CN101153108A - Self-repaired polyalcohol composite material at room temperature - Google Patents
Self-repaired polyalcohol composite material at room temperature Download PDFInfo
- Publication number
- CN101153108A CN101153108A CNA2007100299916A CN200710029991A CN101153108A CN 101153108 A CN101153108 A CN 101153108A CN A2007100299916 A CNA2007100299916 A CN A2007100299916A CN 200710029991 A CN200710029991 A CN 200710029991A CN 101153108 A CN101153108 A CN 101153108A
- Authority
- CN
- China
- Prior art keywords
- mercaptan
- epoxy resin
- capsule
- ester
- self
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 22
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- 239000002775 capsule Substances 0.000 claims abstract description 41
- 239000011159 matrix material Substances 0.000 claims abstract description 32
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 15
- -1 glycidyl ester Chemical class 0.000 claims description 50
- 239000003822 epoxy resin Substances 0.000 claims description 42
- 229920000647 polyepoxide Polymers 0.000 claims description 42
- 239000004593 Epoxy Substances 0.000 claims description 29
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 27
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- 239000011347 resin Substances 0.000 claims description 27
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 16
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- 125000005843 halogen group Chemical group 0.000 claims description 12
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- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 claims description 8
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- WPYCRFCQABTEKC-UHFFFAOYSA-N Diglycidyl resorcinol ether Chemical compound C1OC1COC(C=1)=CC=CC=1OCC1CO1 WPYCRFCQABTEKC-UHFFFAOYSA-N 0.000 claims description 7
- 208000031513 cyst Diseases 0.000 claims description 7
- 229940059574 pentaerithrityl Drugs 0.000 claims description 7
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- 229930185605 Bisphenol Natural products 0.000 claims description 5
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- OWWNFGGOZYTYQL-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxycarbonyl)cyclohex-3-ene-1-carboxylic acid Chemical compound OC(=O)C1CCC=CC1C(=O)OCC1OC1 OWWNFGGOZYTYQL-UHFFFAOYSA-N 0.000 claims description 2
- WKJICCKTDQDONB-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxycarbonyl)cyclohexane-1-carboxylic acid Chemical compound OC(=O)C1CCCCC1C(=O)OCC1OC1 WKJICCKTDQDONB-UHFFFAOYSA-N 0.000 claims description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
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- 125000003545 alkoxy group Chemical group 0.000 claims description 2
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- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
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- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
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- 125000005358 mercaptoalkyl group Chemical group 0.000 claims description 2
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- 150000004714 phosphonium salts Chemical class 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
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- 229920006305 unsaturated polyester Polymers 0.000 claims description 2
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Abstract
The present invention relates to the technological field of self-repairing polymer material and discloses a self-repairing polymer composite material at the room temperature. The self-repairing polymer composite material is made of the following components of the following weight percentages: 40 percent to 98 percent of polymer matrix, 1 percent to 50 percent of capsule containing liquid epoxy resin, 1 percent to 50 percent of capsule containing liquid poly mercaptan and 0.1 percent to 15 percent of catalyst. The capsules containing the liquid epoxy resin and the poly mercaptan of the present invention can bear the external force of processing when the material is prepared. When the matrix material is damaged and cracked, the crack can be split together with the matrix while passing the capsules to release two reaction substances. The two reaction substances are polymerized rapidly so as to prevent the increase of the crack and to repair the crack. The self-repairing composite material of the present invention needs no heating while repairing; and the crack repair can be automatically finished at the room temperature.
Description
Technical field
The present invention relates to a kind of self-repair type polymer composite material.
Background technology
Polymer materials has obtained widespread use in industries such as building, machinery, microelectronics, in use portion produces local damage and tiny crack to polymer materials owing to mechanical fatigue, thermal fatigue, impact, radiation, chemical degradation etc. act on inevitably within it, causes degradation.Therefore, to the early discovery of polymer materials tiny crack with to repair be a very actual problem since the crackle of polymkeric substance often within it the portion depths occur, be difficult to adopt conventional means to survey and repair.If these damages can not in time be repaired, can have a strong impact on normally using and shortening the life-span of material, cause the accident.Therefore, research polymer materials bionical reparation-self-healing, initiatively, automatically to damage location repair, very important to the application of polymer materials.
In recent years, comprise for giving the polymer materials damage method that self-reparing capability develops:
(1) employing is carried out the hot reversible copolymerization of Diels-Alder (DA) as body material with furans polymer and maleimide polymer, can form covalent linkage in the place that need the crackle reparation, also can repeatedly repair crackle and need not add extra monomer by thermal treatment.Referring to people such as Chen, " A Thermally Re-Memdable Cross-Linked PolymericMaterial ", Science, Vol.295, March 2002, pp.1698-1702.Yet this method exists some problem needs perfect, and is too high as: maleimide monomer fusing point, be insoluble to the furans tetramer, needs to reduce the fusing point of reaction monomers and improves mutual solubility; This polymkeric substance is at 130 ℃ of following completion of cures, solidifies consuming time longlyer, needs fast reaction speed.In addition, the use temperature of this polymkeric substance (80-120 ℃) is more satisfactory for the electronic package material that cracks because of thermal expansion coefficient difference, then seems low for the application of other many polymkeric substance.
(2) be that catalyzer forms high crosslinked polymer network in the polymerization of damage field initiation dicyclopentadiene with the metal Ru title complex.Wherein, repair the monomer dicyclopentadiene and deposit in the microcapsule, granules of catalyst directly is scattered in the matrix, or wraps up with paraffin, or is grafted to capsule surface.Referring to patent US 6518330B2, US6858659B2, US 71089142B2, CN1669132A, people such as CN1509298A and document Joseph.D.Rule, Wax-Protected Catalyst Microspheres for Efficient Self-Healing Materials, Advanced Materials, Vol (17), 2005, pp.205-208.The problem that this method exists is: (a) have reactive monomer self instability of two keys, store the long time or temperature is too high all self-polymeric reaction can take place; (b) monomeric physicals instability, vapour pressure height, easily infiltration, volatilization; (c) instability of high activated catalyst, easy inactivation, the environment ability to bear is poor; (d) rise between the bonding composition of repair and matrix and lack chemical action.
(3) adopt polydimethylsiloxane as repair materials, by being separated polydimethylsiloxane is distributed in the polyvinylesters resin, the initiator di-n-butyltin dilaurate is stored in the microcapsule, and promotor is added in the matrix.Referring to people such as Soo Hyoun Cho, Polydimethylsiloxane-Based Self-Healing Materials, AdvancedMaterials, Vol (18), 2006, pp.997-1000.This method existing problems are: (a) rise between the bonding composition of repair and matrix and lack chemical action, thereby repairing effect is poor; (b) range of choice of matrix is limited, must can not dissolve polydimethylsiloxane, otherwise can't be separated.
Summary of the invention
The objective of the invention is defective, provide self-regeneration of a kind of energy and repair process not to need the self-repaired polyalcohol composite material at room temperature based on cross linking of epoxy resin of manual intervention at prior art.
A kind of self-repaired polyalcohol composite material at room temperature, form by following component and weight percentage:
Polymeric matrix 40～98%,
The capsule 1～50% that contains liquid-state epoxy resin,
The capsule 1～50% that contains liquid polythiol,
Catalyzer 0.1～15%,
Wherein, catalyzer is in containing the capsule of liquid polythiol or be distributed in the polymeric matrix.
In above-mentioned self-repaired polyalcohol composite material at room temperature, described polymeric matrix is Resins, epoxy, unsaturated polyester, resol, urethane, polymeric amide or acrylic resin.
In above-mentioned self-repaired polyalcohol composite material at room temperature, the described capsular core that contains liquid-state epoxy resin is a liquid-state epoxy resin, the capsule wall material is melamine formaldehyde resin, urea-formaldehyde resin or its mixture, capsule-core/cyst wall weight ratio is 1: 2～9: 1, capsule mean diameter 1 μ m～1mm, wall thickness 100nm～10 μ m.
In above-mentioned self-repaired polyalcohol composite material at room temperature, described liquid-state epoxy resin is: part bisphenol A type epoxy resin (as dihydroxyphenyl propane glycidyl ether EPON 828), the partial hydrogenation bisphenol A type epoxy resin, the part bisphenol f type epoxy resin, dihydroxyphenyl propane D type Resins, epoxy, Resorcinol type Resins, epoxy (as Resorcinol glycidyl ether J-80), methylol bisphenol A type epoxy resin (as methylol dihydroxyphenyl propane glycidyl ether CEQ-45), the part glycidyl ester type epoxy resin is (as the phthalic acid glycidyl ester, the tetrahydrophthalic acid glycidyl ester, hexahydrophthalic acid glycidyl ester or 1, the mixture of one or more 2 epoxy cyclohexanes 4,5-dioctyl phthalate glycidyl ester).
In above-mentioned self-repaired polyalcohol composite material at room temperature, the preferably combination of described liquid-state epoxy resin has following a few class: (1) a kind of glycidyl ester type epoxy resin; (2) mixture of two or more glycidyl ester type epoxy resins; (3) mixture of Resorcinol glycidyl ether and one or more glycidyl ester type epoxy resins; (4) one or more glycidyl ester type epoxy resins and bisphenol A type epoxy resin, or (with) bisphenol f type epoxy resin, or (with) mixture of dihydroxyphenyl propane D type Resins, epoxy; (5) mixture of one or more glycidyl ester type epoxy resins and methylol dihydroxyphenyl propane glycidyl ether; (6) Resorcinol glycidyl ether and bisphenol A type epoxy resin, or (with) bisphenol f type epoxy resin, or (with) mixture of dihydroxyphenyl propane D type Resins, epoxy; (6) mixture of Resorcinol glycidyl ether and methylol dihydroxyphenyl propane glycidyl ether; (7) mixture of Resorcinol glycidyl ether, methylol dihydroxyphenyl propane glycidyl ether and one or more glycidyl ester type epoxy resins; (8) Resorcinol glycidyl ether, methylol dihydroxyphenyl propane glycidyl ether, one or more glycidyl ester type epoxy resins and bisphenol A type epoxy resin, or (with) bisphenol f type epoxy resin, or (with) mixture of dihydroxyphenyl propane D type Resins, epoxy.
In above-mentioned self-repaired polyalcohol composite material at room temperature, the described capsular core that contains liquid polythiol is liquid polythiol, the capsule wall material is melamine formaldehyde resin, urea-formaldehyde resin or its mixture, capsule-core/cyst wall weight ratio is 1: 5～6: 1, capsule mean diameter 1 μ m～1mm, wall thickness 100nm～10 μ m.
In above-mentioned self-repaired polyalcohol composite material at room temperature, described liquid polythiol is aliphatic mercaptan or its halogen substituted derivative, aromatic mercaptans or its halogen substituted derivative, contain heterocyclic mercaptan or its halogen substituted derivative or have at least two sulfydryls and contain the mercaptan compound of the sulphur atom except that sulfydryl.
Described aliphatic mercaptan or its halogen substituted derivative are methane two mercaptan, propane two mercaptan, hexanaphthene two mercaptan, 2,3-dimercaptosuccinic acid(DMSA)-2-mercaptoethyl ester, 2,3-dimercapto-1-propyl alcohol (2-mercaptoacetate), 1,2-dimercapto propyl group methyl ether, glycol ether two (2-mercaptoacetate), two (2-mercaptoethyl) ether, ethylene glycol dimercapto acetate, trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (mercaptopropionic acid ester), three thiol derivatives of the three-glycidyl ether of propoxylation alkane, tetramethylolmethane four (mercaptoacetate), tetramethylolmethane four (mercaptopropionic acid ester) or dipentaerythritol many (thiopropionates);
Described aromatic mercaptans or its halogen substituted derivative are two, three, four sulfydryl benzene, two, three, four mercaptoalkyl benzene, dimercapto biphenyl, toluene two mercaptan or naphthyl disulfide alcohol.
Described heterocyclic mercaptan or its halogen substituted derivative of containing be for amino-4,6-two mercaptan-s-triazine, alkoxyl group-4,6-two mercaptan-s-triazine, aryloxy-4,6-two mercaptan-s-triazine or 1,3,5-three (tri-thiol propyl group) chlorinated isocyanurates.
The described mercaptan compound that has at least two sulfydryls and contain the sulphur atom except that sulfydryl is two, three, four (sulfydryl alkylthio) benzene, two, three, four (sulfydryl alkylthio) alkane, two (mercaptoalkyl) disulphide, hydroxyalkyl sulphur two (mercaptoacetate), hydroxyalkyl sulphur two (mercaptopropionic acid ester), mercaptoethyl ether two (mercaptopropionic acid ester), 1,4-dithian-2,5-glycol two (2-mercaptoalkyl ester), 4,4-Thiobutyric acid two (2-mercaptoalkyl ester), 34-two thiophene two mercaptan, bismuth mercaptan, 2,5-dimercapto-1,3, the 4-thiadiazoles, LP-33, Thioplast G-44 or CAPCURAE 3-800;
The structural formula of LP-33, Thioplast G-44 and CAPCURAE 3-800 is as follows:
HsC
2H
4-O-CH
2-O-C
2H
4-S-S
nC
2H
4-O-CH
2-O-C
2H
4-SH
ThioplastG44。
In above-mentioned self-repaired polyalcohol composite material at room temperature, described liquid polythiol preferably has mercaptan compound or its mixture of at least three sulfydryls, as one or more mixture among trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (mercaptopropionic acid ester), tetramethylolmethane four (mercaptopropionic acid ester) or the ThioplastG-44.
Contain capsule energy fast-curing epoxy resin in the presence of catalyzer such as tertiary amine of liquid polythiol, can also carry out toughening modifying to Resins, epoxy simultaneously.The multi-thioalcohol compound end be thiol group (SH), activity was very poor when it reacted with epoxy compounds separately, at room temperature reaction is extremely slow, but in the presence of suitable promotor, can form the mercaptan ion, curing reaction carries out with the speed that is several times as much as polyamine, and these characteristics more can show when low-temperature curing.For example thiol group is in the presence of tertiary amine, and the thiolate ion and the epoxy reaction of generation, and the relative nucleophilic displacement reaction speed of this thiolate is far above phenol, carboxyl, amine etc. can be rapidly and the epoxy group(ing) generation addition reaction in the Resins, epoxy.
In above-mentioned self-repaired polyalcohol composite material at room temperature, described catalyzer is amine, tertiary phosphine, contain the anionic quaternary amine of nucleophilic, contain phosphonium salt of anionic season of nucleophilic, imidazoles, contain arsenic salt or contain sulfonium salt of anionic season of nucleophilic of anionic season of nucleophilic.Described amine catalyst comprises primary, the second month in a season and tertiary amine, preferred tertiary amine catalyst be methyldiethanolamine, trolamine, diethyl amino propylamine ,-xylylene two (dimethylamine), N, N '-lupetazin, N-crassitude, N-methyl hydroxy piperidine, N, N, N ', N '-tetramethyl-diaminoethanes, N, N, N ', N ', N '-five methyl diethylentriamine, Tributylamine, Trimethylamine, triethylenediamine, N-methylmorpholine, N-methyl piperidine or pyridine.Best tertiary amine is 1,8-diazo bicyclic [5,4,0] 11 carbon-7-alkene, 1,8-diazabicyclo [2,2,2] octane, 4-dimethylaminopyridine, 4-(N-pyrrolidino) pyridine, triethylamine, benzyl dimethyl amine, benzyl diethylamide, dimethylaminomethyl phenol, 2,6-two (dimethylaminomethyl) phenol or 2,4,6-three (dimethylaminomethyl) phenol.
Contain the preferred TEA chloride of the anionic quaternary ammonium salt of nucleophilic, tetrapropyl ammonium acetate, hexyl trimethylammonium bromide, benzyl trimethyl ammonium cyanide, hexadecyl triethyl ammonium trinitride or N-picoline phenates.
Compared with prior art, the present invention has following beneficial effect:
Self-repaired polyalcohol composite material at room temperature of the present invention is the reparation system of forming with epoxy resin micro-capsule and the polythiol solidifying agent microcapsule that match, and it satisfies the and the following requirement: (1) renovation agent component can be wrapped up by microcapsule respectively; (2) the own stable chemical performance of renovation agent component, standing storage or self-polymeric reaction can not take place under severe condition such as higher temperatures; (3) stable physical property of renovation agent component own has lower zero pour, and viscosity is low, easily flow, and vapour pressure is lower, is difficult in the capsule to exosmosis and volatilization; (4) show high reaction activity and high after the renovation agent component is in contact with one another, can at normal temperature or be lower than fast setting under the normal temperature, consumption relative proportion a wider range; (5) after the renovation agent polyreaction and have chemical action or stronger physical action between matrix, can reach good bonding repairing effect; (6) the renovation agent microcapsule can bear with the body material recombination process in the external force effect; (7) there is bonding preferably between the microcapsule of parcel renovation agent and body material, guarantees that capsule ftractures simultaneously with matrix in the crackle forming process.
Epoxy resin micro-capsule and the polythiol solidifying agent microcapsule that match, two kinds of capsule volume average particle size are close, and capsule density is close, and cyst material is identical.Two kinds of capsules have similar physicals, help their homodisperse in matrix.Capsule-core Resins, epoxy and polythiol solidifying agent have good intermiscibility, help the phase mutual diffusion.There is good cohesive action between cyst wall and the matrix, the external force effect of processing when the physical strength of microcapsule is enough to bear material preparation.When self-repaired polyalcohol composite material at room temperature of the present invention cracked body material destruction, the capsule that crackle passes split simultaneously with matrix, discharges two kinds of reactive material, polymerization rapidly, thus stop crack growth, reparation crackle.The prepared self-repair type matrix material of the present invention need not heating when repairing crackle, at room temperature can finish the crackle reparation automatically.
Description of drawings
Fig. 1 is the crackle repair process synoptic diagram of self-repaired polyalcohol composite material at room temperature of the present invention.
1 is crackle, and 2 is the polythiol capsule, and 3 is the Resins, epoxy capsule, and 4 is matrix, and 5 are the combination renovation agent, and 6 is the polymeric renovation agent.
Embodiment
Embodiment 1
Contain the capsular preparation of liquid-state epoxy resin: 12.5g trimeric cyanamide and 27.1g formaldehyde are generated prepolymer under 70～75 ℃, pH value 9～10 conditions, cool to 60 ℃, add 0.5ml50% (weight ratio) aqueous hydrochloric acid and 28g methyl alcohol, stirred 0.5 hour, solution becomes clarification by muddiness.Add 200ml water and 60g tetrahydrophthalic acid 2-glycidyl ester, with clarifixator 8 * 10
3Rev/min disperseed 5 minutes, splash into 2 tributyl phosphates and eliminate bubbles in the emulsion.Transfer 2.5～3.0,50～55 ℃ of reactions of system pH 1 hour.Cooled and filtered, washing, vacuum-drying.Productive rate: 93.24%.Mean sizes 15.47 μ m.Capsule-core content: 86.13%.
Contain the capsular preparation of liquid polythiol: 50g tetramethylolmethane four (mercaptopropionic acid ester) joins 200ml and contains in 2% (accounting for the ratio of gross weight) styrene maleic acid sodium water solution, and mixture uses mulser with 10
4Rev/min speed disperseed 5 minutes, splash into 2 tributyl phosphates and eliminate bubbles in the emulsion.The prepolymer that 12.5g trimeric cyanamide and 27.1g formaldehyde generate under 70～75 ℃, pH value 9～10 conditions is poured in the above-mentioned emulsion, and pH value to 2.7～3.0 of regulation system were 50 ℃ of reactions 1 hour.Cooled and filtered, washing, vacuum-drying.Productive rate: 90.23%; Capsule mean diameter: 14.35 μ m; Capsule-core content: 84.92%.
Take by weighing 10 weight % by the Resins, epoxy capsule of embodiment 1 preparation and 10 weight % mercaptan capsule by embodiment 2 preparations, under 40～50 ℃ of conditions, evenly spread in 100 parts of EPON 828 Resins, epoxy, after adding 12.5 parts of diethylenetriamine short mix, the degassing, pour in the silicon rubber mould and to solidify 24 hours, 40 ℃ of after fixing 24 hours.
Adopt taper double cantilever beam (TDCB) sample to carry out the remediation efficiency of tearing test and evaluating material: will approach the method that blade raps into the molded otch of sample and produce pre-crackle, with the pin load anchor clamps perpendicular to pre-crackle direction applied load.Determine initial collapse toughness from fracture propagation and sample destructive critical loading.After the damage, remove load and allow crackle (20～25 ℃) reparation at room temperature.Redeterminate fracture toughness property after 24 and 48 hours with the quantitatively characterizing remediation efficiency.The results are shown in Table 1.The crackle repair process synoptic diagram of self-repaired polyalcohol composite material at room temperature as shown in Figure 1.
Take by weighing 10 weight % by the Resins, epoxy capsule of embodiment 1 preparation, mercaptan capsule and the 5 weight % triphenylphosphines that 10 weight % prepare by embodiment 2, under 40～50 ℃ of conditions, evenly spread in 100 parts of EPON 828 Resins, epoxy, after adding 12.5 parts of diethylenetriamine short mix, the degassing, pour in the silicon rubber mould and to solidify 24 hours, 40 ℃ of after fixing 24 hours.
Evaluation method is with embodiment 3.The results are shown in Table 1.
(capsule evenly is soaked in N, in the N-dimethyl benzylamine, keeps 24 hours down at 40 ℃, through ether washing, heat drying by the mercaptan capsule of embodiment 2 preparations by the Resins, epoxy capsule of embodiment 1 preparation and 10 weight % to take by weighing 10 weight %.Capsule-core/cyst wall weight ratio is 4: 1, wherein mercaptan account for 75%, N, the N-dimethyl benzylamine accounts for 5%), under 40～50 ℃ of conditions, evenly spread in 100 parts of EPON 828 Resins, epoxy, after adding 12.5 parts of diethylenetriamine short mix, the degassing, pour in the silicon rubber mould and to solidify 24 hours, 40 ℃ of after fixing 24 hours.
Evaluation method is with embodiment 3.The results are shown in Table 1.
Take by weighing 15 weight % and press trimethylolpropane tris (mercaptopropionic acid ester) the mercaptan capsule and the 5 weight %2 of embodiment 2 preparations by dihydroxyphenyl propane tetraglycidel ether epoxy resin (EPON 828) capsule, the 10 weight % that embodiment 1 prepares, 4,6-three (dimethylaminomethyl) phenol prepares matrix material by the method for embodiment 3.
Evaluation method is with embodiment 3.The results are shown in Table 1.
Embodiment 7
Take by weighing 10 weight % by the Resorcinol tetraglycidel ether epoxy resin capsule of embodiment 1 preparation, ThioplastG-44 mercaptan capsule and the 3 weight %1 that 15 weight % prepare by embodiment 2,8-diazo bicyclic [5,4,0] 11 carbon-7-alkene prepares matrix material by the method for embodiment 3.Evaluation method is with embodiment 3.The results are shown in Table 1.
Comparative example 1
Take by weighing 100 parts of EPON 828 Resins, epoxy, add 12.5 parts of diethylenetriamine short mix, the degassing after, pour in the silicon rubber mould and to solidify 24 hours, 40 ℃ of after fixing 24 hours.
Evaluation method is with embodiment 1.The results are shown in Table 1.
Comparative example 2
Take by weighing the Resins, epoxy of 10 weight % by embodiment 1 preparation, under 40～50 ℃ of conditions, evenly spread in 100 parts of EPON 828 Resins, epoxy, after adding 12.5 parts of diethylenetriamine short mix, the degassing, pour in the silicon rubber mould and to solidify 24 hours, 40 ℃ of after fixing 24 hours.
Evaluation method is with embodiment 1.The results are shown in Table 1.
Comparative example 3
Take by weighing the mercaptan capsule of 15 weight % by embodiment 2 preparations, under 40～50 ℃ of conditions, evenly spread in 100 parts of EPON 828 Resins, epoxy, after adding 12.5 parts of diethylenetriamine short mix, the degassing, pour in the silicon rubber mould and to solidify 24 hours, 40 ℃ of after fixing 24 hours.
Evaluation method is with embodiment 1.The results are shown in Table 1.
Comparative example 4
Take by weighing Resins, epoxy and the 5 weight % triphenylphosphines of 15 weight % by embodiment 1 preparation, under 40～50 ℃ of conditions, evenly spread in 100 parts of EPON 828 Resins, epoxy, after adding 12.5 parts of diethylenetriamine short mix, the degassing, pour in the silicon rubber mould and to solidify 24 hours, 40 ℃ of after fixing 24 hours.
Evaluation method is with embodiment 1.The results are shown in Table 1.
The comparison of table 1 self-repaired polyalcohol composite material at room temperature remediation efficiency
| Material | 24 hours remediation efficiencies (%) | 48 hours remediation efficiencies (%) |
| |
33.1 48.3 79.2 68.9 64.5 0 3.6 0 6.7 | 37.5 54.2 83.4 72.3 67.8 0 5.2 0 9.3 |
Claims (10)
1. self-repaired polyalcohol composite material at room temperature, form by following component and weight percentage:
Polymeric matrix 40～98%,
The capsule 1～50% that contains liquid-state epoxy resin,
The capsule 1～50% that contains liquid polythiol,
Catalyzer 0.1～15%,
Wherein, catalyzer is in containing the capsule of liquid polythiol or be distributed in the polymeric matrix.
2. matrix material as claimed in claim 1 is characterized in that described polymeric matrix is Resins, epoxy, unsaturated polyester, resol, urethane, polymeric amide or acrylic resin.
3. matrix material as claimed in claim 1, it is characterized in that the described capsular core that contains liquid-state epoxy resin is a liquid-state epoxy resin, the capsule wall material is melamine formaldehyde resin, urea-formaldehyde resin or its mixture, capsule-core/cyst wall weight ratio is 1: 2～9: 1, capsule mean diameter 1 μ m～1mm, wall thickness 100nm～10 μ m.
4. matrix material as claimed in claim 3 is characterized in that described liquid-state epoxy resin is: the mixture of one or more in part bisphenol A type epoxy resin, partial hydrogenation bisphenol A type epoxy resin, part bisphenol f type epoxy resin, dihydroxyphenyl propane D type Resins, epoxy, Resorcinol type Resins, epoxy, methylol bisphenol A type epoxy resin or the part glycidyl ester type epoxy resin.
5. matrix material as claimed in claim 4 is characterized in that described part bisphenol A type epoxy resin is the dihydroxyphenyl propane glycidyl ether; Described Resorcinol type Resins, epoxy is the Resorcinol glycidyl ether; Described methylol bisphenol A type epoxy resin is a methylol dihydroxyphenyl propane glycidyl ether; Described part glycidyl ester type epoxy resin is phthalic acid glycidyl ester, tetrahydrophthalic acid glycidyl ester, hexahydrophthalic acid glycidyl ester or 1,2 epoxy cyclohexane 4,5-dioctyl phthalate glycidyl ester.
6. matrix material as claimed in claim 1, the capsular core that it is characterized in that containing liquid polythiol is liquid polythiol, the capsule wall material is melamine formaldehyde resin, urea-formaldehyde resin or its mixture, capsule-core/cyst wall weight ratio is 1: 5～6: 1, capsule mean diameter 1 μ m～1mm, wall thickness 100nm～10 μ m.
7. matrix material as claimed in claim 1 is characterized in that described liquid polythiol is aliphatic mercaptan or its halogen substituted derivative, aromatic mercaptans or its halogen substituted derivative, contains heterocyclic mercaptan or its halogen substituted derivative or have at least two sulfydryls and contain the mercaptan compound of the sulphur atom except that sulfydryl.
8. matrix material as claimed in claim 7, it is characterized in that described aliphatic mercaptan or its halogen substituted derivative are methane two mercaptan, propane two mercaptan, hexanaphthene two mercaptan, 2,3-dimercaptosuccinic acid(DMSA)-2-mercaptoethyl ester, 2,3-dimercapto-1-propyl alcohol (2-mercaptoacetate), 1,2-dimercapto propyl group methyl ether, glycol ether two (2-mercaptoacetate), two (2-mercaptoethyl) ether, ethylene glycol dimercapto acetate, trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (mercaptopropionic acid ester), three thiol derivatives of the three-glycidyl ether of propoxylation alkane, tetramethylolmethane four (mercaptoacetate), tetramethylolmethane four (mercaptopropionic acid ester) or dipentaerythritol many (thiopropionates);
Described aromatic mercaptans or its halogen substituted derivative are two, three, four sulfydryl benzene, two, three, four mercaptoalkyl benzene, dimercapto biphenyl, toluene two mercaptan or naphthyl disulfide alcohol.
Described heterocyclic mercaptan or its halogen substituted derivative of containing be for amino-4,6-two mercaptan-s-triazine, alkoxyl group-4,6-two mercaptan-s-triazine, aryloxy-4,6-two mercaptan-s-triazine or 1,3,5-three (tri-thiol propyl group) chlorinated isocyanurates.
The described mercaptan compound that has at least two sulfydryls and contain the sulphur atom except that sulfydryl is two, three, four (sulfydryl alkylthio) benzene, two, three, four (sulfydryl alkylthio) alkane, two (mercaptoalkyl) disulphide, hydroxyalkyl sulphur two (mercaptoacetate), hydroxyalkyl sulphur two (mercaptopropionic acid ester), mercaptoethyl ether two (mercaptopropionic acid ester), 1,4-dithian-2,5-glycol two (2-mercaptoalkyl ester), 4,4-Thiobutyric acid two (2-mercaptoalkyl ester), 34-two thiophene two mercaptan, bismuth mercaptan, 2,5-dimercapto-1,3, the 4-thiadiazoles, LP-33, Thioplast G-44 or CAPCURAE 3-800;
The structural formula of LP-33, Thioplast G-44 and CAPCURAE 3-800 is as follows:
HSC
2H
4-O-CH
2-O-C
2H
4-S-S
nC
2H
4-O-CH
2-O-C
2H
4-SH
R＝CH
2
2O-CH
2-OCH
2
2 CAPCURE 3-800
a+b+c＝n＜7
Thioplast G44。
9. matrix material as claimed in claim 7 is characterized in that described liquid polythiol is one or more a mixture among trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (mercaptopropionic acid ester), tetramethylolmethane four (mercaptopropionic acid ester) or the ThioplastG-44.
10. matrix material as claimed in claim 1 is characterized in that described catalyzer is amine, tertiary phosphine, contains the anionic quaternary amine of nucleophilic, contains phosphonium salt of anionic season of nucleophilic, imidazoles, contains arsenic salt or contain sulfonium salt of anionic season of nucleophilic of anionic season of nucleophilic.
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Families Citing this family (1)
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|---|---|---|---|---|
| FR2973049B1 (en) | 2011-03-21 | 2016-12-23 | Arjowiggins Security | INFORMATION OR PAPER HOLDER HAVING A SELF-REPAIRING MATERIAL |
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