CN107868232A

CN107868232A - A kind of water-base epoxy porous resin composite and its preparation method and application

Info

Publication number: CN107868232A
Application number: CN201610864274.4A
Authority: CN
Inventors: 黄月文; 王斌; 陈建军; 郑周; 鲁道欢; 姜智聪
Original assignee: Guangzhou Chemical Co Ltd of CAS; Nanxiong Material Production Base of Guangzhou Chemical Co Ltd of CAS
Current assignee: Guoke Guanghua (Nanxiong) New Materials Research Institute Co.,Ltd.; Guangzhou Chemical Co Ltd of CAS
Priority date: 2016-09-28
Filing date: 2016-09-28
Publication date: 2018-04-03
Anticipated expiration: 2036-09-28
Also published as: CN107868232B

Abstract

The invention belongs to field of compound material, discloses a kind of water-base epoxy porous resin composite and its preparation method and application.The material is made up of the component of A, B, C tri-, wherein component A includes 70~100wt% liquid-state epoxy resins, 30~0wt% inorganic fillers 1, B component includes 40~90wt% self-emulsifying acid amides contracting amine schiff bases compounds, the more amine compounds of 10~50wt% amidatioon hydrophobicities, 0~10wt% long-chain carboxylic acids, also include inorganic filler 2, component C includes 40~70wt% inorganic fillers 3,30~60wt% alkaline waters, 0~1wt% auxiliary agents.The water-base epoxy porous resin composite of the present invention has higher-strength and excellent through hole, aperture is smaller, is had broad application prospects in pressure porous mold, seepy material, press filtration material, material for air purification or large volume consolidation by grouting repairing field.

Description

A kind of water-base epoxy porous resin composite and its preparation method and application

Technical field

The invention belongs to field of compound material, more particularly to a kind of water-base epoxy porous resin composite and its preparation side Method and application.

Background technology

Organic polymer porous resin moulding material has excellent porous, larger specific surface area, stability good, again Many advantages, such as amount is light and is easy to functionalization, using being related to building, Aero-Space, atomic energy, medical science, environmental protection, metallurgy, machine The industries such as tool, electrochemistry and petrochemical industry, available for adsorb, separate, filter, gas distribution, noise reduction, absorbing, packaging, shielding, it is heat-insulated, Many occasions such as heat exchange, biological implantation, electrochemical process, sensing, organic photoelectric and heterogeneous catalysis.The porous tree of organic polymer What the research of fat moulding material was most widely used is perforate (or through hole) type porous material, and its gas phase is in each with polymer phase It is continuously distributed.

Epoxy resin-base composite material is one of material studied and be most widely used at present, and epoxy resin-matrix is porous multiple The advantages that low-density of condensation material, high specific strength, makes it in functional structure material, composite, selection sorbing material, catalysis fortune There is wide development space in the fields such as carrier material, medical material.Prepare the most important pore-forming of organic polymer porous material One of method is liquid phase hole forming method, and water is most environmentally friendly liquid phase pore former.Polyamines particularly aliphatic or alicyclic polyamine are normal Epoxy hardener, it is high with the composite material strength after epoxy resin cure in the absence of water, but is not mutually communicated Hole；These curing agent are soluble in water and epoxy hardener use can not be blended together as with water.Prepare at present water-based The most important method of epoxy resin-base composite material is to prepare Water-borne modification epoxy resin ingredient respectively and prepare Water-borne modification epoxy to consolidate Agent component remixes solidification and obtains induration, but the Water-borne modification epoxy resin ingredient complex technical process prepared, and makes The mixing cured rear concretion body strength of Water-borne modification epoxy resin ingredient and curing agent component obtained is not high, and induration is generally in closed pore knot Structure or half-open closed pore state.

The content of the invention

In order to overcome the shortcomings and deficiencies of the prior art described above, primary and foremost purpose of the invention is to provide one kind with higher The water-base epoxy porous resin composite of intensity and high porosity, the water-base epoxy porous resin composite is with acid amides contracting amine Class schiff bases compound and the more amine compounds of amidatioon hydrophobicity are self-emulsifying composite curing agent.

Another object of the present invention is the preparation method for providing above-mentioned water-base epoxy porous resin composite.

Still a further object of the present invention is to provide above-mentioned water-base epoxy porous resin composite porous in pressure Application in the fields such as mould, seepy material, press filtration material, material for air purification, large volume consolidation by grouting repairing work.

The purpose of the present invention is realized by following proposal：

A kind of water-base epoxy porous resin composite, it is mainly made up of the following component of A, B, C tri-：

Wherein, component A includes the component of following mass fraction：

70~100wt% of liquid-state epoxy resin,

1 0~30wt% of inorganic filler,

Both mass fraction sums are 100%；

B component includes the component of following mass fraction：

Self-emulsifying acid amides contracting amine schiff bases 40~90wt% of compound,

More 10~the 50wt% of amine compound of amidatioon hydrophobicity,

0~10wt% of long-chain carboxylic acid,

The mass fraction of three amounts to 100wt%；

Or B component includes following four component：Self-emulsifying acid amides contracting amine schiff bases compound, amidatioon hydrophobicity More amine compounds, long-chain carboxylic acid and inorganic filler 2, the wherein quality of inorganic filler 2 are that self-emulsifying acid amides contracting amine schiff bases is answered Within the 50wt% of compound, the more amine compounds of amidatioon hydrophobicity and long-chain carboxylic acid's mass sum；Self-emulsifying acid amides contracting amine Schiff Alkali compound, the more amine compounds of amidatioon hydrophobicity and long-chain carboxylic acid account for respectively 40~90wt% of three's gross mass, 10~ 50wt% and 0~10wt%.

Component C includes the component of following mass fraction：

3 40~70wt% of inorganic filler,

30~60wt% of alkaline water,

0~1wt% of auxiliary agent,

The mass fraction of three amounts to 100wt%.

Described component A can be single liquid-state epoxy resin, or the mixing of liquid-state epoxy resin and inorganic filler 1 Thing.

Liquid-state epoxy resin in described component A can be in liquid bisphenol A epoxy resin and liquid bisphenol F epoxy resin At least one, described liquid bisphenol A epoxy resin is preferably at least one of E-44 and E-51.

Inorganic filler 1 in described component A is micron order or nano-sized filler calcium carbonate, aluminum oxide, aluminium hydroxide, hydrogen At least one of calcium oxide, calcium oxide, silica, feldspar powder, kaolin, bentonite and talcum powder.

Self-emulsifying acid amides contracting amine schiff bases (Schiff base) compound in described B component can be by following methods It is prepared：

(1) by more polyacids (i.e. polyacid) (R (COOH) m, wherein m are the integer more than or equal to 2) and monoacid At least one of (RCOOH) mol ratio at 50~100 DEG C of low temperature with polyamine according to carboxy CO OH and polynary amine molecule For 1：(1~2) mix, without solvent；

(2) it is warming up to 120~180 DEG C of medium temperature after the mixture in step (1) is stirred to react 3~8 hours, dehydration Polyamide-amide is made；

(3) 200~260 DEG C and then under solvent-free are continuously heating to and continues dehydration 2~6 hours, when dehydrating amount is Cool terminating reaction during more than the 10wt% of theoretical amount, produces the breast certainly containing long chain alkyl group, amido link and C=N double bonds Change acid amides contracting amine schiff bases compound；

Or

The mole of the polyamine added in the step (1) is more than the mole of the carboxyl of long-chain carboxylic acid, in step (2) or (3) on the basis of, the polyamide-amide or self-emulsifying acid amides contracting amine that also the polyamine of excess can tentatively be obtained with carboxylic acid reaction After the modified amines such as schiff bases compound are cooled to 50~100 DEG C, by total carboxy CO OH (including have been added to and below supplement plus The other carboxylic acids entered) the ratio supplement of the mole mole that is not more than the polynary amine molecule of initial feed add other more polyacids Or monoacid, repeat step (2) and (3) further carry out dehydration, the self-emulsifying acid amides contracting amine Schiff of mixing is made Alkali compound；

Described more polyacids can be at least one of dimerization oleic acid, dimerized linoleic acid, trimer acid, and the monoacid can be At least one of oleic acid, castor oil acid, dimerization ricinoleate ester, isooctyl acid, neodecanoic acid；

Add in the step (1) for the mixture of more polyacids and monoacid when, more polyacids account for more polyacids and monoacid is total The ratio of quality is 20~90%, and it is 10~80% that monoacid, which accounts for more polyacids and the percentage of monoacid gross mass,.

Described polyamine can be fat polyamine (molecular formula H more than three N atoms₂N(CH₂CH₂NH)_nH, wherein n For the integer more than or equal to 2), it is fatty alicyclic ring mixing polyamines more than three N atoms, more containing chain extensions more than three N atoms Amine (molecular formula H₂N(CH₂CH₂NH)_mCH₂NH(CH₂CH₂NH)_mAt least one of, m is the integer more than or equal to 1).

Preferably, fat polyamines more than three described N atoms is diethylenetriamine, triethylene tetramine, four ethene five At least one of amine, pentaethylene hexamine, polyethylene polyamine；

Preferably, fatty alicyclic ring mixing polyamines more than three described N atoms can be N- aminoethyl piperazines；

Preferably, after the described chain extension polyamines contained more than three N atoms is by polyamines and paraformaldehyde condensation dehydration chain extension Obtain, specifically include following steps：By polyamines and paraformaldehyde according in polyamine molecule and paraformaldehyde at 60~100 DEG C The mol ratio of formaldehyde unit (unit molal weight is 30) is 2：1 ratio is mixed, and 110~130 DEG C are warming up to after stirring and dissolving Intermolecular dehydration is carried out, when the quality to the water obtained is 90~100wt% of theoretical dehydrating amount, stops reaction, gained is anti- Answer liquid to cool down, produce containing chain extension polyamines more than three N atoms.

The more amine compounds of amidatioon hydrophobicity in described B component are prepared by following methods：By phenol novolac amine, Anacardol phenolic aldehyde amine, C₆~C₁₄One kind in a kind of and long-chain carboxylic acid, carboxylate in long-chain monoglycidyl ether modified polyamine It is prepared by amidation process, wherein phenol novolac amine, anacardol phenolic aldehyde amine or C₆~C₁₄Long-chain monoglycidyl ether changes The molar ratio of the ester group of the carboxyl or carboxylate of property polyamines and long-chain carboxylic acid is (1~3)：1；

Preferably, the more amine compounds of amidatioon hydrophobicity in described B component are prepared by following methods：In low temperature Long-chain carboxylic acid is proportionally added into phenol novolac amine, anacardol phenolic aldehyde amine or C at 50~100 DEG C₆~C₁₄Long-chain list shrinks sweet In oily ether modified polyamine, 130~170 DEG C are warming up to after stirring and is reacted 3~8 hours, dehydration amidatioon produces amidatioon and hated Water-based more amine compounds；

Preferably, the more amine compounds of amidatioon hydrophobicity in described B component are prepared by following methods：15~ Carboxylate is proportionally added into phenol novolac amine, anacardol phenolic aldehyde amine or C at 35 DEG C₆~C₁₄Long-chain monoglycidyl ether is modified In polyamines, 60~80 DEG C are warming up to after stirring and is reacted 2~5 hours, be then warming up to 100~130 DEG C of 2~5h of reaction again, It is evaporated under reduced pressure and removes small molecule by-product, obtains the more amine compounds of amidatioon hydrophobicity.

Described phenol novolac amine can be prepared by following methods：At 60~100 DEG C into polyamines add and polyamines The paraformaldehyde solid powder of equimolar amounts formaldehyde unit, make its gradual stirring and dissolving, added and polyamines equimolar amounts after dissolving Phenol, be warming up to 110~120 DEG C and carry out Mannich reaction 3~6 hours, be cooled to room temperature, phenol novolac amine is made.

Described anacardol phenolic aldehyde amine can be prepared by following methods：At 60~100 DEG C into polyamines add with it is more The paraformaldehyde solid powder of amine equimolar amounts formaldehyde unit, make its gradual stirring and dissolving, added and polyamines equimolar after dissolving The anacardol of amount, it is warming up to 120~140 DEG C and carries out Mannich reaction 3~6 hours, be cooled to room temperature, anacardol phenolic aldehyde is made Amine.

Described C₆~C₁₄Long-chain monoglycidyl ether modified polyamine is prepared by following methods：It is 1 by mol ratio:1 C₆~C₁₄After long-chain monoglycidyl ether mixes reaction 24 hours with polyamines at 15~35 DEG C.

Described polyamines be more than three N atoms fatty amine, fatty alicyclic ring mixing polyamines or containing three N atoms more than Chain extension polyamines (H₂N(CH₂CH₂NH)_mCH₂NH(CH₂CH₂NH)_m, m is the integer more than or equal to 1)；

Preferably, fatty amines more than three above-mentioned N atoms can be diethylenetriamine, triethylene tetramine, four ethene five Amine, pentaethylene hexamine or polyethylene polyamine；Above-mentioned fatty alicyclic ring mixing polyamines is preferably N- aminoethyl piperazines；Above-mentioned contains Chain extension polyamines more than three N atoms is specifically included following by being obtained after chain extension after polyamines and paraformaldehyde condensation dehydration Step：By polyamines and paraformaldehyde according to the formaldehyde unit (unit mole in polyamine molecule and paraformaldehyde at 60~100 DEG C Quality is that mol ratio 30) is 2：1 ratio is mixed, and 110~130 DEG C are warming up to after stirring and dissolving and carries out intermolecular dehydrations, extremely When the quality of the water of acquisition is 90~100wt% of theoretical dehydrating amount, stops reaction, gained reaction solution is cooled down, produced containing three Chain extension polyamines more than individual N atoms.

Described C₆~C₁₄Long-chain monoglycidyl ether can be octyl glycidyl ether, nonyl glycidol ether, decyl contracting Water glycerin ether, lauryl diglycidyl ether, myristyl glycidol ether, benzyl glycidyl ether, phenyl glycidyl ether, O-tolyl glycidol ether and at least one of tert-butyl-phenyl glycidol ether；

Described long-chain carboxylic acid be isooctyl acid, neodecanoic acid, oleic acid, castor oil acid, dimerization ricinoleate ester, dimerization oleic acid and At least one of dimerized linoleic acid；

Described carboxylate can be at least one of ethyl acetate, methyl acetate, dimethyl carbonate and diethyl carbonate；

Long-chain carboxylic acid in described B component can be isooctyl acid, neodecanoic acid, oleic acid, castor oil acid, dimerization ricinoleate ester At least one of with dimerization oleic acid；

Inorganic filler 2 in the B component can be micron order or nanometer grade silica, carbon black, graphite powder, talcum powder, At least one of calcium carbonate, aluminum oxide, aluminium hydroxide, feldspar powder, kaolin and powdered frit.

Inorganic filler 3 in described component C can be micron silica, calcium carbonate, kaolin, talcum powder, feldspar At least one of powder, powdered frit, aluminum oxide, aluminium hydroxide and titanium dioxide.

The alkali described in alkaline water in described component C is at least one of inorganic base KOH, NaOH, and inorganic base accounts for Total content in alkaline water is 0.1~2wt%；Or the alkali described in the alkaline water in described component C is inorganic base and had The total mass fraction that machine alkali DMP-30 mixture, inorganic base and organic base are accounted in buck is 0.2~5wt%.

Auxiliary agent in described component C includes naphthalene system or polycarboxylic-acid disperses water reducer, defoamer；

A kind of composite porous preparation method of above-mentioned aqueous epoxy resins, it is mainly included the following steps that：

(1) preparation of component A：Liquid-state epoxy resin and inorganic filler are well mixed at 20~35 DEG C by proportioning and produced To component A；

(2) preparation of B component：By proportioning by long-chain carboxylic acid and the more amine compounds of amidatioon hydrophobicity at 20~35 DEG C mix Close, then add inorganic filler 2, the curing agent B1 after being well mixed；Using self-emulsifying acid amides contracting amine schiff bases compound as Curing agent B2, curing agent B1 and curing agent B2 is well mixed and produces B component；

The B component includes being pre-mixed by curing agent B1 and curing agent B2 forming single curing agent component, also includes solidification Two kinds of curing agent packet point commercial forms of agent B1 and curing agent B2 are present.

(3) preparation of component C：Alkali is dissolved in water at 20~35 DEG C alkaline water is made, be then dispersed in auxiliary agent In alkaline water, inorganic filler 3 is added, is well mixed to obtain suspension slurry, i.e. component C；

(4) it is 100 in mass ratio by component A and B component:(50~100) mix to uniformly at room temperature, Ran Houzai 1~3 times of component C for adding component A and B component gross mass is quickly well mixed, and being formed has viscosity higher and certain flowing Property compound slurry, cast curing molding produce water-base epoxy porous resin composite.

The temperature of described curing molding is 20~70 DEG C.

Above-mentioned water-base epoxy porous resin composite can be applied to pressure porous mold, seepy material, Press filtration material, material for air purification, or applied to fields such as large volume consolidation by grouting repairing works.

The present invention mechanism be：

Schiff bases (Schiff base, also referred to as Schiff 's base) is primarily referred to as one kind containing imines characteristic group (- RC=N-) Organic compound, typically formed by amine and active carbonyl group condensation, mainly there is contracting amine, amino acids, semicarbazone class, miscellaneous at present The schiff bases such as ring class, hydrazone class.Schiff bases compound has antibacterial, sterilization, antitumor, antiviral bioactivity and good Coordination activity, rust inhibition and characteristic group, itself and its metal complex are in medical science, catalysis, analytical chemistry, corrosion and photic Discoloration field has important application.

Polyacid contains active carbonyl group, is mixed with polyamine under low temperature (50~100 DEG C) and is initially formed weak acid and mild base salt, Include primary amine, secondary amine salt (as shown in Figure 1)；As temperature is increased to 120~180 DEG C of medium temperature, dehydration amidatioon occurs for these salt React (as shown in Figure 2).

With the further rise of temperature, during to 200~260 DEG C of higher temperature, the amido link of generation and self-molecules present, in Mesosome is intermolecular or raw material in primary amine in unreacted polyamines or secondary amine intramolecular addition dehydration cyclization, molecule occurs Between dehydration, form the Schiff bases compound (as shown in Figure 3) containing C=N double bonds.These dehydration degree depend on The content of steric hindrance and free amino in reaction temperature, time and molecule, formed and included with amido link and C=N double bonds Fig. 3 Chinese styles (1) are to formula (7) structure schema Suo Shi and Fig. 2 Chinese styles (8) coexist to the Multiple components such as formula (10) structure schema Suo Shi Acid amides contracting amine schiff bases compound.

Monocarboxylic acid is similarly divided into three steps (see Fig. 4) with polyamines reaction, is finally also formed double with amido link and C=N Key includes Fig. 4 Chinese styles (11) to the acid amides contracting amine schiff bases compound for waiting Multiple components to coexist formula (18) structure schema Suo Shi.

The schiff bases C=N double bonds of high temperature dehydration reaction generation, have reversible reaction, and slowly reversible generation amine is acted on water With carbonyls (including acid amides), its mechanism is as shown in Figure 5.

Acid amides contracting amine schiff bases compound prepared by the present invention has chain alkyl or substitution alkyl, amido link and C=N Double bond, also containing primary amine groups, secondary amine or tertiary amine groups, there is oleophylic (chain alkyl or substitution alkyl), hydrophilic (amido link and C =N double bonds) reactivity amphipathic and with epoxy resin, there is excellent self-emulsifying dispersiveness and water-retaining property, can also make acyl The more amine compounds of amination hydrophobicity are dispersed in water, contribute to stably dispersing and epoxide group of the epoxy resin in aqueous phase Ring-opening polymerization occurs with the N atoms on active amine.Particularly composite curing agent adds after being pre-mixed with epoxy resin During aqueous components, small part amido reacts with epoxy resin, is more beneficial for emulsion dispersion and its solidification of resin.It is polynary Contain multiple amidos, amide groups and C=N double bonds in acid amides Schiff bases compound molecule prepared by acid, be advantageous to emulsification system The formation of network structure and the stabilization of maintenance system, formed under certain water content with flowable more compared with high viscosity Phase liquid.The network node effect of hydrophilic inorganic filler grain, it is more beneficial for the stabilization of heterogeneous system in solidification process and consolidates The lifting of compound intensity, prevents multi-phase separation and cure shrinkage.

The product of long-chain carboxylic acid and amino-contained is neutralized into salt, contributes to water emulsification, while mix progressively with buck slurries Carboxyl discharges the amido in salt-forming reaction, obtains epoxide group reaction and more they tend to completely, have into carboxylate during molecule contacts Beneficial to raising intensity.

Composite curing agent prepared by the present invention, there is excellent self-emulsifying dispersiveness, not only make moisture in heterogeneous system Tiny emulsion droplet is dispersed into, it is more high-strength with network structure that the formation of addition reaction crosslinking curing also occurs with the resin in oil phase The induration of degree, wherein scattered tiny water and milk drops in heterogeneous system and has captured certain space, it is a kind of main liquid phase Pore former, the void network structure being mutually communicated is formed in the curing process, ultimately form through hole type porous resin composite.

Water-base epoxy prepared by the present invention is composite porous, has higher intensity, and its intensity is relevant with water consumption；Together When the porous resin moulds that prepare, solidification ungauged regions, not implode, the mould of shaping has excellent through hole, and aperture is smaller, most Between 3~13 μm, water absorption rate is big in aperture aperture, and porosity is high, and air-and water-permeable performance is excellent.

The present invention is had the following advantages and beneficial effect relative to prior art：

(1) composite curing agent self-emulsifying dispersive property is good, has good water emulsification steady after directly being mixed with epoxy resin Qualitative, mobility and toughness, easy moulding by casting；

(2) stability is good in resin-hardener-filler-water heterogeneous system solidification process, solidifies ungauged regions, and solidfied material is strong Degree is high；

(3) the heterogeneous system curing molding composite prepared has excellent through hole, and aperture is smaller, and water absorption rate is big, Porosity is high, and air-and water-permeable performance is excellent.

Brief description of the drawings

Fig. 1 is polyacid and polyamine in (50~100 DEG C) schematic diagrames neutralized into salt of low temperature.

Fig. 2 is that polyacid and polyamine are de- in (120~180 DEG C) of medium temperature in the salt that (50~100 DEG C) neutralizations of low temperature obtain The schematic diagram of water amidation process.

Fig. 3 is that acid amides high temperature is further dehydrated the acid amides contracting amine schiff bases compound curing agent to form the double bond containing C=N Schematic diagram.

Fig. 4 be monoacid and polyamine from low temperature (50~100 DEG C) to medium temperature (120~180 DEG C) again to high temperature (200~ 260 DEG C) reaction schematic diagram.

Fig. 5 is the schematic diagram that carbonyl reacts reversible formation C=N key Schiff bases with amine.

Fig. 6 is the infrared spectrogram of raw material dimeric dibasic acid in embodiment 1.

Fig. 7 is the infrared spectrogram for the self-emulsifying acid amides Schiff bases compound AMSB1 being prepared in embodiment 1.

Fig. 8 is the infrared spectrogram for the acid amides contracting amine schiff bases compound AMSB4-0 being prepared in embodiment 1.

Fig. 9 is the infrared spectrogram for the acetylation anacardol phenolic aldehyde amine compound AFQA1 being prepared in embodiment 2.

Figure 10 is the graph of pore diameter distribution of the porous resin moulds prepared in the embodiment 4 measured with mercury injection method.

Figure 11 is the graph of pore diameter distribution of the porous resin moulds prepared in the embodiment 5 measured with mercury injection method.

Embodiment

With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited In this.

Agents useful for same can routinely be bought from market unless otherwise specified in embodiment.

Embodiment 1：The preparation of self-emulsifying acid amides Schiff bases compound

(1) 1000g oleic acid dimer (dimeric dibasic acid, acid number 195, Lianyun Harbour is added in 5000mL three-necked flask Close Xinghua work, 1000g dimeric dibasic acids contain 3.48 moles of carboxyl) and 500g castor oil acid (molecular weight 298, the sprouting of Zibo ten thousand Work Co., Ltd), the TEPA (molecular weight of 1300g (6.878 moles) is slowly added to after being warming up to 80 DEG C, under stirring 189) 140 DEG C~150 DEG C, are then heated to react 5 hours, moisture 90.5g (theoretical water outlets are steamed under solvent-free in the process Measure as 92.8g), polyamide-amide PAM1 is now made.Then proceed to be warming up to 260 DEG C to react 2 hours, and in the process without Low-boiling point liquid 56.3g (being 45.5g through chromatogram check analysis wherein moisture, other is polyamines) is steamed under solvent, after cooling To the self-emulsifying acid amides contracting amine schiff bases compound AMSB1 containing acid amides and schiff bases.Sampling, measures PAM1 and AMSB1 exists Viscosity at 30 DEG C of room temperature is respectively 690,230mPas, it is seen that PAM1 partial amides key at high temperature further with amido Generation dehydration forms Schiff bases compound (- N-C=N-).

(2) in 5000mL three-necked flask add 1000g oleic acid dimer (dimeric dibasic acid, 1000g dimeric dibasic acids contain carboxylic 3.48 moles of base), the TEPA of 1315g (6.96 moles) is slowly added to after being warming up to 60 DEG C, under stirring, is then heated to 140 DEG C~150 DEG C are reacted 5 hours, and moisture 60.1g is steamed under solvent-free in the process (theoretical water yield is 62.6g).Cooling To 50 DEG C, 504.5g oleic acid (molecular weight 282.5) is slowly added under stirring, 140 DEG C~150 DEG C is warming up to and reacts 5 hours, During this it is solvent-free under steam moisture 31.6g (theoretical water yield is 32.1g), polyamide-amide PAM2 is now made.Then after It is continuous to be warming up to 260 DEG C and react 2 hours, and it is solvent-free in the process under steam low-boiling point liquid 57.7g (through chromatogram check analysis Wherein moisture is 46.9g, and other is polyamines), the self-emulsifying acid amides contracting amine Schiff containing acid amides and schiff bases is obtained after cooling Alkali compound AMSB2.Sampling, it is respectively 730,240mPas to measure the viscosity of PAM2 and AMSB2 at 30 DEG C of room temperature.It can be seen that PAM2 partial amides key further occurs dehydration with amido at high temperature and forms Schiff bases compound.

(3) in 5000mL three-necked flask add 250g oleic acid dimer (dimeric dibasic acid, 250g dimeric dibasic acids contain carboxyl 0.87 mole) and neodecanoic acid (molecular weight 172) 800g (4.65 moles), after being warming up to 50 DEG C, 810g is slowly added under stirring The triethylene tetramine of (5.55 moles), then heat to 120 DEG C~130 DEG C and react 8 hours, steamed under solvent-free in the process Moisture 96.0g (theoretical water yield is 99.36g), polyamide-amide PAM3 is now made.Then proceed to be warming up to 200 DEG C of reactions 6 Hour, and it is solvent-free in the process under steam low-boiling point liquid 39.7g (be 37.3g through chromatogram check analysis wherein moisture, its It is polyamines), the self-emulsifying acid amides contracting amine schiff bases compound AMSB3 containing acid amides and schiff bases is obtained after cooling.Sampling, It is respectively 540,190mPas to measure the viscosity of PAM33 and AMSB3 at 30 DEG C of room temperature.

(4) in 5000mL three-necked flask add 1000g oleic acid dimer (dimeric dibasic acid, 1000g dimeric dibasic acids contain carboxylic 3.48 moles of base), the triethylene tetramine of 810g (5.55 moles) is slowly added to after being warming up to 70 DEG C, under stirring, is then heated to 120 DEG C~130 DEG C are reacted 8 hours, and moisture 60.8g is steamed under solvent-free in the process (theoretical water yield is 62.6g).Then 200 DEG C are continuously heating to react 3 hours, and it is solvent-free in the process under steam low-boiling point liquid 18.4g and (examined point through chromatogram It is 17.3g to analyse wherein moisture, and other is polyamines).Cooling, acid amides contracting amine schiff bases compound AMSB4-0 is made.It is heated to 60 DEG C, isooctyl acid 273.6g (1.9 moles) is slowly added under stirring, 150 DEG C~160 DEG C is then heated to and reacts 6 hours, mistake herein In journey it is solvent-free under steam moisture 32.7g (theoretical water yield is 34.2g), polyamide-amide PAM4 is made.Then proceed to be warming up to 230 DEG C are reacted 6 hours, and it is solvent-free in the process under steam low-boiling point liquid 54.4g (through chromatogram check analysis wherein moisture For 51.3g, other is polyamines), the self-emulsifying acid amides contracting amine schiff bases compound containing acid amides and schiff bases is obtained after cooling AMSB4.Sampling, it is respectively 510,170mPas to measure the viscosity of PAM4 and AMSB4 at 30 DEG C of room temperature.

(5) diethylenetriamine 1030g (10 moles) is added in 5000mL three-necked flask, 60 DEG C is warming up to, is keeping The common 150g of paraformaldehyde solid powder (5 moles of formaldehyde unit) is gradually added at a temperature of 60~100 DEG C, it is gradually stirred molten Solution；110~130 DEG C are warming up to after dissolving and carries out intermolecular dehydration 4 hours, (theoretical dehydrating amount is by the quality 85g of the water of acquisition 90g), cool down, the modification diethylenetriamine of chain extension is made, its essential molecular structure is (H₂N(CH₂CH₂NH)₂CH₂NH (CH₂CH₂NH)₂H).90 DEG C are then heated to, being gradually added 500g oleic acid dimer, (dimeric dibasic acid, 500g dimeric dibasic acids contain carboxylic 1.74 moles of base), oleic acid 800g (2.83 moles), then heat to 170 DEG C~180 DEG C react 3 hours, in the process without molten Moisture 80.2g (theoretical water yield is 82.26g) is steamed under agent, polyamide-amide PAM5 is now made.Then proceed to be warming up to 240 DEG C reaction 4 hours, and it is solvent-free in the process under steam low-boiling point liquid 30.5g and (be through chromatogram check analysis wherein moisture 28.9g, other is polyamines), the self-emulsifying acid amides contracting amine schiff bases compound containing acid amides and schiff bases is obtained after cooling AMSB5.Sampling, it is respectively 810,290mPas to measure the viscosity of PAM4 and AMSB4 at 30 DEG C of room temperature.

Sampling and testing AMSB1 and raw material dimeric dibasic acid infrared spectrum, wherein raw material dimeric dibasic acid and AMSB1 infrared spectrogram Respectively as shown in Figure 6 and Figure 7, wherein as seen from Figure 7,3355.9,3291cm^-1Neighbouring broad peak is N-H absworption peaks, 2925, 2853cm^-1For alkyl C-H absworption peaks, 1650cm^-1For the carbonyl absorption peak in amido link, 1606cm^-1Absorbed for C=N double bonds Peak, and the 1710.57cm in Fig. 6^-1Carboxyl absworption peak has disappeared, and illustrates that successfully synthesizing self-emulsifying acid amides contracting amine schiff bases answers Compound AMSB1.

Sampling and testing acid amides contracting amine schiff bases compound AMSB4-0 infrared spectrum, as a result as shown in figure 8, wherein 3360、3294.6cm^-1Neighbouring broad peak is N-H absworption peaks, 2924.8,2853cm^-1For alkyl C-H absworption peaks, 1650cm^-1For acyl Carbonyl absorption peak in amine key, 1606cm^-1For C=N double bond absorption peaks, and the 1710.57cm in Fig. 6^-1Carboxyl absworption peak has disappeared Lose, illustrate to successfully synthesize acid amides contracting amine schiff bases compound AMSB4-0.

Embodiment 2：The preparation of amidatioon hydrophobicity polyamines

(1) ethyl acetate is modified anacardol phenolic aldehyde amine AFQA1：292g triethylenes four are added in 1000mL three-necked flask Amine (2 moles), is warming up to 60 DEG C, and (2 moles of the common 60g of paraformaldehyde solid powder is gradually added at a temperature of being kept for 60~100 DEG C Formaldehyde unit), make its gradual stirring and dissolving.Anacardol 600g (2 moles) is added after dissolving, is warming up to 120~140 DEG C of progress amine Methylation reaction 4 hours, is cooled to room temperature, and hydrophobicity polyamines-anacardol phenolic aldehyde amine 916g (2 moles) is made.Then take out one Half is standby, and second half 458g (1 mole) is slowly added to ethyl acetate 88g (1 mole) under 20 DEG C of stirrings, is heated up after stirring Reacted 3 hours to 60~70 DEG C, then heat to 120~130 DEG C of reaction 2h, be evaporated under reduced pressure and remove small molecule by-product ethanol, Obtain acetylation anacardol phenolic aldehyde amine compound AFQA1.

(2) diethyl carbonate is modified anacardol phenolic aldehyde amine AFQA2：The 458g anacardol phenolic aldehyde amines that will be prepared in above-mentioned (1) It is added in 1000mL three-necked flask, is slowly added to diethyl carbonate 59g (0.5 mole) under 20 DEG C of stirrings, is heated up after adding Reacted 2 hours to 60 DEG C, then heat to 80 DEG C and react 2 hours, then be warming up to 100~110 DEG C of reaction 4h, be evaporated under reduced pressure and remove Small molecule by-product ethanol, obtain amidatioon anacardol phenolic aldehyde amine compound AFQA2.

(3) castor oil acid is modified anacardol phenolic aldehyde amine AFQA3：The ethene five of 189g tetra- is added in 1000mL three-necked flask Amine, 60 DEG C are warming up to, the common 30g of paraformaldehyde solid powder (1 moles of formaldehyde lists are gradually added at a temperature of being kept for 60~100 DEG C Member), make its gradual stirring and dissolving.Anacardol 300g (1 mole) is added after dissolving, it is amine-methylated to be warming up to 120~140 DEG C of progress Reaction 6 hours, is cooled to room temperature, and hydrophobic modified polyamines-anacardol phenolic aldehyde amine 501g (1 mole) is made.70 DEG C are then heated to, 119.2g castor oil acids (0.4 mole) are added, 140~150 DEG C are warming up to after stirring and is dehydrated amidation process 5 hours, it is cold But, castor oil acid amidatioon anacardol phenolic aldehyde amine compound AFQA3 is made.

(4) isooctyl acid modified phenol phenolic aldehyde amine AFQ4：206g diethylenetriamines are added in 1000mL three-necked flask, are risen Temperature is gradually added the common 60g of paraformaldehyde solid powder (2 moles of formaldehyde unit) at a temperature of being kept for 60~100 DEG C, made to 60 DEG C Its gradual stirring and dissolving.Phenol 188g (2 moles) is added after dissolving, it is small to be warming up to 110~120 DEG C of progress Mannich reactions 4 When, room temperature is cooled to, hydrophobic modified polyamines-phenol novolac amine 418g (2 moles) is made.50 DEG C are then heated to, adds 144g Isooctyl acid (1 mole), 130~140 DEG C are warming up to after stirring and is dehydrated amidation process 8 hours, cooling, isooctyl acid acyl is made Amination phenol novolac amine compound AFQA4.

(5) ethyl acetate modified lauryl base glycidol ether triethylene tetramine addition product AMPA1：At three mouthfuls of 1000mL 292g (2 moles) triethylene tetramine is added in flask, 2 moles of lauryl diglycidyl ethers are slowly added dropwise at 15 DEG C, drip Room temperature stirring reaction 24 hours after finishing, are made and main lauryl diglycidyl ether triethylene tetramine addition product are shown with following formula (C₁₂H₂₅OCH₂CH(OH)CH₂NH(CH₂CH₂NH)₃H).Then being slowly added to ethyl acetate 158.4g under 20 DEG C of stirrings, (1.8 rub You), 60~70 DEG C are warming up to after stirring and is reacted 3 hours, 120~130 DEG C of reaction 3h is then heated to, is evaporated under reduced pressure and removes Small molecule by-product ethanol, obtain the compound AMPA1 of acetylation glycidol ether polyamine addition product.

(6) oleic acid is modified the more amine additives AMPA2 of benzyl glycidyl ether：Diethyl is added in 1000mL three-necked flask Alkene triamine 206g (2 moles), is warming up to 60 DEG C, and being gradually added paraformaldehyde solid powder at a temperature of being kept for 60~100 DEG C is total to 30g (1 moles of formaldehyde unit), makes its gradual stirring and dissolving；It is small that the intermolecular dehydration 4 of 110~130 DEG C of progress is warming up to after dissolving When, the quality 17.5g (theoretical dehydrating amount is 18g) of the water of acquisition, cooling, the modification diethylenetriamine of chain extension is made, its is main Molecular structure is (H₂N(CH₂CH₂NH)₂CH₂NH(CH₂CH₂NH)₂H).Then it is sweet that 2 moles of benzyls shrinks are slowly added dropwise at 30 DEG C Oily ether, continues stirring reaction 24 hours after being added dropwise, be made and main benzyl glycidyl ether divinyl three is shown with following formula Amine chain extension addition product (C₆H₅CH₂OCH₂CH(OH)CH₂HN(CH₂CH₂NH)₂CH₂NH(CH₂CH₂NH)₂CH₂CH(OH) CH₂OCH₂C₆H₅).Then 90 DEG C are being warming up to, are adding 141g oleic acid (0.5 mole), 140~150 DEG C are warming up to after stirring It is dehydrated amidation process 4 hours, cooling, the compound AMPA2 of obtained oleamide glycidol ether polyamine addition product.

Sampling and testing acetylation anacardol phenolic aldehyde amine compound AFQA1 infrared spectrum, as a result as shown in Figure 9, wherein 3292.4cm^-1It is nearby hydroxyl O-H and amido N-H absworption peaks；3009、3079cm^-1Inhaled for C-H on unsaturated double-bond C=C-H Receive peak；2925、2853cm^-1For the C-H absworption peaks on alkyl；1637.46cm^-1For the carbonyl C=O absworption peaks on amido link, say It is bright to successfully synthesize acetylation anacardol phenolic aldehyde amine compound AFQA1.

Embodiment 3：Curing agent water emulsification dispersive property

Curing agent prepared by above-described embodiment 1 is 1 in mass ratio with water：1 and 1：5 are mixed, and are emulsified Dispersive property is tested, and its result is as shown in table 1 below：

The self-emulsifying dispersancy performance data of curing agent prepared by the embodiment 1 of table 1

By the curing agent prepared in embodiment 1 and embodiment 2 it is compound in proportion at room temperature after, then by composite curing agent Mass ratio with water is 1：1 and 1：5 are mixed, and carry out emulsion dispersion property experiment, and its result is as shown in table 2 below：

Self-emulsifying dispersancy performance data after the curing agent that is prepared in the embodiment 1 of table 2 and embodiment 2 is compound

From table 1, acid amides contracting amine schiff bases compound prepared by the present invention has excellent self-emulsifying dispersive property, The easily homogeneous stably dispersing in water；After its acylation modification hydrophobicity polyamines for preparing with the embodiment of the present invention 2 is compound, still have Good emulsion dispersion stability.

Embodiment 4：The preparation of porous resin composite

A kind of water-base epoxy porous resin material mould, is prepared by following steps：

800g epoxy resin E-44s, 200g fine silica powders (3 μm of average grain diameter) are well mixed and obtained at (1) 35 DEG C The common 1000g of component A；

By curing agent AFQA1 and 65g calcium carbonate made from 70g embodiments 2 (3 μm of average grain diameter), 5g gas phases at (2) 35 DEG C Nano silicon is well mixed to obtain 140g B1 components, then with 660g examples 1 made from curing agent AMSB1 be well mixed Obtain the common 800g of B component；

4.5gKOH is dissolved in 1440g water at (3) 35 DEG C buck is made, then add the feldspar powder (μ of average grain diameter 50 M) 655.5g, silica (3 μm of average grain diameter) 1500g are well mixed obtains the common 3600g of aqueous (40wt%) slurries of component C；

A, B component are quickly stirred 2 minutes at (4) 35 DEG C, then adding component C, quickly stirring is well mixed for 2 minutes, is obtained To a flowable viscous fluid, it is cast in rapidly in corresponding master mold, 35 DEG C of progress solidifies respectively, initial viscosity is tested at 35 DEG C Solidify with being placed in 50 DEG C of environment.35 DEG C solidification 28 days after with reference to Chinese invention patent, " CN201410714456.4- one kind is poured The volume contraction of the hole detection method of injection forming bulk porous resin material " test solidfied material, 24 hours water absorption rates, pressure resistances Spend, ventilative water permeability, and the porosity and most probable pore size of solidfied material are tested with mercury injection method, the results are shown in Table 3.Mercury injection method measure Pore-size distribution is shown in Figure 10.Solidification test result in initial viscosity and heating environment is listed in Table 4 below.

Embodiment 5：The preparation of porous resin composite

By 700g epoxy resin E-51,298g aluminum oxide (5 μm of average grain diameter), 2g gas phase nano titanium dioxides at (1) 20 DEG C Silicon is well mixed to obtain the common 1000g of component A；

By curing agent AFQA2 and 45g silica made from 100g embodiments 2 (3 μm of average grain diameter), 5g at (2) 20 DEG C Carbon black (1 μm of average grain diameter) is well mixed to obtain 150g B1 components, then with 350g examples 1 made from curing agent AMSB2 mix Conjunction uniformly obtains the common 500g of B component；

1.5gNaOH, 8.5gDMP-30 are dissolved in 1200g water at (3) 20 DEG C buck is made, then add feldspar powder (30 μm of average grain diameter) 400g, silica (1 μm of average grain diameter) 390g, calcined kaolin (5 μm of average grain diameter) 1000g mixing Uniformly obtain the common 3000g of aqueous (40wt%) slurries of component C.

A, B component are quickly stirred 10 minutes at (4) 20 DEG C, then adding component C, quickly stirring is well mixed for 5 minutes, A flowable viscous fluid is obtained, is cast in rapidly in corresponding master mold, 20 DEG C of progress solidifies respectively, initial viscosity is surveyed at 35 DEG C Try and be placed on and solidify in 60 DEG C of environment.With reference to the volume contraction, 24 small of correlation method test solidfied material after 20 DEG C of solidifications 28 days When water absorption rate, compression strength, ventilative water permeability, and with mercury injection method test solidfied material porosity and most probable pore size, as a result see Table 3.The pore-size distribution of mercury injection method measure is shown in Figure 11.Solidification test result in initial viscosity and heating environment is listed in Table 4 below.

Embodiment 6：The preparation of porous resin composite

It is at (1) 30 DEG C that 500g epoxy resin E-51,400gE-44 and 50g silica (3 μm of average grain diameter), 50g is high Ridge soil (5 μm of average grain diameter) is well mixed to obtain the common 1000g of component A；

By curing agent AFQA3,120g curing agent AMPA1 and 80g dimerization castor-oil plant made from 200g embodiments 2 at (2) 30 DEG C Oleate is well mixed, and it is well mixed then to add 190g calcium carbonate (5 μm of average grain diameter), 10g calcium oxide (3 μm of average grain diameter) Obtain 600g B1 components, then with 400g examples 1 made from curing agent AMSB3 be well mixed to obtain the common 1000g of B component；

36gKOH, 50gDMP-30 are dissolved in 1800g water at (3) 30 DEG C buck is made, then polycarboxylic acids disperses diminishing Agent powder 5g, 990 defoamer 5g, after stirring, it is (flat to add calcined kaolin (10 μm of average grain diameter) 2000g, silica Equal 3 μm of particle diameter) 2104g is well mixed obtains the common 6000g of aqueous (30wt%) slurries of component C.

A, B component are quickly stirred 3 minutes at (4) 30 DEG C, then adding component C, quickly stirring is well mixed for 8 minutes, is obtained To a flowable viscous fluid, it is cast in rapidly in corresponding master mold, 30 DEG C of progress solidifies respectively, initial viscosity is tested at 35 DEG C Solidify with being placed in 70 DEG C of environment.30 DEG C solidification 28 days after with reference to correlation method test solidfied material volume contraction, 24 hours Water absorption rate, compression strength, ventilative water permeability, and with mercury injection method test solidfied material porosity and most probable pore size, the results are shown in Table 3.Solidification test result in initial viscosity and heating environment is listed in Table 4 below.

Embodiment 7：The preparation of porous resin composite

600g epoxy resin E-51 and 400g E-44 are well mixed at (1) 20 DEG C and obtain the common 1000g of component A；

Curing agent AFQA4,80g curing agent AMPA2 and 20g castor oil acid made from 100g embodiments 2 is mixed at (2) 20 DEG C Conjunction uniformly obtains 200g B1 components, then with 500g examples 1 made from curing agent AMSB3 be well mixed to obtain B component and be total to 700g；

20gKOH is dissolved in 1020g water at (3) 20 DEG C buck is made, then add feldspar powder (30 μm of average grain diameter) 200g, silica (2 μm of average grain diameter) 460g are well mixed to obtain the common 1700g of aqueous (60wt%) slurries of component C.

A, B component are quickly stirred 5 minutes at (4) 20 DEG C, then adding component C, quickly stirring is well mixed for 9 minutes, is obtained To a flowable viscous fluid, it is cast in rapidly in corresponding master mold, 20 DEG C of progress solidifies respectively, initial viscosity is tested at 35 DEG C Solidify with being placed in 70 DEG C of environment.20 DEG C solidification 28 days after with reference to correlation method test solidfied material volume contraction, 24 hours Water absorption rate, compression strength, ventilative water permeability, and with mercury injection method test solidfied material porosity and most probable pore size, the results are shown in Table 3.Solidification test result in initial viscosity and heating environment is listed in Table 4 below.

Embodiment 8：The preparation of porous resin composite

Using 600g epoxy resin E-51 as A1 components, 200g epoxy resin E-44s and talcum powder (average grain at (1) 30 DEG C 10 μm of footpath) 100g, calcium carbonate (3 μm of average grain diameter) 100g are well mixed is used as A2 components；

By curing agent 40gAFQA1,40gAFQA2 and 5g aerosils, 15g charcoals made from embodiment 2 at (2) 30 DEG C Black (1 μm of average grain diameter) is well mixed to obtain B1 component 100g, using 700gAMSB1 made from embodiment 1 as B2 components；

3gKOH, 17gDMP-30 are dissolved in 720g water at (3) 30 DEG C buck 740g is made, it is (average to add feldspar powder 50 μm of particle diameter) 200g, talcum powder (10 μm of average grain diameter) 800g, titanium dioxide (3 μm of average grain diameter) 60g is well mixed obtains C The common 1800g of aqueous (40wt%) slurries of component；

A1, A2, B1, B2 are quickly mixed at (4) 30 DEG C 3 minutes, then adding component C, quickly stirring mixes for 3 minutes Close uniformly, obtain a flowable viscous fluid, be cast in rapidly in corresponding master mold, carry out 30 DEG C respectively and solidify, be first at 35 DEG C Beginning viscosity test and being placed in 60 DEG C of environment solidifies.30 DEG C solidification 28 days after with reference to correlation method test solidfied material volume receive Contract, 24 hours water absorption rates, compression strength, ventilative water permeabilities, and the porosity and most probable pore size of solidfied material tested with mercury injection method, It the results are shown in Table 3.Solidification test result in initial viscosity and heating environment is listed in Table 4 below.

Embodiment 9：The preparation of porous resin composite

At (1) 25 DEG C by 700g epoxy resin E-51,200g epoxy resin E-44, kaolin 90g (5 μm of average grain diameter), Calcium hydroxide 10g (10 μm of average grain diameter) is well mixed to obtain the common 1000g of component A；

By curing agent AMPA2 (100g), AFQA1 (150g) made from embodiment 2 and 90g powdered frits (average grain at (2) 25 DEG C 5 μm of footpath), 10g carbon blacks (1 μm of average grain diameter) it is well mixed, it is well mixed then to add AMSB1 (250g) made from embodiment 1 Obtain the common 600g of B component；

20gKOH, 30gDMP-30 are dissolved in 1200g water at (3) 25 DEG C buck is made, then add naphthalenesulfonateformaldehyde formaldehyde Polymer disperses water reducer powder 20g, 990 defoamer 10g, after stirring, addition feldspar powder (50 μm of average grain diameter) 720g, Calcined kaolin (10 μm of average grain diameter) 1200g, silica (3 μm of average grain diameter) 800g be well mixed, and to obtain component C aqueous The common 4000g of (30wt%) slurries.

A, B component are quickly stirred 3 minutes at (4) 25 DEG C, then adding component C, quickly stirring is well mixed for 5 minutes, is obtained To a flowable viscous fluid, it is cast in rapidly in corresponding master mold, 25 DEG C of progress solidifies respectively, initial viscosity is tested at 35 DEG C Solidify with being placed in 50 DEG C of environment.25 DEG C solidification 28 days after with reference to correlation method test solidfied material volume contraction, 24 hours Water absorption rate, compression strength, ventilative water permeability, and with mercury injection method test solidfied material porosity and most probable pore size, the results are shown in Table 3.Solidification test result in initial viscosity and heating environment is listed in Table 4 below.

Embodiment 10：The preparation of porous resin composite

At (1) 20 DEG C by 700g epoxy resin E-51,150g bisphenol F epoxy resin ARALDITE GY285 (Hensel is graceful), 150g talcum powder (1 μm of average grain diameter) is well mixed to obtain the common 1000g of component A；

It is at (2) 20 DEG C that curing agent AMPA1 (200g), AFQA2 (100g) made from embodiment 2 and 20g graphite powders is (average 1 μm of particle diameter), 80g calcined kaolins (5 μm of average grain diameter) it is well mixed, then add AMSB3 (400g) made from embodiment 1 It is well mixed to obtain the common 800g of B component；

20gKOH, 30gDMP-30 are dissolved in 1400g water at (3) 20 DEG C buck is made, then added polycarboxylic acids and disperse Water reducer powder 5g, 990 defoamer 5g, after stirring, add feldspar powder (30 μm of average grain diameter) 1500g, powdered frit (average grain 3 μm of footpath) 1540g is well mixed obtains the common 4500g of aqueous (30wt%) slurries of component C.

A, B component are quickly stirred 5 minutes at (4) 20 DEG C, then adding component C, quickly stirring is well mixed for 7 minutes, is obtained To a flowable viscous fluid, it is cast in rapidly in corresponding master mold, 20 DEG C of progress solidifies respectively, initial viscosity is tested at 35 DEG C Solidify with being placed in 60 DEG C of environment.20 DEG C solidification 28 days after with reference to correlation method test solidfied material volume contraction, 24 hours Water absorption rate, compression strength, ventilative water permeability, and with mercury injection method test solidfied material porosity and most probable pore size, the results are shown in Table 3.Solidification test result in initial viscosity and heating environment is listed in Table 4 below.

The performance test results of water-base epoxy porous resin material mould in embodiment 4~10 are as shown in table 3：

The performance test results of water-base epoxy porous resin mould in the embodiment 4~10 of table 3

Consolidating in the mixed serum initial viscosity and heating environment of the water-base epoxy porous resin material in embodiment 4~10 It is as shown in table 4 to change test result：

In the mixed serum initial viscosity and heating environment of water-base epoxy porous resin material in the embodiment 4~10 of table 4 Solidification test result

From the water-base epoxy porous resin composite wood that in the test result table 3 of example 4~10, table 4, prepared by the present invention Each raw material components compound tense in material has certain fluidity and viscosity higher, can be solidified into perforate material by moulding by casting at room temperature Material, there is excellent ventilative water permeability and water imbibition, through hole porosity is big (in more than 28%v/v), and intensity is high, and (compression strength exists More than 12MPa), without being separated and volume contraction in solidification process.As can be seen from Figure 9, its most probable pore size is between 3~13 μm, It can be used as pressure porous mold, press filtration material, material for air purification.Meanwhile can see in table 4, in environment temperature Spend at higher 50~70 DEG C, it solidifies still is carried out as usual, forms perforate air-and water-permeable material, does not have implode phenomenon, can use Make large volume mould or Grouting reinforcement project operation.This is due to that the specific heat of water is very big, and the heat of accumulation can pass through the liter of water Temperature is evaporated and taken away from perforate duct.

Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims

A kind of 1. water-base epoxy porous resin composite, it is characterised in that it is made up of the following component of A, B, C tri-, wherein：

Component A includes the component of following mass fraction：

70~100wt% of liquid-state epoxy resin,

1 0~30wt% of inorganic filler,

Both mass fraction sums are 100%；

B component includes the component of following mass fraction：

Self-emulsifying acid amides contracting amine schiff bases 40~90wt% of compound,

More 10~the 50wt% of amine compound of amidatioon hydrophobicity,

0~10wt% of long-chain carboxylic acid,

The mass fraction of three amounts to 100wt%；

Or B component includes following four component：Self-emulsifying acid amides contracting amine schiff bases compound, amidatioon hydrophobicity polyamines Compound, long-chain carboxylic acid and inorganic filler 2, the wherein quality of inorganic filler 2 be self-emulsifying acid amides contracting amine schiff bases compound, Within the more amine compounds of amidatioon hydrophobicity and the 50wt% of long-chain carboxylic acid's mass sum；Self-emulsifying acid amides contracting amine schiff bases is compound Thing, the more amine compounds of amidatioon hydrophobicity and long-chain carboxylic acid account for 40~90wt%, the 10~50wt% and 0 of three's gross mass respectively ~10wt%；

Component C includes the component of following mass fraction：

3 40~70wt% of inorganic filler,

30~60wt% of alkaline water,

0~1wt% of auxiliary agent,

The mass fraction of three amounts to 100wt%.
2. water-base epoxy porous resin composite according to claim 1, it is characterised in that：

Liquid-state epoxy resin in described component A in liquid bisphenol A epoxy resin and liquid bisphenol F epoxy resin at least One kind, described liquid bisphenol A epoxy resin are at least one of E-44 and E-51；

Inorganic filler 1 in described component A is micron order or nano-sized filler calcium carbonate, aluminum oxide, aluminium hydroxide, hydroxide At least one of calcium, calcium oxide, silica, feldspar powder, kaolin, bentonite and talcum powder.
3. water-base epoxy porous resin composite according to claim 1, it is characterised in that：

Self-emulsifying acid amides contracting amine schiff bases compound in described B component is prepared by following methods：

(1) by least one of more polyacids and monoacid at 50~100 DEG C of low temperature with polyamine according to carboxy CO OH with it is more The mol ratio of first amine molecule is 1：(1~2) mix, without solvent；

(2) it is warming up to 120~180 DEG C of medium temperature after the mixture in step (1) is stirred to react 3~8 hours, dehydration is made Polyamide-amide；

(3) 200~260 DEG C and then under solvent-free are continuously heating to and continues dehydration 2~6 hours, when dehydrating amount is theory Cool terminating reaction during more than the 10wt% of amount of calculation, produces the self-emulsifying acyl containing long chain alkyl group, amido link and C=N double bonds Amine contracting amine schiff bases compound；

Or

The mole of the polyamine added in the step (1) is more than the mole of the carboxyl of long-chain carboxylic acid, in step (2) or (3) On the basis of, polyamide-amide or self-emulsifying acid amides contracting amine schiff bases that the polyamine of excess is tentatively obtained with carboxylic acid reaction After compound is cooled to 50~100 DEG C, the mole of the polynary amine molecule of initial feed is not more than by total carboxy CO OH mole Ratio supplement add other more polyacids or monoacid, repeat step (2) and (3) further carry out dehydration, be made and mix The self-emulsifying acid amides contracting amine schiff bases compound of conjunction；

Described more polyacids are at least one of dimerization oleic acid, dimerized linoleic acid, trimer acid, and the monoacid is oleic acid, castor At least one of sesame oil acid, dimerization ricinoleate ester, isooctyl acid, neodecanoic acid；When the middle addition of step (1) is more polyacids and one During the mixture of first acid, it is 20~90% that more polyacids, which account for more polyacids and the ratio of monoacid gross mass, monoacid account for more polyacids and The percentage of monoacid gross mass is 10~80%；

Described polyamine is fat polyamines more than three N atoms, fatty alicyclic ring mixing polyamines more than three N atoms, contained At least one of chain extension polyamines more than three N atoms, wherein the described chain extension polyamines contained more than three N atoms is by polyamines Obtained after being condensed dehydration chain extension with paraformaldehyde, specifically include following steps：Polyamines and paraformaldehyde are pressed at 60~100 DEG C Mol ratio according to the formaldehyde unit in polyamine molecule and paraformaldehyde is 2：1 ratio mixing, it is warming up to 110 after stirring and dissolving~ 130 DEG C carry out intermolecular dehydration, when the quality to the water obtained is 90~100wt% of theoretical dehydrating amount, stop reaction, by institute Reaction solution cooling is obtained, is produced containing chain extension polyamines more than three N atoms.
4. water-base epoxy porous resin composite according to claim 1, it is characterised in that：

The more amine compounds of amidatioon hydrophobicity in described B component are prepared by following methods：By phenol novolac amine, cashew nut Phenol phenolic aldehyde amine, C₆~C₁₄A kind of process in a kind of and long-chain carboxylic acid, carboxylate in long-chain monoglycidyl ether modified polyamine Amidation process is prepared, wherein phenol novolac amine, anacardol phenolic aldehyde amine or C₆~C₁₄Long-chain monoglycidyl ether is modified more The molar ratio of the ester group of the carboxyl or carboxylate of amine and long-chain carboxylic acid is (1~3)：1.
5. water-base epoxy porous resin composite according to claim 1, it is characterised in that：

The more amine compounds of amidatioon hydrophobicity in described B component are prepared by following methods：At 50~100 DEG C of low temperature Long-chain carboxylic acid is proportionally added into phenol novolac amine, anacardol phenolic aldehyde amine or C₆~C₁₄Long-chain monoglycidyl ether modified polyamine In, 130~170 DEG C are warming up to after stirring and is reacted 3~8 hours, it is compound that dehydration amidatioon produces amidatioon hydrophobicity polyamines Thing；

Or the more amine compounds of amidatioon hydrophobicity in described B component are prepared by following methods：At 15~35 DEG C Carboxylate is proportionally added into phenol novolac amine, anacardol phenolic aldehyde amine or C₆~C₁₄Long-chain monoglycidyl ether modified polyamine In, 60~80 DEG C are warming up to after stirring and is reacted 2~5 hours, is then warming up to 100~130 DEG C of 2~5h of reaction, decompression again Small molecule by-product is distilled off, obtains the more amine compounds of amidatioon hydrophobicity.
6. the water-base epoxy porous resin composite according to claim 4 or 5, it is characterised in that：

Described phenol novolac amine is prepared by following methods：Added and polyamines equimolar into polyamines at 60~100 DEG C The paraformaldehyde solid powder of formaldehyde unit is measured, makes its gradual stirring and dissolving, the phenol with polyamines equimolar amounts is added after dissolving, It is warming up to 110~120 DEG C and carries out Mannich reaction 3~6 hours, be cooled to room temperature, phenol novolac amine is made；

Described anacardol phenolic aldehyde amine is prepared by following methods：Add into polyamines at 60~100 DEG C and rubbed with polyamines etc. The paraformaldehyde solid powder of your amount formaldehyde unit, makes its gradual stirring and dissolving, and the waist with polyamines equimolar amounts is added after dissolving Fruit phenol, it is warming up to 120~140 DEG C and carries out Mannich reaction 3~6 hours, be cooled to room temperature, anacardol phenolic aldehyde amine is made；

Described C₆~C₁₄Long-chain monoglycidyl ether modified polyamine is prepared by following methods：It is 1 by mol ratio:1 C₆~ C₁₄Long-chain monoglycidyl ether produces C after reaction being mixed at 15~35 DEG C 24 hours with polyamines₆~C₁₄Long-chain list shrinks Glycerin ether modified polyamine；

Described polyamines is fatty amines more than three N atoms, fatty alicyclic ring mixing polyamines or contains expansions more than three N atoms Chain polyamines；It is described containing chain extension polyamines more than three N atoms by chain extension after polyamines and paraformaldehyde condensation dehydration after Obtain, specifically include following steps：By polyamines and paraformaldehyde according in polyamine molecule and paraformaldehyde at 60~100 DEG C The mol ratio of formaldehyde unit is 2：1 ratio mixing, 110~130 DEG C are warming up to after stirring and dissolving and carries out intermolecular dehydrations, to obtaining When the quality of the water obtained is 90~100wt% of theoretical dehydrating amount, stops reaction, gained reaction solution is cooled down, produced containing three N Chain extension polyamines more than atom；

Described C₆~C₁₄Long-chain monoglycidyl ether is octyl glycidyl ether, nonyl glycidol ether, decyl glycidol Ether, lauryl diglycidyl ether, myristyl glycidol ether, benzyl glycidyl ether, phenyl glycidyl ether, adjacent toluene Base glycidol ether and at least one of tert-butyl-phenyl glycidol ether；

Described long-chain carboxylic acid is isooctyl acid, neodecanoic acid, oleic acid, castor oil acid, dimerization ricinoleate ester, dimerization oleic acid and dimerization At least one of linoleic acid；

Described carboxylate is at least one of ethyl acetate, methyl acetate, dimethyl carbonate and diethyl carbonate.
7. water-base epoxy porous resin composite according to claim 1, it is characterised in that：

Long-chain carboxylic acid in described B component is isooctyl acid, neodecanoic acid, oleic acid, castor oil acid, dimerization ricinoleate ester and dimerization At least one of oleic acid；

Inorganic filler 2 in the B component is micron order or nanometer grade silica, carbon black, graphite powder, talcum powder, calcium carbonate, At least one of aluminum oxide, aluminium hydroxide, feldspar powder, kaolin and powdered frit.
8. water-base epoxy porous resin composite according to claim 1, it is characterised in that：

Inorganic filler 3 in described component C is micron silica, calcium carbonate, kaolin, talcum powder, feldspar powder, glaze At least one of powder, aluminum oxide, aluminium hydroxide and titanium dioxide；

The alkali described in alkaline water in described component C is at least one of inorganic base KOH, NaOH, and inorganic base accounts for alkalescence Total content in water is 0.1~2wt%；Or the alkali described in the alkaline water in described component C is inorganic base and organic base The total mass fraction that DMP-30 mixture, inorganic base and organic base are accounted in buck is 0.2~5wt%；

Auxiliary agent in described component C includes naphthalene system or polycarboxylic-acid disperses water reducer, defoamer.
9. a kind of preparation method of water-base epoxy porous resin composite according to any one of claim 1~8, it is special Sign is to comprise the following steps：

(1) preparation of component A：Liquid-state epoxy resin and inorganic filler are well mixed at 20~35 DEG C by proportioning and obtain A Component；

(2) preparation of B component：Long-chain carboxylic acid and the more amine compounds of amidatioon hydrophobicity are mixed at 20~35 DEG C by proportioning, Then inorganic filler 2 is added, the curing agent B1 after being well mixed；Using self-emulsifying acid amides contracting amine schiff bases compound as solidification Agent B2, curing agent B1 and curing agent B2 is well mixed and produces B component；

(3) preparation of component C：Alkali is dissolved in water at 20~35 DEG C alkaline water is made, auxiliary agent is then dispersed in alkalescence In water, inorganic filler 3 is added, is well mixed to obtain suspension slurry, i.e. component C；

(4) it is 100 in mass ratio by component A and B component:(50~100) mix to uniformly at room temperature, then add 1~3 times of component C of component A and B component gross mass is quickly well mixed, and is formed with viscosity higher and certain fluidity Compound slurry, cast curing molding produce water-base epoxy porous resin composite；

Solidification temperature described in step (4) is 20~70 DEG C.
10. the water-base epoxy porous resin composite according to any one of claim 1~8 is porous in pressure Application in mould, seepy material, press filtration material, material for air purification, or large volume consolidation by grouting repairing work field.