CN101768351B - Method for preparing mesoporous nano particle-enhanced nylon composite material - Google Patents
Method for preparing mesoporous nano particle-enhanced nylon composite material Download PDFInfo
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- CN101768351B CN101768351B CN2008102081027A CN200810208102A CN101768351B CN 101768351 B CN101768351 B CN 101768351B CN 2008102081027 A CN2008102081027 A CN 2008102081027A CN 200810208102 A CN200810208102 A CN 200810208102A CN 101768351 B CN101768351 B CN 101768351B
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 39
- 239000004677 Nylon Substances 0.000 title claims abstract description 38
- 229920001778 nylon Polymers 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 238000002360 preparation method Methods 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229960001866 silicon dioxide Drugs 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- -1 aluminic acid ester Chemical class 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000003657 drainage water Substances 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 239000011147 inorganic material Substances 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical group O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 8
- 230000006837 decompression Effects 0.000 abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 abstract description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000010954 inorganic particle Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 229920002292 Nylon 6 Polymers 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000013335 mesoporous material Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013339 polymer-based nanocomposite Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Abstract
The invention relates to a method for preparing a mesoporous nano particle-enhanced nylon composite material, comprising the following steps: hydrolyzing precursors of inorganic particles in phosphoric acid aqueous solution with pH value of 2-4 to develop hydrosol, mixing the hydrosol, nylon monomer and a molecular weight regulator; and carrying out high-pressure prepolymerization, exhaust depressurization, ordinary polymerization, decompression post polymerization and the like on the mixture in a high-pressure polymerizer to directly obtain the mesoporous nano particle-enhanced nylon composite material in-situ. In the invention, the double in-situ polymerization technology is adopted, and inorganic nano particles and polymer are synchronously generated by in-situ polycondensation, so that the nano particles are in homodisperse with mesoporous structure and superhigh specific surface area, thereby enabling the nano particles to show better enhancing effect.
Description
Technical field
The present invention relates to a kind of preparation method of nano inoganic particle Reinforced Nylon matrix material, relate in particular to a kind of method of utilizing pair in-situ polymerizations to prepare nylon/medium hole nano particles matrix material.
Background technology
Mesoporous material is meant to have the porous material that the aperture is 2～50 nanometers, and because of its unique meso-hole structure, mesoporous material has the specific surface area of superelevation.Except that as using separating of carrier, absorption and the organic macromolecule of catalyzer etc., also can be used for reinforced polymeric material.Exist under the interactional prerequisite of good interface with polymkeric substance, mesoporous material often shows fairly obvious reinforced effects.
Sol-gel method is the most frequently used a kind of method of preparation mesoporous material; Generally be earlier with presoma such as tetraethoxy in the aqueous solution after the hydrolysis; Under the effect of organic masterplate agent, carry out the curing cross-linked of silicic acid, remove the masterplate agent through high-temperature calcination then, can obtain mesoporous silicon oxide.The report that utilizes the Prepared by Sol Gel Method Organic is also arranged, and it is crosslinked that method is that the hydrolysis of in macromolecular solution, carrying out tetraethoxy is carried out then, finally obtains polymer-based nano composite material.This method is an original position synthesizing nano-particle under the situation that polymer exists, and should belong to traditional in-situ polymerization, i.e. the monobasic in-situ polymerization.In order to distinguish mutually conceptive with it, we are referred to as two in-situ synchronization polymerizations with nanoparticle and the synchronous synthetic polyreaction of superpolymer.Also do not find to utilize the report of this method synthetic nylon based nano composite material at present.These polymeric characteristics are to carry out two polyreactions independently separately simultaneously; When monomer polymerization is polymkeric substance; The inorganics presoma also generates inorganic particulate through the shrink crosslinking reaction, because both accomplish synchronously, therefore whole system is in homodisperse state all the time; And; The monomer of polymkeric substance or performed polymer are polymerized to superpolymer in the nano level inorganics network of height swelling, this makes final result in three-dimensional cross-linked network of silica, intert a lot of polymers, and the nanoparticle that obtains has unique meso-hole structure.
Summary of the invention
The object of the invention just provides a kind of preparation method of mesoporous nano particle-enhanced nylon composite material.
The object of the invention can be realized through following technical scheme: a kind of preparation method of mesoporous nano particle-enhanced nylon composite material; It is characterized in that; This method adopts two in-situ polymerization preparations; Nanoparticle and polymkeric substance generate in polymeric kettle synchronously, promptly monomer polymerization are being generated in the process of polymkeric substance, and the presoma of nanoparticle also polymerization becomes inorganic nano-particle.
At first with the presoma of the nanoparticle formation water-sol that in the aqueous solution, is hydrolyzed, the water-sol mixes with nylon monomer, molecular weight regulator then, and polymerization process is divided into the stages such as high pressure prepolymerization, exhaust step-down, normal pressure polycondensation, decompression aftercondensated.
Concrete preparation method comprises that at first being is hydrolysis in 1～5 the phosphate aqueous solution with presoma 1～20 weight part of inorganic particulate in the pH value; Mix with polymerization single polymerization monomer 100 weight parts, 0.2～2 weight part molecular weight regulator of nylon then; Mixed solution joins in the polymeric kettle; Under the condition that has under the condition of water with 200-270 ℃ and 0.2～3.2MPa prepolymerization 1-14 hour; Reduce to normal pressure through the drainage water steam then and under normal pressure polymerase 10 .5-4 hour, under the 220-300 ℃ of condition with 200-60000Pa, reduced pressure post polymerization 0.2-2 hour at last, direct in-situ makes mesoporous nano particle-enhanced nylon composite material.
The presoma of described inorganic particulate for can hydrolysis in the aqueous solution, finally can form the reagent of inorganic materials through crosslinking reaction; Like positive tetraethyl orthosilicate, tetraethyl titanate, aluminic acid ester etc.; Final inorganic nano-particle is silicon-dioxide, titanium oxide and white lake etc., preferred positive tetraethyl orthosilicate; The hydrolysis reaction of the presoma of described inorganic particulate carries out in phosphate aqueous solution, and temperature range for hydrolysis is 20～100 ℃, and the pH value of solution is 1～5.
Described nylon monomer is lactan such as hexanolactam, laurolactam, and perhaps nylon salt such as nylon salt, nylon 1010 salt can be above-mentioned a kind of, two or more mixing.
Described molecular weight regulator is phenylformic acid or hexanodioic acid etc., and consumption is 0.2～2%wt of nylon monomer consumption.
Described high pressure prepolymerisation stage is under HTHP, to carry out having under the condition of water, and the consumption of water is 5～40 times of weight of inorganic precursor, and temperature of reaction is at 200～270 ℃, and pressure is 0.2～3.2MPa, and the reaction times is 1～14 hour.
The temperature of described exhaust buck stage is controlled on the fusing point of product nylon 5～50 ℃, and evacuation time was controlled at 0.5～3 hour.
The temperature of described normal pressure polycondensation phase on the molten point of product nylon 10～40 ℃, the reaction times is 0.5～4 hour.
The pressure-controlling in described decompression aftercondensated stage is at 200～60000Pa, and polymerization temperature exceeds 15～40 ℃ than the fusing point of product nylon, and the reaction times is 0.2～2 hour.
The present invention forms the water-sol with presoma hydrolysis in the aqueous solution of inorganic particulate earlier; This water-sol mixes with monomer, molecular weight regulator according to a certain percentage then; Through operations such as high pressure prepolymerization, exhaust, polymerization under atmospheric pressure, decompression post polymerization, direct in-situ makes the nylon based nano composite material in polymermaking autoclave.In nylon matrix, nanoparticle not only disperses very evenly, and has the unique meso-hole structure and the specific surface area of superelevation, thereby nylon is shown very excellent reinforced effects.
Description of drawings
Fig. 1 (a) is the AFM phasor of matrix material;
Fig. 1 (b) is the transmission electron microscope photo of Nano particles of silicon dioxide;
Fig. 2 is the BET test curve of mesoporous silicon dioxide nano particle: (a) absorption-desorption attaches curve, (b) pore size distribution curve.
Embodiment
Embodiment 1
The inorganic materials that the present invention relates to comprises silicon-dioxide, titanium oxide etc., for better explanation the present invention, is that example is carried out instance explanation at length with meso-porous nano silicon-dioxide/nylon 6 systems below, and the dioxide-containing silica of this instance product is 3%wt.
The first step: the hydrolysis of positive tetraethyl orthosilicate
The positive tetraethyl orthosilicate of 1mol is dispersed in the 1000ml water, and utilizing phosphoric acid regulator solution pH value is 3, under stirring action, forms the water-sol in 2 hours in 80 ℃ of reactions.
React as follows:
Second step: mixing of materials
Restrain oneself lactan, 20 gram phenylformic acid with after the water-sol mixes, the adding polymermaking autoclave with 2000.Utilize the oxygen that vacuumizes the method emptying polymeric kettle that afterwards charges into nitrogen earlier.Prepolymerization is 8 hours under 230 ℃ of conditions with 2.0MPa, through vent water vapor the still internal pressure is reduced to normal pressure then, and temperature in the kettle is controlled at 235～250 ℃ in the exhaust process; Continuation was reacted 2 hours under normal pressure, and the aftercondensated that reduces pressure then is to improve level of response, and the temperature of decompression polycondensation is 280 ℃; Pressure is 2000Pa; The viscosity of material no longer rises in still, and polyreaction finishes, and product is extruded slivering through feed the high pressure nitrogen pressurization to polymeric kettle via the discharge port at the bottom of the still; Through pelletizing after the water-cooled, make the finished product pellet.
As a comparison, with pure nylon 6 with same molecular amount appearance mechanical property relatively as a comparison, both number-average molecular weights are about 1.5 ten thousand.
AFM photo (Fig. 1) shows that silicon-dioxide is nanoparticle and is evenly distributed in the matrix material that makes.In order to prove that Nano particles of silicon dioxide has meso-hole structure in the original position synthetic matrix material, matrix material is calcined at 800 ℃, after removing the nylon-6 matrix body fully, obtain Nano particles of silicon dioxide, then it is carried out transmission electron microscope observing.As shown in Figure 2, silicon dioxide granule has vesicular structure.The gained Nano particles of silicon dioxide is carried out BET aperture and specific area measuring, and the gained test curve is as shown in Figure 3, and recording specific surface area is 632m
2/ g, porosity is 3.21cm
3/ g, mean pore size is 14.2nm.Can know through above characterization result, adopt method of the present invention, but nanoparticle homodisperse not only, and also the nanoparticle in the matrix has meso-hole structure.
Table 1 nylon 6/ meso-porous titanium dioxide silicon composite and pure nylon 6 mechanical properties and heat-drawn wire contrast
| Flexural strength (MPa) | Modulus in flexure (MPa) | Tensile strength (MPa) | Tensile modulus (MPa) | Heat-drawn wire (℃) | |
| Pure nylon 6 | 98.2 | 1760 | 66.4 | 1260 | 57.5 |
| Matrix material | 133.4 | 2980 | 84.5 | 2240 | 113.4 |
Annotate: dioxide-containing silica is 3.0%wt in the matrix material.
Embodiment 2
The first step: the hydrolysis of tetraethyl titanate
The positive tetraethyl orthosilicate of 2mol is dispersed in the 4500ml water, and utilizing phosphoric acid regulator solution pH value is 2.1, under stirring action, forms the water-sol in 4 hours in 45 ℃ of reactions.
Second step: mixing of materials
3000 gram laurolactams, 36 are restrained oneself diacid with after the water-sol mixes, and the utilization of adding polymermaking autoclave vacuumizes the oxygen of the method emptying polymeric kettle that afterwards charges into nitrogen earlier.Prepolymerization is 14 hours under 270 ℃ of conditions with 3.2MPa, through vent water vapor the still internal pressure is reduced to normal pressure then, and temperature in the kettle is controlled at 235～250 ℃ in the exhaust process; Continuation was reacted 4 hours under normal pressure, and the aftercondensated that reduces pressure then is to improve level of response, and the temperature of decompression polycondensation is 220 ℃; Pressure is 60000Pa; The viscosity of material no longer rises in still, and polyreaction finishes, and product is extruded slivering through feed the high pressure nitrogen pressurization to polymeric kettle via the discharge port at the bottom of the still; Through pelletizing after the water-cooled, make the finished product pellet.
Embodiment 3
The first step: the hydrolysis of aluminic acid ester
1mol aluminic acid ester is dispersed in the 4500ml water, and utilizing phosphoric acid regulator solution pH value is 5, under stirring action, forms the water-sol in 4 hours in 100 ℃ of reactions.
Second step: mixing of materials
10000 gram nylon salts, 20 are restrained oneself diacid with after the water-sol mixes, and the utilization of adding polymermaking autoclave vacuumizes the oxygen of the method emptying polymeric kettle that afterwards charges into nitrogen earlier.Prepolymerization is 2 hours under 200 ℃ of conditions with 0.2MPa, through vent water vapor the still internal pressure is reduced to normal pressure then, and temperature in the kettle is controlled at 235～250 ℃ in the exhaust process; Continuation was reacted 1 hour under normal pressure, and the aftercondensated that reduces pressure then is to improve level of response, and the temperature of decompression polycondensation is 300 ℃; Pressure is 200Pa; The viscosity of material no longer rises in still, and polyreaction finishes, and product is extruded slivering through feed the high pressure nitrogen pressurization to polymeric kettle via the discharge port at the bottom of the still; Through pelletizing after the water-cooled, make the finished product pellet.
Claims (6)
1. the preparation method of a mesoporous nano particle-enhanced nylon composite material; It is characterized in that; This method adopts two in-situ polymerization preparations; Nanoparticle and polymkeric substance generate in polymeric kettle synchronously, promptly monomer polymerization are being generated in the process of polymkeric substance, and the presoma of nanoparticle also polymerization becomes inorganic nano-particle;
Concrete preparation method comprises that at first being is hydrolysis in 1～5 the phosphate aqueous solution with presoma 1～20 weight part of inorganic particulate in the pH value; Mix with polymerization single polymerization monomer 100 weight parts, 0.2～2 weight part molecular weight regulator of nylon then; Mixed solution joins in the polymeric kettle; There is under the condition of water under the condition of 200-270 ℃ and 0.2～3.2MPa prepolymerization 1-14 hour; Reduce to normal pressure through the drainage water steam then and under normal pressure polymerase 10 .5-4 hour, under the 220-300 ℃ of condition with 200-60000Pa, reduced pressure post polymerization 0.2-2 hour at last, direct in-situ makes mesoporous nano particle-enhanced nylon composite material.
2. the preparation method of a kind of mesoporous nano particle-enhanced nylon composite material according to claim 1; It is characterized in that; The presoma of described inorganic particulate for can hydrolysis in the aqueous solution, finally can form the reagent of inorganic materials through crosslinking reaction; Comprise one of positive tetraethyl orthosilicate, tetraethyl titanate and aluminic acid ester, final inorganic nano-particle is silicon-dioxide, titanium oxide and white lake; The hydrolysis reaction of the presoma of described inorganic particulate carries out in phosphate aqueous solution, and temperature range for hydrolysis is 20～100 ℃, and the pH value of solution is 1～5.
3. the preparation method of a kind of mesoporous nano particle-enhanced nylon composite material according to claim 1; It is characterized in that; Described nylon monomer is hexanolactam, laurolactam, and perhaps nylon salt, nylon 1010 salt can be above-mentioned a kind of, two or more mixing.
4. the preparation method of a kind of mesoporous nano particle-enhanced nylon composite material according to claim 1 is characterized in that, described molecular weight regulator is phenylformic acid or hexanodioic acid, and consumption is 0.2～2%wt of nylon monomer consumption.
5. the preparation method of a kind of mesoporous nano particle-enhanced nylon composite material according to claim 1; It is characterized in that; Described prepolymerization is under HTHP, to carry out having under the condition of water, and the consumption of water is 5～40 times of weight of inorganic precursor, and temperature of reaction is at 200～270 ℃; Pressure is 0.2～3.2MPa, and the reaction times is 1～14 hour.
6. the preparation method of a kind of mesoporous nano particle-enhanced nylon composite material according to claim 1; It is characterized in that; Described drainage water steam is reduced to non-pressurized temperature and is controlled on the fusing point of product nylon 5～50 ℃, and evacuation time was controlled at 0.5～3 hour.
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| CN102532523B (en) * | 2010-12-30 | 2014-09-10 | 上海杰事杰新材料(集团)股份有限公司 | Method for preparing magnetic polyamide composite material through in-situ hydrolysis |
| CN103602058A (en) * | 2013-11-12 | 2014-02-26 | 无锡市天聚科技有限公司 | Three-dimensional ordered macroporous silicon dioxide and nylon composite |
| CN103802228A (en) * | 2014-02-20 | 2014-05-21 | 如东南天农科化工有限公司 | Method for slicing polyacrylamide |
| CN109321999A (en) * | 2018-10-17 | 2019-02-12 | 浙江方圆聚合纤有限公司 | A kind of efficient far infrared, 6 fiber of ultraviolet resistant nylon and preparation method thereof |
| CN115232302B (en) * | 2022-08-30 | 2024-01-05 | 杭州聚合顺新材料股份有限公司 | Method for simply, conveniently and rapidly preparing nylon 66 nanocomposite |
| CN115572479B (en) * | 2022-11-03 | 2023-06-16 | 贵州省材料产业技术研究院 | Inorganic nanoparticle reinforced polyamide 12 powder and preparation method thereof |
| CN115926441B (en) * | 2022-12-08 | 2024-03-12 | 中国石油化工股份有限公司 | Transparent copolymerized nylon film and biaxially oriented film forming process thereof |
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