CN104804415A - Hydrolysis-resisting glass fiber reinforced polyamide composite and preparation method thereof - Google Patents
Hydrolysis-resisting glass fiber reinforced polyamide composite and preparation method thereof Download PDFInfo
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- CN104804415A CN104804415A CN201510118032.6A CN201510118032A CN104804415A CN 104804415 A CN104804415 A CN 104804415A CN 201510118032 A CN201510118032 A CN 201510118032A CN 104804415 A CN104804415 A CN 104804415A
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- hydrolysis
- reinforced polyamide
- polyamide composite
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/004—Additives being defined by their length
Abstract
The invention discloses a hydrolysis-resisting glass fiber reinforced polyamide composite. The hydrolysis-resisting glass fiber reinforced polyamide composite is characterized in that polyamide, hydrolysis-resisting glass fiber, a maleic acid grafted EPDM (ethylene propylene diene monomer), an antioxidant, a lubricant, a coupling agent and an organosilicon photo-diffusant are cooperatively used, the components in specific weight content are selected under the action of a hydrolysis-resisting agent, the water absorption of the hydrolysis-resisting glass fiber reinforced polyamide composite in a humid environment is reduced greatly, hydrophilic groups of the composite are protected simultaneously, and the hydrolysis resistance of the composite is improved substantially. Meanwhile, a preparation method of the hydrolysis-resisting glass fiber reinforced polyamide composite is simple to operate, low in cost and high in production benefit, the mechanical properties in all aspects are high and stable, the method is quite applicable to industrial production, and the prepared hydrolysis-resisting glass fiber reinforced polyamide composite has excellent hydrolysis resistance as well as good mechanical property retainability after water absorption.
Description
Technical field
The present invention relates to a kind of hydrolysis fiber glass reinforced polyamide composite material and preparation method thereof, belong to High Polymer Material & Porcessing technical field of modification.
Background technology
Polyamide resin (PA) has the characteristics such as excellent wear-resisting, matter is hard, cold-resistant, nontoxic, corrosion-resistant, easy-formation, easy dyeing, and its glass fibre reinforcement is widely used in the fields such as automobile component, electronic apparatus, power tool, perambulator, toy for children.In recent years, fiber glass reinforced polyamide material is applied to the water treatment field such as automobile water chamber, bathroom spool more and more widely; Polymeric amide is due to containing amido and carbonyl, and easily forms hydrogen bond with water molecules, therefore obtained various materials easily absorb water in use, produces plasticization effect, causes material volume expansion, modulus decline, under stress, obvious creep occurs.Polycaprolactam and PA 66 (nylon 6 and nylon66 fiber) are the most frequently used polyamide materials, but their most high energy absorbs the moisture of massfraction 10% from damp atmosphere, under general humidity environment, also can absorb the moisture of massfraction 2% to 4%, hydrolysis reaction occurs and then causes the change of multiple mechanical property.
The existing method preventing polyamide material to be hydrolyzed has following a few class:
(1), reduce water regain thus reduce moisture to the impact of its performance;
(2), by improving the correlated performance of PA material, expect to offset the impact on its performance after absorbing water;
(3), mixed and modified, why water can destroy the established hydrogen bond of industry in polymeric amide (nylon 6/66) and form new hydrogen bond with carbonyl or amido, is exactly because water molecules and carbonyl or amido form the trend of hydrogen bond than height between them.The trend forming hydrogen bond due to phenolic group and carbonyl is higher than water molecules, after adding aldehydes matter, phenolic group occupies carbonyl in nylon 6/66 and amido, and create steric effect because of the phenyl ring contained by it, entering of water molecules can be stoped to a certain extent, but these methods do not change the hydrolytic resistance of nylon in itself.
Summary of the invention
For solving the deficiencies in the prior art, the object of the present invention is to provide polyamide compoiste material of a kind of fiberglass reinforced and preparation method thereof, the mechanical property fall that causes degradation problem up to 50% and under work-ing life after avoiding polymeric amide to be hydrolyzed.
In order to realize above-mentioned target, the present invention adopts following technical scheme:
Hydrolysis fiber glass reinforced polyamide composite material, is characterized in that, comprises each component of following weight part:
Aforesaid hydrolysis fiber glass reinforced polyamide composite material, is characterized in that, described polymeric amide PA is PA6, and relative viscosity is 2.4 ~ 2.8.
Preferably, in aforementioned maleic anhydride graft EPDM, the percentage of grafting of maleic anhydride is 0.8 ~ 1.
Further preferably, the length of aforementioned resistant to hydrolysis glass fibre is 3 ~ 4.5mm, and diameter is 8 ~ 15 μm.
More preferably, aforementioned oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, wherein, primary antioxidant is Hinered phenols antioxidant, auxiliary anti-oxidant is organic phosphorous antioxidant and phosphorous acid esters synergistic oxidation inhibitor, and wherein, the weight part of organic phosphorous antioxidant is 0.2 ~ 2 part, the weight part of Hinered phenols antioxidant is 0.2 ~ 1 part, and the weight part of phosphorous acid esters synergistic oxidation inhibitor is 0.2 ~ 1 part.
Preferably, aforementioned lubricants is silicone based lubricant.
Preferably, aforementioned coupling agents is 3-glycydoxy Trimethoxy silane.
Preferably, aforementioned hydrolysis-resisting agent is Carbodiimides hydrolysis-resisting agent.
In addition, the invention also discloses the preparation method of aforesaid hydrolysis fiber glass reinforced polyamide composite material, it is characterized in that, comprise the steps:
S1, preparation raw material: prepare each raw material according to aforesaid component and weight part;
S2, mixing are extruded: by polymeric amide PA, maleic anhydride graft EPDM, oxidation inhibitor, lubricant, coupling agent, organosilicon light diffusing agent and hydrolysis-resisting agent mixing and stirring, then join in twin screw extruder; In the extrusion of above-mentioned compound, resistant to hydrolysis glass fibre to be joined in twin screw extruder high temperature together by side direction feeding and extrude, cool, draw and pelletizing, extrusion temperature is 235 ~ 275 DEG C, obtains hydrolysis fiber glass reinforced polyamide composite material.
Usefulness of the present invention is: hydrolysis fiber glass reinforced polyamide composite material of the present invention, by with the use of polymeric amide, resistant to hydrolysis glass fibre, toxilic acid grafting EPDM, oxidation inhibitor, lubricant, coupling agent and organosilicon light diffusing agent, simultaneously under the effect of hydrolysis-resisting agent, select the said components of specific weight content, greatly reduce hydrolysis fiberglass reinforced composite polyamide material water-intake rate in wet condition, also protect the hydrophilic radical of material simultaneously, its anti-hydrolytic performance is significantly improved; By this materials application when power tool, garden instrument etc. are chronically exposed to open air and be used in the product of wet environment, effectively can solve the problems such as its product performance decline and product hydrolysis is aging.Simultaneously, the preparation method of hydrolysis fiber glass reinforced polyamide composite material of the present invention, simple to operate, with low cost, productivity effect is high, and each side mechanical property is high and stable, is very applicable to suitability for industrialized production, prepared hydrolysis fiber glass reinforced polyamide material has excellent resistance to hydrolysis, and after water suction, mechanical property retentivity is good.
Embodiment
Below in conjunction with specific embodiment, concrete introduction is done to the present invention.
Without specified otherwise in the present invention, raw materials used be commercial.
Embodiment 1
The hydrolysis fiber glass reinforced polyamide composite material of the present embodiment, is made up of the component of following weight part: 67 parts of polymeric amide PA6,2 parts of maleic anhydride graft EPDM, and 20 parts of hydrolysis glass fibre are (long: 3 ~ 4.5mm; Diameter: 8 ~ 15 μm), 0.3 part of Hinered phenols antioxidant, 0.2 part of phosphorous acid esters synergistic oxidation inhibitor, 0.2 part of organic phosphorous antioxidant, 1 part of organo-silicic oil, 0.1 part of 3-glycydoxy Trimethoxy silane, 0.001 part of organosilicon light diffusing agent, 1 part of hydrolysis-resisting agent.
The preparation method of the hydrolysis fiber glass reinforced polyamide composite material of the present embodiment, comprises the following steps:
S1:PA6, toxilic acid grafting EPDM, oxidation inhibitor, lubricant, coupling agent, organosilicon light diffusing agent and hydrolysis-resisting agent mixing and stirring;
S2: the mixture obtained by step S1 joins in twin screw extruder, twin screw extruder temperature establishes 9 sections altogether, and first paragraph and second segment extrusion temperature are at 250 DEG C, and other several sections of temperature are at 235 DEG C; Engine speed controls at 400 turns/Min, adds resistant to hydrolysis glass fibre, finally extrudes, cools, draws, pelletizing in extrusion from side direction feeding, namely obtains hydrolysis fiber glass reinforced polyamide material.
Material was gas blower drying oven 115 DEG C of dryings 2 ~ 4 hours, and then test bars and goods are prepared in injection moulding.
Embodiment 2
The present embodiment is roughly the same with embodiment 1, and difference is mainly the weight part of each component, specific as follows: 58.5 parts of polymeric amide PA6,5 parts of maleic anhydride graft EPDM, and 30 parts of resistant to hydrolysis glass fibre are (long: 3 ~ 4.5mm; Diameter: 8 ~ 15 μm), 0.5 part of Hinered phenols antioxidant, 0.2 part of phosphorous acid esters synergistic oxidation inhibitor, 0.5 part of organic phosphorous antioxidant, 2 parts of organo-silicic oils, 0.5 part of 3-glycydoxy Trimethoxy silane, 0.1 part of organosilicon light diffusing agent, 3 parts of hydrolysis-resisting agents.
The preparation method of the hydrolysis fiber glass reinforced polyamide material of the present embodiment, comprises the following steps:
S1:PA6, toxilic acid grafting EPDM, oxidation inhibitor, lubricant, coupling agent, organosilicon light diffusing agent JI hydrolysis-resisting agent mixing and stirring;
S2: the mixture obtained by step S1 joins in twin screw extruder, twin screw extruder temperature establishes 9 sections altogether, and first paragraph and second segment extrusion temperature are at 260 DEG C, and other several sections of temperature are at 240 DEG C; Engine speed controls at 380 turns/Min, adds resistant to hydrolysis glass fibre, finally extrudes, cools, draws, pelletizing in extrusion from side direction feeding, namely obtains hydrolysis fiber glass reinforced polyamide material.
Material was gas blower drying oven 115 DEG C of dryings 2 ~ 4 hours, and then test bars and goods are prepared in injection moulding.
Embodiment 3
The present embodiment is roughly the same with embodiment 1, and difference is mainly the weight part of each component, specific as follows: 55.4 parts of polymeric amide PA6,1 part of maleic anhydride graft EPDM, and 40 parts of resistant to hydrolysis glass fibre are (long: 3 ~ 4.5mm; Diameter: 8 ~ 15 μm), 1 part of Hinered phenols antioxidant, 1 part of phosphorous acid esters synergistic oxidation inhibitor, 2 parts of organic phosphorous antioxidants, 3 parts of organo-silicic oils, 0.5 part of 3-glycydoxy Trimethoxy silane, 1 part of organosilicon light diffusing agent, 5 parts of hydrolysis-resisting agents.
The preparation method of the hydrolysis fiber glass reinforced polyamide material of the present embodiment, comprises the following steps:
S1: polyamide 6, toxilic acid grafting EPDM, oxidation inhibitor, lubricant, coupling agent, organosilicon light diffusing agent and hydrolysis-resisting agent mixing and stirring;
S2: the mixture obtained by step S1 joins in twin screw extruder, twin screw extruder temperature establishes 9 sections altogether, first paragraph and second segment extrusion temperature at 260 DEG C, head temperature 235 DEG C; Other several sections of temperature are at 240 DEG C; Engine speed controls at 350 turns/Min, adds resistant to hydrolysis glass fibre, finally extrudes, cools, draws, pelletizing in extrusion from side direction feeding, namely obtains hydrolysis fiber glass reinforced polyamide material.
Performance test
The performance of test and Evaluation operation example resulting materials by the following method.
(1), tensile strength presses ASTM D-638 standard method test.
(2), flexural strength presses ASTM D-790 standard method test.
(3), modulus in flexure presses ASTM D-790 standard method test.
(4), Izod notched Izod impact strength presses ASTM D-256 standard method test.
Table 1 obtains the performance test results of material (original state) for embodiment 1-3, compared for the performance test results of material after poach 100H of each embodiment simultaneously.
Table 1 embodiment 1-3 obtains the contrast of the performance test results after material original state and poach 100H
As can be seen from Table 1, the hydrolysis fiber glass reinforced polyamide material of example 1-3 has excellent anti-hydrolytic performance, confirms that its mechanical property retentivity is good after poach 100H; Improve well polyamide material of the prior art after hydrolyzing mechanical property fall up to the critical defect of 50%, substantially increase the work-ing life of material.
More than show and describe ultimate principle of the present invention, principal character and advantage.The technician of the industry should understand, and above-described embodiment does not limit the present invention in any form, the technical scheme that the mode that all employings are equal to replacement or equivalent transformation obtains, and all drops in protection scope of the present invention.
Claims (9)
1. hydrolysis fiber glass reinforced polyamide composite material, is characterized in that, comprises each component of following weight part:
。
2. hydrolysis fiber glass reinforced polyamide composite material according to claim 1, is characterized in that, described polymeric amide PA is PA6, and relative viscosity is 2.4 ~ 2.8.
3. hydrolysis fiber glass reinforced polyamide composite material according to claim 1, is characterized in that, in described maleic anhydride graft EPDM, the percentage of grafting of maleic anhydride is 0.8 ~ 1.
4. hydrolysis fiber glass reinforced polyamide composite material according to claim 1, is characterized in that, the length of described resistant to hydrolysis glass fibre is 3 ~ 4.5mm, and diameter is 8 ~ 15 μm.
5. hydrolysis fiber glass reinforced polyamide composite material according to claim 1, it is characterized in that, described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, wherein, primary antioxidant is Hinered phenols antioxidant, and auxiliary anti-oxidant is organic phosphorous antioxidant and phosphorous acid esters synergistic oxidation inhibitor, wherein, the weight part of organic phosphorous antioxidant is 0.2 ~ 2 part, and the weight part of Hinered phenols antioxidant is 0.2 ~ 1 part, and the weight part of phosphorous acid esters synergistic oxidation inhibitor is 0.2 ~ 1 part.
6. hydrolysis fiber glass reinforced polyamide composite material according to claim 1, is characterized in that, described lubricant is silicone based lubricant.
7. hydrolysis fiber glass reinforced polyamide composite material according to claim 1, is characterized in that, described coupling agent is 3-glycydoxy Trimethoxy silane.
8. hydrolysis fiber glass reinforced polyamide composite material according to claim 1, is characterized in that, described hydrolysis-resisting agent is Carbodiimides hydrolysis-resisting agent.
9. the preparation method of hydrolysis fiber glass reinforced polyamide composite material as claimed in claim 1, is characterized in that, comprise the steps:
S1, preparation raw material: prepare each raw material according to component according to claim 1 and weight part;
S2, mixing are extruded: by polymeric amide PA, maleic anhydride graft EPDM, oxidation inhibitor, lubricant, coupling agent, organosilicon light diffusing agent and hydrolysis-resisting agent mixing and stirring, then join in twin screw extruder; In the extrusion of above-mentioned compound, resistant to hydrolysis glass fibre to be joined in twin screw extruder high temperature together by side direction feeding and extrude, cool, draw and pelletizing, extrusion temperature is 235 ~ 275 DEG C, obtains hydrolysis fiber glass reinforced polyamide composite material.
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Cited By (4)
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| CN109504080A (en) * | 2018-12-13 | 2019-03-22 | 沈阳科通塑胶有限公司 | A kind of enhancing nylon of hydrolysis and preparation method thereof |
| CN110041695A (en) * | 2018-01-15 | 2019-07-23 | 朗盛德国有限责任公司 | HR glass fibre in vibration component |
| CN110776734A (en) * | 2019-09-26 | 2020-02-11 | 中广核俊尔(浙江)新材料有限公司 | Wear-resistant hydrolysis-resistant alcohol depolymerized amide composite material and preparation method and application thereof |
| CN110903641A (en) * | 2018-09-17 | 2020-03-24 | 汉达精密电子(昆山)有限公司 | Hydrolysis-resistant glass fiber reinforced polyamide composite material and product thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110041695A (en) * | 2018-01-15 | 2019-07-23 | 朗盛德国有限责任公司 | HR glass fibre in vibration component |
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| CN110041695B (en) * | 2018-01-15 | 2021-09-10 | 朗盛德国有限责任公司 | HR glass fiber in vibrating component |
| CN110903641A (en) * | 2018-09-17 | 2020-03-24 | 汉达精密电子(昆山)有限公司 | Hydrolysis-resistant glass fiber reinforced polyamide composite material and product thereof |
| CN109504080A (en) * | 2018-12-13 | 2019-03-22 | 沈阳科通塑胶有限公司 | A kind of enhancing nylon of hydrolysis and preparation method thereof |
| CN110776734A (en) * | 2019-09-26 | 2020-02-11 | 中广核俊尔(浙江)新材料有限公司 | Wear-resistant hydrolysis-resistant alcohol depolymerized amide composite material and preparation method and application thereof |
| CN110776734B (en) * | 2019-09-26 | 2022-04-01 | 中广核俊尔(浙江)新材料有限公司 | Wear-resistant hydrolysis-resistant alcohol depolymerized amide composite material and preparation method and application thereof |
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Application publication date: 20150729 |