CN103881297A - Thermosetting resin-based composite material and preparation method thereof - Google Patents
Thermosetting resin-based composite material and preparation method thereof Download PDFInfo
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- CN103881297A CN103881297A CN201210558249.5A CN201210558249A CN103881297A CN 103881297 A CN103881297 A CN 103881297A CN 201210558249 A CN201210558249 A CN 201210558249A CN 103881297 A CN103881297 A CN 103881297A
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- thermosetting resin
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Abstract
The invention discloses a thermosetting resin-based composite material and a preparation method thereof. The thermosetting resin-based composite material includes a continuous fiber (a), an inorganic nanosheet (b) and a thermosetting resin (c). The thermosetting resin can be one or more of epoxy resin, unsaturated polyester, and polyurethane or polyimide. The continuous fiber can be one or more of a glass fiber, a basalt fiber, and a Kevlar fiber or an ultrahigh molecular weight polyethylene fiber. The inorganic nanosheet can be a graphite nanosheet and/or nano-montmorillonite. The preparation method of the thermosetting resin-based composite material comprises the following steps: mixing the inorganic nanosheet with a thermosetting resin liquid prepolymer composition to prepare a composite dipping liquid, dipping the continuous fiber in the composite dipping liquid to make the continuous fiber attached with the composite dipping liquid, and adopting a pultrusion technology, a winding technology or a molding technology to prepare the composite material. The composite material has excellent mechanical properties and is balanced in a three dimensional direction.
Description
One, technical field
The present invention relates to matrix material and preparation method thereof, particularly thermosetting resin base fibre composite and preparation method thereof, belongs to polymer matrix composite field.
Two, background technology
Continuous fibre/thermosetting resin polymer composites is the most promising current novel texture functional materials.Continuous fibre only presents obvious reinforcing effect in fiber direction to matrix material conventionally, therefore the anisotropy of continuous fibre/polymer composites is very outstanding, its excellent mechanical property all concentrates on fiber direction, and horizontal without fiber booster action at matrix material, horizontal mechanical strength is poor, therefore transverse mechanical intensity, the mechanical moduli etc. of matrix material are all lower, large with longitudinal direction difference.For the Application Areas of the shape goods such as flat board, tubing or section bar and many complicated applied forces, this is obvious deficiency and the shortcoming of continuous fibre/polymer composites, particularly pultrusion composite materials.
Three, summary of the invention
The object of the invention is to provide a kind of mechanical property respectively to comparatively balanced thermosetting resin base fibre composite and preparation method thereof.
The technical solution that realizes the object of the invention is: a kind of thermosetting resin base fibre composite, comprises (a) continuous fibre, (b) nano inorganic thin slice and (c) thermosetting resin.
The thermosetting resin that thermosetting resin base fibre composite of the present invention adopts can be one or more in epoxy resin, unsaturated polyester, urethane or polyimide.
The continuous fibre that thermosetting resin base fibre composite of the present invention adopts can be one or more in glass fibre, basalt fibre, Kevlar fiber or superhigh molecular weight polyethylene fibers.
The nano inorganic thin slice that thermosetting resin base fibre composite of the present invention adopts can be nano graphite sheet and/or nano imvite.
Continuous fibre 10～65 mass parts in thermosetting resin base fibre composite of the present invention, nano inorganic thin slice 5～20 mass parts, thermosetting resin 30～85 mass parts.
The preparation method of thermosetting resin base fibre composite of the present invention, comprises the following steps successively:
(1) liquid to nano inorganic thin slice and thermosetting resin pre-polymerization composition is mixed and is made into the compound dipping solution of nano inorganic thin slice-thermosetting resin;
(2) continuous fibre is immersed to the compound dipping solution of nano inorganic thin slice-thermosetting resin, make continuous fibre enclose the compound dipping solution of nano inorganic thin slice-thermosetting resin;
(3) the continuous fibre set of enclosing the compound dipping solution of nano inorganic thin slice-thermosetting resin is formed to specific shape goods;
(4) the specified shape goods of formation are solidified and obtain matrix material.
In the preparation method of thermosetting resin base fibre composite of the present invention, described in (1) step, in compound dipping solution, thermosetting resin can be 95～70 mass parts, and nano inorganic thin slice can be 5～30 mass parts.
In the preparation method of thermosetting resin base fibre composite of the present invention, before (1) step, can increase nano inorganic thin slice and carry out surface modification treatment step.
The preferably continuous fibre after surface modification of (2) continuous fibre that step adopts in the preparation method of thermosetting resin base fibre composite of the present invention.
Method in the preparation method of thermosetting resin base fibre composite of the present invention described in (3) step can be pultrude process, winding process or mould pressing process.
Continuous fibre described in the preparation method of thermosetting resin base fibre composite of the present invention can be one or more in glass fibre, basalt fibre, Kevlar fiber or superhigh molecular weight polyethylene fibers.
Nano inorganic thin slice described in the preparation method of thermosetting resin base fibre composite of the present invention can be nano graphite sheet and/or nano imvite.
Thermosetting resin described in the preparation method of thermosetting resin base fibre composite of the present invention can be one or more in epoxy resin, unsaturated polyester, urethane or polyimide.
Compared with prior art, the present invention has significant advantage.Continuous fibre is the one dimension reinforcement of high-strength and high-modulus, nano inorganic microplate is the two-dimentional reinforcement of high-strength and high-modulus, continuous fibre only has excellent reinforced effects in fiber direction, and in the resin matrix of nano inorganic microplate disperse between continuous fibre, direction in vertical fibers direction presents enhancement, therefore composite materials property of the present invention is all more excellent and more balanced on three-dimensional, the excellent properties of continuous fiber composite material can be brought into play better than current continuous fibre/same with thermosetting compound material, better application can be obtained in more areas.
Four, embodiment
Thermosetting resin base fibre composite of the present invention, comprises (a) continuous fibre, (b) nano inorganic thin slice and (c) thermosetting resin.
The thermosetting resin that thermosetting resin base fibre composite of the present invention adopts can be one or more in epoxy resin, unsaturated polyester, urethane or polyimide.
The continuous fibre that thermosetting resin base fibre composite of the present invention adopts can be one or more in glass fibre, basalt fibre, Kevlar fiber or superhigh molecular weight polyethylene fibers.
The nano inorganic thin slice that thermosetting resin base fibre composite of the present invention adopts can be nano graphite sheet and/or nano imvite.
Continuous fibre 10～65 mass parts in thermosetting resin base fibre composite of the present invention, nano inorganic thin slice 5～20 mass parts, thermosetting resin 30～85 mass parts.
The preparation method of thermosetting resin base fibre composite of the present invention, comprises the following steps successively:
(1) liquid to nano inorganic thin slice and thermosetting resin pre-polymerization composition is mixed and is made into the compound dipping solution of nano inorganic thin slice-thermosetting resin;
(2) continuous fibre is immersed to the compound dipping solution of nano inorganic thin slice-thermosetting resin, make continuous fibre enclose the compound dipping solution of nano inorganic thin slice-thermosetting resin;
(3) the continuous fibre set of enclosing the compound dipping solution of nano inorganic thin slice-thermosetting resin is formed to specific shape goods;
(4) the specified shape goods of formation are solidified and obtain matrix material.
The liquid pre-polymerization composition of thermosetting resin described in the preparation method of thermosetting resin base fibre composite of the present invention, refer to the fluid composition that thermosetting resin prepolymer and solidifying agent (or linking agent), reaction promoter (as promotor, initiator, catalyzer, promotor etc.) and other additives (as filler, pigment, fire retardant etc.) mix, its under proper condition (as being heated or other) be solidified into solid polymer (as epoxy resin, unsaturated polyester, urethane or polyimide).Such as, the liquid form mixt of epoxy prepolymer and solidifying agent (as fatty amine curing agent, aromatic amine curing agent, acid anhydride type curing agent etc.), promotor (as DMP-30); The liquid form mixt of unsaturated polyester prepolymer and linking agent (as vinylbenzene), initiator (as dibenzoyl peroxide etc.), promotor (as cobalt naphthenate) etc.; The liquid form mixt of isocyanate-monomer and polyvalent alcohol monomer (as polyester polyol or polyether glycol), catalyzer (as tertiary amines, organic tin etc.) etc.; Deng.
In the preparation method of thermosetting resin base fibre composite of the present invention, described in (1) step, in compound dipping solution, thermosetting resin can be 95～70 mass parts, and nano inorganic thin slice can be 5～30 mass parts.
In the preparation method of thermosetting resin base fibre composite of the present invention, before (1) step, can increase nano inorganic thin slice and carry out surface modification treatment step, can improve like this nano inorganic thin slice and be combined with the interface of thermosetting resin, make the performance of thermosetting resin base fibre composite better.
The preferably continuous fibre after surface modification of (2) continuous fibre that step adopts in the preparation method of thermosetting resin base fibre composite of the present invention, can improve like this continuous fibre and be combined with the interface of thermosetting resin, make the performance of thermosetting resin base fibre composite of the present invention better.
Method in the preparation method of thermosetting resin base fibre composite of the present invention described in (3) step can be pultrude process, winding process or mould pressing process.
Continuous fibre described in the preparation method of thermosetting resin base fibre composite of the present invention can be one or more in glass fibre, basalt fibre, Kevlar fiber or superhigh molecular weight polyethylene fibers.
Nano inorganic thin slice described in the preparation method of thermosetting resin base fibre composite of the present invention can be nano graphite sheet and/or nano imvite.
Thermosetting resin described in the preparation method of thermosetting resin base fibre composite of the present invention can be one or more in epoxy resin, unsaturated polyester, urethane or polyimide.
Embodiment 1 adopts epoxy resin E-51, solidifying agent MeHHPA to be mixed in proportion and adds appropriate altax P-30 to be made into the liquid pre-polymerization composition of epoxy resin.Then expanded graphite is sneaked into the liquid pre-polymerization composition mixing of epoxy resin and be made into the compound dipping solution of nano graphite sheet-epoxy resin, expanded graphite massfraction is 20%.Continuous glass fibre is immersed to the compound dipping solution of nano graphite sheet-epoxy resin, make continuous glass fibre enclose the compound dipping solution of nano graphite sheet-epoxy resin, adopt pultrude process set to form block aggregate the continuous glass fibre of enclosing the compound dipping solution of nano graphite sheet-epoxy resin, finally be heated to 100 DEG C from room temperature temperature programming gradually, make the block aggregate forming fully solidify and obtain matrix material (continuous glass fibre massfraction 35%).The tensile strength 750MPa of block matrix material, tensile modulus 38GPa.
Embodiment 2 adopts P61972 unsaturated polyester, dibenzoyl peroxide and promotor cobalt naphthenate to be mixed in proportion and is made into the liquid pre-polymerization composition of unsaturated polyester.Expanded graphite is peeled off and become nano graphite sheet by ultrasonic wave, nano graphite sheet is sneaked into the liquid pre-polymerization composition mixing of unsaturated polyester and be made into the compound dipping solution of nano graphite sheet-unsaturated polyester, expanded graphite massfraction is 30%.Surface treatment continuous basalt fiber is immersed to the compound dipping solution of nano graphite sheet-unsaturated polyester, make continuous basalt fiber enclose the compound dipping solution of nano graphite sheet-unsaturated polyester, adopt pultrude process set to form block aggregate the continuous basalt fiber of enclosing the compound dipping solution of nano graphite sheet-unsaturated polyester, finally be heated to 60 DEG C from room temperature temperature programming gradually, make the block aggregate forming fully solidify and obtain matrix material (continuous basalt fiber massfraction 45%).The tensile strength 820MPa of block matrix material, tensile modulus 35GPa.
Embodiment 3 adopts poly methylene poly phenyl poly isocyanate and polyether glycol 4110 to be mixed in proportion and adds the sub-tin of octoate catalyst to be made into the liquid pre-polymerization composition of urethane.Nano organic montmorillonite is sneaked into the liquid pre-polymerization composition mixing of urethane and be made into the compound dipping solution of nano organic montmorillonite-urethane, nano organic montmorillonite massfraction is 12%.Continuous surface treatment superhigh molecular weight polyethylene fibers is immersed to the compound dipping solution of nano organic montmorillonite-urethane, make continuous superhigh molecular weight polyethylene fibers enclose the compound dipping solution of nano organic montmorillonite-urethane, adopt winding process set to form block aggregate the continuous superhigh molecular weight polyethylene fibers of enclosing the compound dipping solution of nano organic montmorillonite-urethane, finally be heated to 60 DEG C from room temperature temperature programming gradually, make the fully curing matrix material (superhigh molecular weight polyethylene fibers massfraction 55% continuously) that obtains of block aggregate forming.The tensile strength 1.45GPa of block matrix material, tensile modulus 41GPa.
The dimethyl sulphoxide solution mixing that nano organic montmorillonite is sneaked into polyamic acid by embodiment 4 is made into the compound dipping solution of nano organic montmorillonite-polyamic acid, and nano organic montmorillonite massfraction is 15%.Continuous surface treatment Kevlar fiber is immersed to the compound dipping solution of nano organic montmorillonite-polyamic acid, make continuous Kevlar fiber enclose the compound dipping solution of nano organic montmorillonite-polyamic acid, adopt mould pressing process set to form block aggregate the continuous Kevlar fiber of enclosing the compound dipping solution of nano organic montmorillonite-polyamic acid, heat drying is removed dimethyl sulfoxide solvent, finally heat up and be heated to 350 DEG C of cyclodehydrations, make the fully curing polyimide-based composite material (Kevlar fiber quality mark 65% continuously) that obtains of block aggregate forming.The tensile strength 1.35GPa of block matrix material, tensile modulus 29GPa.
Claims (10)
1. a thermosetting resin base fibre composite, is characterized in that: comprise (a) continuous fibre, (b) nano inorganic thin slice and (c) thermosetting resin.
2. thermosetting resin base fibre composite according to claim 1, is characterized in that: thermosetting resin is one or more in epoxy resin, unsaturated polyester, urethane or polyimide.
3. according to thermosetting resin base fibre composite described in claim 1 or 2, it is characterized in that: continuous fibre is one or more in glass fibre, basalt fibre, Kevlar fiber or superhigh molecular weight polyethylene fibers.
4. according to thermosetting resin base fibre composite described in claim 1～3 any one, it is characterized in that: nano inorganic thin slice is nano graphite sheet and/or nano imvite.
5. according to thermosetting resin base fibre composite described in claim 1～4 any one, it is characterized in that: continuous fibre 10～65 mass parts, nano inorganic thin slice 5～20 mass parts, thermosetting resin 30～85 mass parts.
6. according to a preparation method for thermosetting resin base fibre composite described in claim 1～5 any one, it is characterized in that: comprise the following steps successively:
(1) liquid to nano inorganic thin slice and thermosetting resin pre-polymerization composition is mixed and is made into the compound dipping solution of nano inorganic thin slice-thermosetting resin;
(2) continuous fibre is immersed to the compound dipping solution of nano inorganic thin slice-thermosetting resin, make continuous fibre enclose the compound dipping solution of nano inorganic thin slice-thermosetting resin;
(3) the continuous fibre set of enclosing the compound dipping solution of nano inorganic thin slice-thermosetting resin is formed to specified shape aggregate;
(4) the specified shape aggregate of formation is solidified and obtains matrix material.
7. the preparation method of thermosetting resin base fibre composite according to claim 6, is characterized in that: thermosetting resin 95～70 mass parts in compound dipping solution described in (1) step, nano inorganic thin slice 5～30 mass parts.
8. according to the preparation method of thermosetting resin base fibre composite described in claim 6 or 7, it is characterized in that: before (1) step, increase nano inorganic thin slice and carry out surface modification treatment step.
9. according to the preparation method of thermosetting resin base fibre composite described in claim 6～8 any one, it is characterized in that: (2) continuous fibre that step adopts is the continuous fibre after surface modification.
10. according to the preparation method of thermosetting resin base fibre composite described in claim 6～9 any one, it is characterized in that: the method that described in (3) step, the continuous fibre set of enclosing the compound dipping solution of nano inorganic thin slice-thermosetting resin is formed to specified shape aggregate is pultrude process, winding process or mould pressing process.
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| CN201210558249.5A CN103881297A (en) | 2012-12-20 | 2012-12-20 | Thermosetting resin-based composite material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104990813A (en) * | 2015-08-14 | 2015-10-21 | 核工业理化工程研究院 | Gum dipping fiber mechanical property testing method |
| CN105625041A (en) * | 2015-12-25 | 2016-06-01 | 广东生益科技股份有限公司 | Shape-finalized polyimide fabric and manufacturing method thereof |
| CN106221128A (en) * | 2016-07-31 | 2016-12-14 | 长春长光宇航复合材料有限公司 | A kind of low-friction coefficient carbon fibre composite and preparation method thereof |
| CN113652068A (en) * | 2021-08-19 | 2021-11-16 | 国能铁路装备有限责任公司 | Nano composite plastic, preparation method thereof and three-dimensional mark |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102618014A (en) * | 2012-04-06 | 2012-08-01 | 沈阳航空航天大学 | Preparation method of phenolphthalein side group-containing polyarylether ketone (polyarylether sulphone) resin hybrid multi-scale composite material |
| CN102634208A (en) * | 2012-04-27 | 2012-08-15 | 沈阳航空航天大学 | Nanocomposite modification method applied to bismaleimide resin based composite |
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2012
- 2012-12-20 CN CN201210558249.5A patent/CN103881297A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618014A (en) * | 2012-04-06 | 2012-08-01 | 沈阳航空航天大学 | Preparation method of phenolphthalein side group-containing polyarylether ketone (polyarylether sulphone) resin hybrid multi-scale composite material |
| CN102634208A (en) * | 2012-04-27 | 2012-08-15 | 沈阳航空航天大学 | Nanocomposite modification method applied to bismaleimide resin based composite |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104990813A (en) * | 2015-08-14 | 2015-10-21 | 核工业理化工程研究院 | Gum dipping fiber mechanical property testing method |
| CN105625041A (en) * | 2015-12-25 | 2016-06-01 | 广东生益科技股份有限公司 | Shape-finalized polyimide fabric and manufacturing method thereof |
| CN105625041B (en) * | 2015-12-25 | 2018-10-09 | 广东生益科技股份有限公司 | A kind of polyimides setting cloth and preparation method thereof |
| CN106221128A (en) * | 2016-07-31 | 2016-12-14 | 长春长光宇航复合材料有限公司 | A kind of low-friction coefficient carbon fibre composite and preparation method thereof |
| CN113652068A (en) * | 2021-08-19 | 2021-11-16 | 国能铁路装备有限责任公司 | Nano composite plastic, preparation method thereof and three-dimensional mark |
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Application publication date: 20140625 |