CN108060577A - A kind of preparation method of flaxen fiber reinforced resin based composites - Google Patents
A kind of preparation method of flaxen fiber reinforced resin based composites Download PDFInfo
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- CN108060577A CN108060577A CN201711369805.3A CN201711369805A CN108060577A CN 108060577 A CN108060577 A CN 108060577A CN 201711369805 A CN201711369805 A CN 201711369805A CN 108060577 A CN108060577 A CN 108060577A
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- reinforced resin
- fiber reinforced
- based composites
- resin based
- flaxen fiber
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- 239000000835 fiber Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000805 composite resin Substances 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 22
- -1 polysiloxanes Polymers 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 150000001735 carboxylic acids Chemical class 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 5
- 239000004626 polylactic acid Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 239000000443 aerosol Substances 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 2
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000002708 enhancing effect Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004901 spalling Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a kind of preparation methods of flaxen fiber reinforced resin based composites, which is characterized in that comprises the following steps：（1）Fiber pre-processes；（2）Fibre modification：1. prepare polysiloxanes colloidal sol：2. polysiloxanes is sol-gel modified：3. basic hydrolysis；（3）Prepare modified flaxen fiber reinforced resin based composites；Polysiloxanes of the present invention using polybasic carboxylic acid and mixed in hydrochloric acid acid as catalyst preparation is modified tossa, such changes surname fiber and breaks section without apparent fiber withdrawing trace with composite material made of PLA, and the stretch breaking strength of composite material is further enhanced, compared with prior art, have many advantages, such as that simple for process, fibrous mechanical property influence is small, there is excellent interface compatibility and adhesive property.
Description
Technical field：
The invention belongs to composite material manufacturing fields, and in particular to a kind of preparation of flaxen fiber reinforced resin based composites
Method.
Background technology：
Fibre reinforced composites are widely used in space flight because of the excellent properties such as proportion is small, specific strength and specific modulus are big
The fields such as aviation, national defence, traffic, physical culture.In recent years, with people's environmental consciousness continuous improvement and fossil resources it is increasingly withered
It exhausts, staple fibre (such as glass fibre, aramid fiber and carbon fiber) of the tradition using fossil resources as raw material enhances the disadvantage of composite material
First day of the lunar year benefit shows.Plant fiber is a kind of biodegradable renewable resource, just progressively substitutes people in many application fields
Fiber is made as the most important reinforcing material of polymeric matrix.Early-stage study finds that natural plant fibre is because with stronger suction
Moist and polarity, it is poor with non-polar polymer matrix interface compatibility and caking property, and also easily aggregation forms fiber-rich area,
Mechanical strength and intensity distribution generation to composite material seriously affect.As " bridge " that reinforcement is connected with matrix, interface
Microstructure and binding ability decide the overall performance of composite material, composite material interface performance is answered as fiber reinforcement
The research hotspot in condensation material field.
Domestic and international present Research shows to build the coarse microcosmic knot of hydrophobicity in the fiber surface as composite material reinforcement body
Structure is a kind of effective ways for improving fiber and interlaminar resin interface compatibility and adhesive property.Seminar at home and abroad studies existing
On the basis of shape, using water as medium, polymethyl siloxane is prepared for using hydrochloric acid catalysis methyltrimethoxysilane, by roll-
Baking-roasting technology smooth hydrophobic film in tossa surface construction, thin to polymethyl siloxane by basic hydrolysis
Film performs etching, and hydrophobicity rough surface microstructure has been constructed in fiber surface, significantly improves modified fibre surface with gathering
Interface compatibility and adhesion strength between lactic acid (PLA).However, it is found being broken to composite material when section is observed, still
There is fiber to be extracted from resin matrix.
The content of the invention：
It is an object of the invention to provide a kind of preparation method of flaxen fiber reinforced resin based composites, present invention process
Simply, condition is easy to control, and modified flaxen fiber good dispersion in resin, interface binding intensity is high, the composite material enhancing produced
Significant effect, cost are relatively low.
In order to achieve the above objectives, the technical scheme is that：
A kind of preparation method of flaxen fiber reinforced resin based composites, which is characterized in that comprise the following steps：
(1) fiber pre-processes：
Under room temperature, sequentially add the sodium hydroxide of 10-15g/L, 5-8g/L hydrogen peroxide, 3-4g/L sodium metasilicate,
The penetrating agent JFC of 1-2g/L, weight bath raio are 1：10-15 is warming up to 90-100 DEG C with 1-3 DEG C/min, keeps the temperature 120-150min,
Washing, pickling to neutrality are washed, and are dehydrated, drying；
(2) fibre modification：
1. prepare polysiloxanes colloidal sol：
Reaction solution forms：20-30g/L presomas, 0.1-0.5g/L neopelexes, 1-5g/L hydrochloric acid, 10-
20g/L polybasic carboxylic acids；
Reaction condition：Neopelex is added to the mixed acid of 1-5g/L hydrochloric acid and 10-20g/L polybasic carboxylic acids
In aqueous solution, stirred under the conditions of 25 DEG C, neopelex is made fully to dissolve, forerunner is gradually added into 20-30min
Body after presoma adds, continues to stir 30-60min, then 50-60 DEG C is warming up to 1-3 DEG C/min, in the condition of stirring
Lower reaction 3-6h；
2. polysiloxanes is sol-gel modified：
The sodium hypophosphite of 5-10g/L is added in polysiloxanes colloidal sol, then colloidal sol is adjusted to pH value as 5-6, in room temperature
Under, fiber is modified using two leachings, two methods rolled, pick-up 80-100%, dries 15-25min under the conditions of 80-90 DEG C,
130-150 DEG C bakes 5-10min, washing, 80-100 DEG C of drying；
3. basic hydrolysis：
Modified fibre is placed in the sodium hydroxide solution of 3-5g/L, weight bath raio is 1：10-15, with 1-3 DEG C/min liters
Temperature keeps the temperature 15-30min to 50-60 DEG C, washes, and is dehydrated, drying；
(3) modified flaxen fiber reinforced resin based composites are prepared：
Step (2) treated flaxen fiber and resin are removed into moisture removal in 100 DEG C of drying 2-4h, using hot-forming legal system
Standby enhancing composite material.
Further it is provided in：
In step (2), presoma is selected from：Methyltrimethoxysilane, methyltriethoxysilane, ethyl trimethoxy silicon
One or more of alkane, ethyl triethoxysilane.
In step (2), polybasic carboxylic acid is selected from：One or more of succinic acid, glutaric acid, adipic acid.
In step (2), it is 5- to use mass concentration that polysiloxanes colloidal sol is adjusted to pH value for the sodium hydroxide solution of 10g/L
6。
In step (2), the mixture of presoma selection methyltrimethoxysilane and ethyl trimethoxy silane.
In step (2), prepared polysiloxanes colloidal sol, aerosol particle size is 50~100nm.
In step (2), fiber is modified using the method that two leachings two are rolled, pick-up is controlled 90%.
In step (3), the one kind of resin in polylactic acid, polyhydroxyalkanoate.
In step (3), the flaxen fiber reinforced resin based composites of preparation, tossa content is 10-30%.
The beneficial effects of the invention are as follows：
Applicant passes through substantial amounts of exploring experiments, using polybasic carboxylic acid and mixed in hydrochloric acid acid as the poly- silica of catalyst preparation
Alkane is modified tossa, such changes surname fiber and breaks section without apparent fiber withdrawing with composite material made of PLA
Trace, and the stretch breaking strength of composite material is further enhanced.Compared with prior art, have the advantages that following prominent and positive
Effect：
(1) simple for process, technological parameter is stablized easy to control；
(2) method of modifying influences fibrous mechanical property small；
(3) modified flaxen fiber has excellent interface compatibility and adhesive property with interlaminar resin；
(4) the composite material enhancing effect produced is notable.
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Description of the drawings：
Fig. 1 is that the composite material that prior art fiber is extracted from resin matrix breaks section design sketch；
Fig. 2 is that composite material prepared by the present invention breaks section design sketch.
Specific embodiment：
Embodiment 1：
A kind of preparation method of flaxen fiber reinforced resin based composites, which is characterized in that comprise the following steps：
(1) fiber pre-processes：
Under room temperature, sequentially add the sodium hydroxide of 10-15g/L, 5-8g/L hydrogen peroxide, 3-4g/L sodium metasilicate,
The penetrating agent JFC of 1-2g/L, weight bath raio are 1：10-15 is warming up to 90-100 DEG C with 1-3 DEG C/min, keeps the temperature 120-150min,
Washing, pickling to neutrality are washed, and are dehydrated, drying；
(2) fibre modification：
1. prepare polysiloxanes colloidal sol：
Reaction solution forms：20-30g/L presomas, 0.1-0.5g/L neopelexes, 1-5g/L hydrochloric acid, 10-
20g/L polybasic carboxylic acids；
Reaction condition：Neopelex is added to the mixed acid of 1-5g/L hydrochloric acid and 10-20g/L polybasic carboxylic acids
In aqueous solution, stirred under the conditions of 25 DEG C, neopelex is made fully to dissolve, forerunner is gradually added into 20-30min
Body after presoma adds, continues to stir 30-60min, then 50-60 DEG C is warming up to 1-3 DEG C/min, in the condition of stirring
Lower reaction 3-6h；
Presoma is selected from：Methyltrimethoxysilane, methyltriethoxysilane, ethyl trimethoxy silane, ethyl three
One or more of Ethoxysilane；
2. polysiloxanes is sol-gel modified：
The sodium hypophosphite of 5-10g/L is added in polysiloxanes colloidal sol, then colloidal sol is adjusted to pH value as 5-6, in room temperature
Under, fiber is modified using two leachings, two methods rolled, pick-up 80-100%, dries 15-25min under the conditions of 80-90 DEG C,
130-150 DEG C bakes 5-10min, washing, 80-100 DEG C of drying；
3. basic hydrolysis
Modified fibre is placed in the sodium hydroxide solution of 3-5g/L, weight bath raio is 1：10-15, with 1-3 DEG C/min liters
Temperature keeps the temperature 15-30min to 50-60 DEG C, washes, and is dehydrated, drying.
(3) modified flaxen fiber reinforced resin based composites are prepared：
Step (2) treated flaxen fiber and polylactic acid are removed into moisture removal in 100 DEG C of drying 2-4h, using hot pressing formation process
Enhancing composite material is prepared, tossa content is 10-30% (mass content).
Alternative：
Using the preparation method of embodiment 1, set-up procedure (2) fibre modification technological parameter, and it is detected to composite material
The influence of performance.
The influence of table 1, the reaction solution composition and reaction condition of polysiloxanes colloidal sol to composite material tensile break strength
As shown in table 1：
The tensile break strength of composite material is substantially high made of polysiloxane-modified flaxen fiber prepared by hydrochloric acid catalyst
In the tensile break strength of composite material made of polysiloxane-modified flaxen fiber prepared by the catalysis of single dicarboxylic acids.This may
It is because when single carboxylic acid is as catalyst, the acidity of solution is inadequate, the grain size of hydrolysis effect and polysiloxanes to presoma
It has an impact, the final degree of roughness for influencing modified flaxen fiber surface reduces mechanical engagement effect.Table 1 shows hydrochloric acid simultaneously
With polybasic carboxylic acid mixed-acid catalyst prepare polysiloxane-modified flaxen fiber made of composite material tensile break strength compared with
Excellent, the effect of wherein hydrochloric acid and ethanedioic acid mixed acid is weaker, and the effect of other three kinds of mixed acid is similar.Compare No. 2-7,2-10
Number, the tensile break strength of No. 2-11 three composite sample understand, the mass concentration of hydrochloric acid and polybasic carboxylic acid in mixed acid
Respectively 3g/L and 15g/L are more excellent, and when polybasic carboxylic acid concentration is relatively low, enhancing effect is not notable, and excessively high concentration may be right
Fiber causes more serious strong damage.Acid species with dosage it is identical in the case of, No. 2-7, No. 2-12, No. 2-13 three it is compound
The test result of material sample shows that presoma dosage has apparent influence, No. 2-7,2- to the fracture strength of stretching of composite material
The reaction temperature when test result of No. 14, No. 2-15 three composite samples shows to prepare polysiloxanes is equally to composite wood
The fracture strength of stretching of material has apparent influence.
Show in addition, composite material breaks section research using hydrochloric acid and polybasic carboxylic acid mixed acid as the poly- of catalyst preparation
Siloxanes is modified tossa, such changes surname fiber and breaks section without apparent fiber with composite material made of PLA
Withdrawing trace, composite material break cross-section comparison's figure and see Fig. 1 and Fig. 2 respectively.
Alternative：
Using the preparation method of embodiment 1, set-up procedure (2) fibre modification technological parameter, and it is detected to composite material
The influence of performance.
Influence of the 2 fibre modification process conditions of table to composite material tensile break strength
As shown in table 2：
A, the tensile break strength of composite material increases first increases and then decreases with the pH of polysiloxane-modified liquid.This is because
Flaxen fiber belongs to cellulose fibre, and acid resistance is poor, and when the pH value of modification liquid is less than normal, the damage by force of modified fibre is larger, so as to
Influence the tensile strength of composite material.In addition, it is found in experiment, when modification liquid is adjusted to alkalescence, because polysiloxanes grain size is fast
Speed increases and becomes cloudy, so as to affect the microstructure on modified fibre surface.
B, baking temperature and time, which have the tensile break strength of composite material, significantly affects.Composite material stretches disconnected
Resistance to spalling increases with the rise of baking temperature, when temperature, which reaches 150 DEG C, continues to be increased to 160 DEG C, the stretching of composite material
Fracture strength changes there is no apparent.The time is baked to the effect tendency of composite material tensile break strength and baking temperature phase
Seemingly, Best Times are about 8min.
C, table 2 shows that the stretching of composite material is broken when naoh concentration mass concentration is 4g/L in basic hydrolysis liquid
Resistance to spalling is optimal.May be because naoh concentration it is relatively low when, be not enough to fiber surface formed polysiloxane film into
Row effectively etches and forms coarse structure, when naoh concentration is excessively high, is generated due to polysiloxane film hydrolysis is violent big
The hydrophilic radical (such as-OH ,-COOH) of amount, results even in film breaks, so as to influence the hydrophobicity of modified fibre.
Claims (9)
1. a kind of preparation method of flaxen fiber reinforced resin based composites, which is characterized in that comprise the following steps：
（1）Fiber pre-processes：
Under room temperature, sodium hydroxide, 5-8g/L hydrogen peroxide, the sodium metasilicate of 3-4g/L, the 1-2g/ of 10-15g/L is sequentially added
The penetrating agent JFC of L, weight bath raio are 1：10-15 is warming up to 90-100 DEG C with 1-3 DEG C/min, keeps the temperature 120-150min, washes,
Pickling is washed, is dehydrated, dry to neutrality；
（2）Fibre modification：
Prepare polysiloxanes colloidal sol：
Reaction solution forms：20-30g/L presomas, 0.1-0.5g/L neopelexes, 1-5g/L hydrochloric acid, 10-20g/L
Polybasic carboxylic acid；
Reaction condition：The mixed acid that neopelex is added to 1-5g/L hydrochloric acid and 10-20g/L polybasic carboxylic acids is water-soluble
In liquid, stirred under the conditions of 25 DEG C, neopelex made fully to dissolve, presoma is gradually added into 20-30min,
After presoma adds, continue to stir 30-60min, be then warming up to 50-60 DEG C with 1-3 DEG C/min, it is anti-under conditions of stirring
Answer 3-6h；
Polysiloxanes is sol-gel modified：
The sodium hypophosphite of 5-10g/L is added in polysiloxanes colloidal sol, then colloidal sol is adjusted to pH value as 5-6, at room temperature, is adopted
Fiber is modified with two leachings, two methods rolled, pick-up 80-100%, dries 15-25min, 130- under the conditions of 80-90 DEG C
150 DEG C bake 5-10min, washing, 80-100 DEG C of drying；
Basic hydrolysis：
Modified fibre is placed in the sodium hydroxide solution of 3-5g/L, weight bath raio is 1：10-15 is warming up to 1-3 DEG C/min
50-60 DEG C, 15-30min is kept the temperature, is washed, is dehydrated, drying；
（3）Prepare modified flaxen fiber reinforced resin based composites：
By step（2）Treated flaxen fiber and resin remove moisture removal in 100 DEG C of drying 2-4h, are prepared and increased using hot pressing formation process
Strong composite material.
2. a kind of preparation method of flaxen fiber reinforced resin based composites according to claim 1, it is characterised in that：Step
Suddenly（2）In, presoma is selected from：Methyltrimethoxysilane, methyltriethoxysilane, ethyl trimethoxy silane, ethyl three
One or more of Ethoxysilane.
3. a kind of preparation method of flaxen fiber reinforced resin based composites according to claim 1, it is characterised in that：Step
Suddenly（2）In, polybasic carboxylic acid is selected from：One or more of succinic acid, glutaric acid, adipic acid.
4. a kind of preparation method of flaxen fiber reinforced resin based composites according to claim 1, it is characterised in that：Step
Suddenly（2）In, it is 5-6 to use mass concentration that polysiloxanes colloidal sol is adjusted to pH value for the sodium hydroxide solution of 10g/L.
5. a kind of preparation method of flaxen fiber reinforced resin based composites according to claim 1, it is characterised in that：Step
Suddenly（2）In, the mixture of presoma selection methyltrimethoxysilane and ethyl trimethoxy silane.
6. a kind of preparation method of flaxen fiber reinforced resin based composites according to claim 1, it is characterised in that：Step
Suddenly（2）In, prepared polysiloxanes colloidal sol, aerosol particle size is 50~100nm.
7. a kind of preparation method of flaxen fiber reinforced resin based composites according to claim 1, it is characterised in that：Step
Suddenly（2）In, fiber is modified using the method that two leachings two are rolled, pick-up is controlled 90%.
8. a kind of preparation method of flaxen fiber reinforced resin based composites according to claim 1, it is characterised in that：Step
Suddenly（3）In, the one kind of resin in polylactic acid, polyhydroxyalkanoate.
9. a kind of preparation method of flaxen fiber reinforced resin based composites according to claim 1, it is characterised in that：Step
Suddenly（3）In, the flaxen fiber reinforced resin based composites of preparation, tossa content is 10-30%.
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| CN115160750A (en) * | 2022-07-26 | 2022-10-11 | 扬州丽华汽车内饰件有限公司 | Environment-friendly degradable jute fiber reinforced polylactic acid composite material and preparation method thereof |
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