CN105153358A - Amphiphilic acrylic ester random copolymer for toughening epoxy resin and preparation method of amphiphilic acrylic ester random copolymer - Google Patents
Amphiphilic acrylic ester random copolymer for toughening epoxy resin and preparation method of amphiphilic acrylic ester random copolymer Download PDFInfo
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- CN105153358A CN105153358A CN201510564476.2A CN201510564476A CN105153358A CN 105153358 A CN105153358 A CN 105153358A CN 201510564476 A CN201510564476 A CN 201510564476A CN 105153358 A CN105153358 A CN 105153358A
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Abstract
The invention provides an amphiphilic acrylic ester random copolymer for toughening epoxy resin and a preparation method of the amphiphilic acrylic ester random copolymer, and discloses an amphiphilic random copolymer which is synthesized by polymerizing simple free radicals, has a flexible component and an epoxy-philic component, and is applied for toughening the epoxy resin. The epoxy-philic component can improve the compatibility between a polymer and epoxy, and also can react with an epoxy chain section through an active group, so as to realize the strong covalent bond acting force between the polymer and epoxy resin; the existence of the flexible component can relieve the brittleness of the resin, so as to realize the toughening of the epoxy resin. The impact strength of a polymer toughening epoxy resin system prepared by the preparation method is improved by 220 percent in comparison with a pure epoxy system, and the glass-transition temperature is not obviously decreased. Since the synthetic method of the polymer is simple in process and the after-treatment is simple, mass industrialized application is hopefully realized.
Description
Technical field
The present invention relates to the epoxy resin toughened field of random copolymers, be specifically related to the acrylate copolymer of synthesis of amphoteric and utilize the toughness of this polymkeric substance to epoxy resin to improve.
Technical background
The develop rapidly of electronics, electric material, modern aerospace material and matrix material, and development of modern scientific technology need the requirement of the over-all properties to epoxy resin also more and more higher.But epoxy resin itself exists the crisp shortcoming of matter, can not meet the requirement of these fields and some most advanced and sophisticated high skill, use is restricted.Therefore, maintenance or while sacrificing its mechanical property less, the toughness how improving it is the research emphasis of epoxy resin modification always.
Tradition method for toughening joins in epoxy resin by rubber elastomer, and rubber elastomer disperse phase can play crackle, branch crack, inducing shear metamorphosis, thus improve the toughness of EP.But, add caoutchouc elasticity cognition and make the Young's modulus of whole system and second-order transition temperature lose comparatively greatly, this change makes the toughening material obtained be difficult to adapt to the field be out of shape and heat resistant requirements is strict.In addition due to required fluid rubber valuable product, a large amount of use then improves products production cost, and the viscosity of matrix material increases simultaneously, is unfavorable for forming process.Therefore, comprehensively these aspects, its application is subject to certain restrictions.After this, scholar has carried out again testing widely, finds and can improve toughness and the method for modifying that can retain the original Young's modulus of system and thermotolerance.
The fluid rubber that it is main chain that employing solution polymerization process has synthesized with butyl acrylate, ethyl propenoate, glycidyl acrylate, use it for Toughening Modification of Epoxy, although achieve certain toughening effect, because fluid rubber add-on is comparatively large, considerable influence is produced to second-order transition temperature.
Present stage, comparative maturity and have the method for toughening of certain development prospect to comprise to add TLCP (TLCP), nanoparticle polymkeric substance, hyperbranched polymer, nucleocapsid structure polymkeric substance (CSLP), interpenetrating net polymer (IPNs), flexible-chain polymer etc.
Studies have reported that and amphiphilic ethylene-propylene-epoxyethane block copolymer (PEP-PEO) has been joined in epoxy resin, in PEP-PEO, there is the PEO segment good with epoxy resin compatibility, and the PEP segment poor but flexible with epoxy resin compatibility, have amphiphilic.When lower concentration, multipolymer can be self-assembled into the nanoparticle of different structure pattern in the epoxy, has different toughening effects thus to epoxy resin.Research finds that spherical micelle particle diameter size is on the impact of epoxy resin toughness, discovery average particle size is different, also difference is had to the lifting degree of toughness of material, and when median size is 15nm, the toughness of compound system reaches best, and the breaking tenacity of modified resin is than improve 80% before modified.In addition, lower concentration segmented copolymer can be self-assembled into the micro/nano structure of different shape in the epoxy to also have research also to find, different micro/nano structure also shows different toughness reinforcing results, vermiculate glues structure toughening effect is the most remarkable, and the breaking tenacity of modified system is than improving more than 100% before modified.Except above-mentioned employing PEP-PEO based block copolymer is epoxy resin toughened, research is also had to adopt ATRP to synthesize acrylate based block copolymer, micron-scale phase separation can occur in the epoxy, form nanoparticle, about add-on 5wt% reaches best toughening effect.
But block polymer synthesis technique is complicated, and severe reaction conditions, cost is high, is difficult to industrial applications.The present invention adopts simple radical polymerization to synthesize a kind of random copolymers containing soft segment and close epoxide group.Because close epoxy dredges the amphiphilic structure of epoxy, this polymkeric substance self-assembly can form microphase-separated nanostructure in the epoxy, thin epoxy component is elastomerics, there is toughening effect, and close epoxy component can improve the consistency of polymkeric substance and matrix, and be connected with epoxy resin by covalent linkage, participate in the formation of epoxy resin cure network.Compared with toughness reinforcing with conventional rubber, the consistency of the polymkeric substance that this project adopts and epoxy matrix is better, is issued to good toughening effect in the prerequisite not affecting other mechanical property.
Summary of the invention
The novel amphiphilic acrylate random copolymers of design and synthesis.Selecting the acrylic ester monomer of close epoxy and thin epoxy, by free-radical polymerized, preparing the acrylate random copolymers containing dredging epoxy flexible composition and close epoxy component.Join in epoxy resin by above-mentioned polymkeric substance, due to close and distant epoxy effect, polymkeric substance can carry out being self-assembled into polymer nano-particle in resin, forms microphase-separated, can absorb more multi-energy, reaching toughness reinforcing object thus when being subject to external influence.On the other hand, the existence of close epoxy component can strengthen the consistency of polymkeric substance and interlaminar resin, and is connected with epoxy resin by covalent linkage, participates in the formation of epoxy resin cure network, never can lose other mechanical propertys of resin.
The present invention realizes above-mentioned purpose by following technical solution.
The first step: take appropriate close epoxy monomer and thin epoxy monomer, join in 100mL round-bottomed flask, takes appropriate initiator A IBN, fully dissolve with 50mL solvent ethyl acetate, join in flask, mechanical stirring 15min under normal temperature, monomer and initiator are fully dissolved and mixes.20 ~ 24h is reacted, condensate return, mechanical stirring at 80 ~ 90 DEG C.After reaction terminates, be dropwise added drop-wise in precipitation agent by product, precipitation agent is the mixed solvent (volume ratio 1:1) of first alcohol and water, obtain thick white solid, again precipitate with after a small amount of acetic acid ethyl dissolution, repeat 2 ~ 3 times, vacuum-drying, obtains clear, colorless sticky solid.
Second step: get appropriate multipolymer, is dissolved in 10mL acetone, adds appropriate epoxy monomer, stirring is spent the night, and be heated to 50 DEG C, fully mix and remove solvent, vacuum takes off residual solvent, add the solidifying agent with quality such as epoxy monomers, proper quantity of defoaming agent, mixes de-bubbled under final vacuum, then pours into preheated mould, 60 ~ 80 DEG C of solidification 1 ~ 2h, are warming up to 100 ~ 140 DEG C of solidification 6 ~ 8h.
Particular flow sheet as shown in drawings.
The present invention compared with prior art has following beneficial effect:
(1) the epoxy resin toughened add-on of amphiphilic acrylate random copolymers of the designed synthesis of the present invention is low, is only 1 ~ 5%, makes the shock strength of resin improve 2.5 times of virgin resin.
(2) compared with epoxy resin toughened with plain polypropylene acid esters fluid rubber, the consistency of polymkeric substance designed by the present invention and resin is good, and add-on is low, can not lose second-order transition temperature and other mechanical property of resin.
(3) be self-assembled in the epoxy with current reported segmented copolymer micellar nanoparticles epoxy resin toughened compared with, polymkeric substance designed by the present invention not only has better toughening effect, and synthesis technique is more simple, reaction conditions is gentle, aftertreatment is simple, can realize large-batch industrial application.
Accompanying drawing explanation
Accompanying drawing is the synthesis of multipolymer and epoxy resin toughened schema.
Specific implementation method
Below in conjunction with specific examples, set forth the present invention further.These examples are only not used in for illustration of the present invention and limit the scope of the invention.
Embodiment 1
The first step: take monomer HEA1.16g, GMA1.42g, EHA7.37g, LA4.85g, join in 100mL round-bottomed flask, take initiator A IBN0.26g, fully dissolve with 50mL solvent ethyl acetate, join in flask, mechanical stirring 15min under normal temperature, makes monomer and initiator fully dissolve and mixes.24h is reacted, condensate return, mechanical stirring at 80 DEG C.After reaction terminates, be dropwise added drop-wise in precipitation agent by product, precipitation agent is the mixed solvent (volume ratio 1:1) of first alcohol and water, obtain thick white solid, again precipitate with after a small amount of acetic acid ethyl dissolution, repeat 2 ~ 3 times, vacuum-drying, obtains clear, colorless sticky solid.
Second step: get copolymer 1 g, is dissolved in 10mL acetone, adds epoxy monomer 50g, stirring is spent the night, and be heated to 50 DEG C, fully mix and remove solvent, vacuum takes off residual solvent, add the solidifying agent with quality such as epoxy monomers, 3 defoamers, mix de-bubbled under final vacuum, then pour into preheated mould, 60 ~ 80 DEG C of solidification 1 ~ 2h, are warming up to 100 ~ 140 DEG C of solidification 6 ~ 8h.
Embodiment 2
The first step: take monomer HEA1.16g, GMA1.42g, EHA8.85g, LA2.91g, join in 100mL round-bottomed flask, take initiator A IBN0.26g, fully dissolve with 50mL solvent ethyl acetate, join in flask, mechanical stirring 15min under normal temperature, makes monomer and initiator fully dissolve and mixes.24h is reacted, condensate return, mechanical stirring at 80 DEG C.After reaction terminates, be dropwise added drop-wise in precipitation agent by product, precipitation agent is the mixed solvent (volume ratio 1:1) of first alcohol and water, obtain thick white solid, again precipitate with after a small amount of acetic acid ethyl dissolution, repeat 2 ~ 3 times, vacuum-drying, obtains clear, colorless sticky solid.
Second step: get copolymer 1 g, is dissolved in 10mL acetone, adds epoxy monomer 50g, stirring is spent the night, and be heated to 50 DEG C, fully mix and remove solvent, vacuum takes off residual solvent, add the solidifying agent with quality such as epoxy monomers, 3 defoamers, mix de-bubbled under final vacuum, then pour into preheated mould, 60 ~ 80 DEG C of solidification 1 ~ 2h, are warming up to 100 ~ 140 DEG C of solidification 6 ~ 8h.
Embodiment 3
The first step: take monomer HEA1.16g, GMA1.42g, EHA8.85g, LA2.91g, join in 100mL round-bottomed flask, take initiator A IBN0.26g, fully dissolve with 50mL solvent ethyl acetate, join in flask, mechanical stirring 15min under normal temperature, makes monomer and initiator fully dissolve and mixes.24h is reacted, condensate return, mechanical stirring at 80 DEG C.After reaction terminates, be dropwise added drop-wise in precipitation agent by product, precipitation agent is the mixed solvent (volume ratio 1:1) of first alcohol and water, obtain thick white solid, again precipitate with after a small amount of acetic acid ethyl dissolution, repeat 2 ~ 3 times, vacuum-drying, obtains clear, colorless sticky solid.
Second step: get multipolymer 2g, is dissolved in 10mL acetone, adds epoxy monomer 50g, stirring is spent the night, and be heated to 50 DEG C, fully mix and remove solvent, vacuum takes off residual solvent, add the solidifying agent with quality such as epoxy monomers, 3 defoamers, mix de-bubbled under final vacuum, then pour into preheated mould, 60 ~ 80 DEG C of solidification 1 ~ 2h, are warming up to 100 ~ 140 DEG C of solidification 6 ~ 8h.
Claims (4)
1. amphiphilic acrylate random copolymers for flexibilizing epoxy resin and preparation method thereof, is characterized in that concrete synthesis step is as follows:
The first step: add close epoxy monomer and thin epoxy monomer in round-bottomed flask successively, adds the initiator A IBN of appropriate mass mark, and adds ethyl acetate as solvent, reacts 20 ~ 30h at 80 ~ 90 DEG C; After end, product is dropwise dropped in water and methanol mixed solvent and precipitate, obtain thick white solid, dried in vacuo overnight, obtain water white transparency sticky solid, namely synthesized acrylate random copolymers.
Second step: multipolymer is dissolved in acetone, and mix with epoxy resin, stirring is spent the night, and vacuum desolvation agent de-bubbled, pours mould into, be heating and curing.
2. a kind of amphiphilic acrylate random copolymers for flexibilizing epoxy resin according to claim 1 and preparation method thereof, is characterised in that:
(1) the close epoxy monomer adopted during synthesis comprises Hydroxyethyl acrylate (HEA), glycidyl methacrylate (GMA), methacrylic acid N, one or more in the monomers such as N-dimethylamino ethyl ester (DMA), thin epoxy monomer comprises one or more in the monomers such as Isooctyl acrylate monomer (EHA), dodecyl acrylate (LA), methyl methacrylate (MMA).
(3) multipolymer number-average molecular weight Mn is 3.8 × 10
4~ 2.0 × 10
3, PDI is 1.8 ~ 2.1, and second-order transition temperature-50 DEG C ~-20 DEG C, its chemical structural formula is as follows.
。
3. a kind of amphiphilic acrylate random copolymers for flexibilizing epoxy resin according to claim 1 and preparation method thereof, it is characterized in that the ratio of close epoxy component and thin epoxy component in epoxy resin toughened amphiphilic acrylate random copolymers is 3:1,2:1,1:1,1:2,1:3.
4. a kind of parents' random copolymers according to claim 1 is used for the method for modified epoxy, it is characterized in that: the weight of epoxy resin, solidifying agent and parents' random copolymers is 100:100:1 ~ 5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115322523A (en) * | 2022-08-23 | 2022-11-11 | 成都飞机工业（集团）有限责任公司 | Epoxy resin composition containing amphiphilic liquid crystal block copolymer and preparation method thereof |
Citations (1)
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| CN103421140A (en) * | 2013-07-23 | 2013-12-04 | 中蓝晨光化工研究设计院有限公司 | Epoxy resin curing agent and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103421140A (en) * | 2013-07-23 | 2013-12-04 | 中蓝晨光化工研究设计院有限公司 | Epoxy resin curing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115322523A (en) * | 2022-08-23 | 2022-11-11 | 成都飞机工业（集团）有限责任公司 | Epoxy resin composition containing amphiphilic liquid crystal block copolymer and preparation method thereof |
| CN115322523B (en) * | 2022-08-23 | 2023-07-21 | 成都飞机工业（集团）有限责任公司 | Epoxy resin composition containing amphiphilic liquid crystal block copolymer and preparation method thereof |
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Application publication date: 20151216 |