CN102850796A - Polyetherimide composite material and its preparation method and use - Google Patents

Polyetherimide composite material and its preparation method and use Download PDF

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CN102850796A
CN102850796A CN2012102921295A CN201210292129A CN102850796A CN 102850796 A CN102850796 A CN 102850796A CN 2012102921295 A CN2012102921295 A CN 2012102921295A CN 201210292129 A CN201210292129 A CN 201210292129A CN 102850796 A CN102850796 A CN 102850796A
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polyetherimide
composite material
polyphenylene oxide
mixture
polyetherimide composite
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CN102850796B (en
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徐东
徐永
周兵
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Polymer Science Shenzhen New Materials Co Ltd
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Polymer Science Shenzhen New Materials Co Ltd
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Abstract

The invention provides a polyetherimide composite material and its preparation method and use and belongs to the field of engineering plastic. The polyetherimide composite material comprises polyphenyl ether, polyetherimide, a compatilizer and a flexibilizer. The polyetherimide composite material has the advantages that through polyphenyl ether partly replacing polyetherimide, a polyetherimide use amount is reduced so that a polyetherimide production cost is greatly reduced; and through polyphenyl ether-grafted maleic anhydride as the compatilizer, interfacial compatibility between polyphenyl ether and polyetherimide is improved so that good compatibility between polyphenyl ether and polyetherimide is obtained. The preparation method of the polyetherimide composite material has the advantages that through polyphenyl ether partly replacing polyetherimide, a production cost is greatly reduced and production benefits are improved; and the preparation method is suitable for industrial production.

Description

Polyetherimide composite material, its preparation method and application
Technical field
The invention belongs to the engineering plastics field, relate in particular to a kind of polyetherimide composite material, its preparation method and application.
Background technology
Polyphenylene oxide (PPO) belongs to the amorphism engineering plastics, has advantages of that high heat-resisting, good stability of the dimension, relative density are little, electric insulating quality and creep resistance excellence, but its processing fluidity is poor, not organic solvent-resistant, easily stress cracking.
Polyetherimide (PEI) belongs to amorphous special engineering plastics, has splendid high thermal resistance, dimensional stability, high strength, intrinsic flame retardant resistance, organic solvent-resistant, can long term operation under 170 degree, but it is expensive, has limited its application.
Because the high temperature tolerance of PEI, need often to be used to long-term resistant to elevated temperatures field, the case ring of automobile front for example, high temperature resistant electronic devices and components, high temperature resistant and pharmaceutical chemicals sterilization medical facilities, since expensive, only have the product of high-end market just to use the PEI material, the expensive Application Areas that has limited it of PEI.
Summary of the invention
In view of this, the invention provides a kind of polyetherimide composite material, solve in the prior art problems such as polyetherimide is expensive.
The present invention is achieved in that
A kind of polyetherimide composite material comprises the component of following weight percentage:
Figure BDA00002021046300021
This compatilizer is selected from the polyphenylene oxide grafted maleic anhydride.
And,
Above-mentioned polyetherimide composite material preparation method comprises the steps:
Take by weighing this polyphenylene oxide, polyetherimide, compatilizer, toughner by prescription, this polyphenylene oxide, polyetherimide, compatilizer, toughner are mixed, obtain the first mixture;
Take by weighing this oxidation inhibitor and lubricant by prescription, with this oxidation inhibitor and lubricant and the mixing of this first mixture, obtain the second mixture;
The second mixture is happy and harmonious extrudes with this, obtains polyetherimide composite material.
The present invention further provides the application of above-mentioned polyetherimide composite material in automobile, electron device, medical facilities.
Polyetherimide composite material of the present invention replaces the part polyetherimide by using polyphenylene oxide, has reduced the consumption of polyetherimide, and the production cost of polyetherimide is reduced greatly; By using the polyphenylene oxide grafted maleic anhydride as compatilizer, improve the interface compatibility between polyphenylene oxide and the polyetherimide, so that well compatible between polyphenylene oxide and the polyetherimide, simultaneously by using toughner, so that the mechanical property of polyetherimide composite material is enhanced.
Embodiment of the invention polyetherimide composite material preparation method replaces the part polyetherimide by using polyphenylene oxide, and production cost is reduced greatly, and this preparation method is simple to operate, and productivity effect is high, is very suitable for suitability for industrialized production.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the invention provides a kind of polyetherimide composite material, comprises the component of following weight percentage:
Figure BDA00002021046300031
This compatilizer is selected from the polyphenylene oxide grafted maleic anhydride.
Embodiment of the invention polyetherimide composite material, by using the component of above-mentioned weight percentage, so that preparation-obtained polyetherimide has excellent high heat resistance, flame retardancy, good dimension stability and organic solvent resistance, its performance is suitable with pure polyetherimide, needing can be used for long-term resistant to elevated temperatures product.Owing to having used relatively large polyphenylene oxide, the consumption of polyetherimide is reduced greatly, thereby realized the remarkable decline of cost, enlarged the Application Areas of polyetherimide composite plastic.Owing to having compatibility problem between polyphenylene oxide and the polyetherimide, embodiment of the invention polyetherimide is by using the polyphenylene oxide grafted maleic anhydride as both compatilizers, effectively solve the interface compatibility between polyphenylene oxide and the polyetherimide, make and realize between the two holding mutually; Simultaneously, carry out modification by the polyetherimide polyphenylene ether, the flowability of polyphenylene oxide is increased greatly, so that embodiment of the invention polyetherimide composite material has excellent flowability, the easy various products of moulding; By using toughner, so that the mechanical property of polyetherimide composite material is enhanced.
This polyphenylene oxide (PPO) preferred characteristics viscosity is the PPO of 0.35-0.5dl/g, and in polyetherimide composite material, the weight percentage of this PPO is 25~55%, is preferably 30~40%.This PPO can also select other PPO commonly used in this area, for example, and such as blue star Chemical Manufacture, trade names LXR045.
This polyetherimide is amber transparent solid, produces trade names ULTEM1000 such as SABIC company.The weight percentage of this polyetherimide in embodiment of the invention polyetherimide composite material is 30~65%, is preferably 40~50%.
This compatilizer is polyphenylene oxide grafted maleic anhydride (PPO-g-MAH), percentage of grafting is 1.0-1.7%, this compatilizer weight percentage in polyetherimide composite material is 5~10%, be preferably 6~9%, it is 1.3 PPO-g-MAH that this polyphenylene oxide grafted maleic anhydride can be selected percentage of grafting, produce such as SABIC company, trade names are 450C.
This toughner is preferably the SEBS-g-MAH(SEBS grafted maleic anhydride that percentage of grafting is 0.8-1.5%), to produce such as the company of rising of section, trade names are FX1901G; The weight percentage of this toughner in polyetherimide composite material is 3~6%.By selecting this SEBS grafted maleic anhydride as toughner, when matrix material is carried out toughening modifying, can not affect the overall compatibility of matrix material.This toughner can also be selected other toughner commonly used in this area.
This oxidation inhibitor is restriction not, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester for example, and three (2,4-di-t-butyl) phenyl-phosphite selects Ciba company to produce, and trade names are respectively Irganox1010, and Irganox168; This lubricant is restriction not, for example selects polysiloxane-basedly, produces trade names L5-4 such as Wa Ke company.
The embodiment of the invention further provides above-mentioned polyetherimide composite material preparation method, comprises the steps:
Step S01 prepares the first mixture:
Take by weighing this polyphenylene oxide, polyetherimide, compatilizer, toughner by prescription, this polyphenylene oxide, polyetherimide, compatilizer, toughner are mixed, obtain the first mixture;
Step S02 prepares the second mixture:
Take by weighing this oxidation inhibitor and lubricant by prescription, with this oxidation inhibitor and lubricant and the mixing of this first mixture, obtain the second mixture;
Step S03 melt extrudes:
The second mixture is happy and harmonious extrudes with this, obtains polyetherimide composite material.
Among the step S01, this polyphenylene oxide, polyetherimide, compatilizer, toughner do not repeat to set forth at this with aforesaid identical.After taking by weighing each component by prescription among the step S01, each component is imported whipping device, mix, obtain the first mixture;
Among the step S02, this oxidation inhibitor and lubricant do not repeat to set forth at this with aforementioned identical.Among the step S02, take by weighing oxidation inhibitor and lubricant after, the first mixture that this oxidation inhibitor, lubricant and step S01 are obtained is put into together and is mixed in the mixing tank until evenly, obtain the second mixture.
Among the step S03, this second mixture is added in the loading hopper of single screw extrusion machine or twin screw extruder, this second mixture is melt extruded, granulation obtains polyetherimide composite material, and the processing condition that melt extrude are:
One district temperature 310-320 ℃, two district temperature 320-330 ℃, three district temperature 320-330 ℃, four district temperature 310-320 ℃, head 320-330 ℃, the residence time 2~3min, pressure are 12-18MPa.
Embodiment of the invention polyetherimide composite material preparation method replaces the part polyetherimide by using polyphenylene oxide, and production cost is reduced greatly, and this preparation method is simple to operate, and productivity effect is high, is very suitable for suitability for industrialized production.
The embodiment of the invention further provides the application of above-mentioned polyetherimide composite material in automobile, electron device, medical facilities.
Below in conjunction with specific embodiment above-mentioned polyetherimide composite material and preparation method thereof is described in detail.
Embodiment 1
Embodiment of the invention polyetherimide composite material comprises the component of following weight percentage:
Figure BDA00002021046300061
This compatilizer is selected from the polyphenylene oxide grafted maleic anhydride.
Embodiment of the invention polyetherimide composite material preparation method comprises the steps:
With polyphenylene oxide by weight for being weight percentage below the 25%(), polyetherimide 63%, PPO-g-MAH 7%, SEBS-g-MAH 4%, weighs up to pour agitator into, stirs, and obtains the first mixture;
Press 1010/1680.2/0.2%, lubricant 0.6% weighs up again, and pours the agitator that contains the first mixture into and stirs, and obtains the second mixture;
The second mixture is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 310 ℃ of district's temperature, and 330 ℃ of two district's temperature, 330 ℃ of three district's temperature, 320 ℃ of four district's temperature, 330 ℃ of heads, the residence time 2~3min, pressure are 16MPa.
Embodiment 2
Embodiment of the invention polyetherimide composite material comprises the component of following weight percentage:
Figure BDA00002021046300071
This compatilizer is selected from the polyphenylene oxide grafted maleic anhydride.
Embodiment of the invention polyetherimide composite material preparation method comprises the steps:
With polyphenylene oxide by weight for being weight percentage below the 44%(), polyetherimide 44%, PPO-g-MAH 7%, SEBS-g-MAH 4%, weighs up to pour agitator into, stirs, and obtains the first mixture;
Press 1010/1680.2/0.2%, lubricant 0.6% weighs up again, and pours the agitator that contains the first mixture into and stirs, and obtains the second mixture;
The second mixture is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 310 ℃ of district's temperature, and 330 ℃ of two district's temperature, 330 ℃ of three district's temperature, 320 ℃ of four district's temperature, 330 ℃ of heads, the residence time 2~3min, pressure are 16MPa.
Embodiment 3
Embodiment of the invention polyetherimide composite material comprises the component of following weight percentage:
Figure BDA00002021046300081
This compatilizer is selected from the polyphenylene oxide grafted maleic anhydride.
Embodiment of the invention polyetherimide composite material preparation method comprises the steps:
With polyphenylene oxide by weight for being weight percentage below the 55%(), polyetherimide 33%, PPO-g-MAH 7%, SEBS-g-MAH 4%, weighs up to pour agitator into, stirs, and obtains the first mixture;
Press 1010/1680.2/0.2%, lubricant 0.6% weighs up again, and pours the agitator that contains the first mixture into and stirs, and obtains the second mixture;
The second mixture is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 310 ℃ of district's temperature, and 330 ℃ of two district's temperature, 330 ℃ of three district's temperature, 320 ℃ of four district's temperature, 330 ℃ of heads, the residence time 2~3min, pressure are 16MPa.
Embodiment 4
Embodiment of the invention polyetherimide composite material comprises the component of following weight percentage:
Figure BDA00002021046300091
This compatilizer is selected from the polyphenylene oxide grafted maleic anhydride.
Embodiment of the invention polyetherimide composite material preparation method comprises the steps:
With polyphenylene oxide by weight for being weight percentage below the 55%(), polyetherimide 33%, PPO-g-MAH 8%, SEBS-g-MAH 3%, weighs up to pour agitator into, stirs, and obtains the first mixture;
Press 1010/1680.2/0.2%, lubricant 0.6% weighs up again, and pours the agitator that contains the first mixture into and stirs, and obtains the second mixture;
The second mixture is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 310 ℃ of district's temperature, and 330 ℃ of two district's temperature, 330 ℃ of three district's temperature, 320 ℃ of four district's temperature, 330 ℃ of heads, the residence time 2~3min, pressure are 16MPa.
Embodiment 5
Embodiment of the invention polyetherimide composite material comprises the component of following weight percentage:
Figure BDA00002021046300101
This compatilizer is selected from the polyphenylene oxide grafted maleic anhydride.
Embodiment of the invention polyetherimide composite material preparation method comprises the steps:
With polyphenylene oxide by weight for being weight percentage below the 55%(), polyetherimide 33%, PPO-g-MAH 5%, SEBS-g-MAH 6%, weighs up to pour agitator into, stirs, and obtains the first mixture;
Press 1010/1680.2/0.2%, lubricant 0.6% weighs up again, and pours the agitator that contains the first mixture into and stirs, and obtains the second mixture;
The second mixture is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 310 ℃ of district's temperature, and 330 ℃ of two district's temperature, 330 ℃ of three district's temperature, 320 ℃ of four district's temperature, 330 ℃ of heads, the residence time 2~3min, pressure are 16MPa.
Comparative Examples 1
This Comparative Examples composite material and preparation method thereof comprises the steps:
With polyphenylene oxide by weight for being weight ratio below the 88%(), PPO-g-MAH 7%, SEBS-g-MAH 4%, weighs up to pour agitator into, stirs, and presses 1010/1680.2/0.2% again, lubricant 0.6% weighs up, and pours agitator into and stirs.The material that mixes is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 310 ℃ of district's temperature, and 330 ℃ of two district's temperature, 330 ℃ of three district's temperature, 320 ℃ of four district's temperature, 330 ℃ of heads, the residence time 2~3min, pressure are 16MPa.
Comparative Examples 2
This Comparative Examples composite material and preparation method thereof comprises the steps:
With polyetherimide by weight for being weight ratio below the 88%(), PPO-g-MAH7%, SEBS-g-MAH4% weighs up and pours agitator into, stirs, and presses 1010/1680.2/0.2% again, lubricant 0.6% weighs up, and pours agitator into and stirs.The material that mixes is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 310 ℃ of district's temperature, and 330 ℃ of two district's temperature, 330 ℃ of three district's temperature, 320 ℃ of four district's temperature, 330 ℃ of heads, the residence time 2~3min, pressure are 16MPaa.
The material of Comparative Examples 3 is 100% polyphenylene oxide; The material of Comparative Examples 4 is 100% polyetherimide.
Performance test:
Tensile strength is tested by the GB/T1040 standard, and specimen types is II type sample, and batten size (mm): 115(is long) * (6 ± 0.04) (middle parallel portion width) * 2(thickness), draw speed is 200mm/min;
Flexural strength and modulus in flexure are tested by the GB9341/T standard.Specimen types is specimen size (mm): (80 ± 0.4) * (10 ± 0.1) * (4 ± 0.02), rate of bending are 20mm/min;
Thermal distortion test is tested according to ASTM D648 standard, and specimen types is specimen size (mm): (128 ± 0.2) * (13 ± 0.04) * (6.4 ± 0.02). and test pressure is 1.82MPa, and unit is ℃.
The component of embodiment 1~3, Comparative Examples 1~4 and the performance test results such as table 1.
Figure BDA00002021046300121
Table 1
Can be found out by Comparative Examples 1,3, the mobile extreme difference of pure polyphenylene oxide resin, difficult forming is although heat-drawn wire is higher, because poor fluidity is difficult to practical application; Can be found out by Comparative Examples 2,4, polyetherimide resin is better mobile, and mechanical property is high, and heat-drawn wire is high, is a kind of splendid special engineering plastics; The comparative example 1,2,3 and Comparative Examples 1,2,3,4 can find out, after polyphenylene oxide and polyetherimide are made alloy, the flowability of polyphenylene oxide has improved greatly, can be easy to be molded into various products, along with the raising of polyphenylene oxide content, the mechanical property of alloy decreases, but still can satisfy the use of most occasions, heat-drawn wire changes little, and the resistance toheat of material also has lifting a little, aspect shock strength, owing to having added toughner, the whole shock strength of material obtains certain lifting, is higher than polyphenylene oxide resin and polyetherimide resin.
In sum, polyphenylene oxide polyetherimide alloy, excellent combination property be fit to be made high strength, and high heat-resisting, dimensional stability requires preferably product, and the product long-term heat resistance after the moulding is good, dimensional stabilizing, organic solvent-resistant corrosion.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. polyetherimide composite material comprises the component of following weight percentage:
Figure FDA00002021046200011
Described compatilizer is selected from the polyphenylene oxide grafted maleic anhydride.
2. polyetherimide composite material as claimed in claim 1 is characterized in that, the limiting viscosity of described polyphenylene oxide is 0.35-0.5dl/g.
3. polyetherimide composite material as claimed in claim 1 is characterized in that, the weight percentage of described polyphenylene oxide is 30~40%.
4. polyetherimide composite material as claimed in claim 1 is characterized in that, the weight percentage of described polyetherimide is 40~50%.
5. polyetherimide composite material as claimed in claim 1 is characterized in that, the percentage of grafting of described polyphenylene oxide grafted maleic anhydride is 1.0~1.7%.
6. polyetherimide composite material as claimed in claim 1 is characterized in that, the weight percentage of described compatilizer is 6~9%.
7. polyetherimide composite material as claimed in claim 1 is characterized in that, described toughner is selected from the SEBS grafted maleic anhydride.
8. such as each described polyetherimide composite material preparation method of claim 1~7, comprise the steps:
Take by weighing described polyphenylene oxide, polyetherimide, compatilizer, toughner by prescription, described polyphenylene oxide, polyetherimide, compatilizer, toughner are mixed, obtain the first mixture;
Take by weighing described oxidation inhibitor and lubricant by prescription, with described oxidation inhibitor and lubricant and the mixing of described the first mixture, obtain the second mixture;
With happy and harmonious the extruding of described the second mixture, obtain polyetherimide composite material.
9. polyetherimide composite material preparation method as claimed in claim 8 is characterized in that, the described happy and harmonious processing condition of extruding are:
One district temperature 310-320 ℃, two district temperature 320-330 ℃, three district temperature 320-330 ℃, four district temperature 310-320 ℃, head 320-330 ℃, the residence time 2~3min, pressure are 12-18MPa.
10. such as the headlight case ring of each described polyetherimide composite material automobile of claim 1~7, electron device, medical facilities, automobile, fibre-optical splice, the application in the high-temperature sterilization surgical tray.
CN201210292129.5A 2012-08-16 2012-08-16 Polyetherimide composite material and its preparation method and use Expired - Fee Related CN102850796B (en)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN104479332A (en) * 2014-12-17 2015-04-01 安徽科聚新材料有限公司 High-temperature resistant PPE and PEI alloy material and preparation method thereof
CN107903608A (en) * 2017-12-27 2018-04-13 浙江万马泰科新材料有限公司 A kind of halogen-free flame-resistant high-temperature-resistant Polyphenyl ether alloy material and preparation method thereof
CN109370140A (en) * 2018-09-30 2019-02-22 南京聚隆科技股份有限公司 A kind of fog headlight material and preparation method thereof
CN111073257A (en) * 2019-12-23 2020-04-28 南京海兆新材料有限公司 5G special PPO ceramic master batch, injection molding product and application
CN114773845A (en) * 2022-04-20 2022-07-22 张家港大塚化学有限公司 Preparation method of high-performance polyetherimide composite material for intelligent equipment

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104479332A (en) * 2014-12-17 2015-04-01 安徽科聚新材料有限公司 High-temperature resistant PPE and PEI alloy material and preparation method thereof
CN107903608A (en) * 2017-12-27 2018-04-13 浙江万马泰科新材料有限公司 A kind of halogen-free flame-resistant high-temperature-resistant Polyphenyl ether alloy material and preparation method thereof
CN109370140A (en) * 2018-09-30 2019-02-22 南京聚隆科技股份有限公司 A kind of fog headlight material and preparation method thereof
CN111073257A (en) * 2019-12-23 2020-04-28 南京海兆新材料有限公司 5G special PPO ceramic master batch, injection molding product and application
CN111073257B (en) * 2019-12-23 2022-08-12 南京海兆新材料有限公司 5G special-purpose PPO ceramic master batch, injection molding product and application
CN114773845A (en) * 2022-04-20 2022-07-22 张家港大塚化学有限公司 Preparation method of high-performance polyetherimide composite material for intelligent equipment

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