CN105086396A - Preparation method of self-repair nanocapsule-thermosetting-resin-base composite material - Google Patents
Preparation method of self-repair nanocapsule-thermosetting-resin-base composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a self-repair nanocapsule-thermosetting-resin-base composite material, which comprises the following steps: 1) preparing a capsule wall prepolymer from urea, formaldehyde and melamine; 2) preparing a fine emulsion by using an epoxy resin as a core material; 3) uniformly mixing the prepolymer and fine emulsion, polycondensing, washing and drying to obtain the self-repair nanocapsule; and 4) adding the prepared self-repair nanocapsule into a thermosetting-resin-base composite material, curing, and carrying out after-treatment to obtain the composite material. By using the ultrasonic assisted in-situ polymerization process for preparing the self-repair nanocapsule, the method has the advantages of simple technique and controllable parameters, and the prepared nanocapsule has the advantages of small size, high stability and favorable compatibility with the thermosetting resin base, and satisfies the corresponding requirements of the composite material processing technique.
Description
Technical field
The invention belongs to thermosetting resin based composites studying technological domain, particularly a kind of preparation method of selfreparing Nano capsule/thermosetting resin based composites.
Background technology
In recent years, the specific tenacity of thermosetting resin based composites Yin Qigao, specific rigidity and be widely used in aerospace, automobile and other commercial kitchen area.Thermosetting resin based composites, in life-time service process, inevitably damages generation tiny crack when it is subject to External Force Acting, causes mechanical property to decline or afunction.The selfreparing of thermosetting resin based composites is significant for its work-ing life for the stability in use and prolongation improving this material.
Along with reaching its maturity of microcapsulary, Microcapsules Embedded Self-healing Composites development rapidly, becomes the main path of research and development Self-repair Composites.But existing microcapsule self-repair method still exists many deficiencies, as the poor compatibility of renovation agent system and matrix, the introducing of microcapsule and degradation under causing thermosetting resin base composite property.
Nano capsule is except having the distinctive surface effects of nano material, small-size effect and macro quanta tunnel effect, and the structure of microcapsule uniqueness gives the ability of its high-efficient carrier and excellent release performance simultaneously.The utilization of selfreparing Nano capsule not only with thermosetting resin based composites micro-damage in size with quantitatively match, and it can be avoided the disadvantageous effect of thermosetting resin based composites intrinsic performance.Nano capsule, compared with micron capsule, having some superiority to thermosetting resin based composites selfreparing field, will have more wide application prospect.
Summary of the invention
For solving problems of the prior art, the invention provides the preparation method of a kind of selfreparing Nano capsule/thermosetting resin based composites, Nano capsule prepared by the present invention meets that size is little, stability is strong, better with the consistency of thermosetting resin matrix, meet the requirement that composite processing technique adapts.
The present invention is achieved through the following technical solutions:
A preparation method for selfreparing Nano capsule/thermosetting resin based composites, comprises the following steps:
1) by urea, formaldehyde in molar ratio the amount of 1:1 ~ 1:3 join in container and stir, form urea formaldehyde solution; Add again in urea formaldehyde solution and account for the trimeric cyanamide that urea formaldehyde mass ratio is 0% ~ 50%, adopt alkali tune agent adjust ph to be 8 ~ 9, be slowly warming up to 60 ~ 80 DEG C, constant temperature water bath reaction to terminal, heating is stopped to treat that temperature is down to room temperature, the performed polymer of obtained clear viscous; Wherein, wall material raw material is urea, formaldehyde and trimeric cyanamide;
2) getting wall material raw material with core raw materials quality ratio is (3 ~ 5): the epoxy resin of 10 is core, 1.5 ~ 3 parts of capsule-core thinners, 0.5 ~ 3 part of emulsifying agent, 0.05 ~ 1 part of defoamer, add 100 parts of deionized waters, homogenizer 800 ~ 1000rpm stirs 10 ~ 20min and forms emulsion, and then supersound process forms miniemulsion;
3) by step 1) performed polymer that obtains adds step 2) stir constant temperature 60 ~ 80 DEG C in the miniemulsion prepared, reaction 1 ~ 3h, this stage adds acidity regulator solution in batches, slow adjust ph is 2 ~ 3, continue under stir speed (S.S.) 200 ~ 400rpm to stir, 1 ~ 3h completes the solidification process of Nano capsule, finally by adding alkali tune agent solution, system pH being adjusted to 5 ~ 7, obtaining the suspension of Nano capsule;
4) by step 3) suspension that obtains naturally cools to room temperature, and filter, distilled water wash, lyophilize, obtains Nano capsule product;
5) according to parts by weight, take the thermosetting resin of 100 parts, add step 4) the selfreparing Nano capsule of obtain 5 ~ 20 parts, matrix solidifying agent, core epoxy resin lalent solidifying agent 0.5 ~ 5 part, the toughener of 10 ~ 30 parts of 2 ~ 20 parts, mixing is magnetic agitation 5 ~ 30min also, put into vacuum drying oven and vacuumize 10 ~ 60min, slough bubble, obtain thermosetting resin mixed solution, poured in silica gel mould, be put in self-vulcanizing 20 ~ 30h, aftertreatment 1 ~ 2h, obtains selfreparing Nano capsule/thermosetting resin based composites.
As a further improvement on the present invention, described supersound process is specially: by emulsion in ultrasonic cell disruptor, first supersound process 6 ~ 9min under power 1000 ~ 2000W, then supersound process 1 ~ 5min forms miniemulsion under power 200 ~ 400W.
As a further improvement on the present invention, the core materials of described selfreparing Nano capsule is bis-phenol A glycidyl ether type, Bisphenol F diglycidyl ether type, Resorcinol glycidyl ester type or methylol diglycidyl ether type.
As a further improvement on the present invention, described capsule-core thinner is chlorobenzene, 1-butylglycidyl ether, phenylcarbinol, ethyl acetate or ethyl acetic acid phenyl ester;
Described emulsifying agent is Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, alkylphenol polyoxyethylene ether, sorbitan monooleate Soxylat A 25-7, sorbitan monooleate or styrene-maleic anhydride copolymer.
As a further improvement on the present invention, described alkali tune agent is NaOH solution, Carbon Dioxide sodium solution or trolamine;
Described acidity regulator is NH
4cl solution or HCl solution.
As a further improvement on the present invention, described defoamer is lower alcohols or polar organic compounds system, and lower alcohol defoamer is methyl alcohol, ethanol, Virahol, propyl carbinol, n-Octanol; Polar organic compounds defoamer is amylalcohol, diisobutyl carbinol(DIBC), octanol, propylene glycol.
As a further improvement on the present invention, described thermosetting resin matrix is the one in epoxy resin, unsaturated polyester resin, epoxy vingl ester resin or silicone resin.
As a further improvement on the present invention, epoxy resin-base solidifying agent used is organic acid, acid anhydrides, boron trifluoride and complex compound thereof, aliphatie diamine and polyamines, aromatic polyamine, other nitrogenous compound and modified fatty amine etc., be preferably aliphatic polyamine as quadrol, hexanediamine, diethylenetriamine, triethylene tetramine, diethylaminopropylamine etc.; Unsaturated polyester resin matrix solidifying agent used is dibenzoyl peroxide, methylethyl ketone peroxide, cyclohexanone peroxide, cyclohexanone peroxide, DMA or cobalt iso-octoate; Epoxy vingl ester resin matrix solidifying agent used is vinylbenzene; Silicone resin matrix solidifying agent used is diethylenetriamine or triethylene tetramine.
As a further improvement on the present invention, described toughener is glass fibre;
Described core epoxy resin lalent solidifying agent is the one in glyoxal ethyline, 2-ethyl-4-methylimidazole or 2-phenylimidazole.
Compared with prior art, the present invention has following useful technique effect:
The present invention adopts ultrasonic wave added situ aggregation method simple to operate to prepare the technology of selfreparing Nano capsule, the Nano capsule making it prepare meets that size is little, stability is strong, better with the consistency of thermosetting resin matrix, meet the requirement that composite processing technique adapts, this preparation technology is simple, and processing parameter is easy to control; The size and distribution of Nano capsule can be controlled by the power regulating and controlling supersound process; The better heat stability of Nano capsule prepared by this technique, thermotolerance can reach more than 200 DEG C; Clad ratio and the core content of Nano capsule prepared by this technique are higher, and clad ratio can reach 80 ~ 90%, and core content can reach 40 ~ 50%; The method that the present invention prepares Nano capsule matrix material is simple, directly using Nano capsule as raw material, add in matrices of composite material, first magnetic agitation is even, vacuumize de-soak again, after carry out solidification treatment and can prepare Nano capsule and the good matrix material of matrix resin interface cohesion; Nano capsule prepared by the present invention dispersiveness in the composite improves, and the mechanical property of matrix material improves significantly, and Nano capsule is less than the influence degree of microcapsule to matrix material to the reduction of the mechanical property of matrix material.
Accompanying drawing explanation
Fig. 1 is the opticmicroscope figure (magnification is 1000) of thermosetting resin selfreparing uramit coated epoxy resin Nano capsule;
Fig. 2 is the TGA curve of thermosetting resin selfreparing uramit coated epoxy resin Nano capsule;
Fig. 3 is the grain size distribution curve of thermosetting resin selfreparing uramit coated epoxy resin Nano capsule;
The curve that Fig. 4 uramit coated epoxy resin microcapsules and uramit coated epoxy resin Nano capsule affect unsaturated polyester resin tensile strength;
The curve that Fig. 5 uramit coated epoxy resin microcapsules and uramit coated epoxy resin Nano capsule affect unsaturated polyester resin flexural strength.
Embodiment
A kind of selfreparing Nano capsule/thermosetting resin based composites of the present invention, is prepared by following steps:
1) by urea, formaldehyde in molar ratio the amount of 1:1 ~ 1:3 join in there-necked flask and stir, add urea to reduce the amount of free formaldehyde in batches, form urea formaldehyde solution, then add and account for the trimeric cyanamide that urea formaldehyde mass ratio is 0% ~ 50%.Alkali tune agent adjust ph is adopted to be 8 ~ 9, slowly be warming up to 60 ~ 80 DEG C, constant temperature water bath 60 ~ 80 DEG C reaction 30 ~ 60min, the terminal degree of detection reaction, stops heating when temperature is down to room temperature, obtain uramit performed polymer (PUF performed polymer) or the melamine-urea formaldehyde performed polymer (MUF performed polymer) of clear viscous; Wherein, wall material raw material is urea, formaldehyde and trimeric cyanamide;
2) epoxy resin getting 8.0 ~ 20.0g is core, 1.5 ~ 3g capsule-core thinner, 0.5 ~ 3g emulsifying agent, 0.05 ~ 1g defoamer, adds 100mL deionized water emulsification 1 ~ 2h, forms O/W type emulsion.Stir 10 ~ 20min with homogenizer 800 ~ 1000rpm, then use ultrasonic cell disruptor supersound process 6 ~ 9min under power 1000 ~ 2000W, supersound process 1 ~ 5min under power 200 ~ 400W, form miniemulsion;
3) adding in the miniemulsion of preparation by performed polymer, is (3 ~ 5) according to wall material raw material and core raw material: the mass ratio of 10; Stir constant temperature 60 ~ 80 DEG C, reaction 1 ~ 3h, this stage adds acidity regulator solution in batches, slow adjust ph is 2 ~ 3, continue under stir speed (S.S.) 200 ~ 400rpm to stir, 1 ~ 3h completes the solidification process of Nano capsule, finally by adding alkali tune agent solution, system pH being adjusted to 5 ~ 7, obtaining the suspension of Nano capsule;
4) this suspension is naturally cooled to room temperature, filter by ordinary method, distilled water wash 2 ~ 5 times, lyophilize, obtains uramit coated epoxy resin Nano capsule (PUF Nano capsule) or melamine-urea formaldehyde coated epoxy resin Nano capsule (MUF Nano capsule) product;
5) thermosetting resin of 100g is taken, add the toughener of the selfreparing Nano capsule of 5 ~ 20g, the matrix solidifying agent of 2 ~ 20g, core epoxy resin lalent solidifying agent 0.5 ~ 5g, 10 ~ 30g, mixing is magnetic agitation 5 ~ 30min also, put into vacuum drying oven and vacuumize 10 ~ 60min, slough bubble, obtain thermosetting resin mixed solution, poured in silica gel mould, be put in self-vulcanizing 20 ~ 30h, aftertreatment 1 ~ 2h, with to be tested.
Wherein, the cyst material of selfreparing Nano capsule is melmac or urea-formaldehyde resin; The capsule-core epoxy resin used of selfreparing Nano capsule is bis-phenol A glycidyl ether type epoxy resin, Bisphenol F diglycidyl ether type epoxy resin, Resorcinol glycidyl ester type epoxy resin or methylol diglycidyl ether type epoxy resin; The capsule-core thinner of selfreparing Nano capsule is selected from chlorobenzene, 1-butylglycidyl ether, phenylcarbinol, ethyl acetate or ethyl acetic acid phenyl ester.
Emulsifying agent is selected from Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, alkylphenol polyoxyethylene ether, sorbitan monooleate Soxylat A 25-7, sorbitan monooleate or styrene-maleic anhydride copolymer; Alkali tune agent is NaOH solution, Carbon Dioxide sodium solution or trolamine; Acidity regulator is NH
4cl solution or HCl solution; Defoamer is selected from lower alcohols and polar organic compounds system.Lower alcohol defoamer is preferably methyl alcohol, ethanol, Virahol, propyl carbinol or n-Octanol; Polar organic compounds defoamer is preferably amylalcohol, diisobutyl carbinol(DIBC), octanol or propylene glycol.
Thermosetting resin matrix is the one in epoxy resin, unsaturated polyester resin, epoxy vingl ester resin or silicone resin.
Matrix solidifying agent is selected according to the kind of matrices of composite material.Epoxy resin-base solidifying agent used is organic acid, acid anhydrides, boron trifluoride and complex compound thereof, aliphatie diamine and polyamines, aromatic polyamine, other nitrogenous compound and modified fatty amine etc., be preferably aliphatic polyamine as quadrol, hexanediamine, diethylenetriamine, triethylene tetramine, diethylaminopropylamine etc.; Unsaturated polyester resin matrix preferred consolidation system is dibenzoyl peroxide, methylethyl ketone peroxide, cyclohexanone peroxide, cyclohexanone peroxide, DMA, cobalt iso-octoate; The agent of epoxy vingl ester resin matrix preferred consolidation is vinylbenzene; The agent of silicone resin matrix preferred consolidation is diethylenetriamine or triethylene tetramine;
Toughener is preferably glass fiber reinforcements system; Core epoxy resin lalent solidifying agent is glyoxal ethyline, 2-ethyl-4-methylimidazole or 2-phenylimidazole.
Below in conjunction with specific embodiment, the present invention is described in further detail, and the explanation of the invention is not limited.
The following example only for further illustrating the present invention, persons skilled in the art can disclosed in this specification sheets content, adopt other other method multiple to implement the present invention.
Embodiment 1:
1) urea 2.0g, formaldehyde solution (37wt%) 5.4g are joined in there-necked flask and stir.Adopt trolamine adjust ph to be 9, be slowly warming up to 70 DEG C, constant temperature water bath reaction 30min, the terminal degree of detection reaction, stops heating when temperature is down to room temperature, obtain the urea formaldehyde performed polymer (PUF performed polymer) of clear viscous;
2) getting Bisphenol F diglycidyl ether type epoxy resin 8.0g is core, 1-butylglycidyl ether 2.0g, and 1.8g Sodium dodecylbenzene sulfonate is emulsifying agent, n-Octanol 0.5g is defoamer, add 100mL deionized water, stir speed (S.S.) 600rpm stirs 1.5h, forms O/W type emulsion.With homogenizer 900rpm stir 15min, then use ultrasonic cell disruptor supersound process 8min under power 1500W, then under power 300W ultrasonic 4min, formed miniemulsion;
3) PUF performed polymer is poured in the miniemulsion prepared, stir constant temperature 70 DEG C, reaction 2h, this stage adds HCl solution in batches, slow adjust ph is 2, continues to stir the solidification process that 1.5h completes Nano capsule under constant stirring rate 300rpm, finally adds NaOH solution and system pH is adjusted to 6, naturally cooling, obtains the suspension containing Nano capsule;
4) use distilled water wash 3 times, filter, lyophilize, obtains urea formaldehyde coated epoxy resin Nano capsule (PUF Nano capsule) product;
5) 100.0g unsaturated polyester resin is taken, add 10.0g Nano capsule, 2.0g cobalt naphthenate promotor, 2.0g methylethyl ketone peroxide solidifying agent, 2.0g2-phenylimidazole and 15.0g glass fibre, mixing is magnetic agitation 15min also, put into vacuum drying oven and vacuumize 40min, obtain unsaturated polyester mixed solution, poured into through preheating and scribbled in the silica gel mould of releasing agent, be put in self-vulcanizing 25h, 50 DEG C of aftertreatment 1.5h, the casting matrix prepared is cut into desired size sample on cutting machine, with to be tested.
Embodiment 2:
1) urea 2.0g, formaldehyde solution (37wt%) 2.7g are joined in there-necked flask and stir, then add 1.5g trimeric cyanamide.Adopt trolamine adjust ph to be 8, be slowly warming up to 60 DEG C, constant temperature water bath reaction 30min, the terminal degree of detection reaction, stops heating when temperature is down to room temperature, obtain the melamine-urea formaldehyde performed polymer (MUF performed polymer) of clear viscous;
2) getting bis-phenol A glycidyl ether type epoxy resin 11.3g is core, 1-butylglycidyl ether 1.5g, and 0.5g Sodium dodecylbenzene sulfonate is emulsifying agent, n-Octanol 0.05g is defoamer, add 100mL deionized water, stir speed (S.S.) 600rpm stirs 1h, forms O/W type emulsion.Stir 10min with homogenizer 800rpm, then use ultrasonic cell disruptor supersound process 6min under power 1000W, supersound process 1min under power 200W, form miniemulsion;
3) poured into by MUF performed polymer in the miniemulsion prepared, stir constant temperature 60 DEG C, reaction 1h, this stage adds NH in batches
4cl solution, slow adjust ph is 2, continues to stir the solidification process that 1h completes Nano capsule under constant stirring rate 200rpm, finally adds 10wt% sodium carbonate solution and system pH is adjusted to 5, naturally cooling, obtain the suspension containing Nano capsule;
4) use distilled water wash 2 times, filter, lyophilize, obtains melamine-urea formaldehyde coated epoxy resin Nano capsule (MUF Nano capsule) product;
5) 100.0g unsaturated polyester resin is taken, add 5.0g Nano capsule, 1.0g cobalt naphthenate promotor, 1.0g methylethyl ketone peroxide solidifying agent, 0.5g2-phenylimidazole and 10.0g glass fibre, mixing is magnetic agitation 5min also, put into vacuum drying oven and vacuumize 10min, obtain unsaturated polyester mixed solution, poured into through preheating and scribbled in the silica gel mould of releasing agent, be put in self-vulcanizing 20h, 40 DEG C of aftertreatment 1h, the casting matrix prepared is cut into desired size sample on cutting machine, with to be tested.
Embodiment 3:
1) urea 2.0g, formaldehyde solution (37wt%) 8.1g are joined in there-necked flask and stir, then add 1.0g trimeric cyanamide.Adopt trolamine adjust ph to be 8, be slowly warming up to 70 DEG C, constant temperature water bath reaction 40min, the terminal degree of detection reaction, stops heating when temperature is down to room temperature, obtain the melamine-urea formaldehyde performed polymer (MUF performed polymer) of clear viscous;
2) getting Resorcinol glycidyl ester type epoxy resin 20.0g is core, 1-butylglycidyl ether 2.0g, and 1.8g Sodium dodecylbenzene sulfonate is emulsifying agent, n-Octanol 0.5g is defoamer, add 100mL deionized water, stir speed (S.S.) 600rpm stirs 1.5h, forms O/W type emulsion.With homogenizer 900rpm stir 15min, then use ultrasonic cell disruptor supersound process 8min under power 1500W, then under power 300W supersound process 4min, formed miniemulsion;
3) MUF performed polymer is poured in the miniemulsion prepared, stir constant temperature 70 DEG C, reaction 2h, this stage adds HCl solution in batches, slow adjust ph is 2, continues to stir the solidification process that 1.5h completes Nano capsule under constant stirring rate 300rpm, finally adds NaOH solution and system pH is adjusted to 6, naturally cooling, obtains the suspension containing Nano capsule;
4) use distilled water wash 3 times, filter, lyophilize, obtains melamine-urea formaldehyde coated epoxy resin Nano capsule (MUF Nano capsule) product;
5) 100.0g epoxy resin 828 is taken, add 5.0g Nano capsule, 10.0g glass fibre, 1.0g triethylene tetramine, mixing is magnetic agitation 10min also, put into vacuum drying oven and vacuumize 40min, obtain epoxy resin mixed solution, poured into through preheating and scribble in the silica gel mould of releasing agent, be put in self-vulcanizing 24h, 60 DEG C of aftertreatment 2h, are cut into desired size sample by the casting matrix prepared on cutting machine, with to be tested.
Embodiment 4:
1) urea 2.0g, formaldehyde solution (37wt%) 2.7g are joined in there-necked flask and stir, then add 1.5g trimeric cyanamide.Adopt trolamine adjust ph to be 9, be slowly warming up to 80 DEG C, constant temperature water bath reaction 60min, the terminal degree of detection reaction, stops heating when temperature is down to room temperature, obtain the melamine-urea formaldehyde performed polymer (MUF performed polymer) of clear viscous;
2) getting methylol diglycidyl ether type epoxy resin 11.3g is core, and 1-butylglycidyl ether 3.0g is thinner, and 3.0g Sodium dodecylbenzene sulfonate is emulsifying agent, n-Octanol 1.0g is defoamer, add 100mL deionized water, stir speed (S.S.) 700rpm stirs 1h, forms O/W type emulsion.With homogenizer 1000rpm stir 20min, then use ultrasonic cell disruptor supersound process 9min under power 2000W, then under power 400W supersound process 5min, formed miniemulsion;
3) MUF performed polymer is poured in the miniemulsion prepared, stir constant temperature 80 DEG C, reaction 3h, this stage adds HCl solution in batches, slow adjust ph is 3, continues to stir the solidification process that 3h completes Nano capsule under constant stirring rate 400rpm, finally by adding trolamine, system pH is adjusted to 7, naturally cooling, obtains the suspension containing Nano capsule;
4) use distilled water wash 5 times, filter, lyophilize, obtains melamine-urea formaldehyde coated epoxy resin Nano capsule (MUF Nano capsule) product;
5) 100.0g epoxy resin 828 is taken, add 10.0g Nano capsule, 15.0g glass fibre, 4.0g2-phenylimidazole, 1.5g triethylene tetramine, mixing is magnetic agitation 30min also, put into vacuum drying oven and vacuumize 60min, obtain epoxy resin mixed solution, poured into through preheating and scribble in the silica gel mould of releasing agent, be put in self-vulcanizing 24h, 60 DEG C of aftertreatment 2h, are cut into desired size sample by the casting matrix prepared on cutting machine, with to be tested.
Embodiment 5:
1) urea 2.0g, formaldehyde solution (37wt%) 5.4g are joined in there-necked flask and stir, then add 1.2g trimeric cyanamide.Adopt trolamine adjust ph to be 9, be slowly warming up to 80 DEG C, constant temperature water bath reaction 60min, the terminal degree of detection reaction, stops heating when temperature is down to room temperature, obtain the melamine-urea formaldehyde performed polymer (MUF performed polymer) of clear viscous;
2) getting bis-phenol A glycidyl ether type epoxy resin 14.0g is core, 1-butylglycidyl ether 2.0g is thinner, 1.8g alkylphenol polyoxyethylene ether is emulsifying agent, n-Octanol 0.5g is defoamer, add 100mL deionized water, stir speed (S.S.) 700rpm stirs 1.5h, forms O/W type emulsion.Stir 10min with homogenizer 800rpm, then use ultrasonic cell disruptor supersound process 6min under power 1000W, supersound process 5min under power 400W, form miniemulsion;
3) poured into by MUF performed polymer in the miniemulsion prepared, stir constant temperature 80 DEG C, reaction 3h, this stage adds NH in batches
4cl solution, slow adjust ph is 3, continues to stir the solidification process that 1.5h completes Nano capsule under constant stirring rate 300rpm, system pH being adjusted to 6, naturally cooling, obtaining the suspension containing Nano capsule finally by adding 10wt% sodium carbonate solution;
4) use distilled water wash 3 times, filter, lyophilize, obtains melamine-urea formaldehyde coated epoxy resin Nano capsule (MUF Nano capsule) product;
5) 100.0g epoxy vingl ester resin is taken, add 10.0g Nano capsule, 15.0g glass fibre, 6.0g2-phenylimidazole, 3.0g benzoyl peroxide, mixing is magnetic agitation 20min also, put into vacuum drying oven and vacuumize 30min, obtain epoxy vingl ester resin mixed solution, poured into through preheating and scribble in the silica gel mould of releasing agent, be put in self-vulcanizing 24h, 60 DEG C of aftertreatment 2h, are cut into desired size sample by the casting matrix prepared on cutting machine, with to be tested.
Embodiment 6:
1) urea 2.0g, formaldehyde solution (37wt%) 8.1g, 1.0g trimeric cyanamide are joined in there-necked flask and stir.Adopt trolamine adjust ph to be 8, be slowly warming up to 60 DEG C, constant temperature water bath reaction 30min, the terminal degree of detection reaction, stops heating when temperature is down to room temperature, obtain the melamine-urea formaldehyde performed polymer (MUF performed polymer) of clear viscous;
2) getting bis-phenol A glycidyl ether type epoxy resin 20.0g is core, and 1-butylglycidyl ether 3.0g is thinner, and 3.0g Sodium dodecylbenzene sulfonate is emulsifying agent, n-Octanol 1.0g is defoamer, add 100mL deionized water, stir speed (S.S.) 700rpm stirs 1h, forms O/W type emulsion.With homogenizer 1000rpm stir 20min, then use ultrasonic cell disruptor supersound process 9min under power 1500W, then under power 400W supersound process 5min, formed miniemulsion;
3) MUF performed polymer is poured in the miniemulsion prepared, stir constant temperature 60 DEG C, reaction 1h, this stage adds HCl solution in batches, slow adjust ph is 2, continues to stir the solidification process that 1h completes Nano capsule under constant stirring rate 200rpm, finally by adding 10wt% sodium carbonate solution, system pH is adjusted to 5, naturally cooling, obtains the suspension containing Nano capsule;
4) use distilled water wash 3 times, filter, lyophilize, obtains melamine-urea formaldehyde coated epoxy resin Nano capsule (MUF Nano capsule) product;
5) 100.0g silicone resin is taken, add 20.0g Nano capsule, 30.0g glass fibre, 6.0g2-phenylimidazole, 1.5g triethylene tetramine, mixing is magnetic agitation 20min also, put into vacuum drying oven and vacuumize 20min, obtain silicone resin mixed solution, poured into through preheating and scribble in the silica gel mould of releasing agent, be put in self-vulcanizing 24h, 60 DEG C of aftertreatment 2h, are cut into desired size sample by the casting matrix prepared on cutting machine, with to be tested.
A kind of selfreparing Nano capsule prepared by the present invention and the performance introduction of unsaturated polyester composite as follows:
Performance analysis is carried out to selfreparing Nano capsule prepared by embodiment 1, its OM figure (amplifies 1000 times) as described in Figure 1, its grain size distribution as shown in Figure 2, its TGA curve as shown in Figure 3, as shown in Figure 4, the impact of selfreparing Nano capsule and its unsaturated polyester composite flexural strength of microcapsule as shown in Figure 5 in the impact of selfreparing Nano capsule and its unsaturated polyester composite tensile strength of microcapsule.
Fig. 1 shows, the selfreparing Nano capsule of preparation is obvious capsule structure, and according to the aggregation features of reaction, can draw, external bladder wall portion (dark color) is polymkeric substance, and capsule-core part (light color) is renovation agent epoxy resin.Its shape is spherical in shape, and size distribution is comparatively even.
Fig. 2 shows, prepared Nano capsule median size is 100nm, its narrower particle size distribution, and show that Nano capsule particle diameter is comparatively even, its test result schemes (Fig. 1) result with OM is consistent.
Fig. 3 shows, the better heat stability of selfreparing Nano capsule prepared by embodiment 1,200 DEG C about have 10% mass loss.
Fig. 4 and Fig. 5 shows, the unsaturated polyester composite containing Nano capsule of embodiment 1 preparation is compared with the tensile strength of the unsaturated polyester composite containing microcapsule and flexural strength, and the Effect on Mechanical Properties of Nano capsule to unsaturated polyester composite is little.
The foregoing is only several embodiment of the present invention, is not whole or unique embodiment, and the conversion of those skilled in the art by reading specification sheets of the present invention to any equivalence that technical solution of the present invention is taked, is claim of the present invention and contains.
Claims (9)
1. a preparation method for selfreparing Nano capsule/thermosetting resin based composites, is characterized in that, comprise the following steps:
1) by urea, formaldehyde in molar ratio the amount of 1:1 ~ 1:3 join in container and stir, form urea formaldehyde solution; Add again in urea formaldehyde solution and account for the trimeric cyanamide that urea formaldehyde mass ratio is 0% ~ 50%, adopt alkali tune agent adjust ph to be 8 ~ 9, be slowly warming up to 60 ~ 80 DEG C, constant temperature water bath reaction to terminal, heating is stopped to treat that temperature is down to room temperature, the performed polymer of obtained clear viscous; Wherein, wall material raw material is urea, formaldehyde and trimeric cyanamide;
2) getting wall material raw material with core raw materials quality ratio is (3 ~ 5): the epoxy resin of 10 is core, add 100 parts of deionized waters, 1.5 ~ 3 parts of capsule-core thinners, 0.5 ~ 3 part of emulsifying agent, 0.05 ~ 1 part of defoamer, homogenizer 800 ~ 1000rpm stirs 10 ~ 20min and forms emulsion, and then supersound process forms miniemulsion;
3) by step 1) performed polymer that obtains adds step 2) stir constant temperature 60 ~ 80 DEG C in the miniemulsion prepared, reaction 1 ~ 3h, this stage adds acidity regulator solution in batches, slow adjust ph is 2 ~ 3, continue under stir speed (S.S.) 200 ~ 400rpm to stir, 1 ~ 3h completes the solidification process of Nano capsule, finally by adding alkali tune agent solution, system pH being adjusted to 5 ~ 7, obtaining the suspension of Nano capsule;
4) by step 3) suspension that obtains naturally cools to room temperature, and filter, distilled water wash, lyophilize, obtains selfreparing Nano capsule product;
5) according to parts by weight, take the thermosetting resin of 100 parts, add step 4) the selfreparing Nano capsule of obtain 5 ~ 20 parts, matrix solidifying agent, core epoxy resin lalent solidifying agent 0.5 ~ 5 part, the toughener of 10 ~ 30 parts of 2 ~ 20 parts, mixing is magnetic agitation 5 ~ 30min also, put into vacuum drying oven and vacuumize 10 ~ 60min, slough bubble, obtain thermosetting resin mixed solution, poured in silica gel mould, be put in self-vulcanizing 20 ~ 30h, aftertreatment 1 ~ 2h, obtains selfreparing Nano capsule/thermosetting resin based composites.
2. selfreparing Nano capsule/thermosetting resin based composites according to claim 1, it is characterized in that, described supersound process is specially: by emulsion in ultrasonic cell disruptor, first supersound process 6 ~ 9min under power 1000 ~ 2000W, then supersound process 1 ~ 5min forms miniemulsion under power 200 ~ 400W.
3. selfreparing Nano capsule/thermosetting resin based composites according to claim 1, it is characterized in that, the core materials of described selfreparing Nano capsule is bis-phenol A glycidyl ether type, Bisphenol F diglycidyl ether type, Resorcinol glycidyl ester type or methylol diglycidyl ether type.
4. selfreparing Nano capsule/thermosetting resin based composites according to claim 1, is characterized in that,
Described capsule-core thinner is chlorobenzene, 1-butylglycidyl ether, phenylcarbinol, ethyl acetate or ethyl acetic acid phenyl ester;
Described emulsifying agent is Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, alkylphenol polyoxyethylene ether, sorbitan monooleate Soxylat A 25-7, sorbitan monooleate or styrene-maleic anhydride copolymer.
5. selfreparing Nano capsule/thermosetting resin based composites according to claim 1, is characterized in that,
Described alkali tune agent is NaOH solution, Carbon Dioxide sodium solution or trolamine;
Described acidity regulator is NH
4cl solution or HCl solution.
6. selfreparing Nano capsule/thermosetting resin based composites according to claim 1, is characterized in that,
Described defoamer is lower alcohols or polar organic compounds system, and lower alcohol defoamer is methyl alcohol, ethanol, Virahol, propyl carbinol, n-Octanol; Polar organic compounds defoamer is amylalcohol, diisobutyl carbinol(DIBC), octanol, propylene glycol.
7. selfreparing Nano capsule/thermosetting resin based composites according to claim 1, is characterized in that,
Described thermosetting resin matrix is the one in epoxy resin, unsaturated polyester resin, epoxy vingl ester resin or silicone resin.
8. selfreparing Nano capsule/thermosetting resin based composites according to claim 7, it is characterized in that, epoxy resin-base solidifying agent used is organic acid, acid anhydrides, boron trifluoride and complex compound thereof, aliphatie diamine and polyamines, aromatic polyamine, other nitrogenous compound and modified fatty amine etc., be preferably aliphatic polyamine as the one in quadrol, hexanediamine, diethylenetriamine, triethylene tetramine, diethylaminopropylamine; Unsaturated polyester resin matrix solidifying agent used is the one in dibenzoyl peroxide, methylethyl ketone peroxide, cyclohexanone peroxide, cyclohexanone peroxide, DMA or cobalt iso-octoate, and promotor is cobalt naphthenate; Epoxy vingl ester resin matrix solidifying agent used is vinylbenzene; Silicone resin matrix solidifying agent used is the one in diethylenetriamine or triethylene tetramine.
9. selfreparing Nano capsule/thermosetting resin based composites according to claim 1, is characterized in that,
Described toughener is glass fibre;
Described core epoxy resin lalent solidifying agent is the one in glyoxal ethyline, 2-ethyl-4-methylimidazole or 2-phenylimidazole.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440692A (en) * | 2015-12-14 | 2016-03-30 | 华南理工大学 | Microcapsule-type self-repairing polysiloxane elastomer and preparation method thereof |
| CN105536657A (en) * | 2016-01-04 | 2016-05-04 | 江苏金陵特种涂料有限公司 | Synthetic method for light-induced self-repair microcapsules |
| CN106042526A (en) * | 2016-05-27 | 2016-10-26 | 苏州多凯复合材料有限公司 | Novel intermediate full-length yarn enhanced fiber composite and production method thereof |
| CN107233852A (en) * | 2017-06-28 | 2017-10-10 | 常州汉唐文化传媒有限公司 | A kind of preparation method of magnetic self-repairing microcapsule |
| CN107353592A (en) * | 2017-07-05 | 2017-11-17 | 奇瑞汽车股份有限公司 | A kind of selfreparing carbon fibre composite part and preparation method thereof |
| CN109233864A (en) * | 2018-11-20 | 2019-01-18 | 江苏路业新材料有限公司 | A kind of soil curing agent and preparation method thereof |
| CN110358322A (en) * | 2019-07-30 | 2019-10-22 | 浙江互融新材料科技有限公司 | A kind of plastics base composite board and preparation method thereof of flyash filling |
| CN110627413A (en) * | 2019-10-22 | 2019-12-31 | 江苏理工学院 | Self-repairing artificial quartz stone and preparation method thereof |
| CN112428598A (en) * | 2020-10-30 | 2021-03-02 | 浙江华电器材检测研究所有限公司 | Preparation method of self-repairing electrical operation insulating operating rod |
| CN115160093A (en) * | 2022-07-05 | 2022-10-11 | 湖北航天化学技术研究所 | Cast type self-repairing simulated explosive and preparation method thereof |
| CN115850973A (en) * | 2022-12-15 | 2023-03-28 | 国网浙江省电力有限公司湖州供电公司 | Preparation method of self-repairing nano silicon carbide modified wear-resistant rubber block |
| CN116554721A (en) * | 2023-05-12 | 2023-08-08 | 南京林业大学 | Wood material surface water-based paint anti-corrosion self-repairing compatible microcapsule and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604469A (en) * | 2012-02-13 | 2012-07-25 | 中国船舶重工集团公司第七二五研究所 | Latent self-repair microcapsule and preparation method thereof |
-
2015
- 2015-08-14 CN CN201510501236.8A patent/CN105086396B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604469A (en) * | 2012-02-13 | 2012-07-25 | 中国船舶重工集团公司第七二五研究所 | Latent self-repair microcapsule and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 倪卓等: ""微胶囊对微胶囊/ 环氧树脂复合材料增韧作用"", 《复合材料学报》 * |
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| CN105440692A (en) * | 2015-12-14 | 2016-03-30 | 华南理工大学 | Microcapsule-type self-repairing polysiloxane elastomer and preparation method thereof |
| CN105440692B (en) * | 2015-12-14 | 2018-06-22 | 华南理工大学 | A kind of microcapsule-type selfreparing silicone elastomer and preparation method thereof |
| CN105536657A (en) * | 2016-01-04 | 2016-05-04 | 江苏金陵特种涂料有限公司 | Synthetic method for light-induced self-repair microcapsules |
| CN106042526A (en) * | 2016-05-27 | 2016-10-26 | 苏州多凯复合材料有限公司 | Novel intermediate full-length yarn enhanced fiber composite and production method thereof |
| CN107233852A (en) * | 2017-06-28 | 2017-10-10 | 常州汉唐文化传媒有限公司 | A kind of preparation method of magnetic self-repairing microcapsule |
| CN107353592A (en) * | 2017-07-05 | 2017-11-17 | 奇瑞汽车股份有限公司 | A kind of selfreparing carbon fibre composite part and preparation method thereof |
| CN109233864A (en) * | 2018-11-20 | 2019-01-18 | 江苏路业新材料有限公司 | A kind of soil curing agent and preparation method thereof |
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| CN110627413A (en) * | 2019-10-22 | 2019-12-31 | 江苏理工学院 | Self-repairing artificial quartz stone and preparation method thereof |
| CN112428598A (en) * | 2020-10-30 | 2021-03-02 | 浙江华电器材检测研究所有限公司 | Preparation method of self-repairing electrical operation insulating operating rod |
| CN115160093A (en) * | 2022-07-05 | 2022-10-11 | 湖北航天化学技术研究所 | Cast type self-repairing simulated explosive and preparation method thereof |
| CN115850973A (en) * | 2022-12-15 | 2023-03-28 | 国网浙江省电力有限公司湖州供电公司 | Preparation method of self-repairing nano silicon carbide modified wear-resistant rubber block |
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