CN101555348B - Composite material of polycarylene ether nitrile fiberglass and preparation method thereof - Google Patents
Composite material of polycarylene ether nitrile fiberglass and preparation method thereof Download PDFInfo
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- CN101555348B CN101555348B CN2009103020129A CN200910302012A CN101555348B CN 101555348 B CN101555348 B CN 101555348B CN 2009103020129 A CN2009103020129 A CN 2009103020129A CN 200910302012 A CN200910302012 A CN 200910302012A CN 101555348 B CN101555348 B CN 101555348B
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- ether nitrile
- fiberglass
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- -1 ether nitrile Chemical class 0.000 title claims abstract description 88
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000011152 fibreglass Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229920006391 phthalonitrile polymer Polymers 0.000 claims abstract description 49
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003365 glass fiber Substances 0.000 claims description 24
- 239000008188 pellet Substances 0.000 claims description 16
- 239000004902 Softening Agent Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 11
- 238000000748 compression moulding Methods 0.000 claims description 9
- 238000001746 injection moulding Methods 0.000 claims description 9
- 238000005453 pelletization Methods 0.000 claims description 9
- 238000007669 thermal treatment Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000012856 packing Methods 0.000 abstract description 2
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 2
- 238000005452 bending Methods 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 229920000090 poly(aryl ether) Polymers 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
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Abstract
The invention belongs to the technical field of polymer materials, particularly relates to a composite material of polycarylene ether nitrile fiberglass and a preparation method thereof. The inventionaims at providing a composite material of polycarylene ether nitrile fiberglass with superior comprehensive property; the composite material uses polycarylene ether nitrile and fiberglass as raw mate rials and phthalonitrile prepolymer as a plasticizer which are melted and mixed for being prepared into granules; and the finished composite material is obtained by heat treatment after the granules of mixtures are injected or press formed. The polycarylene ether nitrile, the fiberglass and the phthalonitrile prepolymer are proportioned by weight ratio of 45-85:10-40:3-15. The composite material of the polycarylene ether nitrile fiberglass has tensile-strength ranging from 120 MPa to 180 MPa, bending strength ranging from 150 MPa to 250 MPa and heat deflection temperature ranging from 160 DEGC to 180 DEG C. The composite material can be extensively used in the fields of aerial composite materials, electronic packing materials, auto parts, etc.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly poly (arylene ether nitrile) resin glass fiber composite material and preparation method thereof.
Background technology
Poly (arylene ether nitrile) (Polyarylene ether nitriles, PEN) be the semi-crystalline polymer that has itrile group on the class side chain, it is the structure-type macromolecular material of the class excellent combination property that at first grown up for the demand of defence and military and sophisticated technology since the 1980s, has good characteristics such as very high thermotolerance, flame retardant resistance, physical strength, antiultraviolet and creep resistance be good.So outstanding performance is added ideal hypocrystalline melt-processed feasibility and is made people be applied in aspects such as aviation matrix material, electronic package material and automobile component to poly (arylene ether nitrile) to have produced huge interest.
Poly (arylene ether nitrile) research at home arises from the eighties, mainly concentrates on aspects such as research synthesis technique and prescription.The patent of invention of domestic application mainly contains: number of patent application is " a kind of poly (arylene ether nitrile) and manufacture method thereof ", " industrialized preparing process of poly (arylene ether nitrile) ", " industrialized preparing process of poly aromatic ether nitrile high molecular halogen-free fire retardant ", " a kind of copolymer of polyarylether nitrile that contains chian element of iso-benzene and preparation method thereof " of 200610021306.0 of 200510038360.1 of 200610038381.8 of 94113026.6.
In order further to improve poly (arylene ether nitrile) physical strength and resistance toheat, improving its molecular weight and adjusting molecular structure is highly effective approach.The high-molecular weight poly (arylene ether nitrile) has possessed higher physical strength and resistance toheat, but processing fluidity becomes relatively poor, adds fiber glass packing difficulty more, therefore is necessary it is carried out plasticization and modification.Though softening agent commonly used can improve the flowability of poly (arylene ether nitrile), often since cause influence such as consistency, thermotolerance be relatively poor the subjectivity property of poly (arylene ether nitrile) material, can reduce the over-all properties of poly (arylene ether nitrile).Therefore, be badly in need of at present seeking new softening agent, prepare the high poly (arylene ether nitrile) material of over-all properties.So far, do not see the report that the phthalonitrile prepolymer uses as softening agent.
Summary of the invention
First technical problem to be solved by this invention provides the purposes of the phthalonitrile prepolymer shown in the formula I as the softening agent of preparation macromolecular material,
Formula I
Wherein, n=1～10.
The purposes of above-mentioned phthalonitrile prepolymer as the softening agent of preparation composite material of polycarylene ether nitrile fiberglass especially is provided.
Second technical problem to be solved by this invention provides the good composite material of polycarylene ether nitrile fiberglass of a kind of over-all properties.It is to be raw material with poly (arylene ether nitrile) and glass fibre, is softening agent and coupling agent with phthalonitrile prepolymer (structure shown in the formula I, as follows), and melt blending is made pellet, obtains after pellet injection moulding or the compression moulding.
Further, the weight proportion of poly (arylene ether nitrile), glass fibre, phthalonitrile prepolymer is 45～85: 10～40: 3～15.
The 3rd technical problem to be solved by this invention provides the preparation method of above-mentioned composite material of polycarylene ether nitrile fiberglass, specifically may further comprise the steps:
A, take by weighing raw material: poly (arylene ether nitrile): glass fibre: phthalonitrile prepolymer=45～85: 10～40: 3～15 according to following weight proportion;
B, poly (arylene ether nitrile) and phthalonitrile prepolymer are mixed back melt blending extruding pelletization, glass fibre is sheared section at forcing machine and is added, and makes the polycarylene ether nitrile fiberglass pellet;
C, with the polycarylene ether nitrile fiberglass pellet by injection moulding or compression moulding, thermal treatment makes.
The equipment of described extruding pelletization is twin screw extruder.
The melt temperature of step b is 350 ℃.
The heat treated temperature of step c is 250 ℃.
The tensile strength of the composite material of polycarylene ether nitrile fiberglass that obtains of preparation is 120～180MPa, flexural strength 150～250MPa, and heat-drawn wire is 160～180 ℃.
The invention has the beneficial effects as follows:
The present invention proposes the purposes that the phthalonitrile prepolymer uses as softening agent first.The phthalonitrile prepolymer is high temperature resistant, and it is 227～233 ℃ that difference formula DSC thermal analyzer records its melting range, and temperature of initial decomposition is more than 420 ℃, and has good processing flowability, and plasticization effect is good.After the poly (arylene ether nitrile) plasticising, by add 10～40% glass not only mechanical property and thermotolerance be greatly enhanced, and reduced the application cost of poly (arylene ether nitrile) product.And the inventive method has adopted on twin screw extruder melt blending to extrude, and working condition is easy to realize that production process is easy to control, is applicable to suitability for industrialized production.
Figure of description
Fig. 1 be before and after the poly (arylene ether nitrile) plasticising viscosity with the variation of temperature graphic representation, PEN: poly (arylene ether nitrile), No. 1 sample of 1#: embodiment 1 preparation, No. 2 samples of 2#: embodiment 1 preparation, No. 3 samples of 3#: embodiment 1 preparation.
Embodiment
The invention provides the purposes of the phthalonitrile prepolymer shown in the formula I as the softening agent of preparation macromolecular material,
Formula I
Wherein, n=1～10.
It is 227～233 ℃ that described phthalonitrile prepolymer difference formula DSC thermal analyzer records melting range, and temperature of initial decomposition is that viscosity is lower than 1000Pa.S more than 420 ℃.
Described poly (arylene ether nitrile) is provided by Sichuan Feiya New Materials Co., Ltd., and used phthalonitrile prepolymer is provided by little solid Liu of institute filial piety ripple seminar of University of Electronic Science and Technology, and all the other are the commercially available prod.
Because phthalonitrile prepolymer temperature of initial decomposition height, and viscosity is lower than 1000Pa.S, has good processing flowability, can be used as softening agent and uses.General softening agent poor heat resistance, processed and applied seldom at high temperature, though silicone oil can at high temperature use, bad with the consistency of poly (arylene ether nitrile) resin.
Phthalonitrile prepolymer viscosity is very low, has very strong adhesive power with glass fibre etc., the phthalonitrile prepolymer has improved the interface interaction power of resin system and glass fibre simultaneously at plastifying, especially strengthen greatly by this interface interaction power after the thermal treatment, improved the mechanical property of glass fiber composite material.
The present invention especially provides the purposes of above-mentioned phthalonitrile prepolymer as the softening agent of preparation composite material of polycarylene ether nitrile fiberglass.Adopt this softening agent to prepare the good composite material of polycarylene ether nitrile fiberglass of over-all properties.Particularly, it is to be raw material with poly (arylene ether nitrile) and glass fibre, is softening agent and coupling agent with the phthalonitrile prepolymer, and melt blending is made pellet, obtains after pellet injection moulding or the compression moulding.
The reaction of the itrile group of phthalonitrile prepolymer end points and poly (arylene ether nitrile) the product processing fluidity after the plasticising is greatly improved, and every property retention is stable.Abundant itrile group and the good processing flowability of phthalonitrile prepolymer makes to have good dispersiveness and interface interaction power in the composite material of polycarylene ether nitrile fiberglass of glass fibre after modification, and especially performance improves greatly owing to the enhancing of glass and resin boundary surface reactive force at the composite material of polycarylene ether nitrile fiberglass cured article that obtains after Overheating Treatment.
Simultaneously, the phthalonitrile prepolymer has the molecular structure close with poly (arylene ether nitrile), the itrile group of phthalonitrile prepolymer and poly (arylene ether nitrile) structural similitude---guaranteed consistency, the macrocyclic structure of phthalonitrile prepolymer---guarantee thermostability, also guaranteed the thermotolerance and the physicalies such as high strength, high-modulus of poly (arylene ether nitrile) simultaneously.
The preparation method of composite material of polycarylene ether nitrile fiberglass of the present invention specifically may further comprise the steps:
A, take by weighing raw material: poly (arylene ether nitrile): glass fibre: phthalonitrile prepolymer=45～85: 10～40: 3～15 according to following weight proportion;
B, poly (arylene ether nitrile) and phthalonitrile prepolymer are mixed back melt blending extruding pelletization in homogenizer, glass fibre is sheared section at forcing machine and is added and makes the polycarylene ether nitrile fiberglass pellet;
C, with the polycarylene ether nitrile fiberglass pellet by injection moulding or compression moulding, thermal treatment is promptly.
The equipment of described extruding pelletization is twin screw extruder.The melt temperature of step b is 350 ℃.The heat treated temperature of step c is 250 ℃.
Below mode by specific embodiment the present invention is further described, be limitation of the present invention but should not be construed as, all modification, replacement, changes of making based on the above-mentioned thought of the present invention all belong to the present invention.
(1) plasticizer consumption sees Table 1:
Table 1
| Raw material | No. 1 sample | No. 2 samples | No. 3 samples |
| Poly (arylene ether nitrile) | 9.5 kilogram | 9 kilograms | 8.5 kilogram |
| The phthalonitrile prepolymer | 0.5 |
1 kilogram | 1.5 kilogram |
(2) poly (arylene ether nitrile) plasticising production process:
1, twin screw extruder is warming up to 350 ℃.
2, with poly (arylene ether nitrile) and phthalonitrile prepolymer mix on the homogenizer back drop into twin screw extruder melt blending extruding pelletization to obtain speedup after the poly (arylene ether nitrile) pellet, its performance test results sees Table 2:
Table 2
* contrasting sample is poly (arylene ether nitrile).
The add-on that product performance detected result in the table 2 shows the phthalonitrile prepolymer is in 10% mechanical property that does not influence poly (arylene ether nitrile) resin when following.
The melting index of poly (arylene ether nitrile) resin sees Table 3 behind the adding different ratios phthalonitrile prepolymer:
Table 3
The poly (arylene ether nitrile) resin processing fluidity is very poor as can be seen from Table 3, melting index is 0, along with the increase of phthalonitrile prepolymer addition, its melting index increases substantially, and shows that the phthalonitrile prepolymer effectively raises the processing fluidity of poly (arylene ether nitrile).
Fig. 1 has shown that poly (arylene ether nitrile) resin processing viscosity descends significantly along with the increase of phthalonitrile prepolymer addition, illustrates that the phthalonitrile prepolymer has good plastification to poly (arylene ether nitrile) resin.
The preparation of embodiment 2 composite material of polycarylene ether nitrile fiberglass
(1) get the raw materials ready:
60 kilograms of poly (arylene ether nitrile)s
30 kilograms in glass fibre
10 kilograms of phthalonitrile prepolymers
(2) production process:
1, twin screw extruder is warming up to 350 ℃.
2, poly (arylene ether nitrile) and phthalonitrile prepolymer are mixed back input twin screw extruder melt blending extruding pelletization on homogenizer, glass fibre is sheared section at twin screw extruder and is added.
3, the polycarylene ether nitrile fiberglass pellet is heat-treated under 250 ℃ of temperature after by injection moulding or compression moulding obtained high-performance polyarylether nitrile glass fiber composite material in 24 hours.
The product performance detected result sees Table 4:
Table 4
| Composite material of polycarylene ether nitrile fiberglass | Detected result |
| Tensile strength (Mpa) | 192.5 |
| Flexural strength (Mpa) | 259.3 |
| Heat-drawn wire (℃) | 175 |
| Temperature of initial decomposition (℃) | 501 |
| Notched Izod impact strength (KJ/m 2) | 10.2 |
The preparation of embodiment 3 composite material of polycarylene ether nitrile fiberglass
(1) get the raw materials ready according to the proportioning of table 5:
Table 5
(2) production process:
1, twin screw extruder is warming up to 350 ℃.
2, poly (arylene ether nitrile) and phthalonitrile prepolymer are mixed back input twin screw extruder melt blending extruding pelletization on homogenizer, glass fibre is sheared section at twin screw extruder and is added.
3, the polycarylene ether nitrile fiberglass pellet is heat-treated under 250 ℃ of temperature after by injection moulding or compression moulding obtained 3 kinds of high-performance polyarylether nitrile glass fiber composite materials in 24 hours.
The product performance detected result sees Table 6:
Table 6
Data in the table 6 show that the mechanical property of composite material of polycarylene ether nitrile fiberglass increases along with the increase of glass fiber content.
Performance relatively before and after the embodiment 4 composite material of polycarylene ether nitrile fiberglass thermal treatments
(1) get the raw materials ready:
60 kilograms of poly (arylene ether nitrile)s
30 kilograms in glass fibre
10 kilograms of phthalonitrile prepolymers
(2) production process:
1, twin screw extruder is warming up to 350 ℃.
2, poly (arylene ether nitrile) and phthalonitrile prepolymer are mixed back input twin screw extruder melt blending extruding pelletization on homogenizer, glass fibre is sheared section at twin screw extruder and is added.
3, with the polycarylene ether nitrile fiberglass pellet by injection moulding or compression moulding as thermal treatment before sample, will under 250 ℃ of temperature, heat-treat 24 hours as a comparison, obtain composite material of polycarylene ether nitrile fiberglass as thermal treatment after sample.Two kinds of properties of sample detected results see Table 7:
Table 7
Crosslinking reaction can take place at 250 ℃ in the phthalonitrile prepolymer, can make phthalonitrile prepolymer and glass produce reaction simultaneously, thereby improves the interface interaction power of poly (arylene ether nitrile) and glass.Data in the table 7 show that composite material of polycarylene ether nitrile fiberglass mechanical property after heat treatment increases substantially.
Claims (5)
1. composite material of polycarylene ether nitrile fiberglass is characterized in that: it is to be raw material with poly (arylene ether nitrile) and glass fibre, is softening agent with the phthalonitrile prepolymer, and melt blending is made pellet, pellet injection moulding or compression moulding; The weight proportion of poly (arylene ether nitrile), glass fibre, phthalonitrile prepolymer is 45～85: 10～40: 3～15; The structure of phthalonitrile prepolymer is suc as formula shown in the I:
Formula I
Wherein, n=1～10.
2. method for preparing the described composite material of polycarylene ether nitrile fiberglass of claim 1 is characterized in that: may further comprise the steps:
A, take by weighing raw material: poly (arylene ether nitrile): glass fibre: phthalonitrile prepolymer=45～85: 10～40: 3～15 according to following weight proportion;
B, poly (arylene ether nitrile) and phthalonitrile prepolymer are mixed back melt blending extruding pelletization, glass fibre is sheared section at forcing machine and is added, and makes the polycarylene ether nitrile fiberglass pellet;
C, with the polycarylene ether nitrile fiberglass pellet by injection moulding or compression moulding, thermal treatment, promptly.
3. preparation method according to claim 2 is characterized in that: the melt temperature of step b is 350 ℃.
4. preparation method according to claim 2 is characterized in that: step c thermal treatment temp is 250 ℃.
5. the phthalonitrile prepolymer shown in the formula I is as the purposes of the softening agent of preparation composite material of polycarylene ether nitrile fiberglass, and it is characterized in that: described phthalonitrile prepolymer melting range is 227～233 ℃, and temperature of initial decomposition is more than 420 ℃,
Formula I
Wherein, n=1～10.
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| CN101712795B (en) * | 2009-11-27 | 2011-09-14 | 四川飞亚新材料有限公司 | Poly-arylene ether nitrile composite material, poly-arylene ether nitrile material and preparation method thereof |
| CN101913276A (en) * | 2010-07-07 | 2010-12-15 | 电子科技大学 | Poly(arylene ether nitrile) resin and fiber fabric laminated composite material and preparation method thereof |
| CN101914038A (en) * | 2010-07-15 | 2010-12-15 | 电子科技大学 | Bisphenol A type bis-phthalonitrile resin with aryl ether nitrile segments, cured product and preparation method thereof |
| CN101891947B (en) * | 2010-08-27 | 2011-09-07 | 电子科技大学 | Poly (arylene ether nitrile) composite material and preparation method thereof |
| CN101955586B (en) * | 2010-09-30 | 2012-04-25 | 中南大学 | Epoxy terminated polyarylether resins with phthalonitrile side group and curing materials and preparation methods thereof |
| CN109273898B (en) * | 2018-09-12 | 2021-05-28 | 荆州市还祥特种材料有限公司 | Composite material downhole connector and preparation method thereof |
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