CN102585088A - Fiber reinforced foam plastic and preparation method thereof - Google Patents
Fiber reinforced foam plastic and preparation method thereof Download PDFInfo
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- CN102585088A CN102585088A CN2012100105748A CN201210010574A CN102585088A CN 102585088 A CN102585088 A CN 102585088A CN 2012100105748 A CN2012100105748 A CN 2012100105748A CN 201210010574 A CN201210010574 A CN 201210010574A CN 102585088 A CN102585088 A CN 102585088A
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Abstract
The invention discloses a fiber reinforced foam plastic and a preparation method thereof. The foam plastic comprises the following components in parts by weight: 30-60 parts of methacrylic acid, 30-70 parts of (meth)acrylonitrile, 0.1-30 parts of fiber, 0.01-2 parts of initiator, 0.1-10 parts of foaming agent and 0-5 parts of thickening agent. The preparation method comprises the following steps: mixing short fiber into a raw material liquid, or putting long-fiber fabric in a die, and then pouring the raw material liquid for polymerization reaction; and foaming and stretching the obtained plastic plate at a certain temperature to obtain the fiber reinforced foam plastic. The fiber reinforced foam plastic prepared by using the method is expanded uniformly, and the distortion and the internal stress of the foam plastic are obviously reduced, thus the fiber reinforced foam plastic is suitable for being used; and the tensile strength of the fiber reinforced foam plastic is obviously improved, and the density of the foam plastic is not obviously increased.
Description
Technical field
The present invention relates to a kind of fibre foam and preparation method thereof, a kind of specifically fibre-reinforced gathering (methyl) acrylimide porous plastics and preparation method thereof.
Technical background
Sandwich sandwich structure is to adopt polymer matrix composites as covering, employing porous plastics or the honeycomb sandwich structure form as sandwich; This structure has advantages such as lightweight, high specific stiffness and high specific strength; Sandwich structure is widely used on the military and civilian product at present, and main application direction is: blade of wind-driven generator, aircraft, vertiplane wing, large ship, radome etc.Matrix material sandwich sandwich structure can the high performance structures porous plastics kind of employing, comprise SE, polyacrylonitrile/vinylbenzene, gather (methyl) acrylimide (PMI) etc.
Gather (methyl) acrylimide porous plastics (PMI) and in all structural foams, possess the highest intensity and modulus, have splendid thermostability.The USP (patent No. 3627711 and 3708444) of 1969 and 1973 is early about the patent of this material.The composition principle and the synthesis step of this material are seen " polyimide; 20.2 side chain acid imide foam material-gather methyl-prop imide (PMI) " (Ding Mengxian; Science Press, 2006), the perhaps Chinese patent (application number 200610091394.1) of Northwestern Polytechnical University's application.Chinese patent (application number 200610091394.1) discloses main use vinyl cyanide and two kinds of monomers of methylacrylic acid, prepares the method for side chain imide structure polyimide foam.
Polyacrylonitrile (methacrylonitrile)/methylacrylic acid porous plastics gathers (methyl) acrylimide porous plastics (PMI) exactly; Its production stage is; At first prepare reactive liquid mixture, generally include: monomer methylacrylic acid (MAA) and methacrylonitrile (MAN), whipping agent, initiator etc.Second step was that reactive fluid is injected in the mould that is formed by two parallel plates and joint strip, aggregated into transparent copolymerization sheet material.The 3rd step was foaming and aftertreatment: adopt the warm air method that sheet material is heated, be warmed up to more than the second-order transition temperature of these plastics, this moment, the huge bulging force of whipping agent made that plastics expand at elastomeric state, foaming.
Though it is more excellent than other kinds type of foam intensity and thermostability to gather (methyl) acrylimide porous plastics, its mechanical property and fiber and plastics also have very big gap.For example, the tensile strength of PMI porous plastics (60KG/m3) is the 0.8-1.6 MPa usually, and the tensile strength of fiber is generally the 7-8 MPa.
The preparation of fibre foam is fiber to be joined in the polymeric system or reaction system of not foaming homodisperse, foaming then.After the foaming, fiber is uniformly distributed on the bubble wall of foam, and foam materials is played enhancing, increased just and improved stable on heating effect.
For the high temperature foaming, the porous plastics molecular weight is very big, heats up, and can only make it to be in elastomeric state, can not get into LV, molten state.Be mixed with the porous plastics of fiber, in the expanded foamed process of high temperature, the resistance of motion between fiber and the foam base plate is very big, and bigger relative movement will take place for fiber and porous plastics matrix in this process.Fiber expands to the porous plastics matrix and produces huge restriction, constraint effect; Make fiber on every side with huge away from fiber place foamy rate of expansion difference; Therefore foam plastics slab tends to produce huge torsional deformation and internal stress, and the product that obtains does not reach the use standard.
Summary of the invention
Technical problem to be solved by this invention provides a kind of tensile strength height and can effectively reduce the fibre foam of sheet deformation and internal stress.
Another object of the present invention provides the preparation method of above-mentioned fibre foam.
The technical scheme that the present invention takes:
A kind of fibre foam, process by the component of following weight part:
30-60 part methylacrylic acid
(methyl) vinyl cyanide of 30-70 part;
0.1-30 part fiber
0.01-2 part initiator
0.1-10 part whipping agent
0-5 part thickening material.
The blowing temperature of said porous plastics is 150-220 ℃, and said fiber is elastomeric state under above-mentioned blowing temperature.
Said fiber is nylon fiber, polyster fibre, acrylic fiber, vinylon fibre or spandex fibre.
Said fiber is a length less than 10 centimetres staple fibre or length is flat fabric or the stereo fabric that the macrofiber more than 10 centimetres is processed.
Said initiator is Diisopropyl azodicarboxylate or two formyls of peroxo-, and said whipping agent is the trimethyl carbinol, Pentyl alcohol, and said thickening material is a polymethylmethacrylate.
A kind of method for preparing said fibre foam, concrete steps are: take by weighing each component in proportion, earlier with methylacrylic acid, (methyl) vinyl cyanide, initiator, whipping agent and thickening material mix liquid stock; Add again said staple fibre stir mixed solution, above-mentioned mixed solution is injected glass article, perhaps liquid stock is injected and places the flat fabric that said macrofiber is made into or the glass article of stereo fabric; Got plastic plate in 40-60 hour in 40-70 ℃ of reaction; Above-mentioned plastic plate is put into baking oven, be warming up to 140-170 degree centigrade again, after this; Every rising kept 10 minutes for 10 degrees centigrade, up to said blowing temperature; Said blowing temperature insulation 1.5-3 hour, obtain fibre foam at last.
Beneficial effect of the present invention is following:
The present invention adds the fiber of a small amount of unstretched orientation in polymethacrylimide plastic foam or polyacrylamide imines porous plastics; Adopt the warm air method to heat; Be warmed up to more than the second-order transition temperature of this porous plastics and fiber, the huge bulging force of whipping agent makes that porous plastics expands at elastomeric state, foaming; Because there is the coincidence scope in the second-order transition temperature of fiber with the blowing temperature of this porous plastics, and stronger interfacial adhesion power and consistency are arranged between the two, so fiber is along with foam base plate stretches together; Whole foam almost evenly expands, and has obviously reduced the torsional deformation and the internal stress of porous plastics, is more suitable for using.Usually the tensile strength of polyacrylamide imines porous plastics (60Kg/m3) is the 0.8-1.6 MPa, and after adding the small amount of fibers enhancing, tensile strength has obtained remarkable lifting, is the 1.8-2.1 MPa, and the density of porous plastics does not obviously increase.In addition, the porous plastics matrix is strengthened fiber to the stretching of fiber, has increased mechanical property.
Embodiment
Embodiment 1:
(1) according to following formulated liquid stock: 48ml vinyl cyanide, 30ml methylacrylic acid, 0.36g Diisopropyl azodicarboxylate, the 5ml trimethyl carbinol, 5g polymethylmethacrylate; Normal temperature stirs down, dissolved 5 hours;
(2) take by weighing 5g nylon 6 staple fibres and put into confected materials liquid, stir;
(3) be injected into mixed solution in the glass article of clamping, put in 60 ℃ the water-bath and react 50h;
(4) the plastic plate that obtains, put into baking oven, be warming up to 150 degrees centigrade; After this, every rising kept 10 minutes for 10 degrees centigrade, up to 200 degrees centigrade; At 200 degrees centigrade, be incubated 1.5 hours at last, obtain TRPP nitrile (methacrylonitrile)/methylacrylic acid porous plastics.Measure the various parameters of gained porous plastics.
Embodiment 2:
(1) according to following formulated liquid stock: 50ml vinyl cyanide, 50ml methylacrylic acid, 2g Diisopropyl azodicarboxylate, the 10ml trimethyl carbinol, 5g polymethylmethacrylate; Normal temperature stirs down, dissolved 5 hours;
(2) take by weighing 0.1g nylon 6 staple fibres and put into confected materials liquid, stir;
(3) be injected into mixed solution in the glass article of clamping, put in 60 ℃ the water-bath and react 50h;
(4) the plastic plate that obtains, put into baking oven, be warming up to 150 degrees centigrade; After this, every rising kept 10 minutes for 10 degrees centigrade, up to 200 degrees centigrade; At 200 degrees centigrade, be incubated 1.5 hours at last, obtain TRPP nitrile (methacrylonitrile)/methylacrylic acid porous plastics.Measure the various parameters of gained porous plastics.
Embodiment 3:
(1) according to following formulated liquid stock: 60ml vinyl cyanide, 55ml methylacrylic acid, two formyls of 1.5g peroxo-, 0.1ml Pentyl alcohol, 5g polymethylmethacrylate; Normal temperature stirs down, dissolved 5 hours;
(2) take by weighing 5g polyvinyl staple fibre and put into confected materials liquid, stir;
(3) be injected into mixed solution in the glass article of clamping, put in 60 ℃ the water-bath and react 50h;
(4) the plastic plate that obtains, put into baking oven, be warming up to 150 degrees centigrade; After this, every rising kept 10 minutes for 10 degrees centigrade, up to 200 degrees centigrade; At 200 degrees centigrade, be incubated 1.5 hours at last, obtain TRPP nitrile (methacrylonitrile)/methylacrylic acid porous plastics.Measure the various parameters of gained porous plastics.
Embodiment 4:
(1) according to following formulated liquid stock: 70ml vinyl cyanide, 45ml methylacrylic acid, 1.8g Diisopropyl azodicarboxylate, 8ml Pentyl alcohol;
(2) the 10g terylene flat fabric of delivery tool size is fixed in the mould;
(3) be injected into liquid stock in the glass article of clamping, put in 40 ℃ the water-bath and react 40h;
(4) the plastic plate that obtains, put into baking oven, be warming up to 140 degrees centigrade; After this, every rising kept 10 minutes for 10 degrees centigrade, up to 220 degrees centigrade; At 220 degrees centigrade, be incubated 2 hours at last, obtain TRPP nitrile (methacrylonitrile)/methylacrylic acid porous plastics.Measure the various parameters of gained porous plastics.
Embodiment 5:
(1) according to following formulated liquid stock: 30ml methacrylonitrile, 60ml methylacrylic acid, two formyls of 0.01g peroxo-, the 0.1ml trimethyl carbinol;
(2) the 30g acrylic fibers three dimensional fabric of delivery tool size is placed in mould;
(3) be injected into liquid stock in the glass article of clamping, put in 70 ℃ the water-bath and react 60h;
(4) the plastic plate that obtains, put into baking oven, be warming up to 170 degrees centigrade; After this, every rising kept 10 minutes for 10 degrees centigrade, up to 200 degrees centigrade; At 200 degrees centigrade, be incubated 3 hours at last, obtain TRPP nitrile (methacrylonitrile)/methylacrylic acid porous plastics.Measure the various parameters of gained porous plastics.
Comparative Examples:
(1) according to following formulated liquid stock: 40ml methacrylonitrile, 35ml methylacrylic acid, 0.8g Diisopropyl azodicarboxylate, the 3ml trimethyl carbinol;
(2) be injected into liquid stock in the glass article of clamping, put in 80 ℃ the water-bath and react 35h;
(3) the plastic plate that obtains, put into baking oven, be warming up to 170 degrees centigrade; After this, every rising kept 10 minutes for 10 degrees centigrade, up to 200 degrees centigrade; At 200 degrees centigrade, be incubated 2 hours at last, obtain TRPP nitrile (methacrylonitrile)/methylacrylic acid porous plastics.Measure the various parameters of gained porous plastics.
Each embodiment gained porous plastics is measured various parameters, and the result is as shown in table 1.
Table 1
Annotate: 1, the tensile strength test is according to GB/T1452-2005;
2, density measurement is according to ISO845-2006.
Claims (6)
1. fibre foam is characterized in that its component by following weight part processes:
30-60 part methylacrylic acid
(methyl) vinyl cyanide of 30-70 part
0.1-30 part fiber
0.01-2 part initiator
0.1-10 part whipping agent
0-5 part thickening material.
2. fibre foam according to claim 1, the blowing temperature that it is characterized in that said porous plastics is 150-220 ℃, said fiber is elastomeric state under above-mentioned blowing temperature.
3. fibre foam according to claim 2 is characterized in that said fiber is nylon fiber, polyster fibre, acrylic fiber, vinylon fibre or spandex fibre.
4. fibre foam according to claim 3 is characterized in that said fiber be length less than 10 centimetres staple fibre or length is flat fabric or the stereo fabric that the macrofiber more than 10 centimetres is processed.
5. fibre foam according to claim 1 is characterized in that said initiator is Diisopropyl azodicarboxylate or two formyls of peroxo-, and said whipping agent is the trimethyl carbinol, Pentyl alcohol, and said thickening material is a polymethylmethacrylate.
6. method for preparing each said fibre foam of claim 1-5; It is characterized in that concrete steps are: take by weighing each component in proportion, earlier with methylacrylic acid, (methyl) vinyl cyanide, initiator, whipping agent and thickening material mix liquid stock, add again said staple fibre stir mixed solution; Above-mentioned mixed solution is injected glass article; Perhaps liquid stock is injected and places the flat fabric that said macrofiber processes or the glass article of stereo fabric, in 40-70 ℃ of reaction 40-60 hour plastic plate, above-mentioned plastic plate is put into baking oven; Be warming up to 140-170 degree centigrade again; After this, every rising kept 10 minutes for 10 degrees centigrade, up to said blowing temperature; Said blowing temperature insulation 1.5-3 hour, obtain fibre foam at last.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104045952A (en) * | 2014-06-23 | 2014-09-17 | 浙江理工大学 | Shrinkage-free copolymer and preparation method thereof |
| CN106245157A (en) * | 2016-08-30 | 2016-12-21 | 甘木林 | A kind of multifunctional macromolecule filter fiber material |
| CN107603104A (en) * | 2017-09-29 | 2018-01-19 | 句容市武杭传动机械制造有限公司 | A kind of high good damping effect foamed plastics electrical package box of intensity and its production method |
| CN115948014A (en) * | 2023-01-31 | 2023-04-11 | 湖南博翔新材料有限公司 | Nano polymer fiber reinforced polymethacrylimide foam and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045952A (en) * | 2014-06-23 | 2014-09-17 | 浙江理工大学 | Shrinkage-free copolymer and preparation method thereof |
| CN104045952B (en) * | 2014-06-23 | 2015-11-04 | 浙江理工大学 | A kind of ungauged regions multipolymer and preparation method thereof |
| CN106245157A (en) * | 2016-08-30 | 2016-12-21 | 甘木林 | A kind of multifunctional macromolecule filter fiber material |
| CN107603104A (en) * | 2017-09-29 | 2018-01-19 | 句容市武杭传动机械制造有限公司 | A kind of high good damping effect foamed plastics electrical package box of intensity and its production method |
| CN115948014A (en) * | 2023-01-31 | 2023-04-11 | 湖南博翔新材料有限公司 | Nano polymer fiber reinforced polymethacrylimide foam and preparation method thereof |
| CN115948014B (en) * | 2023-01-31 | 2024-02-02 | 湖南博翔新材料有限公司 | Nano polymer fiber reinforced polymethacrylimide foam and preparation method thereof |
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Application publication date: 20120718 |