CN114426732A - Modified long glass fiber reinforced polypropylene composite material and preparation method and application thereof - Google Patents
Modified long glass fiber reinforced polypropylene composite material and preparation method and application thereof Download PDFInfo
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 132
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 94
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 94
- -1 polypropylene Polymers 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 43
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 42
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 42
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 42
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000012986 modification Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 12
- 230000010355 oscillation Effects 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 22
- 239000007822 coupling agent Substances 0.000 claims description 19
- 238000005470 impregnation Methods 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000314 lubricant Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 2
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 3
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- 239000000463 material Substances 0.000 description 18
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- 230000000052 comparative effect Effects 0.000 description 9
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- 239000003795 chemical substances by application Substances 0.000 description 3
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- 238000005452 bending Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
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- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000009775 high-speed stirring Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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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
- 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
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
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- C08K9/10—Encapsulated ingredients
Abstract
The invention relates to a modified long glass fiber reinforced polypropylene composite material and a preparation method and application thereof, belonging to the technical field of high polymer materials. The modified long glass fiber reinforced polypropylene composite material comprises the following components in parts by weightIs prepared by the following steps: 100 parts of polypropylene; 20-60 parts of surface modification treatment glass fiber; 2-10 parts of a compatilizer. The invention utilizes the characteristic of high specific surface area of nano particles and adopts an ultrasonic oscillation mode to disperse nano SiO2Suspending the solution, and mixing the nano SiO2The surface of the glass fiber is modified by a chemical grafting method to prepare the surface modified glass fiber, and the modified long glass fiber reinforced polypropylene composite material is further prepared. The prepared composite material has the characteristics of high strength, high modulus and high toughness; the technical scheme of the invention can simply and efficiently improve the interface performance of the composite material and has the possibility of being put into industrial production.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and in particular relates to a modified long glass fiber reinforced polypropylene composite material and a preparation method and application thereof.
Background
The long glass fiber reinforced thermoplastic composite material taking polypropylene as a matrix has the advantages of light weight and high strength, is easy to manufacture and realize cost optimization, has wider and wider application range as a new high-performance engineering plastic, and is the first choice for the polymer-based composite material used for light weight of automobiles at present. The long fiber reinforced polypropylene composite can be used to manufacture highly integrated components, thereby reducing weight and cost. As a carrier material of the automobile module, the long fiber reinforced polypropylene composite material can not only effectively improve the rigidity, impact strength, creep resistance and dimensional stability of the product, but also reduce the manufacturing cost of the automobile module and shorten the molding period. However, in the forming process of the conventional long glass fiber reinforced polypropylene material, due to the orientation, dispersion, interface combination and other reasons of the fibers, it is difficult to ensure that the components of the long glass fiber reinforced polypropylene material are uniformly distributed, so that the long glass fiber material is limited in the working condition application with high requirements on high rigidity and dynamic balance; in addition, the glass fiber reinforced polypropylene in the market at present is made of a lot of materials, but a glass fiber reinforced polypropylene material with high impact strength and excellent mechanical properties is less, and the development of the material can further expand the application range of the high-performance glass fiber reinforced modified polypropylene material.
Chinese patent CN109749241A discloses a long glass fiber reinforced polypropylene composite material with good degree of impregnation and low odor and a preparation method thereof, which is characterized in that a polypropylene melt is treated on line by ultrasonic waves, the viscosity of the polypropylene melt is reduced, and small molecules in the melt are removed, so that the degree of impregnation of the fibers is improved, and the odor of the material is improved. Chinese patent CN109251413A discloses a long glass fiber reinforced polypropylene composite material with high impregnation degree and a preparation method thereof, which is characterized in that glass fibers are treated by a treatment liquid on line and then directly enter an impregnation tank for production. The former of the prior art uses the effect of ultrasonic waves on the matrix to reduce viscosity; the latter is to treat the surface of the glass fiber by the mixed solution of concentrated sulfuric acid, nitric acid, potassium permanganate and hydrogen peroxide, and has higher requirements for industrial production.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a modified long glass fiber reinforced polypropylene composite material. In particular to a modified long glass fiber reinforced polypropylene composite material and a preparation method and application thereof. The material has the characteristics of high strength, high modulus and high toughness, and is widely applied to the fields of automobiles, household appliances and the like.
One purpose of the invention is to provide a modified long glass fiber reinforced polypropylene composite material, which can be prepared from the following components in parts by weight:
100 parts of polypropylene;
20-60 parts of surface modification treatment glass fiber, preferably 30-50 parts;
2-10 parts of a compatilizer, preferably 2-8 parts.
Wherein the content of the first and second substances,
the polypropylene can be high flow polypropylene;
the melt flow rate of the polypropylene can be 60-150 g/min under the conditions of pressure of 2.16kg and temperature of 230 ℃.
The polypropylene may be at least one of isotactic polypropylene, syndiotactic polypropylene, and atactic polypropylene.
The compatilizer can be maleic anhydride grafted polypropylene, and the density can be 0.89-0.91 g/cm3The melting point can be 160-180 ℃, the melt flow rate (230 ℃, 2.16Kg) can be 10-200 g/10min, and the grafting rate of the maleic anhydride can be 0.8-1.2%.
The surface modified glass fiber is nano SiO2A modified glass fiber; preferably, the nano SiO is treated by ultrasonic oscillation and chemical grafting2A modified glass fiber.
The nano SiO2Has an average particle diameter of 15-150 nm and a specific surface area of not less than 150m2/g。
Specifically, the preparation method of the surface modification treated glass fiber can comprise the following steps:
mixing nano SiO2Adding solvent to prepare nano SiO2A suspension; ultrasonically vibrating the nano SiO2A suspension; immersing glass fiber into the nano SiO2Soaking in the suspension, and drying; and then soaking the treated glass fiber into a coupling agent solution, soaking and drying to obtain the glass fiber.
Preferably, the preparation method of the surface modification treatment glass fiber comprises the following steps:
(1) calcining the glass fiber to remove the original sizing agent on the surface of the glass fiber; wherein the calcining temperature can be 200-400 ℃, and the calcining time can be 15-60 min;
(2) mixing nano SiO2Adding into solvent, stirring to obtain nanometer SiO2A suspension; the nano SiO2Nano SiO in suspension2The concentration of (A) is 0.05 to 1 wt%, preferably 0.1 to 0.8 wt%, more preferably 0.1 to 0.5 wt%, and further preferably 0.15 to 0.3 wt%; specifically, mechanical stirring can be used, the stirring speed can be 1000-2000 r/min, and the stirring time can be 1-2 h;
(3) adding a coupling agent into a solvent, and uniformly stirring to obtain a coupling agent solution; preferably, the concentration of the coupling agent solution can be 0.1 to 1 wt%, preferably 0.25 wt% to 0.75 wt%, more preferably 0.45 to 0.65 wt%;
(4) by ultrasonic oscillation to nano SiO2Treating the suspension; wherein the power of ultrasonic oscillation can be 40-360 w, the frequency can be 25-100 KHz, preferably the power can be 80-120 w, the frequency can be 28-60 KHz, and the ultrasonic oscillation can be carried out for 0.5-1.5 hours; then immersing the glass fiber treated in the step (1) into nano SiO2Taking out the suspension for 5-30 min, and drying; the drying temperature can be 30-120 ℃, preferably 80-100 ℃, and the drying time can be 1-6 hours, preferably 2-3 hours;
(5) immersing the glass fiber treated in the step (4) into a coupling agent solution for 10-30 min, taking out and drying; the drying temperature can be 30-120 ℃, preferably 80-100 ℃, and the drying time can be 1-6 hours, preferably 2-3 hours, thus obtaining the surface modified glass fiber. The specific treatment step can be carried out in a glass fiber pretreatment tank; drying may be carried out by drying means commonly used in the art, such as an electrically heated constant temperature forced air drying cabinet.
Wherein the content of the first and second substances,
in the step (2) and the step (3),
the solvent can be alcohol solution, preferably ethanol solution or polyethylene glycol solution;
the volume concentration of the alcohol solution can be 20-95% (v/v), preferably 50-75%, and more preferably 70-75%.
Wherein the content of the first and second substances,
the glass fiber can be alkali-free high-strength continuous glass fiber, the strength is more than 2300MPa, the diameter is 10-24 um, and the linear density is 1200-4800 TEX.
The surface modification treatment of the glass fiber is to disperse nano SiO by using an ultrasonic oscillation mode2Suspending the solution, and mixing the nano SiO2The glass fiber is prepared by modifying the surface of the glass fiber by a chemical grafting method. The ultrasonic dispersion has the advantages of high quality, high efficiency, environmental protection and the like, and the key point is the cavitation effect, and the cavitation effect of the ultrasonic on the nano SiO2Dispersing and depolymerizing to obtain nano SiO2The dispersion stability in the water phase is obviously improved; silanol generated by the coupling agent after hydrolysis reaction can be mixed with glass fiber and nano SiO2Condensation polymerization of the surface hydroxyl groups to form SiO2Chemically grafted to the surface of the fiber.
The coupling agent can be a silane coupling agent, and specifically can be at least one selected from gamma-aminopropyltriethoxysilane (silane coupling agent KH550) or gamma-2, 3-glycidoxy-propyltrimethoxysilane (KH 560).
In some embodiments of the present application, the modified long glass fiber reinforced polypropylene composite may further comprise a lubricant;
the lubricant can be 0.5-1 part by weight based on 100 parts by weight of the polypropylene;
the lubricant can be one or more of oxidized polyethylene wax and microcrystalline paraffin.
In some embodiments of the present application, the modified long glass fiber reinforced polypropylene composite may further comprise an antioxidant; the amount of the antioxidant is 0.1-3 parts by weight based on 100 parts by weight of the polypropylene;
the antioxidant can be at least one of antioxidant 1010, antioxidant 1076, antioxidant 2246, antioxidant CA, antioxidant 626 and antioxidant 636, preferably one or two.
The modified long glass fiber reinforced polypropylene composite material can also comprise other auxiliary agents, including but not limited to at least one of slipping agents, antistatic agents, plasticizers and the like. In addition, the amount of the other auxiliary agents is selected conventionally in the field, and can be known by those skilled in the art.
The invention also aims to provide a preparation method of the modified long glass fiber reinforced polypropylene composite material, which comprises the following steps:
and mixing the components including the polypropylene and the compatilizer to obtain polypropylene mixed resin, and then impregnating and coating the polypropylene mixed resin and the surface-modified glass fiber to obtain the polypropylene composite material.
Specifically, the preparation method of the modified long glass fiber reinforced polypropylene composite material can comprise the following steps:
(1) adding the components including the polypropylene, the compatilizer and the lubricant into a high-speed mixer, and then adding the mixed polypropylene mixed resin into a hopper of an extruder for standby; the material mixing temperature is controlled to be 40-60 ℃, and the material mixing time is 3-5 minutes.
(2) And (2) adopting continuous fiber reinforced thermoplastic material impregnation equipment, and enabling the polypropylene mixed resin mixed in the step (1) to enter a melting impregnation die connected with the head of an extruder after being melted and plasticized by the extruder.
(3) And (3) the glass fiber subjected to surface modification treatment enters a glass fiber dispersion roller system and a preheating unit to preheat and disperse the glass fiber, then enters a melting impregnation die head, and is impregnated and coated with the molten polypropylene mixed resin.
(4) And pulling out the impregnated and coated composite material strip through a shaping plate and a die plate, and then carrying out bracing, cooling, blow-drying and grain cutting to prepare the modified long glass fiber reinforced polypropylene composite material. Adjusting the content of the continuous glass fiber in the composite material to be 30-50 parts by weight by selecting the size of the die plate; the modified long glass fiber reinforced polypropylene granules with the granule cutting length of 6-25 mm are obtained by adjusting the rotating speed of a cutter of a granulator.
The extruder can be a double-screw extruder, the diameter of the screw can be 40-55 mm, and the length-diameter ratio of the screw can be 40: 1, the processing temperature can be 230-280 ℃, the melt temperature can be 230-260 ℃, and the head temperature can be 240-280 ℃.
The temperature of the dipping equipment can be 220-230 ℃.
The temperature of the dispersion roller system and the preheating unit can be 130-170 ℃.
The size of the sizing neck mold can be 3.0-5.0 mm, and the content of the glass fiber in the composite material is 20-60 parts by weight.
The invention also aims to provide the application of the modified long glass fiber reinforced polypropylene composite material in the industries of transportation, automobiles, electronics, electrics and household appliances.
The invention utilizes the characteristic of high specific surface area of nano particles, and adopts an ultrasonic oscillation mode to disperse nano SiO on the basis of high-speed stirring2Suspending the solution, and mixing the nano SiO2The surface of the glass fiber is modified by a chemical grafting method to prepare the surface modified glass fiber, and the modified long glass fiber reinforced polypropylene composite material is further prepared. Adopting silane coupling agent to mix nano SiO2The interface performance of the composite material can be simply and efficiently improved by grafting the glass fiber/polypropylene thermoplastic composite material onto the surface of the glass fiber, the cost is saved, and the prepared glass fiber/polypropylene thermoplastic composite material has the characteristics of high strength, high modulus and high toughness; the technical scheme of the invention can simply and efficiently improve the interface performance of the composite material and has the possibility of being put into industrial production.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to these examples.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Source of raw materials
Polypropylene, K6100, melt flow rate of 110g/10min, test conditions of 230 ℃ and 2.16Kg, purchased from Chinese petrochemical Yanshan mountain petrochemicals;
glass fiber: alkali-free glass fibers, SE4805, diameter 17 μm, linear density 2400 tex.
Maleic anhydride grafted Polypropylene (PP-g-MAH), trade name BONDYRAM 1001CN, Pullander plastics industries, Inc.
Nano-silica, average particle size: 30nm, specific surface area: 600m2(ii)/g, available from Daidaku island technologies, Inc. of Beijing;
absolute ethanol, B0301002, purchased from beijing chemical plant;
silane coupling agent (3-aminopropyltriethoxysilane), KH550, was purchased from Nanjing Engineers organosilicon materials, Inc.
Examples 1 to 3 and comparative examples 1 to 4
The preparation method of the surface modification treatment glass fiber comprises the following steps：
(1) The glass fiber is calcined at 400 ℃ for 25min to remove the sizing agent on the surface of the glass fiber.
(2) Mixing nano SiO2Adding 75% (v/v) ethanol solution to obtain different concentrations (see Table 1), and stirring in electric stirrer to obtain nanometer SiO2The suspension is stirred at the speed of 1000r/min for 1 h.
(3) The coupling agent KH550 was added to a 75% (v/v) ethanol solution to obtain a coupling agent solution (the specific concentration is shown in Table 1).
(4) Mixing the nano SiO obtained by the step (2)2Placing the suspension in a glass fiber pretreatment tank, and subjecting the nano SiO in the glass fiber pretreatment tank to ultrasonic oscillation2Treating the suspension (the ultrasonic oscillation is not carried out in comparative examples 1-4), and oscillating for 1h at the power of 100w and the frequency of 40 KHz; then immersing the glass fiber treated by the step (1) into nano SiO2The suspension is taken out for 15min and is dried in an electric heating constant temperature blast drying oven for 3h at the temperature of 100 ℃.
(5) And (4) soaking the glass fiber treated in the step (4) into a coupling agent solution for 15min, taking out, and drying in an electric heating constant-temperature air blast drying oven at 100 ℃ for 3h to obtain the surface modified glass fiber.
The formulations of the methods for preparing the surface-modified glass fibers in examples 1 to 3 and comparative examples 1 to 4 are shown in Table 1: (in Table 1, nano SiO2The concentration of the suspension; the concentration of the coupling agent solution; and whether or not to vibrate ultrasonically)
TABLE 1 technical scheme for surface modification treatment of glass fiber
| Mass fraction (Nano SiO)2)％ | Mass fraction (KH 550)/%) | Ultrasonic vibration | |
| Comparative example 1 | 0 | 0 | -- |
| Comparative example 2 | 0.5 | 0 | -- |
| Comparative example 3 | 0 | 0.5 | -- |
| Comparative example 4 | 0.5 | 0.5 | -- |
| Example 1 | 0.25 | 0.5 | √ |
| Example 2 | 0.5 | 0.5 | √ |
| Example 3 | 0.75 | 0.5 | √ |
The preparation method of the modified long glass fiber reinforced polypropylene composite material comprises the following steps：
(1) Adding 100 parts of polypropylene, 3 parts of compatilizer, 0.1 part of antioxidant and 0.5 part of lubricant into a high-speed mixer, controlling the mixing temperature to be 40-60 ℃, mixing for 3-5 minutes, and then adding the mixed polypropylene mixed resin into a hopper of an extruder for later use.
(2) And (2) adopting continuous fiber reinforced thermoplastic material impregnation equipment, and enabling the polypropylene mixed resin mixed in the step (1) to enter a melting impregnation die connected with the head of an extruder after being melted and plasticized by the extruder.
(3) And (3) the glass fiber subjected to surface modification treatment enters a glass fiber dispersion roller system and a preheating unit to preheat and disperse the glass fiber, then enters a melting impregnation die head, and is impregnated and coated with the molten polypropylene mixed resin.
(4) And pulling out the impregnated and coated composite material strip through a shaping plate and a die plate, and then carrying out bracing, cooling, blow-drying and grain cutting to prepare the modified long glass fiber reinforced polypropylene composite material. The size of the die plate is selected to adjust the content of the continuous glass fiber in the composite material to 40 parts by weight; and obtaining modified long glass fiber reinforced polypropylene granules with the grain cutting length of 12mm as prepreg by adjusting the rotating speed of a cutter of a granulator. And (5) drying the prepreg, performing injection molding, and testing the performance.
Example 4
(1) Adding 100 parts of polypropylene, 2 parts of compatilizer, 0.1 part of antioxidant and 0.5 part of lubricant into a high-speed mixer, controlling the mixing temperature to be 40-60 ℃, mixing for 3-5 minutes, and then adding the mixed polypropylene mixed resin into a hopper of an extruder for later use.
(2) And (2) adopting continuous fiber reinforced thermoplastic material impregnation equipment, and enabling the polypropylene mixed resin mixed in the step (1) to enter a melting impregnation die connected with the head of an extruder after being melted and plasticized by the extruder.
(3) The surface-modified glass fiber (the surface-modified glass fiber preparation method is the same as that in example 1) is fed into a glass fiber dispersion roller system and a preheating unit to preheat and disperse the glass fiber, then fed into a melting impregnation die head, and impregnated and coated with the melted polypropylene mixed resin.
(4) And pulling out the impregnated and coated composite material strip through a shaping plate and a die plate, and then carrying out bracing, cooling, blow-drying and grain cutting to prepare the modified long glass fiber reinforced polypropylene composite material. The size of the die plate is selected to adjust the content of the continuous glass fiber in the composite material to be 30 parts by weight; and obtaining modified long glass fiber reinforced polypropylene granules with the grain cutting length of 12mm as prepreg by adjusting the rotating speed of a cutter of a granulator. And (5) drying the prepreg, performing injection molding, and testing the mechanical property.
Example 5
(1) Adding 100 parts of polypropylene, 8 parts of compatilizer, 0.1 part of antioxidant and 0.5 part of lubricant into a high-speed mixer, controlling the mixing temperature to be 40-60 ℃, mixing for 3-5 minutes, and then adding the mixed polypropylene mixed resin into a hopper of an extruder for later use.
(2) And (2) adopting continuous fiber reinforced thermoplastic material impregnation equipment, and enabling the polypropylene mixed resin mixed in the step (1) to enter a melting impregnation die connected with the head of an extruder after being melted and plasticized by the extruder.
(3) The surface-modified glass fiber (the preparation method of the surface-modified glass fiber is the same as that in example 1) is fed into a glass fiber dispersion roller system and a preheating unit to preheat and disperse the glass fiber, then fed into a melting impregnation die head, and impregnated and coated with the melted polypropylene mixed resin.
(4) And pulling out the impregnated and coated composite material strip through a shaping plate and a die plate, and then carrying out bracing, cooling, blow-drying and grain cutting to prepare the modified long glass fiber reinforced polypropylene composite material. The size of the die plate is selected to adjust the content of the continuous glass fiber in the composite material to be 50 parts by weight; and obtaining modified long glass fiber reinforced polypropylene granules with the grain cutting length of 12mm as prepreg by adjusting the rotating speed of a cutter of a granulator. And (5) drying the prepreg, performing injection molding, and testing the mechanical property.
Performance testing
The tensile strength is measured according to GB/T1040-2006, and the tensile rate is 5 mm/min; the bending strength is measured according to GB/T9341-2000, and the experimental speed is 2 mm/min; the impact strength of the gap of the simply supported beam is determined according to GB/T1043-2008.
TABLE 2 test results of Material Properties
Compared with the comparative examples 1 to 4, the nano SiO is treated by ultrasonic oscillation and chemical grafting in the examples 1 to 52The surface of the fiber is modified, so that the comprehensive mechanical property of the composite material interface can be obviously improved; meanwhile, the tensile strength, the bending strength, the modulus and the notch impact strength of the material are obviously improved.
Among them, it was found in the experiment that the nano SiO in example 12Nano SiO in suspension2Best dispersion, nano SiO in example 22Nano SiO of suspension2A small amount of aggregates; example 3 Nano SiO2The suspension presents nano SiO2Large areas of agglomerates. Example 3 use of 0.75 wt% nano SiO2Concentration, nano SiO2Approaching the limit of dispersion in ethanol solution, increasing the concentration does not result in better dispersion, but rather results in large agglomerates of small particles. The formation of large-scale aggregates can lead to nano SiO2The glass fiber is unevenly distributed on the surface of the glass fiber and cannot be well dispersed on a single layer, so that the interface bonding performance of the composite material is influenced, and the effect of the final product is not as good as that of the nano SiO2The effect of the lower concentration of the examples, but still a significant improvement over the performance of the comparative examples.
Claims (13)
1. The modified long glass fiber reinforced polypropylene composite material is prepared from the following components in parts by weight:
100 parts of polypropylene;
20-60 parts of surface modification treatment glass fiber, preferably 30-50 parts;
2-10 parts of a compatilizer, preferably 2-8 parts.
2. The modified long glass fiber reinforced polypropylene composite material of claim 1, wherein:
the polypropylene is high-flow polypropylene;
preferably, the melt flow rate of the polypropylene is 60-150 g/min under the conditions of 2.16kg of pressure and 230 ℃.
3. The long glass fiber reinforced polypropylene composite material of claim 1, wherein:
the compatilizer is maleic anhydride grafted polypropylene, the melting point is 160-180 ℃, the melt flow rate is 10-200 g/10min, and the grafting rate of maleic anhydride is 0.8-1.2%.
4. The modified long glass fiber reinforced polypropylene composite of claim 1, comprising a lubricant;
0.5-1 part by weight of lubricant based on 100 parts by weight of polypropylene;
the lubricant is one or more of oxidized polyethylene wax and microcrystalline paraffin.
5. The modified long glass fiber reinforced polypropylene composite material according to any one of claims 1 to 4, wherein:
the surface modified glass fiber is nano SiO2A modified glass fiber; preferably, the nano SiO is treated by ultrasonic oscillation and chemical grafting2A modified glass fiber.
6. The modified long glass fiber reinforced polypropylene composite material of claim 5, wherein:
the preparation method of the surface modification treatment glass fiber comprises the following steps:
mixing nano SiO2Adding solvent to prepare nano SiO2A suspension; ultrasonically vibrating the nano SiO2A suspension; immersing glass fiber into the nano SiO2Soaking in the suspension, and drying; then soaking the treated glass fiber into a coupling agent solution, soaking and drying to obtain the glass fiber;
preferably, the preparation method of the surface modification treatment glass fiber comprises the following steps:
(1) mixing nano SiO2Adding into solvent, stirring to obtain nanometer SiO2A suspension; preferably, the stirring speed is 1000-2000 r/min, and the stirring time is 1-2 h;
(2) adding a coupling agent into a solvent, and uniformly stirring to obtain a coupling agent solution; preferably, the concentration of the coupling agent solution is 0.1-1 wt%, preferably 0.25-0.75 wt%;
(3) by ultrasonic oscillation to nano SiO2Treating the suspension; then the glass fiber is immersed into the nano SiO2Taking out the suspension and drying;
(4) and (4) immersing the glass fiber treated in the step (3) into a coupling agent solution, taking out the glass fiber, and drying to obtain the surface modified glass fiber.
7. The modified long glass fiber reinforced polypropylene composite material of claim 6, wherein:
the nano SiO2Nano SiO in suspension2Is 0.05 to 1 wt%, preferably 0.1 to 0.8 wt%, more preferably 0.1 wt%0.5 wt%, and more preferably 0.15 to 0.3 wt%.
8. The modified long glass fiber reinforced polypropylene composite material of claim 5, wherein:
the glass fiber is alkali-free high-strength continuous glass fiber, the strength is more than 2300MPa, the diameter is 10-24 um, and the linear density is 1200-4800 TEX.
9. The modified long glass fiber reinforced polypropylene composite material of claim 6, wherein:
the coupling agent is a silane coupling agent, preferably at least one selected from gamma-aminopropyltriethoxysilane or gamma-2, 3-glycidoxy-propyltrimethoxysilane.
10. The modified long glass fiber reinforced polypropylene composite material of claim 6, wherein:
in the step (1) and the step (2),
the solvent is an alcohol solution, preferably an ethanol solution and/or a polyethylene glycol solution;
the volume concentration of the solvent is 20-95%, preferably 50-75%;
in the step (3), the step (c),
the power of the ultrasonic oscillation is 40-360 w, the frequency is 25-100 KHz, preferably the power is 80-120 w, and the frequency is 28-60 KHz; to nano SiO2The time for treating the suspension is 0.5-1.5 h;
immersing glass fiber into nano SiO2The suspension liquid time is 5-30 min;
in the steps (3) and (4),
the drying temperature is 30-120 ℃, preferably 80-100 ℃, and the drying time is 1-6 hours, preferably 2-3 hours;
in the above-mentioned (4), the first and second substrates are,
the time for immersing the coupling agent in the coupling agent solution is 10-30 min.
11. The modified long glass fiber reinforced polypropylene composite material of claim 6, wherein:
the glass fiber is pretreated before use: calcining the glass fiber; wherein the calcining temperature is 200-400 ℃, and the calcining time is 15-60 min.
12. The method for preparing the modified long glass fiber reinforced polypropylene composite material according to any one of claims 1 to 11, comprising the steps of:
and mixing the components including the polypropylene and the compatilizer to obtain polypropylene mixed resin, and then carrying out impregnation coating on the polypropylene mixed resin and the surface modified glass fiber to obtain the polypropylene composite material.
13. The modified long glass fiber reinforced polypropylene composite material according to any one of claims 1 to 11 or the modified long glass fiber reinforced polypropylene composite material prepared by the preparation method according to claim 12 is applied to the industries of transportation, automobiles, electronics and electrical products and household electrical appliances.
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