CN101775151B - Composite sheet consisting of thermoplastic resin and fiber and manufacturing method thereof - Google Patents
Composite sheet consisting of thermoplastic resin and fiber and manufacturing method thereof Download PDFInfo
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- CN101775151B CN101775151B CN2009100763384A CN200910076338A CN101775151B CN 101775151 B CN101775151 B CN 101775151B CN 2009100763384 A CN2009100763384 A CN 2009100763384A CN 200910076338 A CN200910076338 A CN 200910076338A CN 101775151 B CN101775151 B CN 101775151B
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Abstract
The invention relates to a composite sheet consisting of a thermoplastic resin and a fiber and a manufacturing method thereof. The manufacturing method comprises the following steps of: performing surface modification on an ultra-high molecular weight polyethylene fiber and preparing a base material; preparing a preimpregnated base material, coating solution of the thermoplastic resin on the base material, and performing heat drying on the base material; preparing a prefabricated sheet, and coating thermoplastic resin powder on two sides of the base material, wherein the resin is the same as that used by the prefabricated sheet; and performing hot press molding. The composite sheet, consisting of the thermoplastic resin and the fiber, prepared by the method uses the ultra-high molecular weight polyethylene fiber as an enhanced framework fiber phase and uses the thermoplastic resin as a resin phase. The composite sheet consisting of the thermoplastic resin and the fiber and the manufacturing method thereof adopt an original process to ensure that a product is light in weight and low in forming temperature, has high mechanical properties in particular outstanding impact resistance and distortion resistance, has excellent chemical properties and is easy to process.
Description
Technical field
The present invention relates to a kind of matrix material and method of manufacture thereof, particularly relate to a kind of ultrahigh molecular weight polyethylene(UHMWPE) (UHMW-PE) fiber-reinforced thermoplastic resin composite sheet and method of manufacture thereof.
Background technology
In recent years, glass fibre reinforced composion is widely used in each economic fields such as building board, electrically insulating material, structured material, circuit substrate because of its better comprehensive performance.But also there are some defectives in glass fibre reinforced composion, and for example mechanical property is not high, difficult forming, and matter is crisp easily broken under the coldcondition, and weight is bigger than normal, thereby limits its range of application, makes it to satisfy the more use needs of wide spectrum.
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMW-PE) fiber is as a kind of type material; Its intensity can reach 30 lis more than ox/dtex; Intensity considerably beyond 10 lis of ox/dtexs of spun glass; Since it comes out, be composite Materials Design person's expectation thereby give the high-strength character of composite material light as fibrous skeleton with the filamentary material of this high-strength light always, but the difficult and various resin bonds of this kind fiber because of its surface inertness; And its fusing point is low; Use and the reprocessing process in can not surpass 130 ℃, and the fusing point of nearly all thermoplastic resin all is higher than this temperature, thereby; The fusing point problem of UHMW-PE fiber is that superhigh molecular weight polyethylene fibers thermoplastic resin composite sheet is made always, the technological difficulties in the complete processing, thereby influences the development of superhigh molecular weight polyethylene fibers thermoplastic resin composite sheet production technique and promote the use of.It is simple relatively how to research and develop a kind of technology; Can superhigh molecular weight polyethylene fibers better be combined with thermoplastic resin; And can be processed into light-weight high-strength material; To overcome the defective that existing spun glass exists, be one of current important research and development problem in this area, also be the target that current industry is pursued.
Summary of the invention
The objective of the invention is to, overcome the defective that the existing glass fibre composite exists, and a kind of novel ultrahigh molecular weight polyethylene(UHMWPE) (UHMW-PE) fiber-reinforced thermoplastic resin composite sheet is provided; Technical problem to be solved is to make its weight lighter; Mold temperature is lower, has improved comprehensive mechanical performance, especially has outstanding shock resistance, torsional resistance; Have good chemical property, thereby and be easy to processing and be suitable for practicality more.
Another object of the present invention is to; The method of manufacture of a kind of ultrahigh molecular weight polyethylene(UHMWPE) (UHMW-PE) fiber-reinforced thermoplastic resin composite sheet is provided; Technical problem to be solved is to make ME simple relatively; Can overcome the low-melting problem of superhigh molecular weight polyethylene fibers, make it to combine preferably, thereby produce the goods of ultrahigh molecular weight polyethylene(UHMWPE) (UHMW-PE) the fiber-reinforced thermoplastic resin composite sheet of excellent property with thermoplastic resin.
The object of the invention and solve its technical problem and adopt following technical scheme to realize.According to a kind of thermoplastic resin of the present invention's proposition and the method for manufacture of fibre composite sheet, may further comprise the steps: the preparation of the surface-treated of A. superhigh molecular weight polyethylene fibers and superhigh molecular weight polyethylene fibers base material; B. be coated on the thermoplastic resin solution on the base material of steps A preparation and carry out heat and dry by the fire, thereby make preimmersion base material; C. the preimmersion base material coating thermoplastic resin powder on two sides that makes to step B makes preformed sheet, and this toner is identical with the used resin of step B; D. the preformed sheet that will pass through step C acquisition is hot-forming.
Technique scheme also can adopt following technical measures further to realize.
The method of manufacture of aforesaid thermoplastic resin and fibre composite sheet, described step C coated with resins powder adopts spraying and hairbrush roller coating bonded method, and dusting weight calculation formula is: dusting weight/m
2Weight resin/m on=substrate surface density-preimmersion base material
2, the dusting deviation of weight＜± 1g/m
2
The method of manufacture of aforesaid thermoplastic resin and fibre composite sheet also comprises the post forming step after described step D is hot-forming, and condition of molding is identical with hot-forming step.
The method of manufacture of aforesaid thermoplastic resin and fibre composite sheet, the described surface-treated of steps A comprise mechanical grinding, corona treatment and wherein one or more treating processess of low-temperature plasma processing; The substrate surface density of steps A preparation is 50-200g/m
2Step B, the used thermoplastic resin of C are PE, SIS, SBS, PC, polyvinyl acetal resin or Z 150PH; The described thermoplastic resin solution's of step B solvent boiling point is 35 ℃-122 ℃, and the strength of solution mass percent is 2%-30%, and coating method is blade coating, roller coating, spraying or dipping, and the coated with resins amount is the 1/3-1/2 of substrate surface density; The described heat baking of step B is carried out in vacuum drying oven, and heat baking temperature is not higher than thermoplastic resin solution's solvent boiling point, removes the solvent of 60%-70%; Step D described hot-forming be with 105-130 ℃, 200-800T/m on platen-press
2Pressure under hot pressing 10 minutes, exit therebetween two or three times; Also comprising a fire-retardant finish step at last, is to be four (the 2-cyanogen acetaldehyde) bromo-phosphoniums and the bitter salt of 5%-11% that add glue weight 2%-8% in the resin adhesive liquid of 3%-5% at weight percent, and the two-sided material surface that is painted on afterwards stirs.
The object of the invention and solve its technical problem and also adopt following technical scheme to realize.According to a kind of thermoplastic resin of the present invention's proposition and the method for manufacture of fibre composite sheet, may further comprise the steps: the preparation of the surface-treated of A. superhigh molecular weight polyethylene fibers and superhigh molecular weight polyethylene fibers base material; B. the base material coating thermoplastic resin powder on two sides for preparing to steps A, thus make preformed sheet; C. the preformed sheet that will pass through step B acquisition is hot-forming.
Technique scheme also can adopt following technical measures further to realize.
The method of manufacture of aforesaid thermoplastic resin and fibre composite sheet, described step B coated with resins powder adopts spraying and hairbrush roller coating bonded method, and dusting weight calculation formula is: dusting weight/m
2=substrate surface density ± 1g/m
2
The method of manufacture of aforesaid thermoplastic resin and fibre composite sheet also comprises the post forming step after described step C is hot-forming, and condition of molding is identical with hot-forming step.
The method of manufacture of aforesaid thermoplastic resin and fibre composite sheet is mixed with boric acid or the sodium tetraborate of 3-5% in the toner of described step B.
The method of manufacture of aforesaid thermoplastic resin and fibre composite sheet, the described surface-treated of steps A comprise mechanical grinding, corona treatment and wherein one or more treating processess of low-temperature plasma processing; The substrate surface density of steps A preparation is 50-200g/m
2The used thermoplastic resin of step B is PE, SIS, SBS, PC, polyvinyl acetal resin or Z 150PH; Step C described hot-forming be with 105-130 ℃, 200-800T/m on platen-press
2Pressure under hot pressing 10 minutes; Also comprising a fire-retardant finish step at last, is to be four (the 2-cyanogen acetaldehyde) bromo-phosphoniums and the bitter salt of 5%-11% that add glue weight 2%-8% in the resin adhesive liquid of 3%-5% at weight percent, and the two-sided material surface that is painted on afterwards stirs.
The object of the invention and solve its technical problem and also adopt following technical scheme to realize.Thermoplastic resin and fibre composite sheet that the method according to above-mentioned that proposes according to the present invention obtains, it is to strengthen the fibrous skeleton phase with the superhigh molecular weight polyethylene fibers, is the resin phase with the thermoplastic resin.
The present invention compared with prior art has following tangible advantage and beneficial effect at least:
1, ultrahigh molecular weight polyethylene(UHMWPE) of the present invention (UHMW-PE) fiber-reinforced resin composite sheet; With UHMW-PE fiber and thermoplastic resin compatibility; Can be at the condition compacted under that is not higher than the above-mentioned fiber use temperature upper limit (130 ℃), and durability of product is good, mechanical property is excellent, mechanical property more shows excellent under coldcondition; Can also make material have anti-flaming function through fire-retardant finish.
2, the method for manufacture of ultrahigh molecular weight polyethylene(UHMWPE) of the present invention (UHMW-PE) fiber-reinforced resin composite sheet; Be to adopt mechanical grinding, corona treatment and non-thermal plasma trap process combined, improved the adhesive property of fiber the UHMW-PE fiber surface modification; The resin solution, powder coating process conjugated fibre and the resin that adopt; Adopt unique and advanced technology to overcome the low-melting problem of superhigh molecular weight polyethylene fibers; Quantity of solvent and recyclable utilization have again been reduced; Improve the security of production process when reducing production costs, be beneficial to environmental protection, have an innovative significance in that composite material forming is technical.
In sum, thermoplastic resin of the present invention and fibre composite sheet and method of manufacture thereof take to create technology; Overcome the low-melting problem of UHMW-PE fiber, it can be combined with thermoplastic resin preferably, product weight is light; Mold temperature is low; Have strong mechanical performance, especially have outstanding shock resistance, torsional resistance, have good chemical property and be easy to processing.The present invention has above-mentioned plurality of advantages and practical value; Obvious improvement is arranged technically; And produced handy and practical effect; And have the outstanding multinomial effect of enhancement than existing glass fibre composite and method of manufacture thereof, thereby be suitable for practicality more, and have industrial utilization widely.
Above-mentioned explanation only is the general introduction of technical scheme of the present invention; Understand technique means of the present invention in order can more to know; And can implement according to the content of specification sheets; And for let above-mentioned and other purposes of the present invention, feature and advantage can be more obviously understandable, specially lift preferred embodiment and specify as follows.
Embodiment
Reach technique means and the effect that predetermined goal of the invention is taked for further setting forth the present invention; Below in conjunction with accompanying drawing and preferred embodiment; To thermoplastic resin and fibre composite sheet and its embodiment of method of manufacture, method of manufacture, step, characteristic and the effect thereof that proposes according to the present invention, specify as after.
Embodiment one
The making method of fiber-reinforced resin composite sheet of the present invention mainly may further comprise the steps:
1, the surface-treated of ultrahigh molecular weight polyethylene(UHMWPE) (UHMW-PE) fiber.
Surface-treated to the UHMW-PE fiber among the present invention comprises that mainly carrying out mechanical grinding, corona treatment and low-temperature plasma handles, and can select wherein one or more to be suitable for according to concrete working condition, product requirement.Mechanical grinding is that fiber is carried out soft scraped finish repeatedly on special card clothing, makes the protofibril end expenditure of fiber surface, and microscopically can be seen the fiber surface fluffing, as a sparse hairbrush.Corona treatment and non-thermal plasma trap then make reactive group in the fiber surface grafting.
The above-mentioned processing of process has improved the surface inertness of UHMW-PE fiber, has given this fiber surface of good adhesive property, and fiber can well be bondd with most of resins.
2, the preparation of UHMW-PE fiber base material.
To process woven, knit goods or non-woven through the above-mentioned macrofiber of surface-treated or chopped strand, and as the base material of matrix material, adopt the base material of which kind of form to depend on the specific requirement of material applications, substrate surface density can be at 50-200g/m
2Between select.
3, the preparation of preimmersion base material.
Selecting corresponding thermoplastic resin for use according to sheet material purposes needs, for example is Vilaterm (PE), SIS (SIS), styrene-butadiene-styrene block copolymer (SBS), polyvinyl acetal resin, polycarbonate (PC) or Z 150PH.
It is that 35 ℃-122 ℃ solvent is mixed with resin solution that aforementioned resin is used boiling point, and the concentration mass percent of resin solution is 2%-30%.Resin solution evenly is coated on the base material of abovementioned steps preparation, the method for coating can adopt the mode of blade coating, roller coating, spraying or dipping, and the virgin resin amount that is coated on the base material is controlled between the 1/3-1/2 of substrate surface density.
The base material of coated with resins solution is placed the baking of vacuum drying oven heat, and heat baking temperature is not higher than thermoplastic resin solution's solvent boiling point, gets rid of the solvent of about 60%-70%, promptly processes preimmersion base material.Concrete hot baking condition is different because of the thermoplastic resin of selecting for use, can specifically judge drying parameter through the laboratory test monitoring according to prior art.The solvent gas of discharging from vacuum drying oven gets into a plate-type condenser, can be recycled after the condensation and collection.
4, preparation preformed sheet.
Method with spraying and hairbrush roller coating combine is coated in the two sides of preimmersion base material equably with the toner identical with the used resin of step 3, and powdex is adhered to fully, thereby processes preformed sheet.Dusting weight is calculated as follows:
Dusting weight/m
2Weight resin/m on=substrate surface density-preimmersion base material
2
The dusting deviation of weight＜± 1g/m
2
5, hot-forming.
With coated preformed sheet on platen-press with 105-130 ℃, 200-800T/m
2Pressure under hot pressing 10 minutes, exit therebetween two or three times, promptly process fiber-reinforced resin composite sheet of the present invention.
Above-mentioned hot pressing process is independently carrying out in the enclosed space, and the solvent of the gas of emitting for applying in the paste resin coating stage uses fan that it is sent into an absorbent charcoal adsorber, and desorption can be recycled after collecting.
Also can with aforesaid hot press forming technology post forming, promptly process hard plate material, also can be pressed into special-shaped products through mold hot with behind the finished product sheet material multilayer build-up.
6, fire-retardant finish.
After hot-forming, also can comprise one with the two-sided step that is painted on material surface of anti-flaming dope.
Thermoplastic resins such as PVB are mixed with the glue of weight percent 3%-5%; Four (the 2-cyanogen acetaldehyde) bromo-phosphoniums and the bitter salt of 5%-11% that add the 2%-8% of glue weight again; Stir and promptly be made into anti-flaming dope; With the two-sided material surface that is painted on of this coating, to treat promptly to form firm fire-retardant film after the ethanol volatilization, the brush amount is decided according to fire-retardant requirement.
Embodiment two
The making method of fiber-reinforced resin composite sheet of the present invention also can realize through following steps:
1, the surface-treated of ultrahigh molecular weight polyethylene(UHMWPE) (UHMW-PE) fiber.
Surface-treated to the UHMW-PE fiber among the present invention comprises that mainly carrying out mechanical grinding, corona treatment and low-temperature plasma handles, and can select wherein one or more to be suitable for according to concrete working condition, product requirement.Mechanical grinding is that fiber is carried out soft scraped finish repeatedly on special card clothing, makes the protofibril end expenditure of fiber surface, and microscopically can be seen the fiber surface fluffing, as a sparse hairbrush.Corona treatment and non-thermal plasma trap then make reactive group in the fiber surface grafting.
The above-mentioned processing of process has improved the surface inertness of UHMW-PE fiber, has given this fiber surface of good adhesive property, and fiber can well be bondd with most of resins.
2, the preparation of UHMW-PE fiber base material.
To process woven, knit goods or non-woven through the above-mentioned macrofiber of surface-treated or chopped strand, and as the base material of matrix material, adopt the base material of which kind of form to depend on the specific requirement of material applications, substrate surface density can be at 50-200g/m
2Between select.
3, preparation preformed sheet.
With the method that sprays and the hairbrush roller coating combines; The thermoplastic resin powder is coated in equably the base material two sides of above-mentioned steps preparation; For example select Vilaterm (PE), SIS (SIS), styrene-butadiene-styrene block copolymer (SBS), polyvinyl acetal resin, polycarbonate (PC) or polyvinyl alcohol resin powder for use; And powdex is adhered to fully, thereby process preformed sheet.Dusting weight is calculated as follows:
Dusting weight/m
2=substrate surface density ± 1g/m
2
In addition, also can in powdex, sneak into boric acid or the sodium tetraborate of 3-5%, the softening adherent of resin is followed the generation chemically crosslinked simultaneously in hot pressing, and the product after crosslinked has better mechanical property, chemicalstability and solvent resistance.
4, hot-forming.
With coated preformed sheet on platen-press with 105-130 ℃, 200-800T/m
2Pressure under hot pressing 10 minutes, promptly process fiber-reinforced resin composite sheet of the present invention.
Also can with aforesaid hot press forming technology post forming, promptly process hard plate material, also can be pressed into special-shaped products through mold hot with behind the finished product sheet material multilayer build-up.
6, fire-retardant finish.
After hot-forming, also can comprise one with the two-sided step that is painted on material surface of anti-flaming dope.
Thermoplastic resins such as PVB are mixed with the glue of weight percent 3%-5%; Four (the 2-cyanogen acetaldehyde) bromo-phosphoniums and the bitter salt of 5%-11% that add the 2%-8% of glue weight again; Stir and promptly be made into anti-flaming dope; With the two-sided material surface that is painted on of this coating, to treat promptly to form firm fire-retardant film after the ethanol volatilization, the brush amount is decided according to fire-retardant requirement.
Above-mentioned just listing lifted two preferable implementation steps; In the practice; Can also promptly utilize ultrahigh molecular weight polyethylene to be equipped with base material earlier according to the order of concrete condition of production transposing step 1 and 2, again substrate surface carried out modification afterwards; Or part technology done slightly change, can reach the object of the invention and effect preferably equally.
Those skilled in the art have following common recognition: the mechanical property of UHMW-PE fiber, chemical property are higher than the traditional glass fiber far away, and its mechanical property goes up not down under coldcondition; In the sheet forming process, adopt condition of high voltage, can improve the performance index such as drawing, press, dash, turn round, bend of fibre composite sheet.Therefore; The UHMW-PE fiber-reinforced resin composite sheet that aforesaid method obtains according to the present invention; With the UHMW-PE fiber serves as to strengthen the fibrous skeleton phase, is the resin phase with the thermoplastic resin, has guaranteed that from raw material and production technique its product has favorable durability and mechanical property.
The matrix material that product UHMW-PE fiber-reinforced thermoplastic resin sheet of the present invention is a lightweight, have high-strength performance and be easy to process.This material will drive the products innovation of many Application Areass.Its method of manufacture has overcome this kind fiber surface inert obstacle through process of surface treatment; By little solvent or under solvent-free effect; Direct coated thermoplastic powder; Make UHMW-PE fiber and thermoplastic resin avoid its low-melting obstacle, opened up new technological approaches for this kind fiber really gets into the matrix material Application Areas in composite molding below 130 ℃; And can reduce the use of organic solvent to greatest extent, make that production process is safer, environmental protection, cleaning, energy-conservation.
The above; It only is preferred embodiment of the present invention; Be not that the present invention is done any pro forma restriction,, anyly be familiar with the professional and technical personnel though the present invention discloses as above with preferred embodiment; Make a little change or be modified to the equivalent embodiment of equivalent variations when the technology contents of above-mentioned announcement capable of using, all still belong in the scope of technical scheme of the present invention.
Claims (8)
1. the method for manufacture of thermoplastic resin and fibre composite sheet is characterized in that may further comprise the steps:
A. the preparation of the surface-treated of superhigh molecular weight polyethylene fibers and superhigh molecular weight polyethylene fibers base material;
B. be that the thermoplastic resin solution of 2%-30% is coated on the base material of steps A preparation and carries out heat and dry by the fire with the strength of solution mass percent, thereby make preimmersion base material, the coated with resins amount is the 1/3-1/2 of substrate surface density;
C. adopt spraying and hairbrush roller coating bonded method to the preimmersion base material coating thermoplastic resin powder on two sides that step B makes, make preformed sheet, this toner is identical with the used resin of step B, and dusting weight calculation formula does
Dusting weight/m
2Weight resin/m on=substrate surface density-preimmersion base material
2
The dusting deviation of weight＜± 1g/m
2
D. the preformed sheet that will pass through step C acquisition is hot-forming.
2. the method for manufacture of thermoplastic resin according to claim 1 and fibre composite sheet is characterized in that described step D also comprises the post forming step after hot-forming, and condition of molding is identical with hot-forming step.
3. the method for manufacture of thermoplastic resin according to claim 1 and 2 and fibre composite sheet is characterized in that
The described surface-treated of steps A comprises mechanical grinding, corona treatment and wherein one or more treating processess of low-temperature plasma processing;
The substrate surface density of steps A preparation is 50-200g/m
2
Step B, the used thermoplastic resin of C are PE, SIS, SBS, PC, polyvinyl acetal resin or Z 150PH;
The described thermoplastic resin solution's of step B solvent boiling point is 35 ℃-122 ℃, and coating method is blade coating, roller coating, spraying or dipping;
The described heat baking of step B is carried out in vacuum drying oven, and heat baking temperature is not higher than thermoplastic resin solution's solvent boiling point, removes the solvent of 60%-70%;
Step D described hot-forming be with 105-130 ℃, 200-800T/m on platen-press
2Pressure under hot pressing 10 minutes, exit therebetween two or three times;
Also comprising a fire-retardant finish step at last, is to be four (the 2-cyanogen acetaldehyde) bromo-phosphoniums and the bitter salt of 5%-11% that add glue weight 2%-8% in the resin adhesive liquid of 3%-5% at weight percent, and the two-sided material surface that is painted on afterwards stirs.
4. the method for manufacture of thermoplastic resin and fibre composite sheet is characterized in that may further comprise the steps:
A. the preparation of the surface-treated of superhigh molecular weight polyethylene fibers and superhigh molecular weight polyethylene fibers base material;
B. adopt spraying and the hairbrush roller coating bonded method base material coating thermoplastic resin powder on two sides to the steps A preparation, thereby make preformed sheet, dusting weight calculation formula does
Dusting weight/m
2=substrate surface density ± 1g/m
2；
C. the preformed sheet that will pass through step B acquisition is hot-forming.
5. the method for manufacture of thermoplastic resin according to claim 4 and fibre composite sheet is characterized in that described step C also comprises the post forming step after hot-forming, and condition of molding is identical with hot-forming step.
6. the method for manufacture of thermoplastic resin according to claim 4 and fibre composite sheet is characterized in that being mixed with in the toner of described step B boric acid or the sodium tetraborate of 3-5%.
7. according to the method for manufacture of described thermoplastic resin of the arbitrary claim of claim 4-6 and fibre composite sheet, it is characterized in that
The described surface-treated of steps A comprises mechanical grinding, corona treatment and wherein one or more treating processess of low-temperature plasma processing;
The substrate surface density of steps A preparation is 50-200g/m
2
The used thermoplastic resin of step B is PE, SIS, SBS, PC, polyvinyl acetal resin or Z 150PH;
Step C described hot-forming be with 105-130 ℃, 200-800T/m on platen-press
2Pressure under hot pressing 10 minutes;
Also comprising a fire-retardant finish step at last, is to be four (the 2-cyanogen acetaldehyde) bromo-phosphoniums and the bitter salt of 5%-11% that add glue weight 2%-8% in the resin adhesive liquid of 3%-5% at weight percent, and the two-sided material surface that is painted on afterwards stirs.
8. a thermoplastic resin and a fibre composite sheet that obtains according to the described method of the arbitrary claim of claim 1-7 is characterized in that with the superhigh molecular weight polyethylene fibers being to strengthen the fibrous skeleton phase, is the resin phase with the thermoplastic resin.
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| CN2009100763384A CN101775151B (en) | 2009-01-13 | 2009-01-13 | Composite sheet consisting of thermoplastic resin and fiber and manufacturing method thereof |
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| CN102604313B (en) * | 2012-02-22 | 2014-04-16 | 威海洁瑞医用制品有限公司 | SBS (Styrene-Butadiene-Styrene) crosslinking elastomer composite material and preparation method thereof |
| CN104859158B (en) * | 2015-04-30 | 2017-11-24 | 山东大学 | A kind of preparation method of thermoplasticity carbon fibre composite plate |
| CN110561783B (en) * | 2019-08-26 | 2021-11-23 | 华中科技大学鄂州工业技术研究院 | Preparation method of biomass composite board based on hot press molding process |
| CN114161807A (en) * | 2021-12-09 | 2022-03-11 | 江苏安卡新材料科技有限公司 | Manufacturing method of bulletproof plate |
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| CN1686696A (en) * | 2005-06-10 | 2005-10-26 | 中国航空工业第一集团公司北京航空材料研究院 | Preparation method of liquid state shaping composite material preshaped body |
| CN101082182A (en) * | 2007-06-29 | 2007-12-05 | 东华大学 | Preparation of shell micro-powder reinforced super-high molecular weight polyethylene fibre composite non woven cloth |
| CN101163827A (en) * | 2004-12-29 | 2008-04-16 | 欧文斯科宁知识产权资产有限公司 | Thermoplastic composites with improved sound absorbing capabilities |
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| CN101163827A (en) * | 2004-12-29 | 2008-04-16 | 欧文斯科宁知识产权资产有限公司 | Thermoplastic composites with improved sound absorbing capabilities |
| CN1686696A (en) * | 2005-06-10 | 2005-10-26 | 中国航空工业第一集团公司北京航空材料研究院 | Preparation method of liquid state shaping composite material preshaped body |
| CN101082182A (en) * | 2007-06-29 | 2007-12-05 | 东华大学 | Preparation of shell micro-powder reinforced super-high molecular weight polyethylene fibre composite non woven cloth |
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