CN104910520A - EVA (ethylene-vinyl acetate)-post-crosslinking-modified high-performance glass-fiber reinforced polypropylene composite material and preparation method thereof - Google Patents
EVA (ethylene-vinyl acetate)-post-crosslinking-modified high-performance glass-fiber reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention relates to an EVA (ethylene-vinyl acetate)-post-crosslinking-modified high-performance glass-fiber reinforced polypropylene composite material and a preparation method thereof. The composite material is prepared from the following raw materials in percentage by weight: 40-80% of polypropylene, 10-40% of chopped glass fiber, 2-5% of graft compatilizer, 2-10% of EVA block copolymer, 0.5-3% of peroxide crosslinking agent and 1-6% of auxiliary crosslinking agent. The tensile strength and impact strength of the composite material have the most obvious improvement amplitude, and are enhanced by 30-50% as compared with the conventional formula material; and the tensile modulus and bending modulus are correspondingly enhanced to 6000 MPa above. In the 150-DEG C 100-hour long-term hot-oxidative-aging test, the tensile strength, impact strength and other indexes of the composite material can be further enhanced in the early test stage, and the property retention rate is 85% above in the final test stage (>=2000 hours); and thus, the composite material has excellent long-term hot oxidative aging resistance.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to post-crosslinking modified high-performance glass fiber reinforced polypropylene composite material of EVA and preparation method thereof.
Background technology
Polypropylene has the price of excellent over-all properties, good chemical stability, preferably forming process type and relative moderate, and especially add inorganic reinforcement as after glass fibre GF, its mechanical property, thermotolerance can also be significantly improved.At present, glass fiber reinforced polypropylene composite material extensively should in fields such as automobile, household electrical appliances, power tool, building materials.
EVA (vinyl-vinyl acetate copolymer, Ethylene-vinyl acetate copolymer) is a modal class acrylic acid esters co-polymer, has excellent chemical-resistant stability, ageing resistance.Wherein vinyl acetate groups VAC has suitable chemical reactivity, can under the effect of the initiator such as superoxide, metal oxide, participates in the chemical reaction of grafting, the polymer molecular chain such as crosslinked.
For polypropylene, in its molecular chain, the tertiary hydrogen atoms of pending methyl group has quite high chemically reactive, and in combined factors inducibilities such as long-term light, heat, easy chain rupture forms living radical, thus causes the molecular chain degradation transitivity of polypropylene material to be lost.Common way is by selecting suitable anti-oxidant auxiliary agent and assisted class functional agent, improve polyacrylic above-mentioned defect, if number of patent application is CN200510026763.4, the high heatproof and oxygen-aging resistant propene polymer fiber composite that the fiber glass reinforced polypropylene material of a kind of high resistance thermal-oxidative aging property of Chinese patent application of publication number CN1696187A describes, by plurality of stable agent as DSTP, 618,3114 compositely realize the antioxidant improving polypropylene material, number of patent application is CN201210325901.9, publication number is that a kind of long-term polypropylene composite capable of resisting thermal oxidizing aging of the Chinese patent application of CN102827422A and preparation method thereof then substitutes traditional maleic anhydride to achieve the above object by polynary propionic ester grafting auxiliary agent, and number of patent application is CN201310738308.1, publication number is a kind of creep resistance of Chinese patent application of CN103740028A, it is acid-acceptor that polypropene composition of heat oxygen aging resistance and preparation method thereof introduces metal oxide in polypropylene material, add the nucleator of ad hoc structure, thus acquisition has long-term heat oxygen aging resistance, the polypropylene composite material of the characteristics such as creep resistance.But only by adding of a small amount of auxiliary agent, not only produce little effect, its effect is embodied in the lifting of effects on surface situation more, and promote not obvious to the property retention rate of material, and auxiliary agent itself is expensive, reduces the characteristic of polypropylene composite material high performance-price ratio.
Summary of the invention
High-performance glass fiber reinforced polypropylene composite material that the object of the present invention is to provide a kind of EVA post-crosslinking modified and preparation method thereof, utilize the high reactivity of acrylate group in EVA segmented copolymer, easily crosslinked response characteristic, add efficient peroxide initiator BIBP and auxiliary crosslinking agent TAIC, coordinate acrylic ester monomer grafts, realize at specified conditions (high temperature, high pressure) under radical crosslinking reaction, at a kind of Semi-IPN cross-linked structure of polypropylene composite material internal build, strengthen cohering situation between polypropylene matrix and fortifying fibre, simultaneously, tertiary hydrogen atoms number in polypropylene molecular chain is effectively reduced by radical crosslinking reaction, therefore, the weathering resistance of polypropylene composite material is able to obvious improvement, in long-term high temperature thermal oxidation ageing environment, its in a short time mechanical property promote because of the increase of crosslinking degree on the contrary, and long-term property retention rate is obviously better than common polypropylene composite material, contrast current hosts factory is as masses, Ford, the associated materials standard on Great Wall, all there is obvious functional design surplus.
The object of the invention is to be achieved through the following technical solutions:
The high-performance glass fiber reinforced polypropylene composite material that EVA is post-crosslinking modified, is characterized in that: the raw material comprising following weight percent:
Wherein, described polypropylene is Co-polypropylene, 230 DEG C, under the test condition of 2.16Kg, its melting index is 2 ~ 30g/min, and molecular weight is 80000 ~ 150000.Preferred Co-polypropylene crystallinity Xc >=55%, melting index 15 ~ 30g/min (230 DEG C, 2.16Kg).
Described grafts compatilizer is glycidyl methacrylate GMA grafts polypropylene, is 0.5 ~ 3% through chemical titration test percentage of grafting.Preferable methyl glycidyl acrylate GMA grafts polypropylene, chemical titration test percentage of grafting is 0.8%.
Described short glass fiber is glass chopped strand mats, and its filament diameter is 13um, and chopped length is 3 ~ 4.5mm.Preferred glass fibers is short cuts felt, filament diameter 13um, chopped length 4.5mm.
Described EVA segmented copolymer is vinyl-vinyl acetate copolymer, 190 DEG C, under the test condition of 2.16Kg, its melting index is 20 ~ 50g/min.Optimal ethylene-ethyl acetate copolymer EVA, melting index 30g/min (190 DEG C, 2.16Kg).
Described peroxide initiator is dual-tert-butyl dicumyl peroxide BIBP, and theoretical active oxygen content is 5 ~ 12%.Preferred dual-tert-butyl dicumyl peroxide BIBP, theoretical active oxygen content is 9.45%.
Described auxiliary crosslinking agent is cyanacrylate TAIC, and product acid number mgKOH/g is 0.1 ~ 0.8.Preferred cyanacrylate TAIC, product acid number mgKOH/g is 0.2 ~ 0.8.
The method of the high-performance glass fiber reinforced polypropylene composite material that described a kind of EVA is post-crosslinking modified, it is characterized in that, described method comprises the following steps:
(1) take polypropylene, grafts compatilizer and EVA segmented copolymer by described weight percent, mix, gained mixing raw material A; Short glass fiber, peroxide initiator, auxiliary crosslinking agent is taken, the mixing raw material B after mixing by described weight percent.
(2) dried mixing raw material A is positioned in the main feeding bin of tight meshing co rotating twin screw extrusion, join in the machine barrel of forcing machine through feed screw, mixing raw material B is positioned in the feeding bin of side, join in main barrel through feeding spiral shell in the middle part of forcing machine, screw diameter is 35mm, length-to-diameter ratio L/D is 40, each zone temperature (exporting from charging opening to head) of main cylinder is set as: 60 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, engine speed is 200 revs/min, through melt extruding, cooling, granulation, product is obtained after the operations such as drying and processing.
Innovation of the present invention is: high based on acrylate group reactive behavior in EVA segmented copolymer, easily crosslinked performance characteristic, Semi-IPN polymer network structure is formed by radical crosslinking reaction, fiberglass reinforced body in matrix material and polypropylene matrix are effectively cohered, General Promotion composite materials property and weathering resistance, especially long-term heatproof air aging performance.
Technical scheme proposed by the invention is the different chemical modification method of a kind of more conventional physical property blending modification method, consider co-polypropylene, esters of acrylic acid grafts, the structural performance of the threes such as acrylate based block copolymer, by introducing efficient radical crosslinking system, a kind of rear crosslinked half interpenetrating network structure is formed in the inside of fiber glass reinforced polypropylene material, it has fixing fiberglass reinforced body, the double effects of polypropylene molecular chain, the state of interface of matrix material can not only be improved, to the mechanical property of polypropylene matrix, weather resistance also has and improves effect preferably, the reinforced polypropylene compound material of preparation has more excellent resistance to impact shock compared with conventional material, lifting amplitude is more than 30%, and material is at high temperature (150 DEG C), the unique phenomena that mechanical property " first improves and is tending towards steady in a long-term afterwards " is shown in the environment of aerobic, this and traditional reinforced polypropylene compound material have obvious difference, the 2000h of matrix material stretches, impact property conservation rate is still more than 85%, the most harsh standard of current hosts factory about thermo-oxidative ageing can be met, the glass fiber reinforced polypropylene composite material possessing this characteristic is specially adapted to dependency structure and the functional details of nacelle inside.
Embodiment
Below by concrete embodiment, the present invention is described further, and described embodiment is only for illustration of the present invention instead of limitation of the present invention.
The embodiment of the present invention is raw materials used:
PP-1: Co-polypropylene Y1215C, crystallinity Xc >=40%, Yang Zi petro-chemical corporation, melting index 15g/min (230 DEG C, 2.16Kg).
PP-2: Co-polypropylene BX3800, crystallinity Xc >=55%, Exxon Mobil company, melting index 30g/min (230 DEG C, 2.16Kg).
PP-3: Co-polypropylene K8303, crystallinity Xc >=45%, Yanshan Petrochemical company, melting index 2g/min (230 DEG C, 2.16Kg).
Compatilizer-1: glycidyl methacrylate GMA grafts polypropylene, chemical titration test percentage of grafting is 0.8%, and self-control, by twin screw extruder, causes GMA/ vinylbenzene St mixture grafting molten state polypropylene by peroxide initiator and obtains.
Compatilizer-2: maleic anhydride MAH graft polypropylene CMG5001-C, chemical titration test percentage of grafting is 1.0%, commercially available, rises novel material company purchased from Nantong day.
Compatilizer-3: maleic anhydride MAH graft polypropylene CMG9801, chemical titration test percentage of grafting is 0.5%, commercially available, rises novel material company purchased from Nantong day.
Compatilizer-4: maleic anhydride MAH graft polypropylene GPM200A, chemical titration test percentage of grafting is 3%, purchased from the light novel material company of Ningbo energy.
Short glass fiber-1: continuous glass fibre is short cuts felt T438-4.5, diameter 13um, chopped length 4.5mm, Mount Taishan glass.
Short glass fiber-2: continuous glass fibre is short cuts felt T538-3.0, diameter 13um, chopped length 3mm, Mount Taishan glass.
EVA segmented copolymer-1: ethylene-ethyl acetate copolymer EVA-150, Mitsui chemistry, melting index 30g/min (190 DEG C, 2.16Kg).
EVA segmented copolymer-2: ethylene-ethyl acetate copolymer EVA-450, Mitsui chemistry, melting index 20g/min (190 DEG C, 2.16Kg).
EVA segmented copolymer-3: ethylene-ethyl acetate copolymer EVA-240, du pont company, melting index 50g/min (190 DEG C, 2.16Kg).
Peroxide initiator-1: dual-tert-butyl dicumyl peroxide BIBP-90, theoretical active oxygen content is 9.45%, reaches company purchased from Shanghai Fang Rui;
Peroxide initiator-2: dual-tert-butyl dicumyl peroxide BIBP-F40, theoretical active oxygen content is 5%, purchased from French Arkema;
Peroxide initiator-3: dual-tert-butyl dicumyl peroxide BIBP-F40SP2, theoretical active oxygen content is 12%, purchased from French Arkema;
Auxiliary crosslinking agent-1: cyanacrylate TAIC-70, product acid number mgKOH/g is 0.1, reaches company purchased from Shanghai Fang Rui;
Auxiliary crosslinking agent-2: cyanacrylate TAIC-S, product acid number mgKOH/g is 0.2, reaches company purchased from Shanghai Fang Rui;
Auxiliary crosslinking agent-3: cyanacrylate TAIC-B, product acid number mgKOH/g is 0.8, reaches company purchased from Shanghai Fang Rui;
Product performance are tested:
Tensile property: undertaken by ISO527-2 standard, test rate is 5mm/min.
Bending property: undertaken by IS178 standard, span is 64mm, and test rate is 2mm/min.
Impact property: carry out on radial-boom impact tester by ISO180 standard, batten non-notch.
Aging resistance: by method shown in ISO188 standard, standard tensile, impact batten are positioned in air dry oven, be warming up to 150 DEG C, 500h, 2000h is placed respectively under aerobic conditions, 24h under standard environment (23 DEG C, 50%RH) is positioned over after taking-up, observation spline surfaces situation, and test stretches, impact property, calculates corresponding property retention rate respectively.
Embodiment 1
Each component is taken by embodiment 1 data shown in table 1, by polypropylene, grafts compatilizer, the mixing raw material A that EVA segmented copolymer forms is positioned in main feeding bin, short glass fiber, peroxide cross-linking agent, auxiliary crosslinking agent, mixing raw material B after mixing is positioned in the feeding bin of side, and join in the main barrel of twin screw extruder by respective feed screw, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 200 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, through melt extruding, cooling, granulation, particle is obtained after the operations such as drying and processing, in screw injection molding machine, under specific condition of high voltage, be then injection molded into the Mechanics Performance Testing batten of standard.
Embodiment 2
Each component is taken by embodiment 2 data shown in table 1, by polypropylene, grafts compatilizer, the mixing raw material A that EVA segmented copolymer forms is positioned in main feeding bin, short glass fiber, peroxide cross-linking agent, auxiliary crosslinking agent, mixing raw material B after mixing is positioned in the feeding bin of side, and join in the main barrel of twin screw extruder by respective feed screw, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 200 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, through melt extruding, cooling, granulation, particle is obtained after the operations such as drying and processing, in screw injection molding machine, under specific condition of high voltage, be then injection molded into the Mechanics Performance Testing batten of standard.
Embodiment 3
Each component is taken by embodiment 3 data shown in table 1, by polypropylene, grafts compatilizer, the mixing raw material A that EVA segmented copolymer forms is positioned in main feeding bin, short glass fiber, peroxide cross-linking agent, auxiliary crosslinking agent, mixing raw material B after mixing is positioned in the feeding bin of side, and join in the main barrel of twin screw extruder by respective feed screw, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 200 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, through melt extruding, cooling, granulation, particle is obtained after the operations such as drying and processing, in screw injection molding machine, under specific condition of high voltage, be then injection molded into the Mechanics Performance Testing batten of standard.
Embodiment 4
Each component is taken by embodiment 4 data shown in table 1, by polypropylene, grafts compatilizer, the mixing raw material A that EVA segmented copolymer forms is positioned in main feeding bin, short glass fiber, peroxide cross-linking agent, auxiliary crosslinking agent, mixing raw material B after mixing is positioned in the feeding bin of side, and join in the main barrel of twin screw extruder by respective feed screw, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 200 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, through melt extruding, cooling, granulation, particle is obtained after the operations such as drying and processing, in screw injection molding machine, under specific condition of high voltage, be then injection molded into the Mechanics Performance Testing batten of standard.
Embodiment 5
Each component is taken by embodiment 5 data shown in table 1, by polypropylene, grafts compatilizer, the mixing raw material A that EVA segmented copolymer forms is positioned in main feeding bin, short glass fiber, peroxide cross-linking agent, auxiliary crosslinking agent, mixing raw material B after mixing is positioned in the feeding bin of side, and join in the main barrel of twin screw extruder by respective feed screw, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 200 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, through melt extruding, cooling, granulation, particle is obtained after the operations such as drying and processing, in screw injection molding machine, under specific condition of high voltage, be then injection molded into the Mechanics Performance Testing batten of standard.
Embodiment 6
Each component is taken by embodiment 6 data shown in table 1, by polypropylene, grafts compatilizer, the mixing raw material A that EVA segmented copolymer forms is positioned in main feeding bin, short glass fiber, peroxide cross-linking agent, auxiliary crosslinking agent, mixing raw material B after mixing is positioned in the feeding bin of side, and join in the main barrel of twin screw extruder by respective feed screw, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 200 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, through melt extruding, cooling, granulation, particle is obtained after the operations such as drying and processing, in screw injection molding machine, under specific condition of high voltage, be then injection molded into the Mechanics Performance Testing batten of standard.
Embodiment 7
Each component is taken by embodiment 7 data shown in table 1, by polypropylene, grafts compatilizer, the mixing raw material A that EVA segmented copolymer forms is positioned in main feeding bin, short glass fiber, peroxide cross-linking agent, auxiliary crosslinking agent, mixing raw material B after mixing is positioned in the feeding bin of side, and join in the main barrel of twin screw extruder by respective feed screw, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 200 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, through melt extruding, cooling, granulation, particle is obtained after the operations such as drying and processing, in screw injection molding machine, under specific condition of high voltage, be then injection molded into the Mechanics Performance Testing batten of standard.
Comparative example 1
Each component is taken by comparative example 1 data shown in table 1, by polypropylene, the mixing raw material A that grafts compatilizer and processing aid form is positioned in main feeding bin, short glass fiber is positioned in the feeding bin of side, and join in the main barrel of twin screw extruder by respective feed screw, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 200 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, through melt extruding, cooling, granulation, particle is obtained after the operations such as drying and processing, in screw injection molding machine, under specific condition of high voltage, be then injection molded into the Mechanics Performance Testing batten of standard.
The formula table of the high-performance glass fiber reinforced polypropylene composite material that table 1 EVA is post-crosslinking modified (unit: gram)
Comparative example 2
Each component is taken by comparative example 2 data shown in table 1, by polypropylene, the mixing raw material A that grafts compatilizer and processing aid form is positioned in main feeding bin, short glass fiber is positioned in the feeding bin of side, and join in the main barrel of twin screw extruder by respective feed screw, extruder screw diameter is 35mm, length-to-diameter ratio L/D is 40, engine speed is set as 200 revs/min, each zone temperature (exporting from charging opening to head) of main barrel is set as: 60 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, through melt extruding, cooling, granulation, particle is obtained after the operations such as drying and processing, in screw injection molding machine, under specific condition of high voltage, be then injection molded into the Mechanics Performance Testing batten of standard.
The performance test results of the high-performance glass fiber reinforced polypropylene composite material that table 2 EVA is post-crosslinking modified
From the performance test of each embodiment shown in table 2 and comparative example, for the EVA post-crosslinking reaction that peroxide radical causes, suitable linking agent and the amount ratio of auxiliary crosslinking agent are key points prepared by material, only in this way, peroxide radical could by the guiding formation of crosslinking structure of the tendency of reaction instead of the chain-scission degradation of polypropylene molecular chain.Glass fiber reinforced polypropylene composite material material obtained by embodiment 3, not only rigidity of material promotes to some extent, the amplification of shock strength is obvious especially, can more than 40% be reached, and at high temperature afterwards, in the test of long term thermal oxygen aging, the tensile strength of its initial stage 500h, shock strength comparatively initial value also promotes 17% respectively, 9%, show at the thermo-oxidative ageing initial stage, the crosslinking degree of composite inner increases further, its structural integrity also improves thereupon, impel the liter of composite wood performance, and the property retention of aging final 2000h is also all about 90%, in contrast be, the property retention rate of the reinforced polypropylene compound material of conventional preparation is only more than 75%, its gap is fairly obvious.It is worth mentioning that, due to the difference of glass fiber content, cause the change of reinforced polypropylene compound material median surface microstructure content, the cross-linking modified effect of EVA is also corresponding to change, comparative example 3,6 known, because in embodiment 6, glass fiber content is significantly promoted to 40%, interfacial layer occurs that the probability of pore defect increases greatly, in long-term Heat Ageing, easily produce stress concentration and cause tiny crack, even destructive defect, the aging resistance of material being promoted and produces counter productive; And glass fiber content lower time (10% of embodiment 7), EVA is due to the mechanical property inferior position of self, and the fiber-reinforcing effect of polypropylene composite material is not obvious, and overall mechanical performance index is as obviously on the low side in flexural strength, tensile strength etc.
Chemical modification method crosslinked after EVA described in literary composition; the stablizer modification that not only modified effect is more conventional is obvious; and long-term property retention ability is better; modification cost is low; be applicable to large-scale promotion application; the property indices of resulting materials can meet masses, Ford, Great Wall, Shang Qideng main engine plants about performance index the most harsh in the thermo oxidative aging performance of polypropylene composite material; be specially adapted to automobile engine nacelle, the associated structural component of fuel tank periphery and functional part, for the lightweight of current automotive industry, environmental protection process play a role in promoting.
Claims (8)
1. the high-performance glass fiber reinforced polypropylene composite material that EVA is post-crosslinking modified, is characterized in that: the raw material comprising following weight percent:
。
2. the high-performance glass fiber reinforced polypropylene composite material that a kind of EVA according to claim 1 is post-crosslinking modified, is characterized in that: described polypropylene is Co-polypropylene, 230 DEG C, under the test condition of 2.16Kg, its melting index is 2 ~ 30g/min.
3. the high-performance glass fiber reinforced polypropylene composite material that a kind of EVA according to claim 1 is post-crosslinking modified, it is characterized in that: described grafts compatilizer is glycidyl methacrylate GMA grafts polypropylene, is 0.5 ~ 3% through chemical titration test percentage of grafting.
4. the high-performance glass fiber reinforced polypropylene composite material that a kind of EVA according to claim 1 is post-crosslinking modified, is characterized in that: described short glass fiber is glass chopped strand mats, and its filament diameter is 13um, and chopped length is 3 ~ 4.5mm.
5. the high-performance glass fiber reinforced polypropylene composite material that a kind of EVA according to claim 1 is post-crosslinking modified, it is characterized in that: described EVA segmented copolymer is vinyl-vinyl acetate copolymer, 190 DEG C, under the test condition of 2.16Kg, its melting index is 20 ~ 50g/min.
6. the high-performance glass fiber reinforced polypropylene composite material that a kind of EVA according to claim 1 is post-crosslinking modified, is characterized in that: described peroxide initiator is dual-tert-butyl dicumyl peroxide BIBP, and theoretical active oxygen content is 5 ~ 12%.
7. the high-performance glass fiber reinforced polypropylene composite material that a kind of EVA according to claim 1 is post-crosslinking modified, is characterized in that: described auxiliary crosslinking agent is cyanacrylate TAIC, and product acid number mgKOH/g is 0.1 ~ 0.8.
8. the preparation method of the high-performance glass fiber reinforced polypropylene composite material that a kind of EVA according to claim 1 is post-crosslinking modified, is characterized in that, described method comprises the following steps:
(1) take polypropylene, grafts compatilizer and EVA segmented copolymer by described weight percent, mix, gained mixing raw material A; Short glass fiber, peroxide cross-linking agent, auxiliary crosslinking agent is taken, the mixing raw material B after mixing by described weight percent;
(2) dried mixing raw material A is positioned in the main feeding bin of tight meshing co rotating twin screw extrusion, join in the machine barrel of forcing machine through feed screw, mixing raw material B is positioned in the feeding bin of side, join in main barrel through feeding spiral shell in the middle part of forcing machine, screw diameter is 35mm, length-to-diameter ratio L/D is 40, main cylinder exports each zone temperature and is set as from charging opening to head: 60 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, engine speed is 200 revs/min, through melt extruding, cooling, granulation, product is obtained after the operations such as drying and processing.
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| CN108239232A (en) * | 2017-11-20 | 2018-07-03 | 广东聚石化学股份有限公司 | It is a kind of for heat resisting flexibilizer of nylon and preparation method thereof |
| CN109206821A (en) * | 2018-08-31 | 2019-01-15 | 柏力开米复合塑料(昆山)有限公司 | A kind of PP composite material and preparation method thereof |
| CN114121342A (en) * | 2021-11-29 | 2022-03-01 | 安徽电气集团股份有限公司 | Distortion-resistant flexible cable for wind power generation |
| CN114149636A (en) * | 2021-12-14 | 2022-03-08 | 会通新材料股份有限公司 | Fatigue-resistant glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN114805868A (en) * | 2022-04-06 | 2022-07-29 | 浙江中聚材料有限公司 | Polyolefin fiber reinforced layer and application thereof in solar cell adhesive film |
| CN114805868B (en) * | 2022-04-06 | 2024-05-14 | 浙江中聚材料有限公司 | Polyolefin fiber reinforced layer and application thereof in solar cell adhesive film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108239232A (en) * | 2017-11-20 | 2018-07-03 | 广东聚石化学股份有限公司 | It is a kind of for heat resisting flexibilizer of nylon and preparation method thereof |
| CN108127997A (en) * | 2017-12-05 | 2018-06-08 | 安徽艾迪文新材料有限公司 | A kind of high-strength polypropylene foamed board and preparation method thereof |
| CN108127997B (en) * | 2017-12-05 | 2020-11-06 | 安徽艾迪文新材料有限公司 | High-strength polypropylene foam board and preparation method thereof |
| CN109206821A (en) * | 2018-08-31 | 2019-01-15 | 柏力开米复合塑料(昆山)有限公司 | A kind of PP composite material and preparation method thereof |
| CN114121342A (en) * | 2021-11-29 | 2022-03-01 | 安徽电气集团股份有限公司 | Distortion-resistant flexible cable for wind power generation |
| CN114121342B (en) * | 2021-11-29 | 2024-02-09 | 安徽电气集团股份有限公司 | Torsion-resistant flexible cable for wind power generation |
| CN114149636A (en) * | 2021-12-14 | 2022-03-08 | 会通新材料股份有限公司 | Fatigue-resistant glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN114149636B (en) * | 2021-12-14 | 2023-08-04 | 会通新材料股份有限公司 | Fatigue-resistant glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN114805868A (en) * | 2022-04-06 | 2022-07-29 | 浙江中聚材料有限公司 | Polyolefin fiber reinforced layer and application thereof in solar cell adhesive film |
| CN114805868B (en) * | 2022-04-06 | 2024-05-14 | 浙江中聚材料有限公司 | Polyolefin fiber reinforced layer and application thereof in solar cell adhesive film |
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