Be applicable to the solidifying agent preparation method of epoxy resin-matrix micropore ceramics forming mould
Technical field
This invention belongs to the ceramic mould polymeric material field, relates to solidifying agent of micropore ceramics forming mould and preparation method thereof, relates in particular to solidifying agent that is applicable to epoxy resin-matrix micropore ceramics forming mould and preparation method thereof.
Background technology
Traditional ceramic mould material is gypsum, the micropore polymeric mold is the ideal substitute of gypsum mold, and we have reported a kind of manufacture method of the epoxy resin-matrix Microcellar plastic mold for forming process of ceramics in Chinese invention patent ZL200610146610.8.The method is take Resins, epoxy as main raw material, is aided with inorganic strengthening agent, and by forming water-in-oil emulsion, then moulding is coated on the moisture evaporation pore in the Resins, epoxy with the solidifying agent reaction, forms Microcellar plastic mold.
Because this kind mould at first was to form stable water-in-oil emulsion in moulding in the past, the solidifying agent that therefore adopts must have certain wetting ability, helps simultaneously the stable of water-in-oil epoxy resin latex.Most of fatty amines solidifying agent all are water miscible, and Resins, epoxy then is hydrophobic type, so aliphatic amide can't solidified liquid Resins, epoxy in water.Therefore need change the molecular structure of aliphatic amide by introducing hydrophobic group, increase its in water with the consistency of Resins, epoxy, improve simultaneously the ability of its emulsion epoxy resin.
Aqueous epoxy curing agent mainly contains 3 classes: the amidated polyamines that 1) is made by polyamine and mono fatty acid reaction; 2) carry out the polymeric amide that condensation forms by dimeracid and polyamine; 3) polyamines-epoxy adduct that is obtained by polyamine and Resins, epoxy addition.Modal be the third part acid neutralized reaction product (as, Zhou Jiliang etc., 2005,33(2): 25-28), but these waterborne curing agents all were that traditional oil-in-water-type Resins, epoxy is had stabilization in the effect of performance solidifying agent in the past, and were not suitable for curing and the stabilization of water-in-oil-type Resins, epoxy.Be embodied in the hydrophile-lipophile balance value (HLB value) that is applicable in other words the solidifying agent of this water-in-oil system on the quantizating index than little many of traditional waterborne curing agent.The HLB value of general Resins, epoxy is about 3, and the HLB value of the third waterborne curing agent is much higher, can't match.
Therefore, the solidifying agent that requirement is suitable for this invention should have certain wetting ability, and its lipophilicity must be higher than traditional waterborne curing agent simultaneously, considers to have water in oil emulsifying effect concurrently, this lipophilicity requires again can not be too high, and a suitable coupling must be arranged.
Summary of the invention
One of purpose of the present invention is synthetic a kind of synthesized solidified dose of being applicable to water-in-oil epoxy resin latex system and preparation method thereof, and it should have water in oil emulsifying effect concurrently, and the HLB value is between 7-10, and weight-average molecular weight is 1500-2600.And its with should have certain working life after epoxy-resin systems mixes, namely stability requires to have at normal temperatures the stable storing phase more than 30 days.
A kind of synthesized solidified dose of being applicable to water-in-oil epoxy resin latex system, dimeracid and lipid acid and polyethylene polyamine polymerization obtain, and the HLB value is between 7-10, and weight-average molecular weight is 1500-2600.
Described dimeracid refers to dimer (fatty acid) yl, is selected from a kind of in linolic acid dimeracid, eleostearic acid dimeracid, the synourin oil dimeracid, preferably the linolic acid dimeracid.
Described lipid acid is selected from oleic acid, Palmiticacid, stearic acid, preferably oleic acid.
Described polyethylene polyamine is selected from one or both of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, preferably triethylene tetramine;
Described organic acid is liquid organic acid, and preferred, described organic acid is formic acid, acetic acid or lactic acid, more preferably acetic acid.
The molar mass proportioning of dimeracid and lipid acid be 6:4 to 9:1, total carboxyl mol ratio is 0.9~1.1:1 with the amino mole proportioning of the end of polyethylene polyamine in dimeracid and the lipid acid.
Synthesized solidified dose the synthetic method that this is applicable to water-in-oil epoxy resin latex system comprises the following steps:
1) dimeracid and lipid acid are joined in the reaction flask, stir and be warming up to 180-220 ℃, insulation is lower, drips polyethylene polyamine in 3 hours, constantly tells the water of generation simultaneously, after dripping, and restir reaction 1 hour.
2) cool to 40 ℃ after, stir down, in 1 hour, drip the organic acid that is equivalent to polyethylene polyamine 30%-40% mole proportioning.
Preferably, in the step 1) molar mass proportioning of dimeracid and lipid acid be 6:4 to 9:1, total carboxyl mol ratio is 1:1 with the amino mole proportioning of the end of polyethylene polyamine in dimeracid and the lipid acid.
Preferred, the molar mass proportioning of dimeracid and lipid acid is that 7:3 is to 8:2 in the step 1).
Temperature of reaction when preferably, being incubated in the step 1) is 200-210 ℃.
The synthesized solidified dose of molecular weight of most importantly controlling product by the adding of oleic acid of this invention, the ratio of control dimeracid/oleic acid and polyethylene polyamine is controlled its HLB value.It has the function of solidifying agent and emulsifying agent concurrently, can be adsorbed on to help to form stable water-in-oil emulsion on the interface of water and Resins, epoxy, and can stably stored more than 30 days.At above water-in-oil Resins, epoxy-curative systems during for the manufacture of the micropore ceramics forming mould, by adding a certain proportion of T31 and polyamide 6 50 solidifying agent, initial solidification reaction heat is being provided more than 50 ℃, impel above system breakdown of emulsion, cause the hot setting reaction of aforementioned solidifying agent and Resins, epoxy, and make the moisture evaporation pore.
Description of drawings
Fig. 1 is synthesized solidified dose 2 the infrared spectrogram that embodiment 2 obtains.
Embodiment
Following examples are to further specify of the present invention, but the present invention is not limited thereto.
The HLB values determination method is referring to Zhou Jiahua etc., and the analysis of tensio-active agent HLB value is measured and the analysis mensuration of calculating I .HLB value, Speciality Petrochemicals, 2001,2:11-14.Molecular weight adopts efficient gel permeation chromatography-polygonal laser light scattering combined instrument, measures with the tetrahydrofuran (THF) chromatographic column.
1 synthesized solidified dose of embodiment
560 gram linolic acid dimeracids and 72 are restrained the oleic acid adding with the four-hole reaction flask of stirring, thermometer, dropping funnel and condensation division box, be warming up to 200 ℃ under stirring, in 3 hours, drip 164 gram triethylene tetramines, and constantly tell and react the water that produces, after dripping, restir reaction 1 hour, the water of finally telling are approximately 38 grams, obtain low molecular polyamides.After cooling to 40 ℃, under stirring, in 1 hour, drip acetic acid 20 grams, obtain synthesized solidified dose 1 of part neutralization.Its weight-average molecular weight is that 1800, HLB value is 8.5.
2 synthesized solidified doses of embodiment
560 gram linolic acid dimeracids and 105 are restrained the oleic acid adding with the four-hole reaction flask of stirring, thermometer, dropping funnel and condensation division box, be warming up to 200 ℃ under stirring, in 3 hours, drip 200 gram triethylene tetramines, and constantly tell and react the water that produces, after dripping, restir reaction 1 hour, the water of finally telling are approximately 50 grams, obtain low molecular polyamides.After cooling to 40 ℃, under stirring, in 1 hour, drip acetic acid 29 grams, obtain synthesized solidified dose 2 of part neutralization.Its weight-average molecular weight is that 1560, HLB value is 9.1.
3 synthesized solidified doses of embodiment
560 gram eleostearic acid dimeracids and 100 are restrained the oleic acid adding with the four-hole reaction flask of stirring, thermometer, dropping funnel and condensation division box, be warming up to 200 ℃ under stirring, in 3 hours, drip 196 gram triethylene tetramines, and constantly tell and react the water that produces, after dripping, restir reaction 1 hour, the water of finally telling are approximately 49.4 grams, obtain low molecular polyamides.After cooling to 40 ℃, under stirring, in 1 hour, drip acetic acid 27 grams, obtain synthesized solidified dose 3 of part neutralization.Its weight-average molecular weight is that 1670, HLB value is 8.8.
Fig. 1 is synthesized solidified dose 2 the infrared spectrogram that embodiment 2 obtains, by finding out at 3470cm on the figure
-1Near broad peak is the amino peak on the amido linkage, and 1650 cm
-1Near carbonyl absorption peak on the acid amides of feature appears.