CN102838728A

CN102838728A - Improvement of toughness and heat resistance of epoxy resin through organosilicon modification

Info

Publication number: CN102838728A
Application number: CN2011101713500A
Authority: CN
Inventors: 费金华
Original assignee: Individual
Current assignee: Individual
Priority date: 2011-06-23
Filing date: 2011-06-23
Publication date: 2012-12-26

Abstract

The invention relates to improvement of toughness and heat resistance of an epoxy resin through organosilicon modification. According to the present invention, polymethyltriethoxysilane is adopted to modify the epoxy resin, the molecular structure of the polymethyltriethoxysilane contains a plurality of reactive functional groups, and the polymethyltriethoxysilane is introduced to the epoxy resin, such that a moderately cross-linked network system can be formed so as to simultaneously improve mechanical property and heat resistance of a cured material. The synthesis method of the present invention has the following characteristics that: a design is novel, a process is easy to control, a modification effect is significant, simultaneous improvement of heat resistance and mechanical property of an organosilicon epoxy function material can be achieved, and the method can be expected to be applied in fields of electronic polymers, structural bonding materials, laminate materials, and the like.

Description

Organic-silicon-modified raising epoxy resin toughness and thermotolerance

Technical field

The present invention relates to a kind of epoxy resin, especially a kind of organic-silicon-modified raising epoxy resin toughness and thermotolerance.

Background technology

At present, the bibliographical information of existing many organic-silicon-modified epoxies aspect generally takes two kinds of methods of physical blending and chemical reaction to introduce organosilicon both at home and abroad.Physical blending is that different types of polymkeric substance is carried out blend, and target is the polymeric system that preparation has excellent comprehensive performance, though cost is lower, organosilicon and epoxy resin compatibility property are poor, and modified effect is poor.Chemical reaction mainly is to utilize terminal functionality such as the epoxy group(ing) in hydroxyl, amino, alkoxyl group and the epoxy resin on the organosilicon to react; Generate grafting or segmented copolymer; Mechanical properties such as toughness to improving epoxy resin have better effects; But because of having consumed epoxy group(ing), the cured product cross-linking density reduces, and often is unfavorable for the raising of material thermal resistance ability.Therefore, how to solve the common raising of epoxy material mechanical property, resistance toheat, be the key problem in technology and the focus of this research field both at home and abroad always.

Summary of the invention

The present invention provides a kind of organic-silicon-modified raising epoxy resin toughness and thermotolerance, and for addressing the above problem, the present invention comes modified epoxy with gathering Union carbide A-162 (PolymethylTriethoxy Silane writes a Chinese character in simplified form PTS, calls No. three water-resisting agent).Because of containing a lot of reactive functionality in its molecular structure; It is introduced in the epoxy resin; Can form the moderate crosslinked netted system of tool, reach and improve solidify material mechanics, stable on heating purpose simultaneously, compound method of the present invention is novel in design, technology is prone to control, modified effect is obvious; Improve when can realize organosilicon epoxide function material thermal resistance and mechanical property, be expected in fields such as electronic polymer, structure adhesives, laminating material, obtain to use.

Embodiment

1. experiment content

1.1 raw material

Gather Union carbide A-162, dibutyl tin laurate, bisphenol A type epoxy resin E-44 (writing a Chinese character in simplified form EP), oxirane value 0.44, silicon powder, diaminodiphenyl-methane (DDM).

1.2 operation

Being prepared in the there-necked flask that constant pressure funnel, TM, whisking appliance are housed of 1 .2.1 P TS chemical modification epoxy resin; The E-44 epoxy resin and the PTS that add the different mass ratio; M (EP): m (PTS)=100:5,100:10,100:16 are warming up to 80 ℃, drip an amount of zero(ppm) water and dibutyltin dilaurate catalyst again; About 95 ℃, react 6～7h, get faint yellow translucent sticky thing.

The preparation of 1 .2.2 P TS physically modified epoxy resin with E-44 epoxy resin with PTS with different mass than [m (EP): m (PTS)=100:5,100:10 and 100:16], mix, colourless sticky thing.

1.2 .3 curing molding

With modified resin and solidifying agent diaminodiphenyl-methane (DDM) by n (amino hydrogen): n (epoxy group(ing))=1:1 proportioning is mixed, and mould is injected in the back that stirs, and is cured by 80 ℃/3 h, one 150 ℃/2 h ~ 200 ℃/1 h technology.

1.3 performance test

Oxirane value: measure with hydrochloric acid one acetone method; FTIR: measure with the infrared convert light spectrometer of the RFX-65 Fourier of U.S. Analect company; Relative molecular mass and distribution: measure with U.S. Waters 515-410 type gel permeation chromatograph (GPC), THF (THF) is a moving phase; DSC: after the sample solidifies, grinding powder is with the test of Perkin-ElmerDSC-2C type thermal analyzer, N2 atmosphere, 20 ℃/min of temperature rise rate; Tensile strength and elongation at break: newly think carefully on the CMT7503 electronic universal tester that Instr Ltd. produces in Shenzhen by GB1040-92 and to measure; The sample dumb-bell shape; Draw speed 5.Omm/min:TGA: after the sample solidifies, grinding powder is tested with Perkin-ElmerPyris 1 type thermal gravimetric analyzer; Air atmosphere, 20 ℃/min of temperature rise rate; Microtexture: after the sample solidifies, process the thin slice of 60～80 nm, under the JEM-10 of company of NEC II type transmission electron microscope, observe and take pictures.

2. the preparation of organosilicon chemical modification epoxy resin

2.1 gather Union carbide A-162, be the oligopolymer of Union carbide A-162.Because Si-OR is relatively more responsive to water in its structure; Facile hydrolysis in the presence of dibutyltin dilaurate catalyst; Generate a lot of side reaction functional group; Its hydrolysis reaction formula is following: the hydroxyl that the hydrolysis of PTS alkoxyl group generates is except that the self-crosslinking reaction, and the hydroxyl reaction of main and epoxy resin E-44: the author adopts hydrochloric acid one acetone method that above-mentioned reaction process is carried out the tracking detection of oxirane value, and the result sees table 1.Can find out that oxirane value changes smallly in the reaction process, explain that the PTS hydrolyzate mainly and the hydroxyl reaction of epoxy resin E-44.

Different steps product oxirane value in the table 1 PTS chemical modification epoxy resin reaction process

2.3 chemical modification product structure compositional analysis

Table 2 is the m (EP) that gel permeation chromatograph (GPC) is measured: the relative molecular mass and the distribution of the product of m (PTS)=100:10.The result shows that reaction product is made up of 4 kinds of components, and the relative molecular mass of main ingredient is 893, and accounts for 45.23% of product quality.Obviously PTS and EP react, and because PTS contains more reactive functionality, therefore, except that major part forms the oligopolymer of 2～3 epoxy resin, the higher polymkeric substance of a certain proportion of relative molecular mass are arranged also, help the increase of curing system degree of crosslinking.

Table 2 EP and PTS reaction product relative molecular mass and branch

2.4 mechanics property analysis

Table 3 is the mechanical property of PTS physically modified (PM) and chemical modification (CM) epoxy resin cured product.

Can find out that though physically modified epoxy resin its mechanical property in less volume also increases to some extent, the modified effect that is not so good as the chemical modification product is good.Under the chemical modification condition; When m (EP): m (PTS)=100:10; The tensile strength of cured article and elongation at break all have more obviously raising; After explaining that organosilicon is keyed in the cross linking of epoxy resin network, play the effect of network node to a certain extent, helped improving the mechanical properties such as toughness of material.But along with the further increase of PTS add-on, when m (EP): m (PTS)=100:16, condensate performance increases trend and descends to some extent again, and this is because a part has neither part nor lot in the mechanical property that the unnecessary PTS of chemical reaction has influenced material.

The mechanical property of pure EP of table 3 and PTS modification EP

Annotate: CM: chemical modification; PM: physically modified.As follows.

Table 4 is the resistance toheat of PTS chemistry and physically modified epoxy resin cured product.Through the epoxy resin of physical blending modification, T ɡ value obviously reduces, and explains through the method for simple physical blend and introduces the resistance toheat that PTS can not improve epoxy resin, has reduced the resistance toheat of epoxy resin on the contrary.Forefathers' result of study shows, organosilicon and epoxy resin are under the physical blending condition, and is incompatible usually or be separated, and this has just limited organosilyl use.And the epoxy resin of chemical modification, after the PTS hydrolysis, a molecular chain has a lot of reactive functionality; With hydroxyl generation graft reaction on the epoxy chain; Make the organosilicon chain graft on curable epoxide thing network, make segment mean distance between whole system cross-linking set less than pure EP, it is big that cross-linking density becomes; So its Tg raises, the sample of m (EP): m (PTS)=100:10 is higher 17.29 ℃ than pure epoxy resin.But along with the further increase of PTS add-on, though still there is above-mentioned factor, organosilicon segmental flexibility begins to work, and T ɡ value descends again to some extent.

The second-order transition temperature of pure EP of table 4 and PTS modification EP cured article

Claims

1. organic-silicon-modified raising epoxy resin toughness and thermotolerance is characterized in that: come modified epoxy with gathering Union carbide A-162; Because of containing a lot of reactive functionality in its molecular structure, it is introduced in the epoxy resin, can form the moderate crosslinked netted system of tool, reach and improve solidify material mechanics, stable on heating purpose simultaneously.