CN1775513A - Method for preparing microwave in-situ polymerized long glass fiber reinforced ABS composite material - Google Patents
Method for preparing microwave in-situ polymerized long glass fiber reinforced ABS composite material Download PDFInfo
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- CN1775513A CN1775513A CN 200510110969 CN200510110969A CN1775513A CN 1775513 A CN1775513 A CN 1775513A CN 200510110969 CN200510110969 CN 200510110969 CN 200510110969 A CN200510110969 A CN 200510110969A CN 1775513 A CN1775513 A CN 1775513A
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Abstract
The present invention provides a preparation method of microwave in-situ polymerized long glass fibre reinforced ABS composite material. It is mainly characterized by that after the glass fibre cloth is impregnated with polymer monomer with low viscousity and oligopolymer, said glass fibre cloth is laid in a glass fibre reinforced plastic mould, then it utilizes microwave to make in-situ polymerization reaction so as to obtain the invented composite material plate.
Description
Technical field
The present invention relates to the preparation method of microwave in-situ polymerized preparation long glass fiber reinforced ABS composite material, can be used for preparing high-performance glass fiber and strengthen thermoplastic composite, belong to the polymer matrix composite field.
Background technology
ABS is the thermoplastic engineering plastic of a kind of function admirable, relative low price.Along with people are more and more higher to the requirement of the performance of engineering plastics, environmental protection aspects, the development with glass fiber reinforced ABS thermoplastic composite of formedness price ratio just constantly is subject to people's attention, and has a extensive future.
One of key technology of preparation fiber reinforced thermolplastic composite material is the impregnation technology of fiber and thermoplastic resin.The dipping method of present industrial use has melt impregnation, liquation infusion process, suspension impregnation method, assorted fibre method.Melt impregnation technology is simple, it is present industrial complex method commonly used, but, because the melt viscosity of thermoplastic resin is very high, resin is difficult to be impregnated into the surface of single fiber in the fibre bundle, and the mixing of fiber and molten resin generally is to carry out in injection machine or twin-screw, so the industrial preparation that generally is applied to the thermoplastic composite that short glass fiber strengthens of melt impregnation; Though liquation infusion process and suspension impregnation method can make polymer solution or polymer beads more easily soak into fibre bundle, solution can cause boundary defect along the polymer interface diffusion in removing the solution process; The assorted fibre method need solve in the melting process of thermoplastic fibre the problem of coated fortifying fibre equably, and production technology is comparatively complicated.This patent uses in-situ polymerization to solve the impregnation difficulties of thermoplastic resin to fortifying fibre well.
The application of microwave technology in polymer matrix composite is nearly more than ten years new developing technology, majority be used for composite repairing, connect and the aspect such as separate.Aspect polymer matrix composite prepared, the research of microwave on the vulcanization of rubber and resin solidification was more, and Lee etc. are the earliest with the curing of microwave radiation application in composite.The microwave radiation application is studied laterly in the resin polymerization aspect, Murray in 1994 etc. first with microwave applications in emulsion polymerization.The novelty of this patent is that first microwave technology being used for in-situ polymerization prepares thermoplastic composite.
In-situ polymerization is exactly the monomer with fortifying fibre heat of immersion thermoplastic polymer, finishes polymerization and and compound two processes of fiber of monomer then in the process of heating simultaneously.What the polymerization of this patent was adopted is carry out microwave radiation heating, the ecto-entad that it is different from thermal polymerization conducts heat, but inside and outside heating simultaneously, firing rate is fast, efficient is high, because the heat transfer direction of heating using microwave is different with the heat heating with the thermal gradient direction, can improve the bond performance of composite material interface simultaneously.
Therefore the microwave in-situ polymerized preparation composite process of the present invention's proposition and use has promptly solved the impregnation difficulties of thermoplastic resin to fortifying fibre well, operation is few, cost is low, compare with using the vulcanizing press thermal polymerization simultaneously, adopt microwave technology, firing rate is fast, efficient is high, rubber phase tiny, the prepared composite that is evenly distributed has the good mechanical performance in the resin matrix.
Summary of the invention
The object of the present invention is to provide a kind of method of using the long glass fiber reinforced ABS composite material of microwave in-situ polymerized processability excellence.
The objective of the invention is to implement like this: with the butadiene rubber of styrene monomer dissolve uncrosslinked, put into acrylonitrile and initator dibenzoyl peroxide (BPO) again, make low-viscosity polymer monomer solution through slowly stirring, and then the shop layer is put into mould after will fully flooding through the glass fabric that silane coupler is handled, glass epoxy and stainless steel screw close, the ABS composite that long glass fibres strengthens is made in the heating pressurization on microwave applicator.Accompanying drawing 1 is seen in technological process.
Details are as follows for specific implementation process:
One, preparation
1) raw material is prepared
Monomer distillation: respectively styrene monomer and acrylonitrile monemer are distilled to remove impurity and the polymerization inhibitor in the monomer with rotary evaporator.
By a certain percentage rubber is dissolved in styrene, leave standstill and made the rubber dissolving in 5-6 hour through distillation.Put into quantitative acrylonitrile and initiator B PO again, slowly stir evenly, in case of necessity, cross as bubble and to vacuumize one to five minute at most, clarify until solution with glass bar through distillation.The weight ratio of styrene and acrylonitrile is (6～8): (2～: 4), butadiene rubber accounts for 0～10% of melt weight, and the weight of BPO is 1.0～1.5% of solution weight.
2) surface treatment of glass fabric
The main effect of the reinforcing material in the composite is a bearing load, improves the intensity or the toughness of composite.With coupling agent glass fibre is carried out surface treatment, can improve the bonding force between the glass fibre and organic resin in the resin composite materials structure.
Water is transferred to about pH value 4-5 with acetic acid, is under agitation added silane coupler then slowly, preferred silane coupler is the KH-550 silane coupler, and it is transparent until solution to continue stirring, and hydrolysis work is so far finished.Wherein, the chemical name of KH-550 and chemical structural formula are respectively gamma-aminopropyl-triethoxy-silane and [NH
2(CH
2)
3Si (OC
2H
5)
3].
Water is transferred to about pH value 4-5 with acetic acid, is under agitation added the silane coupler that accounts for Total Water 1～2% then slowly, it is transparent until solution to continue stirring, and hydrolysis work is so far finished.The weight of water is greater than 20 times to 60 times of desire processing glass fabric weight.
Needs are carried out the surface-treated glass fabric be placed in the size, soaked into 10～15 minutes, take out then, it is loaded on is positioned over the drying box inner drying in the container, till the glass fabric drying.
3) preparation of mould
Get the thick white silica gel of 5mm that is, being cut into housing is 170mm * 130mm, and inside casing is the rectangular frame structure of 130mm * 90mm, and back gauge is about 20mm, and mould is sticked on the processing release paper.
4) preparation of reinforcing material
Will be cut into the square of inside casing undersized through coupling agent surface-treated glass fabric, and glass fabric is weighed, the weight of this glass fabric is removed in the weight of the composite that finally makes and is content of glass fiber in the composite.
Two, moulding process
Get up and down two than the glass epoxy that can fasten screw on the big surrounding of die size,, again mould is positioned over glass epoxy central authorities at lower-glass steel plate upper berth one deck processing release paper.Earlier in mould, pour into a mould one deck resin solution equably, in then preprepared glass fabric being laid on, solution is soaked into glass fabric evenly, and can not leave bubble.Get a processing release paper, be covered on the glass fabric.Cover the upper glass steel plate then.The upper glass surface of steel plate is equipped with thermometer.Six stainless steel screws have been fastened up and down between two block plates, the pressure when tightening screw with the control polymerization with torque spanner.
1, microwave polymerization: the microwave applicator of above-mentioned mould being put into 1000W, radiation heating under the microwave frequency of 2.45GHz is by the temperature of the heating shelves on the microwave applicator (intermittent time from high-grade, middle-grade to low-grade microwave radiation is from being short to long the prolongation) control heating using microwave.Concrete microwave polymerization technique is:
Heating-up temperature divides three sections to improve gradually: 80 ℃-120 ℃-160 ℃;
Be heat time heating time: every bringing-up section 60 minutes;
Exerting pressure of every bringing-up section is respectively: 2MPa-4MPa-6MPa.
2, thermal polymerization: above-mentioned mould is put into baking oven, and concrete thermal polymerization process is:
Heating-up temperature divides three sections to improve gradually: 80 ℃-120 ℃-160 ℃;
Be heat time heating time: three sections are respectively: 3 hours, 2 hours and 3 hours;
Exerting pressure of every bringing-up section is respectively: 2MPa-4MPa-6MPa.
The preparation method's of microwave in-situ polymerized long glass fiber reinforced ABS composite material provided by the invention characteristics are:
1, adopt low viscous monomer or prepolymer that fiber is soaked into, wellability is good, and infiltration speed is fast, produces and carries out easily, has fundamentally solved long glass fibres and has strengthened in the thermoplastic composite production process resin to the problem of glass fiber impregnated difficulty.
2, because to adopt monomer be raw material, rather than polymer is raw material, and polymerization and compound working procedure are united two into one, and therefore compares with the production technology that existing long glass fibres strengthens thermoplastic composite to significantly reduce operation, saves cost.
3, the microwave polymerization speed is fast, efficient is high.
4, the glass fiber reinforced ABS composite material interface bond performance of making is good, in the resin matrix rubber phase be evenly distributed tinyly, mechanical property is that the mechanical property of in-situ polymerized long glass fiber reinforced ABS composite material is good than what use the vulcanizing press thermal polymerization equally.
Description of drawings
Fig. 1, microwave in-situ polymerized long glass fiber reinforced ABS composite material process chart of the present invention;
The ABS sample ESEM fracture photo that Fig. 2, microwave polymerization of the present invention and thermal polymerization make.
(a) is that ABS sample ESEM fracture photo, (b) that the microwave polymerization makes are the ABS sample ESEM fracture photos that thermal polymerization makes among Fig. 2.
The specific embodiment
Following examples help to understand the present invention, but are not limited to content of the present invention:
Embodiment 1:
7% the long glass fiber reinforced ABS composite material for preparing that the fourth content of glass fiber is 46%, diene rubber content is the resin total content according to above-mentioned processing step, its polymerization total time and main mechanical property relatively see Table 1 under two kinds of situations of microwave polymerization and thermal polymerization, thermal polymerization process is in the time of 80 ℃, molding time is 4 hours, interim every one hour then with 20 ℃ of temperature risings, rise to 160 ℃ up to temperature.
Table 1 rubber content is that the polymerization of composite microwave and the thermal polymerization of resin total content 7% compared
| Polymeric type | Polymerization total time (h) | Layer is cut intensity (MPa) | Notched Izod impact strength (Jm -1) |
| Original position microwave polymerization long fibre reinforced ABS | 3 | 18.8 | 676.9 |
| Original position thermal polymerization long glass fiber reinforced ABS | 8 | 15.1 | 587.5 |
By table 1 as seen, compare with thermal polymerization, microwave is aggregated in polymerization total time, layer is cut intensity and notched Izod impact strength is 38%, 125% and 115% of thermal polymerization.
Embodiment 2:
The preparation content of glass fiber is 52%, butadiene rubber content is the resin total content 5% long glass fiber reinforced ABS composite material, its polymerization total time and main mechanical property relatively see Table 2 under two kinds of situations of microwave polymerization and thermal polymerization.
Table 2 rubber content is that the polymerization of composite microwave and the thermal polymerization of resin total content 5% compared
| Polymeric type | Polymerization total time (h) | Layer is cut intensity (MPa) | Notched Izod impact strength (Jm -1) |
| Original position microwave polymerization long glass fiber reinforced ABS | 3 | 21.6 | 638.2 |
| Original position thermal polymerization long glass fiber reinforced ABS | 8 | 15.1 | 633.1 |
By table 2 as seen, compare with thermal polymerization, microwave is aggregated in polymerization total time, layer is cut intensity and notched Izod impact strength is 38%, 143% and 101% of thermal polymerization.
Embodiment 3:
The preparation content of glass fiber is 58%, butadiene rubber content is the resin total content 3% long glass fiber reinforced ABS composite material, its polymerization total time and main mechanical property relatively see Table 3 under two kinds of situations of microwave polymerization and thermal polymerization.
Table 3 rubber content is that the polymerization of composite microwave and the thermal polymerization of resin total content 5% compared
| Polymeric type | Polymerization total time (h) | Layer is cut intensity (MPa) | Notched Izod impact strength (Jm -1) |
| Original position microwave polymerization glass fiber reinforced ABS | 3 | 24.33 | 617.1 |
| Original position thermal polymerization glass fiber reinforced ABS | 8 | 19.20 | 612.6 |
By table 3 as seen, compare with thermal polymerization, microwave is aggregated in polymerization total time, layer is cut intensity and notched Izod impact strength is 38%, 127% and 101% of thermal polymerization.
Embodiment 4:
Preparation butadiene rubber content is the ABS that 10% of resin total content does not contain glass, and its polymerization total time and main mechanical property relatively see Table 4 under two kinds of situations of microwave polymerization and in-situ polymerization.
Table 4 rubber content is that the polymerization of ABS microwave and the thermal polymerization of resin total content 10% compared
| Polymeric type | Polymerization total time (h) | Hot strength (MPa) | Percentage elongation (%) |
| Microwave polymerization ABS | 3 | 28.66 | 19.49 |
| Thermal polymerization ABS | 8 | 18.10 | 13.65 |
By table 4 as seen, compare with thermal polymerization, the microwave polymerization also improves a lot to the performance of resin matrix.
Embodiment 5:
Adopt ESEM (SEM) that the ABS sample that microwave polymerization and thermal polymerization make is observed heterogeneous microstructure.Figure two (a) and (b) are respectively the high power SEM fracture photos of microwave polymerization ABS and thermal polymerization ABS.White particle in the photo is a rubber phase.Can obviously find out by photo, microwave polymerization ABS (rubber phase of photo in a) is very tiny evenly, and the thick and skewness of rubber phase among the thermal polymerization ABS (photo b).Compare with thermal polymerization, it should be the major reason that microwave in-situ polymerized ABS composite has better performance that the microwave polymerization makes the rubber phase among the ABS distribute more evenly tinyly.
Claims (8)
1, a kind of method of microwave in-situ polymerized long glass fiber reinforced ABS composite material, it is characterized in that butadiene rubber with the styrene monomer dissolve uncrosslinked, put into acrylonitrile and initator dibenzoyl peroxide again, make low-viscosity polymer monomer solution through slowly stirring, and then spread layer with low-viscosity polymer monomer solution with after the glass fabric that silane coupler is handled fully floods and put into mould, glass epoxy closes, with microwave applicator or baking oven heating pressurization, make the ABS composite that long glass fibres strengthens.
2, the method of a kind of microwave in-situ polymerized long glass fiber reinforced ABS composite material as claimed in claim 1, it is characterized in that described low-viscosity polymer monomer solution is that rubber is dissolved in styrene, put into acrylonitrile and initator dibenzoyl peroxide again, stir evenly until solution and clarify, the weight ratio of styrene and acrylonitrile is (8: 2)～(6: 4), butadiene rubber accounts for 0～10% of melt weight, the weight of dibenzoyl peroxide is 1.0～1.5% of solution weight, and described solution weight is the gross weight of styrene, rubber, acrylonitrile and initator.
3, the method for a kind of microwave in-situ polymerized long glass fiber reinforced ABS composite material as claimed in claim 1 is characterized in that the glass fabric that described silane coupler is handled is glass fabric to be placed soak into 10～15 minutes in the size, drying; Described size is the aqueous acetic acid of pH4-5 that contains the gamma-aminopropyl-triethoxy-silane coupling agent of Total Water 1～2%.
4, the method for a kind of microwave in-situ polymerized long glass fiber reinforced ABS composite material as claimed in claim 3 is characterized in that the described weight that contains the aqueous solution of size is greater than 20 times to 60 times of glass fabric weight.
5, the method of a kind of microwave in-situ polymerized long glass fiber reinforced ABS composite material as claimed in claim 1, it is characterized in that described mould is the silica gel mould that sticks on the processing release paper, pour into a mould one deck low-viscosity polymer monomer solution in it equably, in again glass fabric being laid on, processing release paper is covered on the glass fabric, and mould is positioned over up and down in the glass epoxy; Be covered with one deck processing release paper on the described lower-glass steel plate
6, the method of a kind of microwave in-situ polymerized long glass fiber reinforced ABS composite material as claimed in claim 1, it is characterized in that described heating using microwave pressure be with mould as claimed in claim 5 put into microwave applicator divide three sections gradually heating and pressure carry out polymerization: 80 ℃/2MPa, 120 ℃/4MPa and 160 ℃/6MPa; Every bringing-up section time is 60 minutes.
7, the method of a kind of microwave in-situ polymerized long glass fiber reinforced ABS composite material as claimed in claim 1 is characterized in that heating of described baking oven and pressure are the described mould of claim 5 to be put into baking oven heat thermal polymerization with pressure: divide three sections and improve 80 ℃/2MPa, 120 ℃/4MPa and 160 ℃/6MPa gradually; Every heated pressure period respectively is: 3 hours, 2 hours and 3 hours.
8, the method for a kind of microwave in-situ polymerized long glass fiber reinforced ABS composite material as claimed in claim 2 is characterized in that described styrene monomer and acrylonitrile monemer distill earlier to remove impurity and the polymerization inhibitor in the monomer.
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|---|---|---|---|
| CN 200510110969 CN1775513A (en) | 2005-11-30 | 2005-11-30 | Method for preparing microwave in-situ polymerized long glass fiber reinforced ABS composite material |
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| CN 200510110969 CN1775513A (en) | 2005-11-30 | 2005-11-30 | Method for preparing microwave in-situ polymerized long glass fiber reinforced ABS composite material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101939158A (en) * | 2008-01-11 | 2011-01-05 | 空中客车营运有限公司 | Process for producing (part-)annular, fiber reinforced, polymer containing moldings from semifinished fiber composite material products |
| CN102574336A (en) * | 2009-05-04 | 2012-07-11 | 费萨尔.H.-J.纳普 | Fiber composite and method for the production thereof |
| CN103061127A (en) * | 2012-12-11 | 2013-04-24 | 广东工业大学 | Preparation method of microwave in-situ polymerization modified short fibers |
| CN103702822A (en) * | 2011-05-20 | 2014-04-02 | 赫克赛尔控股有限责任公司 | Fibre reinforced composite moulding |
| US11180622B2 (en) | 2018-11-07 | 2021-11-23 | Changzhou Bamstone Composites Co., Ltd. | Thermoplastic polymer-based composite material and preparation method thereof |
| US11505664B2 (en) | 2018-11-07 | 2022-11-22 | Changzhou Bamstone Composites Co., Ltd. | Thermoplastic polymer-based composite material and preparation method thereof |
-
2005
- 2005-11-30 CN CN 200510110969 patent/CN1775513A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101939158A (en) * | 2008-01-11 | 2011-01-05 | 空中客车营运有限公司 | Process for producing (part-)annular, fiber reinforced, polymer containing moldings from semifinished fiber composite material products |
| US8597560B2 (en) | 2008-01-11 | 2013-12-03 | Airbus Operations Gmbh | Method for manufacturing (partly) ring-shaped components, which comprise fibre-reinforced plastic, from fibre-composite semifinished products |
| CN101939158B (en) * | 2008-01-11 | 2014-09-10 | 空中客车营运有限公司 | Process for producing (part-)annular, fiber reinforced, polymer containing moldings from semifinished fiber composite material products |
| CN102574336A (en) * | 2009-05-04 | 2012-07-11 | 费萨尔.H.-J.纳普 | Fiber composite and method for the production thereof |
| CN102574336B (en) * | 2009-05-04 | 2015-05-20 | 费萨尔.H.-J.纳普 | Fiber composite and method for the production thereof |
| CN103702822A (en) * | 2011-05-20 | 2014-04-02 | 赫克赛尔控股有限责任公司 | Fibre reinforced composite moulding |
| CN103061127A (en) * | 2012-12-11 | 2013-04-24 | 广东工业大学 | Preparation method of microwave in-situ polymerization modified short fibers |
| US11180622B2 (en) | 2018-11-07 | 2021-11-23 | Changzhou Bamstone Composites Co., Ltd. | Thermoplastic polymer-based composite material and preparation method thereof |
| US11505664B2 (en) | 2018-11-07 | 2022-11-22 | Changzhou Bamstone Composites Co., Ltd. | Thermoplastic polymer-based composite material and preparation method thereof |
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