CN103755922A - Latent curing agent with fire resistance and preparation method thereof - Google Patents
Latent curing agent with fire resistance and preparation method thereof Download PDFInfo
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- CN103755922A CN103755922A CN201410023183.9A CN201410023183A CN103755922A CN 103755922 A CN103755922 A CN 103755922A CN 201410023183 A CN201410023183 A CN 201410023183A CN 103755922 A CN103755922 A CN 103755922A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 76
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000003063 flame retardant Substances 0.000 claims abstract description 16
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 52
- 239000003822 epoxy resin Substances 0.000 abstract description 51
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 description 31
- 230000004048 modification Effects 0.000 description 20
- 238000012986 modification Methods 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 150000002460 imidazoles Chemical class 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 235000010585 Ammi visnaga Nutrition 0.000 description 3
- 244000153158 Ammi visnaga Species 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
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Abstract
The invention discloses a latent curing agent with fire resistance and a preparation method thereof. The structural formula of the latent curing agent with fire resistance is shown in the specification. The dicyandiamide is modified by DOPO, so that the compatibility of the curing agent and the epoxy resin can be improved. By adopting the curing agent disclosed by the invention, good flame retardant property is provided for epoxy resin when good flame retardancy is ensured, the limit oxygen index of a cured product is 25.3, and the latent curing agent belongs to a nonflammable material.
Description
One, technical field
The present invention relates to a kind of solidifying agent and preparation method thereof, a kind of latent curing agent with flame retardant resistance and preparation method thereof specifically, for single-component epoxy resin system.
Two, background technology
Epoxy resin has good mechanical property, adhesiveproperties, electrical insulating property, chemical stability and processibility, is widely used in the fields such as building, machinery, electronic apparatus, aerospace.Epoxy resin needs to add solidifying agent in use, and is cured under certain conditions crosslinkedly, forms three-dimensional netted three dimensional structure, just can present various good performances, realizes its value.Therefore in the application and development of epoxy resin, solidifying agent has very important effect.Conventional epoxies solidifying agent is two component curing agents; under normal temperature this class solidifying agent with regard to can be rapidly and epoxy resin react and solidify; during use, need now with the current; product performance are subject to operator's the impact of state of the art very large, can not meet the need of production of modernization mass-producing automatization day by day.There have been a lot of single-component epoxy resins to appear on the market abroad, the part of this class single-component system most critical is exactly the Novel curing agent with latent, under normal temperature, react with epoxy resin hardly, give certain condition, such as being warmed up to suitable temperature, just can react rapidly curing.In this respect, domestic development is relatively backward, and the needs in production and application mainly rely on import, and the single-component epoxy resin curing agent that research has independent intellectual property right has very important significance.
In recent years, the research of latent curing agent heats up gradually, develops the approach of multiple acquisition latent, thermal initiation, moisture activation, illumination activation etc.Dyhard RU 100 is the thermal initiation type latent curing agent developing rapidly in recent years, and while using as solidifying agent, latent is good, and highly stable under normal temperature, storage period is long.But solidification value is too high, need about 180 ℃ could be curing preferably, well beyond the temperature that can bear of a lot of devices and production technique, thereby limited its application.Satisfied, having under the prerequisite of good storage stability, will reduce curing reaction temperature, and don't affect its use properties, is the focus of current latent curing agent research.There is for a long time with aromatic amine, Dyhard RU 100 being carried out the product of modification abroad, as the HT-2833 of Switzerland Ciba-Geigy company exploitation, HT-2844, the domestic report that Dyhard RU 100 is carried out to modification seldom, in bibliographical information, be still and take aromatic amine modification Dyhard RU 100 as main direction at present, cause modification Dyhard RU 100 class solidifying agent product structure single, restrict its development.
Epoxide resin material is when bringing huge interests to people, because its incendivity has brought some potential safety hazards.Aspect fire retardant material, additive flame retardant may move and cause flame retarding efficiency to decline, halogenated flame retardant is heated and may discharges objectionable impurities, the organophosphorus that flame retarding efficiency is high, flue dust is few is that reactive flame retardant day by day receives much attention in competition, be combined the flame retardant resistance solidifying agent of rear formation with epoxy curing agent, become the fire-retardant main trend of epoxide resin material.
At present, the research of latent curing agent, flame retardant resistance solidifying agent is all separately carried out, and the solidifying agent that simultaneously possesses these two kinds of performances is domestic still less than report.
Three, summary of the invention
The present invention aims to provide a kind of latent curing agent with flame retardant resistance and preparation method thereof, technical problem to be solved is to select suitable solidifying agent structure by molecular designing, makes it when having better latent, reduce the curing reaction temperature of epoxy resin.
The present invention obtains novel latent curing agent by DOPO modification Dyhard RU 100, solidifying agent of the present invention is applied in epoxy-resin systems except retaining epoxy resin good bonding, chemical stability, electrical insulating property and processibility, also have easy to use, storage period is long, solidification value declines, the advantages such as good flame-retardance.
The structural formula that the present invention has the latent curing agent of flame retardant resistance is:
The preparation method that the present invention has the latent curing agent of flame retardant resistance operates according to the following steps:
Dyhard RU 100 (DICY) and water are added in reactor, be warming up to 60 ℃ of stirring and dissolving, obtain Dyhard RU 100 solution; In described Dyhard RU 100 solution, add DOPO(9, mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy), in 110-130 ℃ of reaction 4-6 hour, after reaction finishes, reaction solution is placed in to ice-water bath cooling, after filtering and being dried, obtaining target product (DD), is white powder;
The mol ratio of DOPO and Dyhard RU 100 is 1:1.
Reaction process is as follows:
In the process of reaction, add DOPO, the molar weight of the DOPO adding is 1:0.1-0.2 with the ratio of the molar weight of described Dyhard RU 100.Additional time is preferably in reaction 3-4 hour.
The Dyhard RU 100 of adding preferably adds at twice, and twice add-on is equal, and be 0.5-1 hour the interval time adding for twice.
The reason that Dyhard RU 100 is added is: 1., in reaction process, Dyhard RU 100 has partial hydrolysis, adds Dyhard RU 100 and can improve productive rate; 2. in order to make DOPO total overall reaction.If DOPO is excessive or do not have total overall reaction, be difficult to and product separation, product purity declines, and unreacted DOPO also can make epoxy resin end-blocking, cross-linking density declines, and causes product defects, even if Dyhard RU 100 part is excessive, Dyhard RU 100 water soluble, can not be precipitated out, and product purity is high.
Raw material DOPO of the present invention adds with the form of powder, and this is to carry out in water because of this reaction, and the solvability of DOPO in water is bad, directly with block DOPO, adds in reactor speed of reaction extremely busy, and productive rate is lower, and side reaction is many.The present invention is precipitated and is obtained pulverous DOPO by poor solvent, can form the homogeneous reaction system of approximate emulsion under the condition stirring, and is conducive to the raising of speed of reaction and productive rate.
The preparation method of DOPO powder is as follows:
Block DOPO and ethanol are added in beaker, heat and stir DOPO is dissolved, pour into while hot in 0 ℃ of water, and rapid stirring, filter, stand-by.
The preparation of single-component epoxy resin material:
Solidifying agent of the present invention was ground to 400 mesh sieves, under normal temperature, mixed by the mass ratio of 20-30:0.5-2:100 with imidazoles and epoxy resin (E44), after solidifying, obtained single-component epoxy resin.Curing process is as follows:
First the temperature rise rate with 10 ℃/min is warming up to 80 ℃, at 80 ℃ of constant temperature 30min, temperature rise rate with 10 ℃/min is warming up to 100 ℃ again, and at 100 ℃ of constant temperature 30min, the temperature rise rate with 10 ℃/min is warming up to 110 ℃ subsequently, at 110 ℃ of constant temperature 30min, temperature rise rate with 10 ℃/min is warming up to 115 ℃ again, and at 115 ℃ of constant temperature 30min, finally the temperature rise rate with 10 ℃/min is warming up to 120 ℃, at 120 ℃ of constant temperature 120min, cooling.
Solidifying agent of the present invention need to coordinate imidazoles to use, and while using separately solidifying agent cured epoxy resin of the present invention, set time is long and bubble is more, while adding a small amount of imidazoles and solidifying agent to be used in conjunction with, without bubble, cured article homogeneous transparent, also obviously shorten set time.Embodiment 5,6,7, and for not adding the curing system of imidazoles, embodiment 8 is for adding the system of imidazoles, and contrast can be found out the synergy of solidifying agent of the present invention and imidazoles intuitively.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, in the situation that modified amine product structure is single at home, the invention provides a kind of novel method of modification Dyhard RU 100, can effectively reduce epoxy resin cure temperature.
2, solidifying agent of the present invention is also given the flame retardant properties that epoxy resin is good when guaranteeing good latent, and the limiting oxygen index(LOI) of cured article is 25.3, belongs to nonflammable material.
3, the present invention, with DOPO to dicyandiamide modified, can improve the consistency between solidifying agent and epoxy resin.
4, raw material sources are extensive, with low cost.
5, preparation technology is simple, is easy to realize suitability for industrialized production.
Four, accompanying drawing explanation
Fig. 1 is the infrared spectrum of Dyhard RU 100 (DICY) and solidifying agent of the present invention (DD).As can be seen from Figure 1, the 2208cm of DICY
-1and 2165cm
-1for the stretching vibration of C ≡ N, and do not absorb in this region of product D D, at 1745cm
-1and 1692cm
-1absorption ArO (O=P) C=NH and N (C=N) N that have occurred respectively two carbon-to-nitrogen double bons, illustrate that cyano group generation addition reaction generates two keys.The 3100-3000cm of DD in addition
-1the weak absorption occurring is C-H stretching vibration on phenyl ring, and above structural analysis can prove, DOPO and DICY generation nucleophilic addition(Adn), generation DD.
Fig. 2 is the DSC curve of the epoxy resin (DICY/E44) that obtains after solidifying agent solidifies of the epoxy resin (DD/E44) obtaining after solidifying with solidifying agent of the present invention and the Dyhard RU 100 of take.As can be seen from Figure 2, the solidification value of DD/E44 system has reduced nearly 40 ℃ compared with DICY/E44 system.
Five, embodiment
Below in conjunction with embodiment, the present invention is described in detail, but the present invention is not limited to following examples.
Embodiment 1:
1, the preparation of powder DOPO:
21.6g DOPO is dissolved in 45ml ethanol, and 60 ℃ of heated and stirred are dissolved it, pour into while hot in the 0 ℃ of water that is placed in ice bath, stir 10min, filter and be drying to obtain powder DOPO.
2, the preparation of modification Dyhard RU 100:
Oil bath temperature is controlled at 60 ℃, 0.1mol (8.40g) Dyhard RU 100 and 100ml water are joined in 150ml there-necked flask, stir, Dyhard RU 100 is dissolved, the powder DOPO that adds step 1 preparation, stirring makes system even, be warmed up to 120 ℃, after back flow reaction 3h, add the aqueous solution 10ml(of 1mol/L Dyhard RU 100 containing Dyhard RU 100 0.84g), after reaction 0.5h, add again the aqueous solution 10ml(of 1mol/L Dyhard RU 100 containing Dyhard RU 100 0.84g), continue reaction 0.5h, while hot reaction solution is poured out, be placed in ice bath rapid stirring, filter and be dried the solidifying agent that obtains white powder.
3, the preparation of modification Dyhard RU 100/epoxy resin
The solidifying agent of step 2 preparation was ground to 400 mesh sieves, and described solidifying agent, imidazoles and epoxy resin the E44 in mass ratio ratio of 30:0.5:100 mix, and obtain epoxide resin material, abbreviation DD/E44 after solidifying.
4, the preparation of Dyhard RU 100/epoxy resin:
Dyhard RU 100 was ground to 400 mesh sieves, by Dyhard RU 100 and epoxy resin in mass ratio the ratio of 30:100 mix, after solidifying, obtain epoxide resin material, be called for short DICY/E44.
Two kinds of epoxide resin materials of step 3 and step 4 preparation are carried out to dsc analysis, 10 ℃/min of temperature rise rate, result is by Fig. 2.
Embodiment 2: the preparation of Dyhard RU 100/epoxy resin
Dyhard RU 100 was ground to 400 mesh sieves, by Dyhard RU 100 and epoxy resin in mass ratio the ratio of 8.4:100 mix, be placed in 8h at 140 ℃, baking oven, cooling, Preblend is still that thickness is liquid, fails better to solidify, temperature is too low.In curing process, solidifying agent has the phenomenon of precipitation, after stirring, continues to solidify with toothpick.
Embodiment 3: the preparation of Dyhard RU 100/epoxy resin
Dyhard RU 100 was ground to 400 mesh sieves, by Dyhard RU 100 and epoxy resin in mass ratio the ratio of 8.4:100 mix, be placed in 8h at 160 ℃, baking oven, cooling, Preblend is still that thickness is liquid, fails better to solidify, temperature is too low.In curing process, solidifying agent has the phenomenon of precipitation, after stirring, continues to solidify with toothpick.
Embodiment 4: the preparation of Dyhard RU 100/epoxy resin
Dyhard RU 100 was ground to 400 mesh sieves, by Dyhard RU 100 and epoxy resin in mass ratio the ratio of 8.4:100 mix, be placed in 8h at 180 ℃, baking oven, cooling, Preblend is successfully solidified.In curing process, solidifying agent has the phenomenon of precipitation, after stirring, continues to solidify with toothpick.
Embodiment 5:
1, the preparation of powder DOPO:
21.6g DOPO is dissolved in 45ml ethanol, and 60 ℃ of heated and stirred are dissolved it, pour into while hot in the 0 ℃ of water that is placed in ice bath, stir 10min, filter and be drying to obtain powder DOPO.
2, the preparation of modification Dyhard RU 100:
Oil bath temperature is controlled at 60 ℃, 0.1mol (8.40g) Dyhard RU 100 and 100ml water are joined in 150ml there-necked flask, stir, Dyhard RU 100 is dissolved, the powder DOPO that adds step 1 preparation, stirring makes system even, be warmed up to 120 ℃, after back flow reaction 3h, add the aqueous solution 10ml(of 1mol/L Dyhard RU 100 containing Dyhard RU 100 0.84g), after reaction 0.5h, add again the aqueous solution 10ml(of 1mol/L Dyhard RU 100 containing Dyhard RU 100 0.84g), continue reaction 0.5h, while hot reaction solution is poured out, be placed in ice bath rapid stirring, filter and be dried the solidifying agent that obtains white powder.
3, the preparation of modification Dyhard RU 100/epoxy resin
The solidifying agent of step 2 preparation was ground to 400 mesh sieves, described solidifying agent and epoxy resin the E44 in mass ratio ratio of 30:100 mix, be placed in baking oven, at 160 ℃, become solid during constant temperature 1h, and there are a lot of bubbles, illustrate that solidification value is too high, solidify too quickly, do not occur the phenomenon of solidifying agent precipitation.
Embodiment 6:
1, the preparation of powder DOPO:
21.6g DOPO is dissolved in 45ml ethanol, and 60 ℃ of heated and stirred are dissolved it, pour into while hot in the 0 ℃ of water that is placed in ice bath, stir 10min, filter and be drying to obtain powder DOPO.
2, the preparation of modification Dyhard RU 100:
Oil bath temperature is controlled at 60 ℃, 0.1mol (8.40g) Dyhard RU 100 and 100ml water are joined in 150ml there-necked flask, stir, Dyhard RU 100 is dissolved, the powder DOPO that adds step 1 preparation, stirring makes system even, be warmed up to 120 ℃, after back flow reaction 3h, add the aqueous solution 10ml(of 1mol/L Dyhard RU 100 containing Dyhard RU 100 0.84g), after reaction 0.5h, add again the aqueous solution 10ml(of 1mol/L Dyhard RU 100 containing Dyhard RU 100 0.84g), continue reaction 0.5h, while hot reaction solution is poured out, be placed in ice bath rapid stirring, filter and be dried the solidifying agent that obtains white powder.
3, the preparation of modification Dyhard RU 100/epoxy resin
The solidifying agent of step 2 preparation was ground to 400 mesh sieves, described solidifying agent and epoxy resin the E44 in mass ratio ratio of 30:100 mix, be placed in baking oven, at 140 ℃, become solid during constant temperature 2h, still have a lot of bubbles, illustrate that solidification value is too high, solidify too quickly, do not occur the phenomenon of solidifying agent precipitation.
Embodiment 7:
1, the preparation of powder DOPO:
21.6g DOPO is dissolved in 45ml ethanol, and 60 ℃ of heated and stirred are dissolved it, pour into while hot in the 0 ℃ of water that is placed in ice bath, stir 10min, filter and be drying to obtain powder DOPO.
2, the preparation of modification Dyhard RU 100:
Oil bath temperature is controlled at 60 ℃, 0.1mol (8.40g) Dyhard RU 100 and 100ml water are joined in 150ml there-necked flask, stir, Dyhard RU 100 is dissolved, the powder DOPO that adds step 1 preparation, stirring makes system even, be warmed up to 120 ℃, after back flow reaction 3h, add the aqueous solution 10ml(of 1mol/L Dyhard RU 100 containing Dyhard RU 100 0.84g), after reaction 0.5h, add again the aqueous solution 10ml(of 1mol/L Dyhard RU 100 containing Dyhard RU 100 0.84g), continue reaction 0.5h, while hot reaction solution is poured out, be placed in ice bath rapid stirring, filter and be dried the solidifying agent that obtains white powder.
3, the preparation of modification Dyhard RU 100/epoxy resin
The solidifying agent of step 2 preparation was ground to 400 mesh sieves, and described solidifying agent and epoxy resin the E44 in mass ratio ratio of 30:100 mix, and are placed in baking oven, have become solid during constant temperature 8h at 120 ℃, have bubble, do not occur the phenomenon that solidifying agent precipitates.
Embodiment 8:
1, the preparation of powder DOPO:
21.6g DOPO is dissolved in 45ml ethanol, and 60 ℃ of heated and stirred are dissolved it, pour into while hot in the 0 ℃ of water that is placed in ice bath, stir 10min, filter and be drying to obtain powder DOPO.
2, the preparation of modification Dyhard RU 100:
Oil bath temperature is controlled at 60 ℃, 0.1mol (8.40g) Dyhard RU 100 and 100ml water are joined in 150ml there-necked flask, stir, Dyhard RU 100 is dissolved, the powder DOPO that adds step 1 preparation, stirring makes system even, be warmed up to 120 ℃, after back flow reaction 3h, add the aqueous solution 10ml(of 1mol/L Dyhard RU 100 containing Dyhard RU 100 0.84g), after reaction 0.5h, add again the aqueous solution 10ml(of 1mol/L Dyhard RU 100 containing Dyhard RU 100 0.84g), continue reaction 0.5h, while hot reaction solution is poured out, be placed in ice bath rapid stirring, filter and be dried the solidifying agent that obtains white powder.
3, the preparation of modification Dyhard RU 100/epoxy resin
The solidifying agent of step 2 preparation was ground to 400 mesh sieves, described solidifying agent, imidazoles and epoxy resin the E44 in mass ratio ratio of 30:0.5:100 mix, with 10 ℃/min, be warming up to respectively constant temperature 1h at 100 ℃, constant temperature 1h at 110 ℃, at 120 ℃, during 2h, powered-down is lowered the temperature naturally, and system becomes transparent solid, very smooth without bubble, there is not the phenomenon that solidifying agent precipitates.Embodiment 9:
1, the preparation of powder DOPO:
21.6g DOPO is dissolved in 45ml ethanol, and 60 ℃ of heated and stirred are dissolved it, pour into while hot in the 0 ℃ of water that is placed in ice bath, stir 10min, filter and be drying to obtain powder DOPO.
2, the preparation of modification Dyhard RU 100:
Oil bath temperature is controlled at 60 ℃, 0.1mol (8.40g) Dyhard RU 100 and 100ml water are joined in 150ml there-necked flask, stir, Dyhard RU 100 is dissolved, the powder DOPO that adds step 1 preparation, stirring makes system even, be warmed up to 120 ℃, after back flow reaction 3h, add the aqueous solution 10ml(of 1mol/L Dyhard RU 100 containing Dyhard RU 100 0.84g), after reaction 0.5h, add again the aqueous solution 10ml(of 1mol/L Dyhard RU 100 containing Dyhard RU 100 0.84g), continue reaction 0.5h, while hot reaction solution is poured out, be placed in ice bath rapid stirring, filter and be dried the solidifying agent that obtains white powder.
3, the preparation of modification Dyhard RU 100/epoxy resin
The solidifying agent of step 2 preparation was ground to 400 mesh sieves, described solidifying agent, imidazoles and epoxy resin the E44 in mass ratio ratio of 30:0.5:100 mix, the mould that adds 4mm * 10mm * 10cm, be placed in baking oven, first the temperature rise rate with 10 ℃/min is warming up to 80 ℃, at 80 ℃ of constant temperature 30min, temperature rise rate with 10 ℃/min is warming up to 100 ℃, at 100 ℃ of constant temperature 30min, temperature rise rate with 10 ℃/min is warming up to 110 ℃, at 110 ℃ of constant temperature 30min, temperature rise rate with 10 ℃/min is warming up to 115 ℃, at 115 ℃ of constant temperature 30min, temperature rise rate with 10 ℃/min is warming up to 120 ℃, at 120 ℃ of constant temperature 120min, powered-down is lowered the temperature naturally, the liquid Preblend of thickness is solidified into transparent batten, very smooth without bubble, the phenomenon that does not occur solidifying agent precipitation in solidification process.
4, the mensuration of cured article oxygen index
By XZT-100A type limiting oxygen index(LOI) instrument, according to GB GB/T2406, the sample of step 4 preparation is tested.In cured article, phosphorus content is 2.4%, and recording LOI is 25.3, belongs to nonflammable material, can be lighted, but only can continue the burning of 2-3s in air, shows to dicyandiamide modified, to have given curing system good flame retardant resistance by DOPO.
Embodiment 10:
1, the preparation of powder DOPO:
21.6g DOPO is dissolved in 45ml ethanol, and 60 ℃ of heated and stirred are dissolved it, pour into while hot in the 0 ℃ of water that is placed in ice bath, stir 10min, filter and be drying to obtain powder DOPO.
2, the preparation of modification Dyhard RU 100:
Oil bath temperature is controlled at 60 ℃, 0.1mol (8.40g) Dyhard RU 100 and 100ml water are joined in 150ml there-necked flask, stir, Dyhard RU 100 is dissolved, the powder DOPO that adds step 1 preparation, stirring makes system even, be warmed up to 120 ℃, after back flow reaction 3h, add the aqueous solution 10ml(of 1mol/L Dyhard RU 100 containing Dyhard RU 100 0.84g), after reaction 0.5h, add again the aqueous solution 10ml(of 1mol/L Dyhard RU 100 containing Dyhard RU 100 0.84g), continue reaction 0.5h, while hot reaction solution is poured out, be placed in ice bath rapid stirring, filter and be dried the solidifying agent that obtains white powder.
3, the preparation of modification Dyhard RU 100/epoxy resin
The solidifying agent of step 2 preparation was ground to 400 mesh sieves, and described solidifying agent, imidazoles and epoxy resin the E44 in mass ratio ratio of 30:0.5:100 mix, standing under normal temperature, in 50 days, do not precipitate, and the phenomenons such as sclerosis, storage period was over 50 days.
Solidifying agent of the present invention need to coordinate imidazoles to use, and while using separately solidifying agent cured epoxy resin of the present invention, set time is long and bubble is more, while adding a small amount of imidazoles and solidifying agent to be used in conjunction with, without bubble, cured article homogeneous transparent, also obviously shorten set time.Embodiment 5,6,7, and for not adding the curing system of imidazoles, embodiment 8 is for adding the system of imidazoles, and contrast can be found out the synergy of solidifying agent of the present invention and imidazoles intuitively.
Claims (5)
1. a latent curing agent with flame retardant resistance, is characterized in that its structural formula is:
2. a preparation method with the latent curing agent of flame retardant resistance claimed in claim 1, is characterized in that operating according to the following steps:
Dyhard RU 100 and water are added in reactor, be warming up to 60 ℃ of stirring and dissolving, obtain Dyhard RU 100 solution; In described Dyhard RU 100 solution, add DOPO, in 110-130 ℃ of reaction 4-6 hour, after reaction finishes, reaction solution is placed in to ice-water bath cooling, after filtering and being dried, obtain target product;
The mol ratio of DOPO and Dyhard RU 100 is 1:1.
3. preparation method according to claim 2, is characterized in that:
In the process of reaction, add DOPO, the molar weight of the DOPO adding is 1:0.1-0.2 with the ratio of the molar weight of described Dyhard RU 100.
4. preparation method according to claim 3, is characterized in that:
The DOPO adding adds at twice, and twice add-on is equal, and be 0.5-1 hour the interval time adding for twice.
5. preparation method according to claim 2, is characterized in that:
Raw material DOPO is Powdered.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108976260A (en) * | 2018-07-27 | 2018-12-11 | 武汉工程大学 | A kind of new compound D-DICY and its synthetic method |
| CN110205037A (en) * | 2019-05-30 | 2019-09-06 | 深圳市华星光电技术有限公司 | Sealant and liquid crystal display device |
| CN111535034A (en) * | 2020-04-09 | 2020-08-14 | 安徽福斯特渔具有限公司 | Preparation method of high-temperature-resistant composite material for fire-fighting protective clothing |
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| EP2116549A2 (en) * | 2008-04-11 | 2009-11-11 | Chang Chun Plastics Co., Ltd. | Novel phosphorus-containing compounds and their preparing process and use |
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| US20030120021A1 (en) * | 2001-09-20 | 2003-06-26 | Chun-Shan Wang | Phosphorus-containing flame-retardant hardeners, epoxy resins, advanced epoxy resins and cured epoxy resins |
| EP2116549A2 (en) * | 2008-04-11 | 2009-11-11 | Chang Chun Plastics Co., Ltd. | Novel phosphorus-containing compounds and their preparing process and use |
| CN101914265A (en) * | 2010-07-24 | 2010-12-15 | 广州美嘉伟华电子材料有限公司 | A kind of non-halogen phosphorus-containing flame retardant high-frequency epoxy resin based composition and the application in bonding sheet and copper-clad plate thereof |
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| CN110205037A (en) * | 2019-05-30 | 2019-09-06 | 深圳市华星光电技术有限公司 | Sealant and liquid crystal display device |
| CN111535034A (en) * | 2020-04-09 | 2020-08-14 | 安徽福斯特渔具有限公司 | Preparation method of high-temperature-resistant composite material for fire-fighting protective clothing |
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