CN104356284A - Epoxy functional group containing nano-reinforcer for hybrid polymer epoxy resin - Google Patents
Epoxy functional group containing nano-reinforcer for hybrid polymer epoxy resin Download PDFInfo
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- CN104356284A CN104356284A CN201410612454.4A CN201410612454A CN104356284A CN 104356284 A CN104356284 A CN 104356284A CN 201410612454 A CN201410612454 A CN 201410612454A CN 104356284 A CN104356284 A CN 104356284A
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Abstract
The invention discloses an epoxy functional group containing nano-reinforcer for hybrid polymer epoxy resin. The preparation method of the epoxy functional group comprises the following steps: taking gamma-(2,3-epoxypropyoxy)propyltrimethoxysilane as a raw material, conducting condensation polymerization to prepare the raw material to hydroxyl octapolyhedral oligomeric silsesquioxane (POSS-OH), then transforming the substance to form a macroinitiator, taking methyl methacrylate and glycidyl methacrylate as monomers to conduct atom transfer radical polymerization (ATRP), under the control action of the ATRP polymerization to molecular weight, adjusting the ratio of an inorganic component to a high polymer component in the star hybrid polymer, so as to control the properties; synthesizing the nano-reinforcer containing the epoxy functional group for hybrid polymer epoxy resin, which regards the inorganic component POSS-OH as a core, and the copolymer chain segment as an arm. The polymer nano-reinforcer can be added to the powered epoxy resin to modify the resin; the impact strength of the modified and cross-linked epoxy resin is 1.8-2.9 times of that before modification, the glass transition temperature is increased by 21 DEG C, and the tensile strength is increased by 44%.
Description
Technical field
Containing a synthesis for the hybridized polymer epoxide resin nano toughener of epoxide function base, relate to the preparation of a kind of inorganic nano-particle and superpolymer thing hybrid systems, belong to new material technology field.
Background technology
Organic-inorganic nanocomposite refers to that dispersed phase size has at least one dimension to be less than the matrix material of 100nm magnitude.This material is that organic phase and inorganic phase are composited in nanometer range.Because interfacial area between two-phase is very large, and the Chemical bond between Presence of an interface, therefore there is desirable adhesiveproperties.In recent years, the compound research of inorganic materials and organic polymer thing causes the great interest of people, by the synergy between organic and inorganic component, bill of material can be made to reveal the over-all properties with organic polymer material and inorganic functional material.Inorganic component being uniformly distributed on nanoscale, can optimize the interaction between material component further, and the performance of material is more effectively improved.The research of inorganic/organic Hybrid Materials, particularly inorganic nano thing/polymer composite, oneself is through becoming one of most active field in macromolecular material research.
Cage modle eight polysilsesquioxane (being called for short POSS) is that a class is inner skeleton by the connection thing of Si-O, is externally connected to the nanoscale three-dimensional system of machine group, the intramolecular hybrid structure of POSS has inorganic Si-O hexahedron framework core, Si summit connects organic group or polymer segment, belong to inorganic/organic (polymkeric substance) hybrid systems on molecular level, diameter is 1 ~ 3nm.This system has structure designability, and the Si atom on hexahedron summit connects various reactivity or non-reacted group by chemical reaction, gives its reactivity with functional, prepares the POSS of different structure.Because POSS has very high structural symmetry, and there is the inorganic structure framework of Si-O-Si, remain the general feature of inorganics, therefore there is good stability.POSS, by melt blending, solution blending and polymer compound, prepares polymkeric substance/POSS intermingling material.In recent years due to the constructional feature of cage-type silsesquioxane, it is made to be used widely at field of new, space flight and aviation, modifying plastics and medical field.
Epoxy resin, owing to having excellent processing performance, mechanical property and physicals, is widely used in each fields such as machinery, electron and electrician, space flight and aviation, communications and transportation, building, light industry by as coating, sizing agent, matrices of composite material, electronic package material etc.But after epoxy resin cure, cross-linking density is high, internal stress is comparatively large, matter is crisp, shock-resistance and weathering resistance poor, limit its application to a certain extent.Current investigator adopts and has carried out large quantifier elimination to Toughening Epoxy Resin in many ways, is summed up its toughness reinforcing approach and mainly contains following four kinds: in epoxy resin-base, add the second-phases such as elastomerics, thermoplastic resin, rigid particles or special construction polymkeric substance carry out toughening modifying; With thermoplastic resin run through continuously with epoxy networks in form inierpeneirating network structure toughness reinforcing; Come toughness reinforcing by the chemical structure (as introduced " soft segment " in cross-linked network) changing cross linking of epoxy resin network with the mobility improving molecule on network chain; The ununiformity controlling molecule crosslinked state is formed with the structure being beneficial to viscous deformation and realizes.
Summary of the invention
The invention provides a kind of synthetic method of the hybridized polymer epoxide resin nano toughener containing epoxide function base, from small molecules γ-(2, 3-epoxy third oxygen) propyl trimethoxy silicane (KH-560 silane coupling agent) beginning, first the eight poly-cage-type silsesquioxanes (code name POSS-OH) that drift angle contains hydroxyl are prepared into, then macromole evocating agent is changed into, pass through the multipolymer of atom transfer radical polymerization (ATRP) synthesizing methylmethacrylate and glycidyl methacrylate again, and be connected on POSS simultaneously, by the selection of monomer, make the side chain of superpolymer with epoxide group, the nano material of synthesis POSS and superpolymer hydridization.By the control action kou of ATRP polymerization to molecular weight, regulate the ratio of inorganic component and superpolymer component in star-like hybridized polymer, thus reach the object of control performance.This hybrid material containing epoxide function base is joined in epoxy resin, toughening modifying is carried out to epoxy resin.Good modifying function should be had for epoxy resin containing the hybridized polymer epoxide resin nano toughener of epoxide function base, wherein POSS part can improve mechanical strength, the thermotolerance of epoxy resin, superpolymer segment wherein increases the consistency of hybrid and epoxy resin, epoxide group can be used as the curing reaction that endurable active toughener participates in epoxy resin, toughner is made to be connected on epoxy resin in chemical bond mode, ensure that toughner is evenly distributed in the epoxy, improve toughening effect.
Beneficial effect of the present invention:
1. the superpolymer segment of the cage-type silsesquioxane contained in this hybridized polymer epoxide resin nano toughener structure and band function base is a kind of particulate of nano-scale.Due to special construction and the nano effect thereof of POSS, this hybridized polymer nanometer strengthener has good toughening effect for epoxy resin.
2. when the synthesis of arm, by the method for living polymerization, polymer segment is received on POSS, chain length is effectively controlled, thus conveniently can regulate the performance of hybridized polymer nanometer strengthener.
3. in hybridized polymer nanometer strengthener molecule with epoxide group, the curing reaction of epoxy resin can be participated in, nanometer toughner is evenly distributed in the epoxy, is connected firmly, reinforced effects.
Accompanying drawing explanation
Fig. 1 is containing the synthetic route chart of the hybridized polymer epoxide resin nano toughener of epoxide function base
Fig. 2 hydroxyl eight gathers the infrared spectrum of cage-type silsesquioxane
Shock strength after Fig. 3 modified epoxy is cross-linked is with the change curve of toughner consumption
Embodiment
Embodiment 1:
In 500 milliliters of there-necked flasks, add 80 milliliters of acetone and 120 ml deionized water, add 80 milliliters of KH-560 and 10 milliliter hydrochloric acid under magnetic stirring, 70 DEG C of reflux 24h.Products therefrom Rotary Evaporators evaporation of solvent, precipitation tetrahydrofuran (THF) is dissolved, be added dropwise in water under whipped state and again precipitate, purify through three multi-cycle separation, finally product is put into vacuum drying oven (40 DEG C) freeze-day with constant temperature 24h, obtain micro-yellow solid, name is called that hydroxyl eight gathers cage-type silsesquioxane.Adopt coating method sample preparation, a small amount of product is dissolved in tetrahydrofuran (THF), dries under infrared lamp, carry out examination of infrared spectrum analytical structure.
Embodiment 2:
Take obtain in embodiment 1 hydroxyl eight gather cage-type silsesquioxane 14.72 grams, join 80 milliliters of N, in dinethylformamide (DMF), stir ice bath after 1 hour and be cooled to 0 DEG C, add the triethylamine of 20 milliliters to mixed solution, under whipped state, 18.08 grams of 2-chloroacetyl chlorides are slowly added drop-wise to mixed solution, after dropwising, under room temperature, react 24h.After reaction terminates, reaction solution is used successively 0.5mol/L sodium hydroxide solution, 0.5mol/L hydrochloric acid soln and a large amount of washed with de-ionized water reactant, after separation, subnatant is joined in excessive methanol, by obtain be deposited in 40 DEG C at vacuum-drying 48h, the macromole evocating agent obtained is designated as: POSS-Cl.
Embodiment 3:
In 50 milliliters of reaction flasks, add 0.27 gram of (0.1mmol) macromole evocating agent POSS-Cl, be dissolved in 15 milliliters of DMF, then add 2.72 grams of MMA and 3.86 gram GMA stirring and dissolving, carry out vacuum suction-inflated with nitrogen and circulate three times.0.33 gram of CuCl and 0.77 gram of three [2-(dimethylamino) ethyl] amine (ME6TREN) is dissolved in DMF, with syringe, this solution is moved in reaction flask, under magnetic stirring in 50 DEG C of reaction 3h.After reaction terminates, reaction solution DMF dilutes, and is separated by neutral alumina separator column, then dialyses 2 days, by the aqueous solution lyophilize of dialysis, obtains product and is designated as: POSS-P (MMA-co-GMA).
Embodiment 4:
With embodiment 3, but the consumption changing MMA is 4.80 grams, and the consumption of GMA is 6.81 grams.
Embodiment 5:
Hybridized polymer epoxide resin nano toughener POSS-P (MMA-co-GMA) is mixed according to different ratios respectively with the epoxy resin (oxirane value: 0.09 ~ 0.14 equivalent/100 gram) of bisphenol A-type solid, POSS-P (MMA-co-GMA) changes to 20:100 with the weight ratio of epoxy resin from 3:100, heating and melting carries out physical blending, phenols curing agent is added by 20% of weight epoxy, cooling extruded by forcing machine, finally carries out pulverizing the co-mixing system obtaining powdered epoxy resin, toughner and solidifying agent.The co-mixing system powder obtained is carried out pressing plate on thermocompressor, is finally processed into batten, carry out Mechanics Performance Testing.
Embodiment 6:
The modified epoxy obtained is carried out thermal performance test, records second-order transition temperature by differential scanning calorimeter (DSC).
Second-order transition temperature change after table 1 modified epoxy is crosslinked
Claims (3)
1. the hybridized polymer epoxide resin nano toughener containing epoxide function base, it is characterized in that with eight of hydroxyl poly-cage-type silsesquioxanes (code name: POSS-OH) be core, methyl methacrylate and glycidyl methacrylate copolymer (code name: P (MMA-co-GMA)) be connected to the summit of this cage-type silsesquioxane for arm, define inorganic/polymer hybrid star copolymer, structure comprises a core and 16 arm, the polymerization degree n=20-58 in every one arm P (MMA-co-GMA).
2. the synthetic method of a kind of hybridized polymer epoxide resin nano toughener containing epoxide function base described in claim 1, is characterized in that have passed through three-step reaction:
(1) first from small molecules γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (code name: KH-560) beginning, polycondensation is carried out in acetone and deionized water and under the katalysis of hydrochloric acid, be prepared into the cage-type silsesquioxane (code name POSS-OH) that drift angle contains hydroxyl, when reacting, the volume ratio of KH-560, acetone and deionized water is 1:1:1.2, concentration be 36% hydrochloric acid volume account for 10% ~ 20% of KH-560 volume, at 60 DEG C of reflux 24h.Products therefrom Rotary Evaporators evaporation of solvent, precipitation tetrahydrofuran (THF) is dissolved, be added dropwise in excessive deionized water under whipped state and again precipitate, purify through three multi-cycle separation, finally product is put into vacuum drying oven constant temperature (40 DEG C) dry 24h, obtain faint yellow solid thing, i.e. POSS-OH;
(2) reaction of hydroxyl in cage-type silsesquioxane is gathered by hydroxyl eight, be converted into macromole evocating agent, POSS-OH is dissolved in N, in dinethylformamide (DMF), the concentration formed is 15% ~ 25%, stir ice bath after 1 hour and be cooled to 0 DEG C, add the triethylamine of DMF volume 1/4th to mixed solution, under whipped state, 2-chloroacetyl chloride is slowly added drop-wise to mixed solution, take the mole number such as hydroxyl and 2-chloroacetyl chloride in POSS-OH, after dropwising, 24h is reacted under room temperature, reaction solution is used 0.5mol/L sodium hydroxide solution successively, 0.5mol/L hydrochloric acid soln and a large amount of washed with de-ionized water reactant, after separation, subnatant is joined in excessive methanol, by obtain be deposited in 40 DEG C at vacuum-drying, the macromole evocating agent obtained is designated as: POSS-Cl,
(3) methyl methacrylate (code name: MMA) and glycidyl methacrylate (code name: GMA) is selected to be monomer, cause MMA and GMA by the method for atom transfer radical polymerization (ATRP) and copolyreaction occurs, multipolymer segment is made to receive on POSS-OH, in reaction ratio, the mol ratio of MMA and GMA is 10:1 ~ 1:1, in POSS-Cl, initiating group mole number and the total moles of MMA and GMA are than being 1:20 ~ 1:60, by etc. catalyzer cuprous chloride and three [2-(dimethylamino) ethyl] amine of mole ratio be dissolved in DMF, with syringe, this solution is moved in reaction flask, under magnetic stirring in 50 DEG C of reaction 3h, after reaction terminates, reaction solution DMF dilutes, be separated by neutral alumina separator column, dialyse again 2 days, by the aqueous solution lyophilize of dialysis, finally obtain hybridized polymer epoxide resin nano toughener, be designated as: POSS-P (MMA-co-GMA).
3. the hybridized polymer epoxide resin nano toughener containing epoxide function base according to claim 1 is to the modification application of powdered epoxy resin, it is characterized in that the epoxy resin (oxirane value: 0.09 ~ 0.14) mix of POSS-P (MMA-co-GMA) with bisphenol A-type solid, weight ratio 3:100 ~ the 20:100 of POSS-P (MMA-co-GMA) and epoxy resin, heating and melting is blended, phenols curing agent is added by 20% of weight epoxy, cooling extruded by forcing machine, pulverizing obtains powdered epoxy resin, the co-mixing system of toughner and solidifying agent, co-mixing system powder is carried out pressing plate on thermocompressor, be processed into the batten carrying out testing, carry out performance test, after adding nanometer strengthener, the resistance to impact shock of cross-linked epoxy resin is 1.8 ~ 2.9 times before adding, second-order transition temperature improves 21 DEG C, tensile strength increases by 44%.
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| CN106397676A (en) * | 2016-09-14 | 2017-02-15 | 西安交通大学 | Preparation method of breathable POSS-based epoxy grafted copolymer for silicate cultural relics |
| CN106832151A (en) * | 2017-01-13 | 2017-06-13 | 浙江泰普森休闲用品有限公司 | A kind of dissaving polymer with POSS as core and its preparation method and application |
| CN106995641A (en) * | 2017-04-25 | 2017-08-01 | 晶锋集团股份有限公司 | Epoxy resin-matrix heat conductive insulating coating that a kind of epoxy radicals polyhedral silsesquioxane is modified and preparation method thereof |
| CN107099106A (en) * | 2017-04-25 | 2017-08-29 | 晶锋集团股份有限公司 | A kind of polysiloxane grafted barium strontium titanate/polyvinylidene fluoride composite material of high dielectric and preparation method thereof |
| CN107141631A (en) * | 2017-04-25 | 2017-09-08 | 晶锋集团股份有限公司 | A kind of ethylene propylene diene rubber polyvinyl chloride composite jacket pipe of carbon black toughening modifying and preparation method thereof |
| CN112358849A (en) * | 2020-11-10 | 2021-02-12 | 常州艾卡新材料科技有限公司 | Peelable gasket adhesive and preparation method thereof |
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| CN107141631A (en) * | 2017-04-25 | 2017-09-08 | 晶锋集团股份有限公司 | A kind of ethylene propylene diene rubber polyvinyl chloride composite jacket pipe of carbon black toughening modifying and preparation method thereof |
| CN112358849A (en) * | 2020-11-10 | 2021-02-12 | 常州艾卡新材料科技有限公司 | Peelable gasket adhesive and preparation method thereof |
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