CN102051038A - High-liquidity modified polyphenyl ether plastics and production method thereof - Google Patents
High-liquidity modified polyphenyl ether plastics and production method thereof Download PDFInfo
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- CN102051038A CN102051038A CN 201110009584 CN201110009584A CN102051038A CN 102051038 A CN102051038 A CN 102051038A CN 201110009584 CN201110009584 CN 201110009584 CN 201110009584 A CN201110009584 A CN 201110009584A CN 102051038 A CN102051038 A CN 102051038A
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- polyphenylene oxide
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- polyphenyl ether
- phenol
- softening agent
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Abstract
The invention discloses high-liquidity modified polyphenyl ether plastics and a production method thereof. In the invention, an additive of which the melting point is higher than the glass transition temperature of polyphenyl ether is mixed with polyphenyl ether raw powder, and the additive is molten at the processing temperature of the polyphenyl ether and dissolved into the polyphenyl ether melt so as to reduce the melt viscosity of the polyphenyl ether and improve the liquidity of the polyphenyl ether melt; and when the polyphenyl ether melt is cooled and solidified, the molten additive crystallizes in a polyphenyl ether matrix, and the glass transition temperature and the thermal deformation temperature of the polyphenyl ether are not reduced. The invention not only can reduce the melt viscosity of the polyphenyl ether, but also cannot influence the rigidity, the strength and the heat resistance of the polyphenyl ether, and also can improve the impact toughness of the polyphenyl ether.
Description
Technical field
The invention belongs to the thermoplastic engineering plastic modification, be specifically related to high flow modifier polydiphenyl ether plastics and production method.
Background technology
Amorphous polymer polyphenylene oxide is a kind of novel thermoplastic engineering plastic, and it not only has excellent physical and mechanical properties, and also has other advantages such as good thermotolerance and chemical resistance.The proportion of pure polydiphenyl ether plastics is slightly larger than 1, about 50 ppm/ of thermal expansivity ℃.The Young's modulus of polyphenylene oxide is 2.5 GPa under the room temperature, and tensile strength is about 80 MPa, and is suitable with the performance of thermosetting resin, and the breach hit intensity is in 35 J/m levels, far above the shock resistance of common thermosetting resin.About 200 ℃ of the second-order transition temperature of polyphenylene oxide and heat-drawn wire keep good rigidity and intensity at polyphenylene oxide below 200 ℃, can be used as structural part at 150 ℃ of temperature life-time service.The performance of polyphenylene oxide excellence stems from the constructional feature of its molecule.The long-chain macromolecule that the aromatic nucleus that polyphenylene oxide divides subsystem to be replaced by carbon oxygen-ether linkage C-O connection ortho position is formed.The adjacent substituting group hinders the rotation of carbon oxygen-ether linkage C-O in the molecular chain, and the molecule of polyphenylene oxide connects the segment length, and dyskinesia is given high rigidity of material and intensity.The rigidity of polyphenylene oxide excellence, intensity, thermotolerance and stability should make polyphenylene oxide that wide Application Areas is arranged.Yet, because the polyphenylene oxide molecule connects the section dyskinesia, the viscosity height of polyphenylene oxide melt, mobile poor, difficult forming, the seldom directly melt-processed moulding of the former powder of polyphenylene oxide needs the former powder of polyphenylene ether to carry out flow modifier.
It is long-pending little that the molecule of polystyrene connects segment body, and good fluidity, second-order transition temperature are about 100 ℃.Industrial unmodified polystyrene improves the flowability of polyphenylene oxide, mixes polystyrene in the former powder of polyphenylene oxide, makes Noryl pellet supply the market.But it is right that polystyrene and polyphenylene oxide are compatible polymers, and polystyrene also reduces the thermotolerance of polyphenylene oxide when reducing the polyphenylene oxide melt viscosity.The polyphenyl ether/styrene blend only shows a glass transition, and second-order transition temperature is relevant with the composition of blend, descends with the rising of polystyrene content.The heat-drawn wire of polyphenyl ether/styrene blend reduces with the increase of polystyrene content, has dwindled the range of application of polyphenylene oxide.Engineering plastic nylon has good mobility and thermotolerance, about 260 ℃ of fusing point, and incompatible with polyphenylene oxide.Under the effect of compatilizer,, can improve the processing characteristics of polyphenylene oxide to a certain extent and the heat-drawn wire of not remarkably influenced polyphenylene oxide with nylon and polyphenylether blending.Yet nylon reduces the effect of polyphenylene oxide melt viscosity far away from polystyrene, and when the moulding of large-scale complex thin-wall goods, the defective of the mobile difference of polyphenylene oxide is particularly outstanding.Still lack on the market processing fluidity good, use the good modified polyphenylene ether resin of thermotolerance.
Summary of the invention
The objective of the invention is to overcome the prior art above shortcomings, high flow modifier polyphenylene oxide and production method thereof are provided, overcome existing polyphenylene oxide flow modifier method and reducing the polyphenylene oxide melt viscosity, when improving the polyphenylene oxide processing characteristics, also reduce the defective of polydiphenyl ether plastics heat-drawn wire.Method of modifying of the present invention can improve the flowability of polyphenylene oxide melt effectively and not influence the thermotolerance of polydiphenyl ether plastics.The present invention is achieved through the following technical solutions:
The present invention adopts the additive that can undergo phase transition to improve the flowability of polyphenylene oxide melt and does not influence the thermotolerance of polyphenylene oxide.The fusing point of additive is higher than the second-order transition temperature of polyphenylene oxide, at high temperature additive and polyphenylene oxide thermodynamic compatibility, and additive and polyphenylene oxide became incompatible when temperature reduced.
The production method of high flow modifier polyphenylene oxide specifically is to add 0.5 to 12 part of exsiccant crystallization additive in 100 parts of former powder of exsiccant polyphenylene oxide, as the small molecules crystallization of bis-phenol-S, phthalic imidine one class.Former powder of polyphenylene oxide and additive powder are mixed, and melt blending promptly gets the Noryl pellet.
Above-mentioned production method, described polyphenylene oxide have the backbone of xylenol polycondensate or the backbone of other fragrant phenol polycondensate.The fusing point of described phase transformation softening agent is at 200 ℃-300 ℃, and when temperature drops to below the phase transformation softening agent fusing point, the phase transformation softening agent of fusing can crystallization in the polyphenylene oxide matrix.Described phase transformation softening agent comprises bis-phenol-S, phthalic imidine or substituted phthalimide.
Above-mentioned production method, described melt blending carries out in 220-330 ℃ at forcing machine, and blend is through head extruding pelletization or extrusion moulding.
Above-mentioned production method, described melt blending carries out in 220-330 ℃ at injection moulding machine, and blend is through injection moulding.
Above-mentioned production method, described melt blending carries out in 240-300 ℃ at Banbury mixer, and blend is through compressing tablet, or compression molding or extruding pelletization.
The melt viscosity of Noryl pellet of the present invention is than the low 8-50% of melt viscosity of unmodified polyphenylene oxide, and second-order transition temperature remains unchanged.The heat-drawn wire of high flow modifier polyphenylene oxide can not be lower than 5 ℃ of unmodified polyphenylene oxide.Height flows, high heat resistance modified polyphenylene oxide pellet is easy to extrude or be injection molded into heat-stable polydiphenyl ether plastics goods 270-300 ℃ temperature.Also can with do mixed polyphenylene oxide and additive powder on injection moulding machine in 280-320 ℃ the direct injection moulding of temperature melting mixing, the additive of fusing improves the flowability of polyphenylene oxide, improves processing characteristics and does not reduce polydiphenyl ether plastics goods use temperature.
The second-order transition temperature of unmodified polyphenylene oxide is about 200 ℃, and general processing temperature is about 300 ℃.About 250 ℃ of the fusing point of bis-phenol-S, the fusing point of phthalic imidine is at 235 ℃.The fusing point of additive is lower than that polyphenylene oxide is extruded or the processing temperature of injection moulding, when spiro rod plasticizing section melting mixing, the additive fusing is also dissolved in the polyphenylene oxide melt, plays the effect of softening agent, reduce the viscosity of polyphenylene oxide melt, improve the flowability and the processibility of polyphenylene oxide melt.Extrude or injection moulding after polyphenylene oxide melt cooling and shaping, temperature reduces, additive descends with the polyphenylene oxide consistency, produces to be separated more than the polyphenylene oxide second-order transition temperature, the additive of fusing is separated out also crystallization from the polyphenylene oxide matrix, forms nano level crystallite.The fusing point of crystallite is higher than the second-order transition temperature of polyphenylene oxide, and additive can not influence the company's section motion and the heat-drawn wire of polyphenylene oxide molecule.
Existing relatively poly-The Modification of Polyphenylene Oxide method, the present invention has advantage: 5 parts of additives can reduce by 100 parts of polyphenylene oxide melt viscosity 35 %, when reducing the polyphenylene oxide melt viscosity, improving the flow modifier of polyphenylene oxide stream polyphenylene oxide, do not influence the physical and mechanical properties and the heat-drawn wire of polyphenyl ether material, do not reduce rigidity, intensity and the thermotolerance of polyphenylene oxide, more can improve the toughness of polyphenylene oxide.
Embodiment
Below in conjunction with embodiment concrete enforcement of the present invention is described further, but enforcement of the present invention and protection domain are not limited thereto.
Example 1
5 mass parts exsiccant bis-phenol-S are added the former powder of 100 mass parts exsiccant polyphenylene oxide, the former powder of polyphenylene oxide and bis-phenol-S are mixed at homogenizer.In Haake 252 single screw extrusion machine extruding pelletizations, three sections temperature of forcing machine are set to 250,275 with mixture, and 285 ℃, head temperature is controlled at 290 ℃.Bis-phenol-S Noryl pellet is measured rheological property at Haake 600 rheometer mixing tanks; Be injection molded into standard model in 290 ℃ with injection moulding machine and carry out Mechanics Performance Testing.
Example 2
0.5 mass parts exsiccant phthalic imidine is added the former powder of 100 mass parts exsiccant polyphenylene oxide, former powder of polyphenylene oxide and phthalic imidine are mixed at homogenizer.In Haake 252 single screw extrusion machine extruding pelletizations, three sections temperature of forcing machine are set to 250,275 with mixture, and 285 ℃, head temperature is controlled at 290 ℃.Phthalic imidine Noryl pellet is measured rheological property at Haake 600 rheometer mixing tanks; Be injection molded into standard model in 290 ℃ with injection moulding machine and carry out Mechanics Performance Testing.
Example 3
12 mass parts exsiccant nitro phthalic imidines are added the former powder of 100 mass parts exsiccant polyphenylene oxide, former powder of polyphenylene oxide and nitro phthalic imidine are mixed at homogenizer.In Haake 252 single screw extrusion machine extruding pelletizations, three sections temperature of forcing machine are set to 250,275 with mixture, and 285 ℃, head temperature is controlled at 290 ℃.Nitro phthalic imidine Noryl pellet is measured rheological property at Haake 600 rheometer mixing tanks; Be injection molded into standard model in 290 ℃ with injection moulding machine and carry out Mechanics Performance Testing.
Comparative sample 1
In Haake 252 single screw extrusion machine extruding pelletizations, three sections temperature of forcing machine are set to 250,275 with the former powder of exsiccant polyphenylene oxide, and 310 ℃, head temperature is controlled at 310 ℃.The polyphenylene oxide pellet is measured rheological property at Haake 600 rheometer mixing tanks; Be injection molded into standard model in 310 ℃ with injection moulding machine and carry out Mechanics Performance Testing.
Comparative sample 2
7 parts of polystyrene are added in 100 parts of former powder of exsiccant polyphenylene oxide, former powder of polyphenylene oxide and polystyrene are stirred at stirrer.In Haake 252 single screw extrusion machine extruding pelletizations, three sections temperature of forcing machine are set to 250,275 with mixture, and 285 ℃, head temperature is controlled at 290 ℃.Polystyrene Noryl pellet is measured rheological property at Haake 600 rheometer mixing tanks; Be injection molded into standard model in 300 ℃ with injection moulding machine and carry out Mechanics Performance Testing.
Table 1 has been listed processing fluidity, second-order transition temperature and the mechanical property under differing temps of Noryl.The physical and mechanical properties of unmodified polyphenylene oxide and thermotolerance are all very high.Modulus under the room temperature, intensity are respectively 2.6 GPa and 78 MPa, and second-order transition temperature is 209 ℃, about 195 ℃ of the temperature of modulus 2.0 GPa; Tensile strength when 150 ℃ of temperature has 36 MPa.But melt viscosity is big, and is mobile poor.It is 11.5 Nm that Haake torque rheometer records at 280 ℃, torque during 20 rpm, and injection temperature will be more than 310 ℃.Bis-phenol-S can improve the flowability of polyphenylene oxide and the mechanical property and the thermotolerance of not remarkably influenced polyphenylene oxide greatly.Torque with 5 parts of bis-phenols-S Noryl is 7.4Nm, and than low 4.1 Nm of pure polyphenylene oxide, torque reduces by 36%.And modulus under the room temperature and intensity and unmodified polyphenylene oxide quite, second-order transition temperature is too; Tensile strength when 150 ℃ of temperature has 35MPa, and resistance to impact shock more is better than pure polyphenylene oxide.But the Noryl pellet is in 290 ℃ of just injection mouldings of temperature.
The mechanical property under differing temps of table 1. polyphenylene oxide and Noryl
Claims (8)
1. the production method of a high flow modifier polyphenylene oxide is characterized in that the mass fraction of described phase transformation softening agent is 0.5-12 part with polyphenylene oxide and phase transformation softening agent melt blending, and the polyphenylene oxide mass fraction is 100 parts.
2. production method according to claim 1 is characterized in that described polyphenylene oxide has the backbone of xylenol polycondensate or the backbone of other fragrant phenol polycondensate, and described fragrant phenol comprises substituted dimethyl phenol, phenol or how to replace phenol how.
3. according to the described production method of claim 1, the fusing point that it is characterized in that described phase transformation softening agent is at 200 ℃-300 ℃; When temperature drops to below the phase transformation softening agent fusing point, the phase transformation softening agent of fusing can crystallization in the polyphenylene oxide matrix.
4. according to the described production method of claim 1, it is characterized in that described phase transformation softening agent comprises bis-phenol-S, phthalic imidine or substituted phthalimide.
5. according to the described production method of claim 1, it is characterized in that described melt blending carries out in 220-330 ℃ at forcing machine, blend is through head extruding pelletization or extrusion moulding.
6. production method according to claim 1 is characterized in that described melt blending carries out in 220-330 ℃ at injection moulding machine, and blend is through injection moulding.
7. according to the described production method of claim 1, it is characterized in that described melt blending carries out in 240-300 ℃ at Banbury mixer, blend is through compressing tablet, or compression molding or extruding pelletization.
8. the high flow modifier polyphenylene oxide that is made by the described production method of claim 1 is characterized in that the melt viscosity low 8-50% of the melt viscosity of Noryl pellet than unmodified polyphenylene oxide.
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| CN 201110009584 CN102051038A (en) | 2011-01-18 | 2011-01-18 | High-liquidity modified polyphenyl ether plastics and production method thereof |
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| CN 201110009584 CN102051038A (en) | 2011-01-18 | 2011-01-18 | High-liquidity modified polyphenyl ether plastics and production method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829827A (en) * | 2015-05-12 | 2015-08-12 | 威海市泓淋电子有限公司 | Modified polyarylene ether resin and composite halogen-free flame-retardant material thereof, preparation methods and application of modified polyarylene ether resin and composite halogen-free flame-retardant material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101040004A (en) * | 2004-10-14 | 2007-09-19 | 旭化成化学株式会社 | Resin composition |
| CN101175804A (en) * | 2005-08-31 | 2008-05-07 | 通用电气公司 | High flow polyester composition |
| CN101698736A (en) * | 2009-10-30 | 2010-04-28 | 华南理工大学 | Modification method for enhancing polarity and flowability of polypropylene |
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2011
- 2011-01-18 CN CN 201110009584 patent/CN102051038A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101040004A (en) * | 2004-10-14 | 2007-09-19 | 旭化成化学株式会社 | Resin composition |
| CN101175804A (en) * | 2005-08-31 | 2008-05-07 | 通用电气公司 | High flow polyester composition |
| CN101698736A (en) * | 2009-10-30 | 2010-04-28 | 华南理工大学 | Modification method for enhancing polarity and flowability of polypropylene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829827A (en) * | 2015-05-12 | 2015-08-12 | 威海市泓淋电子有限公司 | Modified polyarylene ether resin and composite halogen-free flame-retardant material thereof, preparation methods and application of modified polyarylene ether resin and composite halogen-free flame-retardant material |
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Application publication date: 20110511 |