CN114213686B - Low-warpage glass fiber reinforced polypropylene composite material and preparation method thereof - Google Patents
Low-warpage glass fiber reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-warpage glass fiber reinforced polypropylene composite material and a preparation method thereof, wherein the low-warpage glass fiber reinforced polypropylene composite material comprises, by weight, 30-80 parts of polypropylene resin, 10-30 parts of chopped glass fiber, 1-30 parts of modified nano lamellar all-silicon molecular sieve, 2-8 parts of compatilizer, and 0.2-3 parts of antioxidant, light stabilizer and lubricant. By adding a certain proportion of chopped glass fibers and specific nano lamellar fillers for composite reinforcement, the added minerals can effectively reduce the molecular chain orientation degree caused by the high-length-diameter ratio glass fibers, thereby reducing the buckling deformation caused by the anisotropy of the materials in the injection molding process, and simultaneously having excellent mechanical properties and high strength.
Description
Technical Field
The invention relates to a polypropylene composite material, in particular to a low-warpage glass fiber reinforced polypropylene composite material and a preparation method thereof.
Background
Because of its performance characteristics, polypropylene resin needs to be reinforced when in use, and polypropylene is reinforced by glass fibers, and mainly comprises two types, namely, short glass fibers are used as reinforcing materials, and continuous long glass fibers are used as reinforcing materials, so that the reinforced polypropylene material has wide application in the fields of household electrical appliance manufacturing, automobile manufacturing and the like.
As a general thermoplastic reinforced composite material, the glass fiber reinforced polypropylene has the advantages of high elastic modulus, high strength, high heat distortion temperature, good dimensional stability, low price and the like. However, due to the needle-shaped morphology characteristics of the glass fiber, the glass fiber has extremely high length-diameter ratio, so that the shrinkage rate of the material in the flowing direction and the vertical direction in the injection molding process is greatly different, and the obvious difference can cause serious buckling deformation of the material. This feature also limits the application of glass fiber reinforcement to some high precision parts.
Chinese patent CN102250420A discloses a warpage-resistant reinforced polypropylene composite material and a preparation method thereof, wherein the invention selects a low-orientation glass fiber with elliptical cross section, the warpage-resistant effect of the glass fiber is better than that of a common chopped glass fiber, the other properties of the material are not affected, but the addition proportion of a compatilizer is too high and reaches 5% -15%, so that the preparation cost is higher; patent CN102532682a discloses a low-warpage high-gloss filling reinforced polypropylene material and a preparation method thereof, and an effect of preventing warpage is achieved by adding 5-15 parts of wollastonite, but the aspect ratio of wollastonite is still larger, so that improvement on warpage is limited.
In view of the defects of the prior glass fiber reinforced polypropylene composite material, the inventor develops a low-warpage glass fiber reinforced polypropylene composite material and a preparation method thereof based on years of rich experience and expertise of the material and cooperation with theoretical analysis, and has higher strength while improving the warpage phenomenon.
Disclosure of Invention
The first object of the invention is to provide a glass fiber reinforced polypropylene composite material with low warpage, which can ensure good mechanical properties of the material and improve warpage phenomenon, in particular to have high strength.
The technical aim of the invention is realized by the following technical scheme:
the invention provides a low-warpage glass fiber reinforced polypropylene composite material which comprises the following components in parts by weight,
the mass ratio of the antioxidant, the light stabilizer and the lubricant is 4-6:1-4:1-4, and the mass ratio of the antioxidant, the light stabilizer and the lubricant is preferably 4:3:3.
Preferably, the polypropylene is a propylene copolymer or propylene homopolymer having a melt flow rate of 3 to 30g/10min at 230℃C.2.16 kg.
Preferably, the antioxidant can be hindered phenol antioxidant or phosphite antioxidant, the light stabilizer is hindered amine light stabilizer, and the lubricant is one of metal soap lubricant, stearic acid composite ester lubricant or amide lubricant.
Preferably, the nano-platelet all-silicon molecular sieve in the modified nano-platelet all-silicon molecular sieve is prepared by the following method,
(1) Silicon source, alkali source (NaOH), structureThe directing agent (SDA) was mixed with deionized water to form a sol at room temperature in the following molar ratio: h 2 O/SiO 2 ＝20-25，SDA/SiO 2 ＝0.02-0.05，NaOH/SiO 2 In this alkaline environment, =2-5, rapid nucleation is favored, the crystallization period is reduced, and the formation of impurity crystals during nucleation is greatly reduced. And after ageing at room temperature, carrying out hydrothermal synthesis for 12 hours at 140 ℃ to obtain crystals, wherein in the process, the initial gel is depolymerized and rearranged to form a specific structural unit, and further forms a crystal polyhedron around a template agent (SDA), and the crystal nucleus is formed by aggregation, so that the molecular sieve crystals are gradually formed. And then repeatedly washing, centrifuging and drying the prepared molecular sieve crystal by deionized water to obtain the nanoscale all-silicon molecular sieve, wherein the size of the molecular sieve is 50-100nm.
(2) Calcining the nanoscale all-silicon molecular sieve prepared in the step (1) in a muffle furnace at 460 ℃ for 4 hours to obtain the nano lamellar all-silicon molecular sieve.
Preferably, the nano lamellar all-silicon molecular sieve is modified by preparing a silane coupling agent into an organic solution with the concentration of 10% -15%, adding the prepared nano lamellar all-silicon molecular sieve into the organic solution, stirring, carrying out suction filtration, washing with absolute ethyl alcohol and distilled water for multiple times, and drying to obtain the modified nano lamellar all-silicon molecular sieve, wherein the silane coupling agent can well combine an organic functional group in the silane coupling agent with a polymer substrate due to a special chemical structure, and can hydrolyze and combine with the surface of the molecular sieve in a chemical bond (condensation) or physical (hydrogen bond) mode. Therefore, the molecular sieve treated by the silane coupling agent can well improve the wettability and the dispersibility of the filler in the polymer and improve the performance of the material.
Preferably, the silicon source is at least one of silica sol, tetraethyl orthosilicate or sodium silicate, and a sufficient silicon source is provided for the synthesized molecular sieve to construct a molecular sieve structural framework.
Preferably, the structure directing agent is at least one of tetrapropylammonium hydroxide, tetrapropylammonium bromide or tetraethylammonium bromide, and mainly provides structure directing effect for synthesis of molecular sieves, promotes formation of crystal cage-like structures, and can shorten nucleation crystallization time.
Preferably, the chopped glass fibers have a length of 0.5-6mm and a diameter of 6-15 μm, and belong to one of alkali-free glass fibers.
Preferably, the compatibilizer is maleic anhydride grafted polypropylene.
The invention also aims to provide a preparation method of the low-warpage glass fiber reinforced polypropylene composite material, which ensures that the material has better mechanical properties and improves warpage through optimizing the preparation process.
The technical effects of the invention are realized by the following technical scheme:
the preparation method of the low-warpage glass fiber reinforced polypropylene composite material provided by the invention comprises the following operation steps,
s1, preparing a modified nano lamellar all-silicon molecular sieve;
s2, mixing the modified nano lamellar all-silicon molecular sieve prepared in the step S1 with a polypropylene material in a high-pressure mixing pot according to a proportion to obtain a mixture;
s3, the mixture prepared in the step S2, a compatilizer, an antioxidant and other auxiliary agents enter from a main feeding port according to mass ratio, the chopped glass fibers enter from a side feeding port according to mass ratio, and the temperature of the extruder is controlled as follows: the target product is obtained by melting, extruding, cooling, granulating and drying the materials at 160-180 ℃ in the first region, 180-200 ℃ in the second region, 190-200 ℃ in the third region, 190-210 ℃ in the fourth region, 190-210 ℃ in the fifth region, 190-210 ℃ in the sixth region, 190-210 ℃ in the seventh region and 190-210 ℃ in the eighth region and 190-220 ℃ in the ninth region.
Preferably, the nano-platelet all-silicon molecular sieve in the modified nano-platelet all-silicon molecular sieve is prepared by a method which is beneficial to the perfect crystal with few growth defects and easy to control the granularity and morphology of the product crystal.
(1) Mixing a silicon source, an alkali source, a structure directing agent and deionized water, wherein the mol ratio of sol formed at room temperature is as follows: h 2 O/SiO 2 ＝20-25，SDA/SiO 2 ＝0.02-0.05，NaOH/SiO 2 After aging at room temperature, hydrothermal synthesis is carried out for 12h at 140 ℃, and the preparation is carried outRepeatedly washing the prepared crystal with deionized water, centrifuging and drying to obtain the nanoscale all-silicon molecular sieve;
(2) Calcining the nano-scale all-silicon molecular sieve prepared in the step (1) in a muffle furnace at 460 ℃ to obtain the nano-lamellar all-silicon molecular sieve.
Preferably, the nano lamellar all-silicon molecular sieve is modified by preparing a silane coupling agent into an organic solution with the concentration of 10% -15%, adding the prepared nano lamellar all-silicon molecular sieve into the organic solution, stirring, filtering, washing with absolute ethyl alcohol and distilled water for multiple times, and drying to obtain the modified nano lamellar all-silicon molecular sieve.
Preferably, the silicon source is at least one of silica sol, tetraethyl orthosilicate or sodium silicate.
Preferably, the structure directing agent is at least one of tetrapropylammonium hydroxide, tetrapropylammonium bromide or tetraethylammonium bromide, which provides structure directing effect for the synthesis of the molecular sieve and promotes the formation of crystal cage-like structures.
Preferably, the length of the chopped glass fiber is 0.5-6mm, and the diameter is 6-15 mu m, so that the dispersion of the glass fiber in the processing process is facilitated, and the related mechanical properties of the material are improved.
Preferably, the compatibilizer is maleic anhydride grafted polypropylene.
Preferably, the antioxidant is a mixture of a primary antioxidant 1010 and an auxiliary antioxidant 168, and the weight ratio of the mixture is 1:1-1:4.
preferably, the lubricant is mainly a mixture of calcium stearate and EBS, and the weight ratio of the additive is 0.1-0.0.6: 0.1 to 0.5.
In summary, the invention has the following beneficial effects:
according to the low-warpage glass fiber reinforced polypropylene composite material provided by the invention, the chopped glass fibers and the specific nano lamellar filler in a certain proportion are added for composite reinforcement, and the added minerals can effectively reduce the molecular chain orientation degree caused by the glass fibers with high length-diameter ratio, so that the warpage deformation caused by the anisotropy of the material in the injection molding process is reduced, and meanwhile, the low-warpage glass fiber reinforced polypropylene composite material has excellent mechanical properties and high strength.
Detailed Description
In order to further describe the technical means and effects adopted by the invention to achieve the preset aim, the invention provides a low-warpage glass fiber reinforced polypropylene composite material and a preparation method thereof, and specific embodiments, characteristics and effects thereof are described in detail below.
In the following examples, the sources of commercially available materials are as follows:
polypropylene resin: homo-polypropylene, HP500N, pucheng energy
Chopped glass fibers: CS248A-13P, europeanism
Talc powder: 3000 mesh Liaoning Ai Hai
And (3) a compatilizer: maleic anhydride grafted PP (KT-1), shenyang Ketong plastics technology Co., ltd
An antioxidant: 1010 and 168, beijing extremely easy chemical industry
And (3) a lubricant: calcium stearate, shandong Baolilai plastics auxiliary Co., ltd; TAF, xingtailing photochemical auxiliary
All-silicon molecular sieve: products in general on the market
Silicon source: LUDOX TM-40
Alkali source: naOH, chinese medicine
Structure directing agent: TMADaOH, alpha
Silane coupling agent: KH-550, zhongjie New Material Co., ltd
Absolute ethyl alcohol: chinese medicine selling device
Example 1
The low-warpage glass fiber reinforced polypropylene composite material comprises the following components in parts by weight, 76 parts of polypropylene resin, 10 parts of chopped glass fiber, 10 parts of modified nano lamellar all-silicon molecular sieve, 4 parts of compatilizer, 0.4 part of antioxidant, light stabilizer and lubricant in total, wherein the mass ratio of the antioxidant, the light stabilizer and the lubricant is 4:3:3.
The preparation method of the low-warpage glass fiber reinforced polypropylene composite material comprises the following operation steps,
weighing the components according to the mass ratio,
s1, preparing a modified nano lamellar all-silicon molecular sieve;
s2, mixing the modified nano lamellar all-silicon molecular sieve prepared in the step S1 with polypropylene resin in a high-pressure mixing pot according to a proportion to obtain a mixture;
s3, the mixture prepared in the step S2, the compatilizer, the antioxidant, the light stabilizer and the lubricant enter from a main feeding port according to the mass ratio, the chopped glass fibers enter from a side feeding port according to the mass ratio, and the temperature of the extruder is controlled as follows: the target product is obtained by melting, extruding, cooling, granulating and drying the materials at 160-180 ℃ in the first region, 180-200 ℃ in the second region, 190-200 ℃ in the third region, 190-210 ℃ in the fourth region, 190-210 ℃ in the fifth region, 190-210 ℃ in the sixth region, 190-210 ℃ in the seventh region and 190-210 ℃ in the eighth region and 190-220 ℃ in the ninth region.
The modified nano lamellar all-silicon molecular sieve is prepared by the following method:
(1) Mixing a silicon source, an alkali source, a structure directing agent and deionized water, wherein the mol ratio of sol formed at room temperature is as follows: h 2 O/SiO 2 ＝20-25，SDA/SiO 2 ＝0.02-0.05，NaOH/SiO 2 After being aged at room temperature, the preparation method comprises the steps of (1) hydrothermally synthesizing crystals, repeatedly washing the prepared crystals with deionized water, centrifuging and drying to obtain the nanoscale all-silicon molecular sieve;
(2) Calcining the nanoscale all-silicon molecular sieve prepared in the step (1) in a high-temperature muffle furnace to obtain the nano lamellar all-silicon molecular sieve.
(3) Preparing a silane coupling agent into 10% organic solution, adding the prepared nano lamellar all-silicon molecular sieve into the organic solution, stirring, filtering, washing with absolute ethyl alcohol and distilled water for multiple times, and drying to obtain the modified nano lamellar all-silicon molecular sieve.
Example 2
The low-warpage glass fiber reinforced polypropylene composite material comprises the following components in parts by weight, 66 parts of polypropylene resin, 10 parts of chopped glass fiber, 20 parts of modified nano lamellar all-silicon molecular sieve, 4 parts of compatilizer, 0.4 part of antioxidant, light stabilizer and lubricant in total, wherein the mass ratio of the antioxidant, the light stabilizer and the lubricant is 4:3:3.
The preparation method of the low-warpage glass fiber reinforced polypropylene composite material comprises the following operation steps,
weighing the components according to the mass ratio,
s1, preparing a modified nano lamellar all-silicon molecular sieve;
s2, mixing the modified nano lamellar all-silicon molecular sieve prepared in the step S1 with polypropylene resin in a high-pressure mixing pot according to a proportion to obtain a mixture;
s3, the mixture prepared in the step S2, the compatilizer, the antioxidant, the light stabilizer and the lubricant enter from a main feeding port according to the mass ratio, the chopped glass fibers enter from a side feeding port according to the mass ratio, and the temperature of the extruder is controlled as follows: the target product is obtained by melting, extruding, cooling, granulating and drying the materials at 160-180 ℃ in the first region, 180-200 ℃ in the second region, 190-200 ℃ in the third region, 190-210 ℃ in the fourth region, 190-210 ℃ in the fifth region, 190-210 ℃ in the sixth region, 190-210 ℃ in the seventh region and 190-210 ℃ in the eighth region and 190-220 ℃ in the ninth region.
The modified nano lamellar all-silicon molecular sieve is prepared by the following method:
(1) Mixing a silicon source, an alkali source, a structure directing agent and deionized water, wherein the mol ratio of sol formed at room temperature is as follows: h 2 O/SiO 2 ＝20-25，SDA/SiO 2 ＝0.02-0.05，NaOH/SiO 2 After being aged at room temperature, the preparation method comprises the steps of (1) hydrothermally synthesizing crystals, repeatedly washing the prepared crystals with deionized water, centrifuging and drying to obtain the nanoscale all-silicon molecular sieve;
(2) Calcining the nanoscale all-silicon molecular sieve prepared in the step (1) in a high-temperature muffle furnace to obtain the nano lamellar all-silicon molecular sieve.
(3) Preparing a silane coupling agent into a 12% organic solution, adding the prepared nano lamellar all-silicon molecular sieve into the organic solution, stirring, filtering, washing with absolute ethyl alcohol and distilled water for multiple times, and drying to obtain the modified nano lamellar all-silicon molecular sieve.
Example 3
The low-warpage glass fiber reinforced polypropylene composite material comprises the following components in parts by weight, 56 parts of polypropylene resin, 10 parts of chopped glass fiber, 30 parts of modified nano lamellar all-silicon molecular sieve, 4 parts of compatilizer, 0.4 part of antioxidant, light stabilizer and lubricant in total, wherein the mass ratio of the antioxidant, the light stabilizer and the lubricant is 4:3:3.
The preparation method of the low-warpage glass fiber reinforced polypropylene composite material comprises the following operation steps,
weighing the components according to the mass ratio,
s1, preparing a modified nano lamellar all-silicon molecular sieve;
s2, mixing the modified nano lamellar all-silicon molecular sieve prepared in the step S1 with polypropylene resin in a high-pressure mixing pot according to a proportion to obtain a mixture;
s3, the mixture prepared in the step S2, the compatilizer, the antioxidant, the light stabilizer and the lubricant enter from a main feeding port according to the mass ratio, the chopped glass fibers enter from a side feeding port according to the mass ratio, and the temperature of the extruder is controlled as follows: the target product is obtained by melting, extruding, cooling, granulating and drying the materials at 160-180 ℃ in the first region, 180-200 ℃ in the second region, 190-200 ℃ in the third region, 190-210 ℃ in the fourth region, 190-210 ℃ in the fifth region, 190-210 ℃ in the sixth region, 190-210 ℃ in the seventh region and 190-210 ℃ in the eighth region and 190-220 ℃ in the ninth region.
The modified nano lamellar all-silicon molecular sieve is prepared by the following method:
(1) Mixing a silicon source, an alkali source, a structure directing agent and deionized water, wherein the mol ratio of sol formed at room temperature is as follows: h 2 O/SiO 2 ＝20-25，SDA/SiO 2 ＝0.02-0.05，NaOH/SiO 2 After being aged at room temperature, the preparation method comprises the steps of (1) hydrothermally synthesizing crystals, repeatedly washing the prepared crystals with deionized water, centrifuging and drying to obtain the nanoscale all-silicon molecular sieve;
(2) Calcining the nanoscale all-silicon molecular sieve prepared in the step (1) in a high-temperature muffle furnace to obtain the nano lamellar all-silicon molecular sieve.
(3) Preparing a 14% organic solution from a silane coupling agent, adding the prepared nano lamellar all-silicon molecular sieve into the organic solution, stirring, filtering, washing with absolute ethyl alcohol and distilled water for multiple times, and drying to obtain the modified nano lamellar all-silicon molecular sieve.
Example 4
The low-warpage glass fiber reinforced polypropylene composite material comprises the following components in parts by weight, 45 parts of polypropylene resin, 20 parts of chopped glass fiber, 20 parts of modified nano lamellar all-silicon molecular sieve, 5 parts of compatilizer, 0.4 part of antioxidant, light stabilizer and lubricant in total, wherein the mass ratio of the antioxidant, the light stabilizer and the lubricant is 4:3:3.
The preparation method of the low-warpage glass fiber reinforced polypropylene composite material comprises the following operation steps,
weighing the components according to the mass ratio,
s1, preparing a modified nano lamellar all-silicon molecular sieve;
s2, mixing the modified nano lamellar all-silicon molecular sieve prepared in the step S1 with polypropylene resin in a high-pressure mixing pot according to a proportion to obtain a mixture;
s3, the mixture prepared in the step S2, the compatilizer, the antioxidant, the light stabilizer and the lubricant enter from a main feeding port according to the mass ratio, the chopped glass fibers enter from a side feeding port according to the mass ratio, and the temperature of the extruder is controlled as follows: the target product is obtained by melting, extruding, cooling, granulating and drying the materials at 160-180 ℃ in the first region, 180-200 ℃ in the second region, 190-200 ℃ in the third region, 190-210 ℃ in the fourth region, 190-210 ℃ in the fifth region, 190-210 ℃ in the sixth region, 190-210 ℃ in the seventh region and 190-210 ℃ in the eighth region and 190-220 ℃ in the ninth region.
The modified nano lamellar all-silicon molecular sieve is prepared by the following method:
(1) Mixing a silicon source, an alkali source, a structure directing agent and deionized water, wherein the mol ratio of sol formed at room temperature is as follows: h 2 O/SiO 2 ＝20-25，SDA/SiO 2 ＝0.02-0.05，NaOH/SiO 2 After being aged at room temperature, the preparation method comprises the steps of (1) hydrothermally synthesizing crystals, repeatedly washing the prepared crystals with deionized water, centrifuging and drying to obtain the nanoscale all-silicon molecular sieve;
(2) Calcining the nanoscale all-silicon molecular sieve prepared in the step (1) in a high-temperature muffle furnace to obtain the nano lamellar all-silicon molecular sieve.
(3) Preparing a silane coupling agent into a 15% organic solution, adding the prepared nano lamellar all-silicon molecular sieve into the organic solution, stirring, filtering, washing with absolute ethyl alcohol and distilled water for multiple times, and drying to obtain the modified nano lamellar all-silicon molecular sieve.
Example 5
The low-warpage glass fiber reinforced polypropylene composite material comprises the following components in parts by weight, 44 parts of polypropylene resin, 30 parts of chopped glass fiber, 20 parts of modified nano lamellar all-silicon molecular sieve, 6 parts of compatilizer, 0.4 part of antioxidant, light stabilizer and lubricant in total, wherein the mass ratio of the antioxidant, the light stabilizer and the lubricant is 4:3:3.
The preparation method of the low-warpage glass fiber reinforced polypropylene composite material comprises the following operation steps,
weighing the components according to the mass ratio,
s1, preparing a modified nano lamellar all-silicon molecular sieve;
s2, mixing the modified nano lamellar all-silicon molecular sieve prepared in the step S1 with polypropylene resin in a high-pressure mixing pot according to a proportion to obtain a mixture;
s3, the mixture prepared in the step S2, the compatilizer, the antioxidant, the light stabilizer and the lubricant enter from a main feeding port according to the mass ratio, the chopped glass fibers enter from a side feeding port according to the mass ratio, and the temperature of the extruder is controlled as follows: the target product is obtained by melting, extruding, cooling, granulating and drying the materials at 160-180 ℃ in the first region, 180-200 ℃ in the second region, 190-200 ℃ in the third region, 190-210 ℃ in the fourth region, 190-210 ℃ in the fifth region, 190-210 ℃ in the sixth region, 190-210 ℃ in the seventh region and 190-210 ℃ in the eighth region and 190-220 ℃ in the ninth region.
The modified nano lamellar all-silicon molecular sieve is prepared by the following method:
(1) Mixing a silicon source, an alkali source, a structure directing agent and deionized water, wherein the mol ratio of sol formed at room temperature is as follows: h 2 O/SiO 2 ＝20-25，SDA/SiO 2 ＝0.02-0.05，NaOH/SiO 2 After being aged at room temperature, the preparation method comprises the steps of (1) hydrothermally synthesizing crystals, repeatedly washing the prepared crystals with deionized water, centrifuging and drying to obtain the nanoscale all-silicon molecular sieve;
(2) Calcining the nanoscale all-silicon molecular sieve prepared in the step (1) in a high-temperature muffle furnace to obtain the nano lamellar all-silicon molecular sieve.
(3) Preparing a silane coupling agent into a 12% organic solution, adding the prepared nano lamellar all-silicon molecular sieve into the organic solution, stirring, filtering, washing with absolute ethyl alcohol and distilled water for multiple times, and drying to obtain the modified nano lamellar all-silicon molecular sieve.
Example 6
The invention relates to a low-warpage glass fiber reinforced polypropylene composite material which comprises the following components in parts by weight, 80 parts of polypropylene resin and 20 parts of modified nano lamellar all-silicon molecular sieve.
The preparation method of the low-warpage glass fiber reinforced polypropylene composite material comprises the following operation steps,
weighing the components according to the mass ratio,
s1, preparing a modified nano lamellar all-silicon molecular sieve;
s2, mixing the modified nano lamellar all-silicon molecular sieve prepared in the step S1 with polypropylene resin in a high-pressure mixing pot according to a proportion to obtain a mixture;
s3, the mixture prepared in the step S2 enters from a main feeding port according to the mass ratio, and the temperature of an extruder is controlled to be: the target product is obtained by melting, extruding, cooling, granulating and drying the materials at 160-180 ℃ in the first region, 180-200 ℃ in the second region, 190-200 ℃ in the third region, 190-210 ℃ in the fourth region, 190-210 ℃ in the fifth region, 190-210 ℃ in the sixth region, 190-210 ℃ in the seventh region and 190-210 ℃ in the eighth region and 190-220 ℃ in the ninth region.
The modified nano lamellar all-silicon molecular sieve is prepared by the following method:
(1) Mixing a silicon source, an alkali source, a structure directing agent and deionized water, wherein the mol ratio of sol formed at room temperature is as follows: h 2 O/SiO 2 ＝20-25，SDA/SiO 2 ＝0.02-0.05，NaOH/SiO 2 After being aged at room temperature, the preparation method comprises the steps of (1) hydrothermally synthesizing crystals, repeatedly washing the prepared crystals with deionized water, centrifuging and drying to obtain the nanoscale all-silicon molecular sieve;
(2) Calcining the nanoscale all-silicon molecular sieve prepared in the step (1) in a high-temperature muffle furnace to obtain the nano lamellar all-silicon molecular sieve.
(3) Preparing a silane coupling agent into a 12% organic solution, adding the prepared nano lamellar all-silicon molecular sieve into the organic solution, stirring, filtering, washing with absolute ethyl alcohol and distilled water for multiple times, and drying to obtain the modified nano lamellar all-silicon molecular sieve.
Comparative example 1
The traditional reinforced polypropylene composite material comprises the following components in parts by weight, 66 parts of polypropylene resin, 10 parts of chopped glass fibers, 20 parts of talcum powder, 4 parts of compatilizer, 0.4 part of antioxidant, light stabilizer and lubricant in total, wherein the mass ratio of the antioxidant, the light stabilizer and the lubricant is 4:3:3.
The preparation method comprises the following operation steps of,
weighing the components according to the mass ratio,
s1, mixing talcum powder and polypropylene resin in a high-pressure mixing pot according to a proportion to obtain a mixture;
s2, the mixture prepared in the step S1, a compatilizer, an antioxidant, a light stabilizer and a lubricant enter from a main feeding port according to mass ratio, the chopped glass fibers enter from a side feeding port according to mass ratio, and the temperature of an extruder is controlled as follows: the target product is obtained by melting, extruding, cooling, granulating and drying the materials at 160-180 ℃ in the first region, 180-200 ℃ in the second region, 190-200 ℃ in the third region, 190-210 ℃ in the fourth region, 190-210 ℃ in the fifth region, 190-210 ℃ in the sixth region, 190-210 ℃ in the seventh region and 190-210 ℃ in the eighth region and 190-220 ℃ in the ninth region.
Comparative example 2
The traditional reinforced polypropylene composite material comprises the following components in parts by weight, 55 parts of polypropylene resin, 20 parts of chopped glass fibers, 20 parts of talcum powder, 5 parts of compatilizer, 0.4 part of antioxidant, light stabilizer and lubricant in total, wherein the mass ratio of the antioxidant, the light stabilizer and the lubricant is 4:3:3.
The preparation method comprises the following operation steps of,
weighing the components according to the mass ratio,
s1, mixing talcum powder and polypropylene resin in a high-pressure mixing pot according to a proportion to obtain a mixture;
s2, the mixture prepared in the step S1, a compatilizer, an antioxidant, a light stabilizer and a lubricant enter from a main feeding port according to mass ratio, the chopped glass fibers enter from a side feeding port according to mass ratio, and the temperature of an extruder is controlled as follows: the target product is obtained by melting, extruding, cooling, granulating and drying the materials at 160-180 ℃ in the first region, 180-200 ℃ in the second region, 190-200 ℃ in the third region, 190-210 ℃ in the fourth region, 190-210 ℃ in the fifth region, 190-210 ℃ in the sixth region, 190-210 ℃ in the seventh region and 190-210 ℃ in the eighth region and 190-220 ℃ in the ninth region.
Comparative example 3
The traditional reinforced polypropylene composite material comprises the following components in parts by weight, 44 parts of polypropylene resin, 30 parts of chopped glass fibers, 20 parts of talcum powder, 6 parts of compatilizer, 0.4 part of antioxidant, light stabilizer and lubricant in total, wherein the mass ratio of the antioxidant, the light stabilizer and the lubricant is 4:3:3.
The preparation method comprises the following operation steps of,
weighing the components according to the mass ratio,
s1, mixing talcum powder and polypropylene resin in a high-pressure mixing pot according to a proportion to obtain a mixture;
s2, the mixture prepared in the step S1, a compatilizer, an antioxidant, a light stabilizer and a lubricant enter from a main feeding port according to mass ratio, the chopped glass fibers enter from a side feeding port according to mass ratio, and the temperature of an extruder is controlled as follows: the target product is obtained by melting, extruding, cooling, granulating and drying the materials at 160-180 ℃ in the first region, 180-200 ℃ in the second region, 190-200 ℃ in the third region, 190-210 ℃ in the fourth region, 190-210 ℃ in the fifth region, 190-210 ℃ in the sixth region, 190-210 ℃ in the seventh region and 190-210 ℃ in the eighth region and 190-220 ℃ in the ninth region.
Comparative example 4
The traditional reinforced polypropylene composite material comprises the following components in parts by weight, 75 parts of polypropylene resin, 20 parts of chopped glass fibers, 5 parts of compatilizer, 0.4 part of antioxidant, light stabilizer and lubricant in total, wherein the mass ratio of the antioxidant, the light stabilizer and the lubricant is 4:3:3.
The preparation method comprises the following operation steps of,
weighing the components according to the mass ratio, feeding polypropylene resin, a compatilizer, an antioxidant, a light stabilizer and a lubricant from a main feeding port according to the mass ratio, feeding chopped glass fibers from a side feeding port according to the mass ratio, and controlling the temperature of an extruder to be: the target product is obtained by melting, extruding, cooling, granulating and drying the materials at 160-180 ℃ in the first region, 180-200 ℃ in the second region, 190-200 ℃ in the third region, 190-210 ℃ in the fourth region, 190-210 ℃ in the fifth region, 190-210 ℃ in the sixth region, 190-210 ℃ in the seventh region and 190-210 ℃ in the eighth region and 190-220 ℃ in the ninth region.
Comparative example 5
The traditional reinforced polypropylene composite material comprises the following components in parts by weight, 80 parts of polypropylene resin and 20 parts of talcum powder.
The preparation method comprises the following operation steps of,
weighing the components according to the mass ratio,
s1, mixing talcum powder and polypropylene resin in a high-pressure mixing pot according to a proportion to obtain a mixture;
s2, the mixture prepared in the step S1 enters from a main feeding port according to the mass ratio, and the temperature of an extruder is controlled to be: the target product is obtained by melting, extruding, cooling, granulating and drying the materials at 160-180 ℃ in the first region, 180-200 ℃ in the second region, 190-200 ℃ in the third region, 190-210 ℃ in the fourth region, 190-210 ℃ in the fifth region, 190-210 ℃ in the sixth region, 190-210 ℃ in the seventh region and 190-210 ℃ in the eighth region and 190-220 ℃ in the ninth region.
Performance test:
the performance test criteria and methods for the various embodiments are as follows:
(1) Tensile properties were carried out according to ISO 527;
(2) Bending properties are performed according to ISO 178;
(3) Impact properties are carried out according to ISO 179;
(4) And (3) warping: injecting a square plate with the thickness of 100mm multiplied by 2mm, and visually observing the warping degree after standing for one day at normal temperature; the specific performance test results are shown in table 1:
table 1 shows the performance test data of examples 1 to 6 and comparative examples 1 to 5:
note that: * The more the warpage is, the more severe the warpage is, and the less the warpage is, the less pronounced the warpage is
From the above performance test examples 1,2 and 3, it can be seen that under the same glass fiber conditions, the warpage of the material is more obviously improved with the increase of the lamellar molecular sieve content, and the tensile strength and modulus of the material are also increased, so that the impact change is smaller; in combination with comparative example 1 and example 2, comparative example 2 and example 4, and comparative example 3 and example 5, it can be seen that the addition of lamellar molecular sieves improves the warpage of the material most significantly under the same glass fiber conditions, and the modulus is higher than that of talc under the same conditions. In conclusion, the composite material prepared by the method of the invention not only can effectively improve the warp resistance performance of the material, but also can improve the flexural modulus of the material by adding the chopped glass fibers and the self-made modified nano all-silicon molecular sieve.
The present invention is not limited to the above-mentioned embodiments, but is not limited to the above-mentioned embodiments, and any simple modification, equivalent changes and modification made to the above-mentioned embodiments according to the technical matters of the present invention can be made by those skilled in the art without departing from the scope of the present invention.
Claims (6)
1. A low-warpage glass fiber reinforced polypropylene composite material is characterized in that: comprises the following components in parts by weight, 30-80 parts of polypropylene resin; 10-30 parts of chopped glass fiber; 1-30 parts of modified nano lamellar all-silicon molecular sieve; 2-8 parts of compatilizer; 0.2-3 parts of an antioxidant, a light stabilizer and a lubricant; the mass ratio of the antioxidant to the light stabilizer to the lubricant is 4-6:1-4:1-4; the nano lamellar all-silicon molecular sieve in the modified nano lamellar all-silicon molecular sieve is prepared by the following method, (1) mixing a silicon source, an alkali source, a structure directing agent and deionized water, and forming sol with the molar ratio of room temperature of：H 2 O/SiO 2 =20~25，SDA/SiO 2 =0.02~0.05，NaOH/SiO 2 After being aged at room temperature, carrying out hydrothermal synthesis on the crystal, repeatedly washing the prepared crystal by deionized water, centrifuging and drying to obtain the nanoscale all-silicon molecular sieve, wherein the size of the molecular sieve is 50-100 nm; (2) Calcining the nanoscale all-silicon molecular sieve prepared in the step (1) in a high-temperature muffle furnace to obtain the nanosheet all-silicon molecular sieve; the nano lamellar all-silicon molecular sieve is modified by preparing a silane coupling agent into an organic solution with the concentration of 10% -15%, adding the prepared nano lamellar all-silicon molecular sieve into the organic solution, stirring, filtering, washing with absolute ethyl alcohol and distilled water for many times, and drying to obtain the modified nano lamellar all-silicon molecular sieve.
2. The low warp glass fiber reinforced polypropylene composite of claim 1, wherein: the silicon source is at least one of silica sol, tetraethyl orthosilicate or sodium silicate.
3. The low warp glass fiber reinforced polypropylene composite of claim 1, wherein: the structure directing agent is at least one of tetrapropylammonium hydroxide, tetrapropylammonium bromide or tetraethylammonium bromide.
4. A low warpage glass fiber reinforced polypropylene composite according to claim 3, wherein: the length of the chopped glass fiber is 0.5-6mm, and the diameter is 6-15 mu m.
5. A low warpage glass fiber reinforced polypropylene composite according to claim 3, wherein: the compatilizer is maleic anhydride grafted polypropylene.
6. The method for preparing the low-warpage glass fiber reinforced polypropylene composite material according to any one of claims 1 to 5, which is characterized in that: s1, preparing a modified nano lamellar all-silicon molecular sieve; s2, mixing the modified nano lamellar all-silicon molecular sieve prepared in the step S1 with polypropylene resin in a high-pressure mixing pot according to a proportion to obtain a mixture; s3, the mixture prepared in the step S2, a compatilizer, an antioxidant and other auxiliary agents enter from a main feeding port according to mass ratio, the chopped glass fibers enter from a side feeding port according to mass ratio, and the temperature of the extruder is controlled as follows: the target product is obtained by melting, extruding, cooling, granulating and drying the materials at 160-180 ℃ in the first region, 180-200 ℃ in the second region, 190-200 ℃ in the third region, 190-210 ℃ in the fourth region, 190-210 ℃ in the fifth region, 190-210 ℃ in the sixth region, 190-210 ℃ in the seventh region and 190-210 ℃ in the eighth region and 190-220 ℃ in the ninth region.
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