics, two core factors influencing the glass fiber reinforcement effect are mainly provided, wherein the glass fiber retention length in the composite material is longer, the reinforcement effect is more excellent, and the interface strength of the glass fiber and polypropylene is better in compatibility and higher, so that the reinforcement effect is more obvious. At present, the reinforcing effect of the chopped glass fiber reinforced polypropylene material is in a bottleneck, and is difficult to further improve, so that the development of a new modification technology and a new method are urgently needed. The short glass fiber reinforced polypropylene composite material has the advantages that after glass fibers with high rigidity are added into a double-screw extruder, the length of the glass fibers is rapidly reduced under the action of heat and shearing, so that the reinforcing effect is limited, and therefore, how to improve the glass fiber retention length of the glass fiber reinforced polypropylene composite material becomes an industrial research hotspot and difficulty. The LFT technology is a reinforced modification technology developed from the aspect of improving the retention length of glass fibers, and compared with the traditional chopped glass fiber reinforced polypropylene technology, the strength and toughness of the composite material of the LFT technology are obviously improved, but the production equipment of the LFT composite material is expensive, and a special injection molding machine is needed in the downstream processing process to keep good performance.
CN111635590A discloses a glass fiber reinforced polypropylene material and a preparation method thereof, wherein the surface of glass fiber is treated by white oil and a coupling agent, so that the strength of the material is improved, and the linear expansion coefficient is reduced.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polypropylene composition, and preparation and application thereof, and overcoming the defects of the existing glass fiber reinforced composite material technology that the compatibility is improved and the reinforcing effect is limited.
The invention relates to a polypropylene composition, which comprises the following raw materials in parts by weight:
the surface treatment glass fiber is prepared by soaking glass fiber in liquid hydrocarbon at 60-100 deg.C,
and (4) obtaining.
The polypropylene is one or more of homopolymerized polypropylene, block copolymerization polypropylene and random copolymerization polypropylene, and the melt index of the polypropylene is 10-150g/10min under the condition of 230 ℃/2.16 kg.
The compatilizer is maleic anhydride grafted polypropylene, wherein the molar grafting rate of the maleic anhydride is 0.5-1.5%.
The antioxidant is at least one of hindered phenol antioxidant and phosphite antioxidant; including but not limited to, for example, one or a mixture of two of 3, 5-di-tert-butyl-4-hydroxyphenylpropionyl-hexamethylenediamine (antioxidant 1098), tris (2, 4-di-tert-butylphenol) phosphite (antioxidant 168), and pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010).
The lubricant includes but is not limited to one or more of silicone-based, amide-based, polyethylene-based, stearic acid-based, and ester-based lubricants, which can be selected as required.
The glass fiber is chopped glass fiber, the length of the chopped glass fiber is 3-10mm, and the diameter of the chopped glass fiber is 14-21 mu m, preferably 16-18 mu m.
The liquid hydrocarbon is ElevastTMOne or more of them, e.g. ElevastTM A80，ElevastTMD50、ElevastTMC30、ElevastTMD20、ElevastTMD10。
Wherein the liquid hydrocarbon is ElevastTMHas a kinematic viscosity (40 ℃) of 65-3200mm2The flash point is 260 ℃ and 300 ℃.
The soaking time is 30-60 min.
The invention provides a preparation method of a polypropylene composition, which comprises the following steps:
weighing the raw materials according to the proportion, placing the polypropylene, the compatilizer, the antioxidant and the lubricant in a high-speed mixer, and mixing at the rotating speed of 300-500rpm for 10-30min to obtain a premix;
and (3) placing the premix into a main feeding port of a double-screw extruder, placing the surface-treated glass fiber into a side feeding port of the double-screw extruder, and carrying out melt mixing, extrusion and granulation to obtain the polypropylene composition.
The polypropylene composition disclosed by the invention is applied to the fields of the automobile industry and household appliances, such as thin-wall extruded pipes.
Advantageous effects
The invention starts from the angle of improving the shearing resistance of the glass fiber, and realizes that the retention length of the glass fiber in the composite material is greatly increased, thereby improving the glass fiber reinforcing effect and realizing the high performance of the composite material; according to the invention, the surface treatment is carried out on the glass fiber by using the hydrocarbon fluid under the specific process conditions, so that the shearing resistance of the glass fiber is obviously improved, and the hydrocarbon fluid and polypropylene have excellent compatibility and more excellent interface compatibility compared with the traditional surface sizing agent; the invention optimizes the diameter of the glass fiber, and can obviously improve the dispersion effect of the glass fiber.
The composite material prepared by the invention has excellent mechanical properties, the glass fiber glass length is obviously improved, and the composite material is suitable for the fields of automobile industry and household electrical appliances with higher requirements on material strength and toughness.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
(1) Sources of raw materials
Polypropylene: the trade mark Z30S, the melt index under the condition of 230 ℃/2.16kg is 30g/10min, and the manufacturer is China petrochemical land and sea refining chemical division.
Glass fiber: the mark ECS13-04-508C, the diameter of the glass fiber is 13 μm, and the manufacturer is boulder group.
Glass fiber: the mark ECS17-04-508C, the diameter of the glass fiber is 17 μm, and the manufacturer is boulder group.
Glass fiber: the product is ECS14-04-508C, the diameter of the glass fiber is 14 μm, and the product is a boulder group product.
Glass fiber: the product is ECS21-04-508C, the diameter of the glass fiber is 21 μm, and the product is a boulder group product.
A compatilizer: the trade name BONDYRAM 1001CN, manufactured by Prill Lang corporation.
Liquid hydrocarbon compound: elevastTM A80，ElevastTMThe D50 manufacturer is Exxon Mobil.
Antioxidant: the brand antioxidant 1010 is produced by Rianlong New Material GmbH.
Lubricant: the trade name BS-3818, made by Huaming Tai chemical Co., Ltd
The glass fiber after surface treatment adopted in the embodiment:
soaking glass fiber in liquid hydrocarbon Elevast at 80 DEG CTMSoaking in A80 for 45min, taking out, and cooling to obtain surface-treated glass fiber A1;
soaking the glass fiber inLiquid hydrocarbon at 80 ℃ of ElevastTMD50, soaking for 45min, taking out and cooling for later use to obtain surface-treated glass fiber A2;
(Note: surface-treated glass fiber, for example, 17 μm surface-treated glass fiber A1 shows that glass fiber having a diameter of 17 μm is soaked in liquid hydrocarbon Elevast at 80 ℃TMA80, soaking for 45min, taking out, cooling, and getting 17 μm surface treated glass fiber A1, 17 μm represents glass fiber diameter, and so on)
Glass fiber A1 after surface treatment of 17 μm in practice, wherein ElevastTMThe content of A80 is about 0.8% by mass of the glass fiber. White oil 10# white oil, Shanghai Bright chemical Co., Ltd
Surface-modified glass fiber B used in comparative example: mixing white oil and KH550 silane coupling agent according to a mass ratio of 5:1, mixing with glass fiber (glass fiber mark ECS17-04-508C, diameter of 17 μm), and performing surface treatment on the glass fiber to obtain surface modified glass fiber B; wherein the dosage of KH550 is 1 percent of the mass of the glass fiber.
(2) Test standards and methods
The composite materials prepared in the specific examples and comparative examples are subjected to various mechanical property and glass fiber retention length test standards and test methods as follows:
tensile strength: the test was carried out according to ISO527 with a tensile speed of 10 mm/min.
Bending strength: the test was carried out according to ISO178, bending speed 2 mm/min.
Flexural modulus: the test was carried out according to ISO178, bending speed 2 mm/min.
Notched izod impact strength: test according to ISO180, notch type: and (B) type A.
Testing the retention length of the glass fiber: and (3) injecting a mechanical sample strip into the composite material, then placing the composite material in a muffle furnace at 800 ℃ for firing, collecting ash glass fibers, counting the average retention length of the glass fibers under a microscope, and randomly sampling 600 glass fibers.
Examples 1 to 9
Weighing the components according to the weight part ratio in the table 1, and then placing the polypropylene, the compatilizer, the antioxidant and the lubricant into a high-speed mixer to mix for 10-30min at the rotating speed of 300-500rpm to obtain a premix;
placing the obtained pre-mixture into a main feeding port of a double-screw extruder, placing the glass fiber subjected to surface treatment into a side feeding port of the double-screw extruder, and performing melting mixing, extrusion and granulation to obtain a high-performance glass fiber reinforced polypropylene composite material; wherein the screw rotating speed of the double-screw extruder is 300-500rpm, and the melting temperature of the double-screw extruder is 200-250 ℃.
Comparative examples 1 to 4
Weighing the components according to the weight part ratio in the table 1, and then placing the polypropylene, the compatilizer, the antioxidant and the lubricant into a high-speed mixer to mix for 10-30min at the rotating speed of 300-500rpm to obtain a premix;
placing the obtained pre-mixture into a main feeding port of a double-screw extruder, placing glass fiber (or surface modified glass fiber B) into a side feeding port of the double-screw extruder, and performing melting, mixing, extrusion and granulation to obtain a glass fiber reinforced polypropylene composite material; wherein the screw rotating speed of the double-screw extruder is 300-500rpm, and the melting temperature of the double-screw extruder is 200-250 ℃.
Comparative example 5
Weighing the components according to the weight part ratio in the table 1, and then placing the polypropylene, the liquid hydrocarbon, the compatilizer, the antioxidant and the lubricant in a high-speed mixer to mix for 10-30min at the rotating speed of 300-500rpm to obtain a premix;
placing the obtained pre-mixture into a main feeding port of a double-screw extruder, placing glass fibers into a side feeding port of the double-screw extruder, and performing melting, mixing, extrusion and granulation to obtain a glass fiber reinforced polypropylene composite material; wherein the screw rotating speed of the double-screw extruder is 300-500rpm, and the melting temperature of the double-screw extruder is 200-250 ℃.
TABLE 1 EXAMPLES 1-9 AND COMPARATIVE EXAMPLES 1-5 amounts of the respective ingredients
TABLE 2 results of the Performance test of the specific examples and comparative examples
As can be seen from table 2, compared with the conventional glass fiber reinforced polypropylene composite material, the high-performance glass fiber reinforced polypropylene composite material of the present application has the advantages that the glass fiber retention length is significantly increased, and the mechanical property performance is more excellent; compared with the comparative example 1, the comparison of the example 2 and the comparative example 1 shows that the glass fiber treated by the liquid hydrocarbon can greatly improve the shearing resistance, and the retention length of the glass fiber is obviously improved; comparing the example 2 with the comparative example 3, it can be found that the diameter of the glass fiber has an important influence on the effect of the invention; compared with the glass fiber reinforced polypropylene system, the composite material disclosed by the invention realizes high performance of glass fiber reinforced polypropylene, and the prepared polypropylene composite material is suitable for the fields of automobile industry and household appliances with higher requirements on material strength.
Claims (9)
1. The polypropylene composition is characterized by comprising the following raw materials in parts by weight:
the surface treatment glass fiber is obtained by soaking the glass fiber in liquid hydrocarbon at 60-100 ℃.
2. The composition according to claim 1, wherein the polypropylene is one or more of homo-polypropylene, block co-polypropylene and random co-polypropylene, and the melt index of the polypropylene is 10-150g/10min at 230 ℃/2.16 kg.
3. The composition of claim 1, wherein the compatibilizer is maleic anhydride grafted polypropylene, and the molar grafting ratio of maleic anhydride is 0.5 to 1.5%.
4. The composition of claim 1, wherein the antioxidant is at least one of a hindered phenolic antioxidant and a phosphite antioxidant; the lubricant is one or more of silicone lubricant, amide lubricant, polyethylene lubricant, stearic acid lubricant and ester lubricant.
5. The composition of claim 1, wherein the glass fibers are chopped glass fibers having a length of 3 to 10mm and a diameter of 14 to 21 μm.
6. The composition of claim 1, wherein the liquid hydrocarbon is ElevastTMOne or more of them.
7. The composition of claim 1, wherein the soaking time is 30-60 min.
8. A method of making a polypropylene composition comprising:
weighing the raw materials according to the proportion of claim 1, placing the polypropylene, the compatilizer, the antioxidant and the lubricant in a high-speed mixer, and mixing at the rotating speed of 300-500rpm for 10-30min to obtain a premix;
and (3) placing the premix into a main feeding port of a double-screw extruder, placing the surface-treated glass fiber into a side feeding port of the double-screw extruder, and carrying out melt mixing, extrusion and granulation to obtain the polypropylene composition.
9. Use of the polypropylene composition according to claim 1 in the automotive industry and in the field of household electrical appliances.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113881136A (en) * | 2021-09-18 | 2022-01-04 | 江苏金发科技新材料有限公司 | High-pressure-resistance and stress-whitening-resistance polypropylene composition and preparation method and application thereof |
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