CN103012968A - Weather-resistant glass fiber reinforced polypropylene composite and preparation method thereof - Google Patents
Weather-resistant glass fiber reinforced polypropylene composite and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a weather-resistant glass fiber reinforced polypropylene composite. The weather-resistant glass fiber reinforced polypropylene composite comprises polypropylene, glass fibers, compatilizer, antioxidant, light stabilizer and acid scavenger. The acid scavenger disclosed by the invention can effectively remove the free acid from the lass fiber reinforced polypropylene composite to change the acid environment in the system, thus the composite material becomes neutral or alkalescence; and furthermore, the antagonism effect between the hindered anime light stabilizer and the compatilizer can be removed by the acid scavenger, and as a result, the mechanical strength and the weather resistance of the composite can be improved. The preparation process of the product is simple, the producing cost is low, and no secondary pollution is caused.
Description
Technical field
The invention belongs to technical field of polymer composite materials, be specifically related to a kind of weather-proof glass fiber reinforced polypropylene composite material and preparation method thereof.
Technical background
Glass reinforced plastics is a kind of light-high-strength structural timber, because fiber has good mechanical property, when External Force Acting is arranged, load is by the fiber transmission, so the stretching of glass reinforced plastics, bending, shock strength and creep resistance, resistent fatigue characteristic are much better than non-reinforced plastics, and have excellent rigidity, toughness, anti-warpage properties, and its price is far below engineering plastics.The application of glass reinforced plastics is very extensive, has approximately 50% glass reinforced plastics to be applied to automotive industry in West Europe.The performance of glass reinforced plastics depends primarily on following factor: 1. glass fiber content: in general, glass fiber content is higher, and the mechanical property of glass reinforced plastics is also higher, but glass fiber content is too high, to the processing units serious wear, and material fragility is improved and the density increase; After glass fiber content surpassed a certain threshold value (50 wt%), along with glass fiber content further increases, mechanical property descended on the contrary simultaneously; 2. the length of glass in resin matrix; 3. the cohesive force between glass and the resin matrix with and the homogeneity of disperseing.
Glass fiber reinforced polypropylene composite material becomes a kind of matrix material of extensive employing with its excellent mechanical property and high cost performance.In order to prepare the glass fibre reinforced composite material of excellent combination property, key is the interaction force that increases between glass and the resin matrix, avoids simultaneously the antagonistic action between the various functional agents at present.Therefore, in order to increase reactive force between the two-phase, polypropylene grafted maleic anhydride class compatilizer is widely adopted, yet remaining free acid and the anhydride bond in the maleic anhydride causes that system presents acidity in this type of compatilizer, and has reduced the weathering resistance of glass fiber reinforced polypropylene composite material.Also have in order to realize that glass strengthens the open air use of class material, the steady agent of all kinds of light is used to this type of composite system, the steady agent of hindered amines light is the efficient radical scavenger of a class, the main effective constituent of the steady agent of light, but the steady agent of hindered amines light is weakly alkaline, there is antagonistic action in the slightly acidic that this and glass strengthen system, causes the mechanical property of such matrix material and weather resistance all relatively poor.
Chinese invention patent CN102329448A has announced a kind of glass fiber reinforced polypropylene composite material and preparation method thereof, has wherein introduced and has utilized high-alkali glass to strengthen toughened polypropylene composite for the preparation of the washing tub of washing machine.This matrix material has excellent mechanical property, can satisfy the washing machine drum service requirements, but this material does not have weathering resistance, therefore is used for only lucifuge place product and uses.
Chinese invention patent CN101338051A has announced a kind of long fiber reinforced polypropylene composite material and preparation method thereof, material is comprised of polypropylene, long glass fibres, coupling agent, compatilizer etc., the preparation method is after first polypropylene and auxiliary being mixed together, extrude solution by forcing machine, long glass fibres is introduced in the solution again and fully flooded, coat, last discharging gets product.Because not adding the steady agent of light or adopting the method for effective anti-ultraviolet ageing, do not possess the anti-ultraviolet ageing performance in this matrix material.
Chinese invention patent CN101735513A has announced alkali-free short fiber reinforced polypropylene compound material, this matrix material has excellent mechanical property, improve light stability energy by adding the steady agent of hindered amines light simultaneously, but because the antagonism between the alkalescence of the acidity of compatilizer and the steady agent of light is with the thoroughly solution of failing, and cause the mechanical property of such matrix material and weather resistance all relatively poor.
From the above as can be known, how to realize to realize weather resistance when glass fiber composite material has excellent mechanical property, then become a problem demanding prompt solution.And the weathering resistance problem of solution glass fiber reinforced polypropylene composite material, key is the sour environment that changes this matrix material, and make it change neutrality or weakly alkaline environment into, to improve the weathering resistance of glass fiber reinforced polypropylene composite material, also avoid the acidity of slightly acidic photostabilizer and compatilizer to have antagonistic action.
Summary of the invention
The present invention is directed to problems of the prior art, provide a kind of and be applicable to industrialized mass production, have the glass fiber reinforced polypropylene composite material of excellent tensile strength, shock strength and weathering resistance.Another object of the present invention provides the preparation method of above-mentioned weather-proof glass fiber reinforced polypropylene composite material.
In order to achieve the above object, the present invention realizes by following technical proposal:
A kind of weather-proof glass fiber reinforced polypropylene composite material, described matrix material are to be made of by weight following component: polypropylene: 40-87 part, glass fibre: 10-40 part, compatilizer: 2-7 part, oxidation inhibitor: 0.1-0.4 part, photostabilizer: 0.1-1 part, acid scavenger: 0.02-0.5 part.
The preferred version of such scheme is, described polypropylene is Co-polypropylene, and its melting index under 230 ℃/2.16Kg condition is greater than 10 g/10min, and the ethylene content in the described Co-polypropylene is 2-12 wt%.
Described glass fibre is alkali free glass fibre, and its diameter is 8-15um, and its alkali metal oxide content is low, has all fine characteristics of chemical stability, electrical insulation capability, intensity.
Described compatilizer is at least a in polypropylene grafted maleic anhydride (PP-g-MAH), polypropylene grafted glycidyl methacrylate (PP-g-GMA), grafting maleic anhydride with ethylene propylene terpolymer (EPDM-g-MAH), the terpolymer EP rubber graft glycidyl methacrylate (EPDM-g-GMA).
Described photostabilizer is the mixture of UV light absorber and the steady agent of hindered amines light.
The preferred version of such scheme is, described UV light absorber is salicylic acid phenyl ester, 2-(2'-hydroxyl-5'-aminomethyl phenyl) benzotriazole, 2,4-dihydroxy benaophenonel, Octabenzone, 2-(2'-hydroxyl-3', 5'-two uncle's phenyl)-5-chlorination benzotriazole or polyolefin-based black masterbatch; The steady agent of described hindered amines light is two (2,2,6, the 6-tetramethyl--4-piperidines) esters of sebacic acid or two (2,2,6,6-tetramethyl--4-piperidyl) sebate.
Described oxidation inhibitor is for being selected from four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) at least a in the two stearyl alcohol esters (oxidation inhibitor DSTDP) of pentaerythritol ester (antioxidant 1010), three (2,4-di-tert-butyl-phenyl) phosphorous acid ester (irgasfos 168), thio-2 acid.
Described acid scavenger is calcium oxide, zinc oxide, hydrotalcite, zinc oxide master batch, calcium oxide master batch or hydrotalcite master batch.Wherein the zinc oxide master batch is zinc oxide and polypropylene or the master batch that forms through melt pelletization with polyethylene; The calcium oxide master batch is calcium oxide and polypropylene or the master batch that forms through melt pelletization with polyethylene; The hydrotalcite master batch is hydrotalcite and polypropylene or the master batch that forms through melt pelletization with polyethylene.
A kind of method for preparing above-mentioned weather-proof glass fiber reinforced polypropylene composite material may further comprise the steps:
(1) polypropylene, glass fibre, compatilizer, oxidation inhibitor, the steady agent of light, acid scavenger are mixed;
(2) with mixed material through the melting of twin screw extruder forcing machine, extrude rear granulation, namely get weather-proof glass fiber reinforced polypropylene composite material.
The present invention compared with prior art has following some advantage:
1, adopting acid scavenger among the present invention is the material that the stronger persistence of a class alkalescence consumes free acid, can effectively remove free acid in the glass fiber reinforced polypropylene composite material and sour environment in the change system, thereby make matrix material present neutrality or weakly alkaline, thereby improve the weathering resistance of glass fiber reinforced polypropylene composite material.
2, owing in the compositing formula of the present invention acid scavenger is arranged, thereby eliminate the antagonistic action between the steady agent hindered amine of light and the compatilizer, thereby improve mechanical property and the weather resistance of its matrix material.
3, glass fiber reinforced polypropylene composite material of the present invention is surveyed its performance according to testing experiment, and tensile strength is not less than 45Mpa, shock strength is not less than 12KJ/m
2, through its physical strength retention rate behind 2000 hours ultraviolet ageings all greater than 90%, show this matrix material have excellent mechanical property superior with the anti-ultraviolet ageing characteristic.
4, glass fiber reinforced polypropylene composite material among the present invention, by with base material with after functional agent directly mixes, adopt twin screw to melt extrude preparation.Such production technique is simple, does not produce secondary pollution.
Embodiment:
The below provides embodiment so that the present invention is carried out concrete description; be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, content still belongs to protection scope of the present invention to some nonessential improvement and the adjustment that the present invention makes to the person skilled in the art in this field according to the present invention.
In the present invention, a kind of weather-proof glass fiber reinforced polypropylene composite material is to take by weighing respectively by weight ratio first polypropylene, glass fibre, compatilizer, oxidation inhibitor, photostabilizer and acid scavenger, then by the twin screw extruder extruding pelletization, prepare weather-proof glass fiber reinforced polypropylene composite material after mixing through high-speed mixer.
Used raw material all is commercially available prod among the present invention, wherein:
It is all fine that glass fibre is elected chemical stability, electrical insulation capability, intensity as, and the alkali free glass fibre that alkali metal oxide content is low, the diameter of its glass fibre are 8-15um.
Polypropylene select melting index greater than 10 g/10min (230 ℃, 2.16Kg), ethylene content is the Co-polypropylene of 2-12wt%.
Embodiment 1
Take by weighing respectively by weight ratio dry Co-polypropylene 87.0%; alkali free glass fibre 10.0%; Compatibilizer PP-g-MAH is 2%; antioxidant 1010 is 0.3%; irgasfos 168 is 0.1%; photostabilizer salicylic acid phenyl ester is 0.05%; sebacic acid two (2,2,6; 6-tetramethyl--4-piperidines) ester is 0.05%; acid scavenger zinc oxide is 0.5%, puts into high-speed mixer and mixes, and the material that mixes is joined in the twin screw extruder; through melt extruding; then after passing through water-cooled, be cut into the particle that length is 1-5mm by dicing machine, obtain the finished product.Wherein, the processing temperature of forcing machine is followed successively by 180 ℃ by feed opening to die orifice, and 195 ℃, 210 ℃, 210 ℃, 220 ℃, engine speed is 60-80rpm, and vacuum tightness is 0.3MPa.
Embodiment 2
Take by weighing by weight ratio dry good Co-polypropylene 80.0%; alkali free glass fibre 17.0%; Compatibilizer PP-g-MAH is 2.17%; antioxidant 1010 is 0.3%; oxidation inhibitor DSTDP is 0.1%; the surely steady agent Octabenzone of light is 0.2%, sebacic acid two (2; 2,6,6-tetramethyl--4-piperidines) ester is 0.2%; the acid scavenger calcium oxide is 0.03%; put into high-speed mixer and mix, the material that mixes is joined in the twin screw extruder, through melt extruding; then after passing through water-cooled, be cut into the particle that length is 1-5mm by dicing machine.Wherein, the processing temperature of forcing machine is followed successively by 180 ℃ by feed opening to die orifice, and 195 ℃, 210 ℃, 210 ℃, 220 ℃, engine speed is 60-80rpm, and vacuum tightness is 0.3MPa.
Embodiment 3
Take by weighing by weight ratio dry good Co-polypropylene 75.0%; alkali free glass fibre 20.0%; compatilizer PP-g-GMA is 4%; antioxidant 1010 is 0.1%; photostabilizer 2; the 4-dihydroxy benaophenonel is 0.3%, two (2; 2,6,6-tetramethyl--4-piperidyl) sebate is 0.5%; acid scavenger hydrotalcite 0.1%; put into high-speed mixer and mix, the material that mixes is joined in the twin screw extruder, through melt extruding; then after passing through water-cooled, be cut into the particle that length is 1-5mm by dicing machine.Wherein, the processing temperature of forcing machine is followed successively by 180 ℃ by feed opening to die orifice, and 195 ℃, 210 ℃, 210 ℃, 220 ℃, engine speed is 60-80rpm, and vacuum tightness is 0.3MPa.
Embodiment 4
Take by weighing by weight ratio dry good Co-polypropylene 70.0%; alkali free glass fibre 24.0%; compatilizer EPDM-g-GMA is 4.3%; antioxidant 1010 is 0.1%; oxidation inhibitor DSTDP is 0.2%; irgasfos 168 is 0.1%; photostabilizer 2-(2'-hydroxyl-5'-aminomethyl phenyl) benzotriazole is 0.4%; sebacic acid two (2; 2,6,6-tetramethyl--4-piperidines) ester is 0.4%; acid scavenger is zinc oxide master batch 0.5%; put into high-speed mixer and mix, the material that mixes is joined in the twin screw extruder, through melt extruding; then after passing through water-cooled, be cut into the particle that length is 1-5mm by dicing machine.Wherein, the processing temperature of forcing machine is followed successively by 180 ℃ by feed opening to die orifice, and 195 ℃, 210 ℃, 210 ℃, 220 ℃, engine speed is 60-80rpm, and vacuum tightness is 0.3MPa.
Embodiment 5
Take by weighing by weight ratio dry good Co-polypropylene 64.4.0%; alkali free glass fibre 32.0%; compatilizer EPDM-g-GMA is 1 %; PP-g-MAH 1%; antioxidant 1010 is 0.2%; irgasfos 168 is 0.2%; photostabilizer salicylic acid phenyl ester is 0.6%; sebacic acid two (2; 2,6,6-tetramethyl--4-piperidines) ester is 0.2%; acid scavenger calcium oxide master batch is 0.4%; put into high-speed mixer and mix, the material that mixes is joined in the twin screw extruder, through melt extruding; then after passing through water-cooled, be cut into the particle that length is 1-5mm by dicing machine.Wherein, the processing temperature of forcing machine is followed successively by 180 ℃ by feed opening to die orifice, and 195 ℃, 210 ℃, 210 ℃, 220 ℃, engine speed is 60-80rpm, and vacuum tightness is 0.3MPa.
Embodiment 6
Take by weighing by weight ratio dry good Co-polypropylene 57.0%; alkali free glass fibre 35.0%; Compatibilizer PP-g-MAH is 6.8 %; antioxidant 1010 is 0.3%, irgasfos 168 is 0.1%; photostabilizer salicylic acid phenyl ester is 0.4%, two (2; 2; 6; 6-tetramethyl--4-piperidyl) sebate 0.2%, acid scavenger are that the hydrotalcite master batch is 0.2%, put into high-speed mixer and mix; the material that mixes is joined in the twin screw extruder; through melt extruding, then pass through water-cooled after, be cut into the particle that length is 1-5mm by dicing machine.Wherein, the processing temperature of forcing machine is followed successively by 180 ℃ by feed opening to die orifice, and 195 ℃, 210 ℃, 210 ℃, 220 ℃, engine speed is 60-80rpm, and vacuum tightness is 0.3MPa.
Embodiment 7
Take by weighing by weight ratio dry good Co-polypropylene 54.0%; alkali free glass fibre 40.0%; Compatibilizer PP-g-MAH is 2.8 %; EPDM-g-GMA is 2%; oxidation inhibitor DSTDP is 0.1%; irgasfos 168 is 0.1 %; photostabilizer 2-(2'-hydroxyl-3'; 5'-two uncle's phenyl)-5-chlorination benzotriazole is 0.5%; two (2; 2,6,6-tetramethyl--4-piperidyl) sebate is 0.48%; acid scavenger zinc oxide is 0.02%; put into high-speed mixer and mix, the material that mixes is joined in the twin screw extruder, through melt extruding; then after passing through water-cooled, be cut into the particle that length is 1-5mm by dicing machine.Wherein, the processing temperature of forcing machine is followed successively by 180 ℃ by feed opening to die orifice, and 195 ℃, 210 ℃, 210 ℃, 220 ℃, engine speed is 60-80rpm, and vacuum tightness is 0.3MPa.
Embodiment 8
Take by weighing by weight ratio dry good Co-polypropylene 42.0%; alkali free glass fibre 50.0%; Compatibilizer PP-g-MAH is 4 %; EPDM-g-MAH is 2.6%; antioxidant 1010 is 0.3%; oxidation inhibitor DSTDP is 0.1%; photostabilizer polyvinyl black masterbatch PE2772 is 0.3%; photostabilizer 2-(2'-hydroxyl-3'; 5'-two uncle's phenyl)-and 5-chlorination benzotriazole is 0.4%, acid scavenger hydrotalcite master batch is 0.3%, puts into high-speed mixer and mixes; the material that mixes is joined in the twin screw extruder; through melt extruding, then pass through water-cooled after, be cut into the particle that length is 1-5mm by dicing machine.Wherein, the processing temperature of forcing machine is followed successively by 180 ℃ by feed opening to die orifice, and 195 ℃, 210 ℃, 210 ℃, 220 ℃, engine speed is 60-80rpm, and vacuum tightness is 0.3MPa.
Simultaneous test:
Sample among above-described embodiment 1-8 is injection molded into the GB batten according to unified technique, according to testing standard listed in the table 1 and condition it is carried out respectively measuring mechanical property, and the sample of each embodiment is put into ultraviolet accelerated deterioration case wear out, test data is as shown in table 2 below.
Table 1: performance test standard and the condition of matrix material
Table 2: the performance test results of each matrix material among the embodiment 1-8
| Embodiment | Tensile strength/Mpa | Elongation at break/% | Notched Izod impact strength (KJ/m2) | Flexural strength/Mpa |
| Embodiment 1 | 45 | 20 | 12 | 46 |
| After 2000h is aging | 44 | 18 | 11 | 44 |
| Retention rate | 0.98 | 0.90 | 0.92 | 0.96 |
| Embodiment 2 | 50 | 19 | 15 | 51 |
| After 2000h is aging | 48 | 18 | 14 | 49 |
| Retention rate | 0.96 | 0.95 | 0.93 | 0.96 |
| Embodiment 3 | 53 | 20 | 17 | 53 |
| After 2000h is aging | 52 | 19 | 16 | 51 |
| Retention rate | 0.98 | 0.95 | 0.94 | 0.96 |
| Embodiment 4 | 58 | 15 | 18 | 62 |
| After 2000h is aging | 55 | 13 | 17 | 60 |
| Retention rate | 0.95 | 0.87 | 0.94 | 0.97 |
| Embodiment 5 | 61 | 13 | 23 | 73 |
| After 2000h is aging | 58 | 12 | 21 | 70 |
| Retention rate | 0.95 | 0.92 | 0.91 | 0.96 |
| Embodiment 6 | 65 | 11 | 24 | 76 |
| After 2000h is aging | 62 | 10 | 23 | 74 |
| Retention rate | 0.95 | 0.91 | 0.96 | 0.97 |
| Embodiment 7 | 70 | 9 | 27 | 85 |
| After 2000h is aging | 69 | 6 | 25 | 82 |
| Retention rate | 0.99 | 0.67 | 0.93 | 0.96 |
| Embodiment 8 | 72 | 8 | 28 | 87 |
| After 2000h is aging | 68 | 5 | 25 | 81 |
| Retention rate | 0.94 | 0.63 | 0.89 | 0.93 |
Data from table 2 can be found out, along with the increase of content of glass fiber, the mechanical property of this matrix material increases gradually, and its intensity has has met and exceeded the intensity of engineering plastics, alternative traditional engineering plastics are used, thereby improve the cost performance of this matrix material.Acid scavenger among the present invention is effectively removed free acid in the glass fiber reinforced polypropylene composite material and sour environment in the change system, and makes this matrix material present neutrality or weakly alkaline; Eliminate simultaneously the antagonistic action between the steady agent hindered amine of light and the compatilizer, thereby improve mechanical property and the weather resistance of this matrix material.Data can be found out from table 2, the embodiment batten of 1-8 is through behind 2000 hours ultraviolet ageings, the physical strength retention rate is all greater than 90%, show that this matrix material has excellent anti-ultraviolet ageing characteristic, be that weathering resistance is strong, can satisfy the requirement of outdoor selection, thereby expand the range of application of glass fiber reinforced polypropylene composite material, open up new Application Areas.
Claims (9)
1. weather-proof glass fiber reinforced polypropylene composite material, it is characterized in that: described matrix material is to be made of by weight following component:
Polypropylene: 40-87 part, glass fibre: 10-50 part, compatilizer: 2-7 part, oxidation inhibitor: 0.1-0.4 part, photostabilizer: 0.1-1 part, acid scavenger: 0.02-0.5 part.
2. a kind of weather-proof glass fiber reinforced polypropylene composite material according to claim 1, it is characterized in that: described polypropylene is Co-polypropylene, its melting index under 230 ℃/2.16Kg condition is greater than 10 g/10min, and the ethylene content in the described Co-polypropylene is 2-12 wt%.
3. a kind of weather-proof glass fiber reinforced polypropylene composite material according to claim 1, it is characterized in that: described glass fibre is alkali free glass fibre, its diameter is 8-15um.
4. a kind of weather-proof glass fiber reinforced polypropylene composite material according to claim 1 is characterized in that: described compatilizer is to be selected from least a in polypropylene grafted maleic anhydride, polypropylene grafted glycidyl methacrylate, grafting maleic anhydride with ethylene propylene terpolymer, the terpolymer EP rubber graft glycidyl methacrylate.
5. a kind of weather-proof glass fiber reinforced polypropylene composite material according to claim 1, it is characterized in that: described photostabilizer is the mixture of UV light absorber and the steady agent of hindered amines light.
6. a kind of weather-proof glass fiber reinforced polypropylene composite material according to claim 5, it is characterized in that: described UV light absorber is salicylic acid phenyl ester, 2-(2'-hydroxyl-5'-aminomethyl phenyl) benzotriazole, 2,4-dihydroxy benaophenonel, Octabenzone, 2-(2'-hydroxyl-3', 5'-two uncle's phenyl)-5-chlorination benzotriazole or polyolefin-based black masterbatch are at least a;
The steady agent of described hindered amines light is two (2,2,6, the 6-tetramethyl--4-piperidines) esters of sebacic acid or two (2,2,6,6-tetramethyl--4-piperidyl) sebate.
7. a kind of weather-proof glass fiber reinforced polypropylene composite material according to claim 1, it is characterized in that: described oxidation inhibitor is for being selected from four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) at least a in the two stearyl alcohol esters of pentaerythritol ester, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, thio-2 acid.
8. a kind of weather-proof glass fiber reinforced polypropylene composite material according to claim 1, it is characterized in that: described acid scavenger is calcium oxide, zinc oxide, hydrotalcite, zinc oxide master batch, calcium oxide master batch or hydrotalcite master batch.
9. one kind prepares a kind of weather-proof glass fiber reinforced polypropylene composite material method as claimed in claim 1, it is characterized in that: may further comprise the steps:
(1) polypropylene, glass fibre, compatilizer, oxidation inhibitor, the steady agent of light, acid scavenger are mixed;
(2) with mixed material through the melting of twin screw extruder forcing machine, extrude rear granulation, namely get weather-proof glass fiber reinforced polypropylene composite material.
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