CN105504497A - Heat-resistant and ageing-resistant long glass fiber reinforced PP (Polypropylene) material and preparation method as well as application thereof - Google Patents
Heat-resistant and ageing-resistant long glass fiber reinforced PP (Polypropylene) material and preparation method as well as application thereof Download PDFInfo
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Abstract
The invention discloses a heat-resistant and ageing-resistant long glass fiber reinforced PP (Polypropylene) material and a preparation method as well as application thereof. A heat stabilizer is particularly added into a long glass fiber reinforced PP material; the mechanical property of the material at high temperature is effectively improved; the long glass fiber reinforced PP material is guaranteed to be still capable of stably working in a high-temperature environment; the application range of the long glass fiber reinforced PP material is effectively expanded; meanwhile, according to the heat-resistant and ageing-resistant long glass fiber reinforced PP material and the preparation method as well as the application thereof, an antioxidant is also particularly added into the long glass fiber reinforced PP material; the ageing resistance of the long glass fiber reinforced PP material is promoted; the service life and the reliability of the long glass fiber reinforced PP material can be effectively prolonged and improved. The long glass fiber reinforced PP material provided by the invention has better mechanical strength at the high temperature, has the outstanding ageing resistance at the same time, and is especially applicable to the application to the preparation of parts and components for automobiles, components for instruments and meters, electromechanical parts and components and electronic and electrical elements.
Description
Technical field
The present invention relates to field of material technology, long glass fiber reinforced PP material being specifically related to a kind of heat-resisting ageing-resisting and its preparation method and application.
Background technology
Long glass fiber reinforced PP((LFRT-PP)) material has excellent shock-resistance and excellent mechanical property and electrical insulating property, its use temperature scope is generally between-100 ~ 160 DEG C, dimensional stability is high, and creep resistant is high, is a kind ofly to integrate firm, hard, tough typical plastics.Just because of these advantages, poly-fiberglass reinforced PP has now been widely used in the fields such as electronic apparatus, office appliance, precision machinery, medical treatment, labour protection, household supplies and automobile.But at some special dimension, because environment for use temperature is higher, existing fiberglass reinforced PP material thermal resistance is poor, and when temperature is higher, mechanical property obviously reduces.And existing long glass fiber reinforced PP material at high temperature also very easily occurs aging, shock resistance declines and easily ruptures, the demand of life-time service can not be met, especially cannot be used as that working temperature is higher, raw materials for production to the higher automobile component of reliability requirement, aviation accessory.
Summary of the invention
In view of this, open a kind of high temperature resistant, the aging-resistant long glass fiber reinforced PP matrix material of the present invention.
Object of the present invention is achieved through the following technical solutions:
A long glass fiber reinforced PP material for heat-resisting ageing-resisting, its raw material comprises by weight:
Roving glass fiber 20-35 part;
PP70-80 part
Thermo-stabilizer 0.01-0.25 part;
Oxidation inhibitor 0.2-0.9 part;
Fire retardant 1-3 part;
Its raw material of described thermo-stabilizer comprises propylene glycol 0.3-0.7 part, sodium carbonate 1-7 part, 0.01-0.08 part Natvosol by weight; Described oxidation inhibitor comprises the antioxidant 1010 of 1-6 part, the aubepine of 0.5-1.5 part by weight.
Described propylene glycol is preferably 1,2-PD, is a kind of chemical reagent, with water, ethanol and multiple immiscible organic solvent.Propylene glycol can be used as the raw material of unsaturated polyester resin. and can coordinate with glycerine or sorbyl alcohol in makeup, toothpaste and perfumed soap and be used as wetting agent.Described sodium carbonate has another name called soda or sode ash.It is a kind of important Organic Chemicals, is mainly used in the production of sheet glass, glasswork and ceramic glaze.Also be widely used in life washing, acids neutralization and food-processing etc.Natvosol is a kind of white or faint yellow, and tasteless, nontoxic threadiness or pulverulent solids are prepared through etherification reaction by alkali cellulose and oxyethane (or chloroethanol), belongs to non-ionic type soluble fiber element ethers.Due to HEC, there is good thickening, suspension, dispersion, emulsification, bonding, film forming, protection moisture and the characteristics such as protective colloid are provided, being widely used in the fields such as oil production, coating, building, medicine food, weaving, papermaking and macromolecular polymerization reaction.In the present invention, with the addition of the long glass fiber reinforced PP matrix material of sodium carbonate and Natvosol, heat-drawn wire can reach 175 DEG C, still can maintain higher modulus in flexure time more than 120 DEG C.Adopt fiberglass reinforced PP material of the present invention at high temperature still to have higher rigid, be particularly suitable for manufacturing working temperature higher electronic instrument, flyer part and auto parts.The present invention also selects antioxidant 1010 and aubepine as oxidation inhibitor especially.Antioxidant 1010 can select any one existing techniques in realizing; Be colourless to weak yellow liquid under aubepine normal temperature, there is the smell of similar hawthorn.Under the effect of aubepine, antioxidant 1010 effectively can improve the ageing resistance of fiberglass reinforced PP material, enables the shock resistance that long-term maintenance is higher, guarantees working life and the reliability of material.
Further, described roving glass fiber is alkali-free continuous glass-fiber, and described alkali-free continuous glass-fiber diameter is 11-20 μm.
In addition, roving glass fiber also can select any one existing techniques in realizing.
Further, described roving glass fiber its preparation method is:
(1) normal heptane immersion treatment: roving glass fiber is immersed in normal heptane and carry out swelling treatment, the treatment time is 22h ~ 30h;
(2) washing with alcohol: the roving glass fiber after swelling is heated to 120-150 DEG C, drops in the dehydrated alcohol of 20-25 DEG C and adopts the ultrasonic oscillation of 25-30KHz to wash, be then placed in the drying in oven of 150-200 DEG C to constant weight.
Easily there is floating fine phenomenon in roving glass fiber, cause material property to decline in PP material.Designer finds under study for action, roving glass fiber after swelling is heated to 120-150 DEG C, dropping in the dehydrated alcohol of 20-25 DEG C adopts the ultrasonic oscillation of 25-30KHz to wash, effectively can suppress the floating fine problem of roving glass fiber, make that obtained fiberglass reinforced PP material injection part is homogeneous, any surface finish, apparent quality is excellent.
The present invention provides a kind of preparation method of long glass fiber reinforced PP material of described heat-resisting ageing-resisting simultaneously, and it comprises following operation:
A. thermo-stabilizer is prepared: adopt airbath to be heated to 50 DEG C in Natvosol, sodium carbonate, instillation propylene glycol, after insulation 30min, add magnesium chlorate;
B. by setting weight part PP, thermo-stabilizer, oxidation inhibitor, fire retardant added after super mixer mixes and be heated to through twin screw extruder the PP mixture that 160 ~ 199 DEG C obtain plasticizing, then the PP mixture plastified is by twin screw extruder press-in dipping die head, the roving glass fiber of impregnating dispersion setting weight part, being prepared into length through traction, cooling forming, cutting process is that 10-15mm low is distributed, high-performance long glass fiber reinforced PP matrix material.
The application in electronic instrument, flyer part, auto parts prepared by a kind of long glass fiber reinforced PP material of described heat-resisting ageing-resisting.
The present invention adds thermo-stabilizer especially in roving glass fiber increase PP material, effectively improves material mechanical property at high temperature, guarantees that long glass fiber reinforced PP material still can stably work in hot environment, the range of application of efficient extn long glass fiber reinforced PP material; The present invention simultaneously also special increasing in PP material to roving glass fiber adds oxidation inhibitor, promotes the ageing resistance of long glass fiber reinforced PP material, effectively can extend work-ing life and the reliability of long glass fiber reinforced PP material.Roving glass fiber can form three-dimensional net structure in thermoplastic PP resin, thus improves the comprehensive mechanical property of matrix material.Matrix material glass emergence on the surface of the present invention is few simultaneously, and apparent quality is excellent.Long glass fiber reinforced PP material of the present invention at high temperature has preferably physical strength, have both outstanding anti-aging characteristic simultaneously, be particularly useful for being applied in and prepare in automobile component (as bumper beam, chair framework, spare tyre etc.), instrument parts (housing of intelligent electric meter and water meter or terminal block), electromechanical component (as motor filter cover, guide bearing, coil axes etc.), electric element (as rly.).
Embodiment
The present invention to be described in further detail below in conjunction with embodiment for the ease of it will be appreciated by those skilled in the art that:
Embodiment 1
The present embodiment provides a kind of long glass fiber reinforced PP material being applied to the heat-resisting ageing-resisting preparing intelligent ammeter shell, and its raw material comprises by weight:
Roving glass fiber 25 parts;
PP75 part
Thermo-stabilizer 0.10 part;
0.7 part, oxidation inhibitor;
Fire retardant 2 parts;
Its raw material of described thermo-stabilizer comprises propylene glycol 0.4 part, 3 parts, sodium carbonate, 0.06 part of Natvosol by weight; Described oxidation inhibitor comprises the antioxidant 1010 of 3 parts, the aubepine of 1.2 parts by weight.
Further, described roving glass fiber is alkali-free continuous glass-fiber, and described alkali-free continuous glass-fiber diameter is 11-20 μm.
Further, described roving glass fiber its preparation method is:
(1) normal heptane immersion treatment: roving glass fiber is immersed in normal heptane and carry out swelling treatment, the treatment time is 25h;
(2) washing with alcohol: the roving glass fiber after swelling is heated to 140 DEG C, drops in the dehydrated alcohol of 22 DEG C and adopts the ultrasonic oscillation of 28KHz to wash, be then placed in the drying in oven of 180 DEG C to constant weight.
The present invention provides a kind of preparation method of long glass fiber reinforced PP material of described heat-resisting ageing-resisting simultaneously, and it comprises following operation:
A. thermo-stabilizer is prepared: adopt airbath to be heated to 50 DEG C in Natvosol, sodium carbonate, instillation propylene glycol, after insulation 30min, add magnesium chlorate;
B. by setting weight part PP, thermo-stabilizer, oxidation inhibitor, fire retardant added after super mixer mixes and be heated to through twin screw extruder the PP mixture that 160 ~ 199 DEG C obtain plasticizing, then the PP mixture plastified is by twin screw extruder press-in dipping die head, the roving glass fiber of impregnating dispersion setting weight part, being prepared into length through traction, cooling forming, cutting process is that 10-15mm low is distributed, high-performance long glass fiber reinforced PP matrix material.
Adopt the rapid prototyping material of prior art to be prepared into the plate part of a 1000mm × 1000mm × 20mm in the matrix material of the present embodiment, adopt ASTM standard to carry out performance test to it, its result is as shown in table 1.
Table 1.
| Project | Method | Unit | Result |
| Tensile strength | ASTM D638 | Mpa | 95 |
| Flexural strength | ASTM D790 | Mpa | 158 |
| Flexural strength (120 DEG C) | ASTM D790 | Mpa | 133 |
| Bending modulus | ASTM D790 | Mpa | 6680 |
| Bending modulus (120 DEG C) | ASTM D790 | Mpa | 6350 |
| Notched Izod impact hit intensity (1/8) (process of xenon lamp aging case is after 3000 hours) | ASTM D256 | KJ/M | 17.8 |
| Melting index | ASTM D1238 | g/10min | 13 |
| Flame resistivity | UL94 | 1.6mm | HB |
| Melt temperature | - | ℃ | 180-215 |
Embodiment 2
The present embodiment provides a kind of long glass fiber reinforced PP material of the heat-resisting ageing-resisting for the manufacture of flyer part, and its raw material comprises by weight:
Roving glass fiber 35 parts;
PP70 part
Thermo-stabilizer 0.25 part;
0.2 part, oxidation inhibitor;
Fire retardant 3 parts;
Its raw material of described thermo-stabilizer comprises propylene glycol 0.3 part, 7 parts, sodium carbonate, 0.01 part of Natvosol by weight; Described oxidation inhibitor comprises the antioxidant 1010 of 6 parts, the aubepine of 0.5 part by weight.
Further, described roving glass fiber is alkali-free continuous glass-fiber, and described alkali-free continuous glass-fiber diameter is 20 μm.
Further, described roving glass fiber its preparation method is:
(1) normal heptane immersion treatment: roving glass fiber is immersed in normal heptane and carry out swelling treatment, the treatment time is 22h;
(2) washing with alcohol: the roving glass fiber after swelling is heated to 150 DEG C, drops in the dehydrated alcohol of 20 DEG C and adopts the ultrasonic oscillation of 30KHz to wash, be then placed in the drying in oven of 150 DEG C to constant weight.The present embodiment adopts the method preparation of embodiment 1.
Adopt the rapid prototyping material of prior art to be prepared into the plate part of a 1000mm × 1000mm × 20mm in the matrix material of the present embodiment, adopt ASTM standard to carry out performance test to it, its result is as shown in table 2.
Table 2.
| Project | Method | Unit | Result |
| Tensile strength | ASTM D638 | Mpa | 95 |
| Flexural strength | ASTM D790 | Mpa | 160 |
| Flexural strength (120 DEG C) | ASTM D790 | Mpa | 135 |
| Bending modulus | ASTM D790 | Mpa | 6550 |
| Bending modulus (120 DEG C) | ASTM D790 | Mpa | 6350 |
| Notched Izod impact hit intensity (1/8) (process of xenon lamp aging case is after 3000 hours) | ASTM D256 | KJ/M | 17.5 |
| Melting index | ASTM D1238 | g/10min | 13 |
| Flame resistivity | UL94 | 1.6mm | HB |
| Melt temperature | - | ℃ | 180-215 |
Embodiment 3
The present embodiment provides a kind of long glass fiber reinforced PP material of heat-resisting ageing-resisting, and its raw material comprises by weight:
Roving glass fiber 20 parts;
PP80 part
Thermo-stabilizer 0.01 part;
0.9 part, oxidation inhibitor;
Fire retardant 1 part;
Its raw material of described thermo-stabilizer comprises propylene glycol 0.3-0.7 part, sodium carbonate 1-7 part, 0.01-0.08 part Natvosol by weight; Described oxidation inhibitor comprises the antioxidant 1010 of 1-6 part, the aubepine of 0.5-1.5 part by weight.Further, described roving glass fiber is alkali-free continuous glass-fiber, and described alkali-free continuous glass-fiber diameter is 11-20 μm.The blending method preparation of the long glass fiber reinforced PP material selection prior art of the present embodiment.
Adopt the rapid prototyping material of prior art to be prepared into the plate part of a 1000mm × 1000mm × 20mm in the matrix material of the present embodiment, adopt ASTM standard to carry out performance test to it, its result is as shown in table 3.
Table 3.
| Project | Method | Unit | Result |
| Tensile strength | ASTM D638 | Mpa | 95 4 --> |
| Flexural strength | ASTM D790 | Mpa | 160 |
| Flexural strength (120 DEG C) | ASTM D790 | Mpa | 130 |
| Bending modulus | ASTM D790 | Mpa | 6630 |
| Bending modulus (120 DEG C) | ASTM D790 | Mpa | 6250 |
| Notched Izod impact hit intensity (1/8) (process of xenon lamp aging case is after 3000 hours) | ASTM D256 | KJ/M | 16.5 |
| Melting index | ASTM D1238 | g/10min | 13 |
| Flame resistivity | UL94 | 1.6mm | HB |
| Melt temperature | - | ℃ | 180-215 |
Embodiment 4
A long glass fiber reinforced PP material for heat-resisting ageing-resisting, its raw material comprises by weight:
Roving glass fiber 21 parts;
PP79 part
Thermo-stabilizer 0.03 part;
0.8 part, oxidation inhibitor;
Fire retardant 3 parts;
Its raw material of described thermo-stabilizer comprises propylene glycol 0.4 part, 4 parts, sodium carbonate, 0.02 part of Natvosol by weight; Described oxidation inhibitor comprises the antioxidant 1010 of 5 parts, the aubepine of 1 part by weight.
In the present embodiment, described roving glass fiber is commercially available prod.
Adopt the rapid prototyping material of prior art to be prepared into the plate part of a 1000mm × 1000mm × 20mm in the matrix material of the present embodiment, adopt ASTM standard to carry out performance test to it, its result is as shown in table 4.
Table 4.
| Project | Method | Unit | Result |
| Tensile strength | ASTM D638 | Mpa | 95 |
| Flexural strength | ASTM D790 | Mpa | 163 |
| Flexural strength (120 DEG C) | ASTM D790 | Mpa | 125 |
| Bending modulus | ASTM D790 | Mpa | 6600 |
| Bending modulus (120 DEG C) | ASTM D790 | Mpa | 6300 |
| Notched Izod impact hit intensity (1/8) (process of xenon lamp aging case is after 3000 hours) | ASTM D256 | KJ/M | 178 |
| Melting index | ASTM D1238 | g/10min | 13 |
| Flame resistivity | UL94 | 1.6mm | HB |
| Melt temperature | - | ℃ | 180-215 |
Comparative example 1
This comparative example provides a kind of long glass fiber reinforced PP material, and its raw material comprises by weight:
Roving glass fiber 25 parts;
PP75 part
Thermo-stabilizer 0.10 part;
0.7 part, oxidation inhibitor;
Fire retardant 2 parts;
Its raw material of described thermo-stabilizer comprises propylene glycol 0.4 part, 0.06 part of Natvosol by weight; Described oxidation inhibitor comprises antioxidant 1010,2 parts of irgasfos 168s of 3 parts by weight.
Adopt the rapid prototyping material of prior art to be prepared into the plate part of a 1000mm × 1000mm × 20mm in the matrix material of the present embodiment, adopt ASTM standard to carry out performance test to it, its result is as shown in table 5.
Table 5.
| Project | Method | Unit | Result |
| Tensile strength | ASTM D638 | Mpa | 90 |
| Flexural strength | ASTM D790 | Mpa | 130 |
| Flexural strength (120 DEG C) | ASTM D790 | Mpa | 115 |
| Bending modulus | ASTM D790 | Mpa | 6550 |
| Bending modulus (120 DEG C) | ASTM D790 | Mpa | 5900 |
| Notched Izod impact hit intensity (1/8) (process of xenon lamp aging case is after 3000 hours) | ASTM D256 | KJ/M | 15.5 |
| Melting index | ASTM D1238 | g/10min | 13 |
| Flame resistivity | UL94 | 1.6mm | HB |
| Melt temperature | - | ℃ | 180-215 |
Injection moulding is tested.
Adopt prior art to carry out injection moulding in PP matrix material, be shaped to the square of 30cm × 30cm × 30cm, observe its surface floating fiber situation.Cut out the epidermis of 30cm × 30cm × 2cm on 6 surfaces of square, and obtain the dice that cuts epidermis; The density rate of test epidermis and dice.Density rate ρ=(ρ epidermis-ρ dice) × 100%.Its result is as shown in table 6.
Table 6.
| Experimental group | ρ（%） |
| Embodiment 1 | 0.030±0.003 |
| Embodiment 4 | 0.042±0.004 |
| Comparative example 1 | 4.565±0.002 |
Be more than wherein specific implementation of the present invention, it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these apparent replacement forms all belong to protection scope of the present invention.
Claims (5)
1. a long glass fiber reinforced PP material for heat-resisting ageing-resisting, its raw material comprises by weight:
Roving glass fiber 20-35 part;
PP70-80 part
Thermo-stabilizer 0.01-0.25 part;
Oxidation inhibitor 0.2-0.9 part;
Fire retardant 1-3 part;
Its raw material of described thermo-stabilizer comprises propylene glycol 0.3-0.7 part, sodium carbonate 1-7 part, 0.01-0.08 part Natvosol by weight; Described oxidation inhibitor comprises the antioxidant 1010 of 1-6 part, the aubepine of 0.5-1.5 part by weight.
2. matrix material according to claim 1, is characterized in that: described roving glass fiber is alkali-free continuous glass-fiber, and described alkali-free continuous glass-fiber diameter is 11-20 μm.
3. matrix material according to claim 1, is characterized in that: described roving glass fiber its preparation method is:
(1) normal heptane immersion treatment: roving glass fiber is immersed in normal heptane and carry out swelling treatment, the treatment time is 22h ~ 30h;
(2) washing with alcohol: the roving glass fiber after swelling is heated to 120-150 DEG C, drops in the dehydrated alcohol of 20-25 DEG C and adopts the ultrasonic oscillation of 25-30KHz to wash, be then placed in the drying in oven of 150-200 DEG C to constant weight.
4. the preparation method of the long glass fiber reinforced PP material of the heat-resisting ageing-resisting as described in claim 1-3, it comprises following operation:
A. thermo-stabilizer is prepared: adopt airbath to be heated to 50 DEG C in Natvosol, sodium carbonate, instillation propylene glycol, after insulation 30min, add magnesium chlorate;
B. by setting weight part PP, thermo-stabilizer, oxidation inhibitor, fire retardant added after super mixer mixes and be heated to through twin screw extruder the PP mixture that 160 ~ 199 DEG C obtain plasticizing, then the PP mixture plastified is by twin screw extruder press-in dipping die head, the roving glass fiber of impregnating dispersion setting weight part, being prepared into length through traction, cooling forming, cutting process is that 10-15mm low is distributed, high-performance long glass fiber reinforced PP matrix material.
5. the application in automobile component, instrument parts, electromechanical component, electric element prepared by the long glass fiber reinforced PP material of the heat-resisting ageing-resisting as described in claim 1-3.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314838A (en) * | 2018-01-26 | 2018-07-24 | 唐山开滦化工科技有限公司 | A kind of high-strength high-glowing-filament-temperature flame-retardancy polypropylene and preparation method thereof |
| CN112321940A (en) * | 2020-09-23 | 2021-02-05 | 句容市百事特复合材料有限公司 | Heat-resistant and aging-resistant long glass fiber reinforced PP material and preparation method thereof |
| CN114874549A (en) * | 2022-06-14 | 2022-08-09 | 秦建涛 | Universal meter pincer-type meter shell material and preparation method thereof |
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2015
- 2015-12-31 CN CN201511015888.7A patent/CN105504497A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314838A (en) * | 2018-01-26 | 2018-07-24 | 唐山开滦化工科技有限公司 | A kind of high-strength high-glowing-filament-temperature flame-retardancy polypropylene and preparation method thereof |
| CN112321940A (en) * | 2020-09-23 | 2021-02-05 | 句容市百事特复合材料有限公司 | Heat-resistant and aging-resistant long glass fiber reinforced PP material and preparation method thereof |
| CN114874549A (en) * | 2022-06-14 | 2022-08-09 | 秦建涛 | Universal meter pincer-type meter shell material and preparation method thereof |
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