CA1246817A - Hardening slurry of eopxy resin and amide compound of ethylene amine ad fatty acid - Google Patents
Hardening slurry of eopxy resin and amide compound of ethylene amine ad fatty acidInfo
- Publication number
- CA1246817A CA1246817A CA000444929A CA444929A CA1246817A CA 1246817 A CA1246817 A CA 1246817A CA 000444929 A CA000444929 A CA 000444929A CA 444929 A CA444929 A CA 444929A CA 1246817 A CA1246817 A CA 1246817A
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- Canada
- Prior art keywords
- fatty acid
- porous material
- slurry
- producing
- amide compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
TITLE OF THE INVENTION
ABSTRACT OF THE DISCLOSURE
Disclosed is a method of producing a porous material having open pores, comprising the steps of preparing a slurry from a mixture comprising a bisphenol-type epoxy resin, a specific mixture amide compound as a hardener, a filler and water, casting the slurry in a water-impermeable mold, hardening the slurry while it contains the water and dehydrating the hardened body.
ABSTRACT OF THE DISCLOSURE
Disclosed is a method of producing a porous material having open pores, comprising the steps of preparing a slurry from a mixture comprising a bisphenol-type epoxy resin, a specific mixture amide compound as a hardener, a filler and water, casting the slurry in a water-impermeable mold, hardening the slurry while it contains the water and dehydrating the hardened body.
Description
~l24~i8~
B.~CKG~QUND OF THE INV~NTION
The pre6ent ~nvention relat~s to a method of producing a porous ~aterlal having open pores. ~Sore particularly, the lnvention i~ ooncerned with a method o~ producing a porous ~.aterial h~Ying open pore~ from a raw material whic~ comprise~
a bisphenol-type epoxy re~ln, a fipecific mixture amide compound as a hardener, iller and water.
~ itherto, as me~ure~ for producing a porous material having open pore~ for uBe a~ a filtering mediu~, air di~fusion l~ med~um, casting mold and so forth~ var~ous methods have been produced ~uch as ~ln~ering of met~l powder, sintering of powdered thermoplast~c resin, ~intering of inorganic powder, hydration ~etting of cement or the like, press~ng or stamping of a mi~ture of thermos~eting resln and filler, hardening of a re~n 11qu~d containlng por~-formi~g agent followed by the remo~l of the pore~formlng ~gent by dis~olving, extracti~n or eYaporation, us~ of a ~lo~ing agent, evaporation of water from ~ater-containing polye~ter resin, an~ ~o forth.
The~e known method~ of producing porou~ material having open pore~, however, encountered one or more of the following problems in connectlon wlth the molding proces~. First of all, it i~ to be pointefl out that the~e known methods impractically limit or restrict the shape and size of the pr~duct. In addition, these method~ ot~n require a heat tr~atment at high temperature, a~ well as a press work at high pre~urefi. ~he method which makes use of the pore-~orming agent mu~t em~loy a st~p of heating or vacuum operation for the rem~val o~ the pore-forming agent hy evaporation,
B.~CKG~QUND OF THE INV~NTION
The pre6ent ~nvention relat~s to a method of producing a porous ~aterlal having open pores. ~Sore particularly, the lnvention i~ ooncerned with a method o~ producing a porous ~.aterial h~Ying open pore~ from a raw material whic~ comprise~
a bisphenol-type epoxy re~ln, a fipecific mixture amide compound as a hardener, iller and water.
~ itherto, as me~ure~ for producing a porous material having open pore~ for uBe a~ a filtering mediu~, air di~fusion l~ med~um, casting mold and so forth~ var~ous methods have been produced ~uch as ~ln~ering of met~l powder, sintering of powdered thermoplast~c resin, ~intering of inorganic powder, hydration ~etting of cement or the like, press~ng or stamping of a mi~ture of thermos~eting resln and filler, hardening of a re~n 11qu~d containlng por~-formi~g agent followed by the remo~l of the pore~formlng ~gent by dis~olving, extracti~n or eYaporation, us~ of a ~lo~ing agent, evaporation of water from ~ater-containing polye~ter resin, an~ ~o forth.
The~e known method~ of producing porou~ material having open pore~, however, encountered one or more of the following problems in connectlon wlth the molding proces~. First of all, it i~ to be pointefl out that the~e known methods impractically limit or restrict the shape and size of the pr~duct. In addition, these method~ ot~n require a heat tr~atment at high temperature, a~ well as a press work at high pre~urefi. ~he method which makes use of the pore-~orming agent mu~t em~loy a st~p of heating or vacuum operation for the rem~val o~ the pore-forming agent hy evaporation,
- 2 -~6~
Furthermore~ the~e known me'chod~ ar~ generally complicated and dif f icult to conductO
Another problem i5 that, ~ith these kno~n me~hod~, lt i8 ~uite difficult to effect the pore ~ize control wh~ch i~ the 5 most i~portant factor when the porous mater ial i~ use~ as a filtering medium, ~ir diffu~ >n mediumt ca~ting mold or the like du~ to the following reason~.
In the production of a pOroslB m8ter ial f ~om metal powder by ~interirlg, i~ difficu11: ~o obtaln a pore ~ize ~maller 10 than 5 mic:ror~& because of a specif ic relation be~ween the par~lcle siæe of the metal powa~r and the ~urface energy durlng the B1nter ing. Con~equently~ it i8 quite dlficul~ to effect control of the pore ize to obtain pores on the order of 1 ~ic:ron or ~o. In 'che case of the ~interlng of the p:3wd~r 15 of a cer~ .materia:L or resln, the pas:king den~ity at the time of moldiny i8 almost impo~sible to control although the particle size of the mater Lal can be controll~d f inely. In additlon~ th$s method ~uffer~ from ~ large change in the pore structure in the cour~e ~f the ~intering, 80 that the pore 20 si~e is distributed over a wlde range to hinder the control o~
th~ pore ~ize.
Referring now to ~he pressing and ~tamping of a solid powder together w~th a hinder such as an adhesi~e, the control of the pore ~lze ie impaired particularly when the product has 25 a compl~cated shape, for the re~son~ s~ch a~ non-uniform packing due to non-uniform application of the molding pressure attributahle to the complicated shape of the product, non-uniform mixing of the binder, and sc on.
~6~
In the case of the hydr~ti~n ~ardening of a ce~lent, gyp~um, plaster or the like, difficulty is l~olved 1n thecontrol of the nucleation and srowth of the crystal~ o~ the hydrate, and preci~e control of the mean pore size to ob~ain pores on the order of 0.5 to 10 microns car.not easily be effected.
~ ith resard to the method in which the pore for~ing agen~
is evaporate~ or ex~racted from ~he hardened resin con~ainirg the agent, a techni~ue has been proposed for the production of a thin film having pores of pore ~izes ranging between 1000 and 100~. This ~e~hod, however, cannot be applied to the production of a ~roduct havlng ~ large shape. In the method in which a resin in the form of 0/W- or ~/0-type emul~ion i5 hardene~ followed ~y the evaporatlon o~ th~
di~per80id, it i~ not easy to control the size of the disper80id, ~nd many disconnected pores are in~vitably for~ed.
The control of the pore size on the order of ~.5 to 10 mlcrQns a6 a mean ts also difficult in thi~ method.
In order to obviate these problems of the known methods, ~a~anese PaL2~-L .~o. 924,027 issued on septem~er 2~, 197~ -,o t~e ~L~plicanL ~-o~oses a met'nod o~ pro~ucing a ~orous mateli21 having open pores and ~ complicated shape, at a high precision and w~th a good control of the pore si2e. More ~pecifically, this method compri~e6 the steps of preparing an 0~' type 2S slurry as a mixture of a glycidyl-type epoxy re5in, polymeric fatty acid polyamide hardener, filler and ~ater, casting the ~lurry in a water-~permeable mold, hardening the water-containing 81urry, and then dehydratlng the hardened body.
a~ ~
:~4~
According to this metho~ i8 possible to e~ect the~ c:ontrol of the pore si~e by varylng and ~dJu~tin~ factor~ such ~ the part~cle size of the filler~ amount of the reactive diluent, mixing ratio of the epoxy r~sln, hardener, filler and water, S and so on. P,mong th~se factors, the amount of the reactive diluent and the mi~ing ratio of the ~poxy re~in~ hardeneL ~
filler and water a~e limited from the viewpoint of contraction durlns~ hardening and al~o in view of the ~reng~h of 'che hardened body. ~or thi~ rea~on, it i~ not pos~ible to c:ontrol 10 the pore ~ize over a wlde range. In order to control the pore ~i2e to obtain pores on the order of O. 5 to lO micron~, it is neces~ary to largely vary the particle ~ize of the filler.
The use of the filler having large -partlcle slze, however, reduces the ~trer~gth o~ the hardened body undesirably. The 15 reduct~on of streng~ch can be avoided only through a reduction ln th~ Elmoun~ of watar added, wh~ch ~n turn is accompaniel9 by a new proble~ of an increa~ in tne ~l~co~lty of the ~lurry.
The lncreased part~le slze of the ~iller cause~ alæo anotber problem namely that the effic~ency of the ~ork is lmpaired due to sedimentation of the filler in the slurry which consist~ of water and the filler. When ~ flller having a mean slze ~uitable for the work i~ used, t~e mean pore size in the product porous materlal i8 unde~lrably concentrated to an ext~eme~y sm~ll level o~ le6~ than 1.5 microns. The poro~
m~terial having such extremely small pore slze can hardly be used for the a~ore~entioned application~ ~uch ~q filtering ~edium, alr diffu~ion mediu~ ca ting mold and ~o forth and, hence, has only ~ small pr~ctical utillty. Furthermore, thi~
~4~
propo~ed method ~uffers rom problems such a~ the impract1cally long tlme requlr~d for the slurry to flow into the ~old ~nd difflculey ln forming a porous materlal having an intricate and compllcat~d ~hape, due to the high viscosi~y of the ~lurry attributabl~ ~o the u~e of a polymerlc ~tty acid polya~ide solely as the hardener.
~U~ARY ~F T~ V~NTIO~
.... _ _ .
Under this circumstance, the preBent lnvent~on ~lm~ at 1~ provid~ng a method of producing a porou6 material havlng open pores of a desired mean pore ~ixe (opening), thereby to obv~ate the problems of the prior art~
Namely, it ~ an object of th~ inventlon to .prov~e a method o~ produclng a porou~ materi~, wh~ch 1~ improved to permit the control of the maan pore ~ize over a wide range without requiring any change in th~ partl~l~ s~ze of the filler.
~ nother oh~ect of the inYentiOn iB to provide a method of produ~ing a porous material, whlch is improved to permit the precise control of the me~n pore ~ize of the open pores within the range of between 0.5 and 1~ micron6, u~ing a filler of such a s~all particle size a~ not to cause filler sed~mentation wh~ch ~ould impair the handling of the flller.
Still another object of the inventlon i~ to provide a 25 methoa of produclng a poro~s material in which the visco~ity of the ~lurry i~ lowered to permit quick filling of the mvld and high prec~ BlOn of the product even when the product has a complicated and intricate shape.
Other o~jects, featur~s and advantage~ of the invention wlll becQme clear from th~ followins de~cription of the preferred embodlment~ of the invention.
l~hese ob~ect~ are achieved by using the following specific ~ixt~re amide compound as the hardener in the production of the porous materi~l having o~en porPs.
DESCRIPTION OF TB~ INVENTION INCLUDIN~ T~E PREFE~R~D
.. . .. .. . .. .
EMBODIMENTS
1~ In order to ~c&omplish the above-de~cribed objects of the lnvention, the pre~ent invention propose~ a method of produclnq a porous materlal compris~ng the ~teps of preparing a slurry by vigorously stlrrins a mixture c~mpr~ing a blsphenol-typ~ epoxy resin, a hardener, a filler ~nd water, c~t~ng the slurry in a wat~r-imper~eable mold, h2rdening the ~lurry wh~le lt con ~lins ~ter r and dehydrating the h~rdened body, wher¢in the l~prov~ment comprises that the hardener is ei~her (a) a mlxture of li) an amide compound whlch i6 obt~lned throu~b a re~ction between a monomeric fatty acld and an ethyleneamine expre~sed by the formula of H2N-(C~2-C~2-NH)n-~ where "n~ i8 3 to S, and (il) an amide compound of polymeric atty acld (referred to as ~pol.ymeric fatty acid polyamlde~ in this speclficat~on) obtained through a reactlon of a polymeri~ fatty acid and the ethyleneamine, or (~ a reaction mlxture obtained by mixinq reaction of the monomeric fatty acid, the polymeric fatty acid ~nd the ethylenea~ine.
The monomer~c at~y ac~d mentioned ahove is a f~tty acid having a num~er of carbon atoms ranglng between 10 and 2~ per moleeule. Preferably, tl~e ~onomeric L~tty acid u~ea in the method of ~he invention }~ con~ti~ute~ ~neinly b~ an o~eic acid, linolei~ 2cid ~nu/or erucic asicl.
T~le ethylene~mine mentioned a~o~e is the or)e wilich is S e~:pressed ~y the rollowing orrdula;
H2~-~CH2-Ch2-~)n-~ where n i~ 3 to 5, prefecably 4 to 5~
The amide compound of the monomeric fatty acid and the polymeric fatty acid polyamide, as weLl as the reaction IO mixture, as mentioned above, are prepared by re~cting the fatty acld(s) with the above ethylene amine in a ratio of about 0. 8 to abQUt 20 0 mol per one carboxyl group of fatty acid.
The weight ratio o~ the amide compound of monomeric fatty ~cid to the polymerlc fatty aci~ polya~.ide in the mixture amide co~pound u~ed as the hardener in th~ invention i~
preferably 90:10 tO 5:95, and more preferably 80:20 to 20:80.
The filler used in the method of the invention is of a m~terial which can be bound by mean of a bisphenol~type epoxy resin. The material of the fill~r should have a small content of ~-oluble 6alts, or otherwi~e ~ large contraction will occur during the hardening. The material should al~o be one which permit~ control o the particle s~ze. Preferably, the filler is constituted by hn lnorganic ~ateri~1 haviny a large surface energy 6uch as powders of silica stone or silica san~.
Ae stated befoce, the known method proposed in Japane~e Patent Publication No. ~464/1978 makes u~e of a polymeric ", ~
., 6~
fatty acid polyamide ~olely a8 the hardener. In contrast, in the pre~ent invention, the mi~ture amide compound aB the hardener usad in the ~ethod ia either (a) a mixture of an amide compound produced througb reactlon between a monomeric fst~y acid and ethyleneamine and a polymeric fatty acid poly~mide or (b~ reaction ~ixture produced through reaction of a mo~omeric fat~y aci~ pol~eric fatty acid and ethyleneamine. In addition, the invention i~ characterized also in that the hardener contains a ~ignificant amount of amide compound of monomeric fatty acid.
The ~o-called polymeric fatty acid i8 produced from tal}ow oleic acid, tall oil fatty acid, ~oybean oil fatty acid and ~o forth, and i~ composed mainly of di~er acids, although trimmer acid~ and monomer acids are not exclude~. Th~ content 15 of tbe monomer acid, bowever, is les3 than a~out ~ and the ~ide compound of monomeric fatty acid ~n the polymeri~ fatty acid polyamide thus produçed i8 ~180 less than about ~. On the other han~, in the method of the invention, as ~tated ~efore, the amount of the amide compound of monomeric fat~y acld to be u~ed is higher than that in th~ ordinary polymeric fatty acld.
The present inventors have found that the mean pore size in the product porou~ material is llnearly increased while the vi~cosity of the slurry for the productlon of porous material having open pores i8 linearly dQcreased as the rate o~ a~ide compound of the monomeric fatty acid i.n the haraener i~
incre~se~. With ~his knowledge, the inventor~ have accomplished the pre~ent invention through seeking for the ~L2~6817 optimum conditions such as the kind of the monomeric fatty acid, kind of the ethyleneamine, and the ratio between -the fatty acid and ethyleneamine, in relation to the properties or characteristics in the production of the porous material and the properties of the hardened porous material.
The invention will become apparent from the following detailed description of the invention.
According to the invention, the amide compound of the monomeric fatty acid in the hardener produces the following effect.
The known me-thod disclosed in Japanese Patent Publication No. 2464/1978 employs solely a polymeric fatty acid polyamide as the hardener. This polymeric fatty acid polyamide may be one such as obtained as a product of reaction between VERSADYME V216 (trademark;
produced by Henkel Japan) and tetraethylenepentamine. As shown in Table l, the porous material produced by this method showed a concentration of pore size to the smaller side and cannot have a mean pore size exceeding 1.5 microns, even when the particle size of the filler and the amount of addition and mixing of the reactive diluent are varied, insofar as the particle size of the filler is within a range easy to handle. Also, the viscosity of the slurry used in the production of the porous material showed extremely high viscosity.
;~ - 1 0 ~246817 . T~ble 1 _ flller pa ~ cla S~ > 50% 5~ ~ 30~
-~\ epoxy _ _.... _ ._ ~ .~ _ .. , \~ ~ sin EP828 EPB15 EP8 ~ ~P~ 15 \~ .
f ~ none ~x~t 10~ none about 10~
. .__ ~ _ _ .. .___ . _ , __ ~~slu~m3a~ 81u~ ~~ ~lllrry mea~l 5111rry pO~ ~!5509it~ pc~e v~ ~7 pore Vi~ 3it~t pore vi~
81~ ~CD5 at ~iæ (cps at siæ (cps at size ~cps at O~) ~oo~) ~/~) 30C) (t~) 3~C) (t~) 30~C) , .. __ . .... _ 1.2 n~7 73,000 1.0 ~6,000 1.1 55,000 103 6Q,000 . _ . . _ .. . . . .
1.~ O.fi 5~,000 lo.9 40,000 100 ,000 1.3 39,000 Note) i) EP828 and EP815 (trademarks) are bisphenol-type epoxy resin produced by Yuka Cell Epoxy Company.
ii) ~f~ mean~ he volume ratio of filler to sum of re~infi .
iii) Water content i6 41% ln terms of volume ratio.
iv) The reactive diluent 15 butylglycldylether.
v) The mean pore size is shown in term of the least diameter of pores which are filled with mercury, when 50% of the total pore volume is filled with mercury, as measured by a mercury press-feeding porosimeter.
vi) The filler is produced by pulverizing a silica sand for glass produced in Seto district (manufactured by . ~-:lZ4681~
Nippo Keisa Kogyo K.K.) into a desired particle size.
vii) The slurry viscosity was measured with the slurry prepared in accordance with the method of Japanese Patent Publication No. 2464/1978, using a B-type viscosi-meter with No. 4 rotor at 6RPM.
In contrast to the above, in the method of the invention an oleic acid, NNA 35 (trademark; produced by Nippon Ushi K.K ) was used as the monomeric fatty acid, while the VERSADYME V216 (produced by ~enkel Japan) was used as the polymeric fatty acid. At the same time, tetraethylene-pentamine was used as the ethyleneamine. A porous material was produced in accordance with the method of the invention, using the reaction mixture of these three substances as the hardener. As will be seen from Table 2, the mean pore size is increased as the content of the amide compound of the monomeric fatty acid is increased, so that the mean pore size is controllable within the range of between 1 and 8 microns even when the kinds and the contents of the materials other than the hardener are unchanged. From Table 2, it will be seen also that the viscosity of the slurry becomes lower as the content of the amide compound of monomeric fatty acid is increased.
~,.
~24~ 17 Tabl~ 2 ~ __, , _ ~ _ m~XJe ~ I f W filler dl~ter ccntrac~on ~lurry fatty acl~ ~ p~cle æ~ze ~.~) (~3 ~3CPogc~t _ __ ~ _ _ __ 0 1~2 41 5,L~ > 3~6 1D3 Q~ll 4!~,~10D
~i .. u o~ 1.~ o~ 11 4~000 ~ R 1 ~ ~i O~ 13 32~ OOtl
Furthermore~ the~e known me'chod~ ar~ generally complicated and dif f icult to conductO
Another problem i5 that, ~ith these kno~n me~hod~, lt i8 ~uite difficult to effect the pore ~ize control wh~ch i~ the 5 most i~portant factor when the porous mater ial i~ use~ as a filtering medium, ~ir diffu~ >n mediumt ca~ting mold or the like du~ to the following reason~.
In the production of a pOroslB m8ter ial f ~om metal powder by ~interirlg, i~ difficu11: ~o obtaln a pore ~ize ~maller 10 than 5 mic:ror~& because of a specif ic relation be~ween the par~lcle siæe of the metal powa~r and the ~urface energy durlng the B1nter ing. Con~equently~ it i8 quite dlficul~ to effect control of the pore ize to obtain pores on the order of 1 ~ic:ron or ~o. In 'che case of the ~interlng of the p:3wd~r 15 of a cer~ .materia:L or resln, the pas:king den~ity at the time of moldiny i8 almost impo~sible to control although the particle size of the mater Lal can be controll~d f inely. In additlon~ th$s method ~uffer~ from ~ large change in the pore structure in the cour~e ~f the ~intering, 80 that the pore 20 si~e is distributed over a wlde range to hinder the control o~
th~ pore ~ize.
Referring now to ~he pressing and ~tamping of a solid powder together w~th a hinder such as an adhesi~e, the control of the pore ~lze ie impaired particularly when the product has 25 a compl~cated shape, for the re~son~ s~ch a~ non-uniform packing due to non-uniform application of the molding pressure attributahle to the complicated shape of the product, non-uniform mixing of the binder, and sc on.
~6~
In the case of the hydr~ti~n ~ardening of a ce~lent, gyp~um, plaster or the like, difficulty is l~olved 1n thecontrol of the nucleation and srowth of the crystal~ o~ the hydrate, and preci~e control of the mean pore size to ob~ain pores on the order of 0.5 to 10 microns car.not easily be effected.
~ ith resard to the method in which the pore for~ing agen~
is evaporate~ or ex~racted from ~he hardened resin con~ainirg the agent, a techni~ue has been proposed for the production of a thin film having pores of pore ~izes ranging between 1000 and 100~. This ~e~hod, however, cannot be applied to the production of a ~roduct havlng ~ large shape. In the method in which a resin in the form of 0/W- or ~/0-type emul~ion i5 hardene~ followed ~y the evaporatlon o~ th~
di~per80id, it i~ not easy to control the size of the disper80id, ~nd many disconnected pores are in~vitably for~ed.
The control of the pore size on the order of ~.5 to 10 mlcrQns a6 a mean ts also difficult in thi~ method.
In order to obviate these problems of the known methods, ~a~anese PaL2~-L .~o. 924,027 issued on septem~er 2~, 197~ -,o t~e ~L~plicanL ~-o~oses a met'nod o~ pro~ucing a ~orous mateli21 having open pores and ~ complicated shape, at a high precision and w~th a good control of the pore si2e. More ~pecifically, this method compri~e6 the steps of preparing an 0~' type 2S slurry as a mixture of a glycidyl-type epoxy re5in, polymeric fatty acid polyamide hardener, filler and ~ater, casting the ~lurry in a water-~permeable mold, hardening the water-containing 81urry, and then dehydratlng the hardened body.
a~ ~
:~4~
According to this metho~ i8 possible to e~ect the~ c:ontrol of the pore si~e by varylng and ~dJu~tin~ factor~ such ~ the part~cle size of the filler~ amount of the reactive diluent, mixing ratio of the epoxy r~sln, hardener, filler and water, S and so on. P,mong th~se factors, the amount of the reactive diluent and the mi~ing ratio of the ~poxy re~in~ hardeneL ~
filler and water a~e limited from the viewpoint of contraction durlns~ hardening and al~o in view of the ~reng~h of 'che hardened body. ~or thi~ rea~on, it i~ not pos~ible to c:ontrol 10 the pore ~ize over a wlde range. In order to control the pore ~i2e to obtain pores on the order of O. 5 to lO micron~, it is neces~ary to largely vary the particle ~ize of the filler.
The use of the filler having large -partlcle slze, however, reduces the ~trer~gth o~ the hardened body undesirably. The 15 reduct~on of streng~ch can be avoided only through a reduction ln th~ Elmoun~ of watar added, wh~ch ~n turn is accompaniel9 by a new proble~ of an increa~ in tne ~l~co~lty of the ~lurry.
The lncreased part~le slze of the ~iller cause~ alæo anotber problem namely that the effic~ency of the ~ork is lmpaired due to sedimentation of the filler in the slurry which consist~ of water and the filler. When ~ flller having a mean slze ~uitable for the work i~ used, t~e mean pore size in the product porous materlal i8 unde~lrably concentrated to an ext~eme~y sm~ll level o~ le6~ than 1.5 microns. The poro~
m~terial having such extremely small pore slze can hardly be used for the a~ore~entioned application~ ~uch ~q filtering ~edium, alr diffu~ion mediu~ ca ting mold and ~o forth and, hence, has only ~ small pr~ctical utillty. Furthermore, thi~
~4~
propo~ed method ~uffers rom problems such a~ the impract1cally long tlme requlr~d for the slurry to flow into the ~old ~nd difflculey ln forming a porous materlal having an intricate and compllcat~d ~hape, due to the high viscosi~y of the ~lurry attributabl~ ~o the u~e of a polymerlc ~tty acid polya~ide solely as the hardener.
~U~ARY ~F T~ V~NTIO~
.... _ _ .
Under this circumstance, the preBent lnvent~on ~lm~ at 1~ provid~ng a method of producing a porou6 material havlng open pores of a desired mean pore ~ixe (opening), thereby to obv~ate the problems of the prior art~
Namely, it ~ an object of th~ inventlon to .prov~e a method o~ produclng a porou~ materi~, wh~ch 1~ improved to permit the control of the maan pore ~ize over a wide range without requiring any change in th~ partl~l~ s~ze of the filler.
~ nother oh~ect of the inYentiOn iB to provide a method of produ~ing a porous material, whlch is improved to permit the precise control of the me~n pore ~ize of the open pores within the range of between 0.5 and 1~ micron6, u~ing a filler of such a s~all particle size a~ not to cause filler sed~mentation wh~ch ~ould impair the handling of the flller.
Still another object of the inventlon i~ to provide a 25 methoa of produclng a poro~s material in which the visco~ity of the ~lurry i~ lowered to permit quick filling of the mvld and high prec~ BlOn of the product even when the product has a complicated and intricate shape.
Other o~jects, featur~s and advantage~ of the invention wlll becQme clear from th~ followins de~cription of the preferred embodlment~ of the invention.
l~hese ob~ect~ are achieved by using the following specific ~ixt~re amide compound as the hardener in the production of the porous materi~l having o~en porPs.
DESCRIPTION OF TB~ INVENTION INCLUDIN~ T~E PREFE~R~D
.. . .. .. . .. .
EMBODIMENTS
1~ In order to ~c&omplish the above-de~cribed objects of the lnvention, the pre~ent invention propose~ a method of produclnq a porous materlal compris~ng the ~teps of preparing a slurry by vigorously stlrrins a mixture c~mpr~ing a blsphenol-typ~ epoxy resin, a hardener, a filler ~nd water, c~t~ng the slurry in a wat~r-imper~eable mold, h2rdening the ~lurry wh~le lt con ~lins ~ter r and dehydrating the h~rdened body, wher¢in the l~prov~ment comprises that the hardener is ei~her (a) a mlxture of li) an amide compound whlch i6 obt~lned throu~b a re~ction between a monomeric fatty acld and an ethyleneamine expre~sed by the formula of H2N-(C~2-C~2-NH)n-~ where "n~ i8 3 to S, and (il) an amide compound of polymeric atty acld (referred to as ~pol.ymeric fatty acid polyamlde~ in this speclficat~on) obtained through a reactlon of a polymeri~ fatty acid and the ethyleneamine, or (~ a reaction mlxture obtained by mixinq reaction of the monomeric fatty acid, the polymeric fatty acid ~nd the ethylenea~ine.
The monomer~c at~y ac~d mentioned ahove is a f~tty acid having a num~er of carbon atoms ranglng between 10 and 2~ per moleeule. Preferably, tl~e ~onomeric L~tty acid u~ea in the method of ~he invention }~ con~ti~ute~ ~neinly b~ an o~eic acid, linolei~ 2cid ~nu/or erucic asicl.
T~le ethylene~mine mentioned a~o~e is the or)e wilich is S e~:pressed ~y the rollowing orrdula;
H2~-~CH2-Ch2-~)n-~ where n i~ 3 to 5, prefecably 4 to 5~
The amide compound of the monomeric fatty acid and the polymeric fatty acid polyamide, as weLl as the reaction IO mixture, as mentioned above, are prepared by re~cting the fatty acld(s) with the above ethylene amine in a ratio of about 0. 8 to abQUt 20 0 mol per one carboxyl group of fatty acid.
The weight ratio o~ the amide compound of monomeric fatty ~cid to the polymerlc fatty aci~ polya~.ide in the mixture amide co~pound u~ed as the hardener in th~ invention i~
preferably 90:10 tO 5:95, and more preferably 80:20 to 20:80.
The filler used in the method of the invention is of a m~terial which can be bound by mean of a bisphenol~type epoxy resin. The material of the fill~r should have a small content of ~-oluble 6alts, or otherwi~e ~ large contraction will occur during the hardening. The material should al~o be one which permit~ control o the particle s~ze. Preferably, the filler is constituted by hn lnorganic ~ateri~1 haviny a large surface energy 6uch as powders of silica stone or silica san~.
Ae stated befoce, the known method proposed in Japane~e Patent Publication No. ~464/1978 makes u~e of a polymeric ", ~
., 6~
fatty acid polyamide ~olely a8 the hardener. In contrast, in the pre~ent invention, the mi~ture amide compound aB the hardener usad in the ~ethod ia either (a) a mixture of an amide compound produced througb reactlon between a monomeric fst~y acid and ethyleneamine and a polymeric fatty acid poly~mide or (b~ reaction ~ixture produced through reaction of a mo~omeric fat~y aci~ pol~eric fatty acid and ethyleneamine. In addition, the invention i~ characterized also in that the hardener contains a ~ignificant amount of amide compound of monomeric fatty acid.
The ~o-called polymeric fatty acid i8 produced from tal}ow oleic acid, tall oil fatty acid, ~oybean oil fatty acid and ~o forth, and i~ composed mainly of di~er acids, although trimmer acid~ and monomer acids are not exclude~. Th~ content 15 of tbe monomer acid, bowever, is les3 than a~out ~ and the ~ide compound of monomeric fatty acid ~n the polymeri~ fatty acid polyamide thus produçed i8 ~180 less than about ~. On the other han~, in the method of the invention, as ~tated ~efore, the amount of the amide compound of monomeric fat~y acld to be u~ed is higher than that in th~ ordinary polymeric fatty acld.
The present inventors have found that the mean pore size in the product porou~ material is llnearly increased while the vi~cosity of the slurry for the productlon of porous material having open pores i8 linearly dQcreased as the rate o~ a~ide compound of the monomeric fatty acid i.n the haraener i~
incre~se~. With ~his knowledge, the inventor~ have accomplished the pre~ent invention through seeking for the ~L2~6817 optimum conditions such as the kind of the monomeric fatty acid, kind of the ethyleneamine, and the ratio between -the fatty acid and ethyleneamine, in relation to the properties or characteristics in the production of the porous material and the properties of the hardened porous material.
The invention will become apparent from the following detailed description of the invention.
According to the invention, the amide compound of the monomeric fatty acid in the hardener produces the following effect.
The known me-thod disclosed in Japanese Patent Publication No. 2464/1978 employs solely a polymeric fatty acid polyamide as the hardener. This polymeric fatty acid polyamide may be one such as obtained as a product of reaction between VERSADYME V216 (trademark;
produced by Henkel Japan) and tetraethylenepentamine. As shown in Table l, the porous material produced by this method showed a concentration of pore size to the smaller side and cannot have a mean pore size exceeding 1.5 microns, even when the particle size of the filler and the amount of addition and mixing of the reactive diluent are varied, insofar as the particle size of the filler is within a range easy to handle. Also, the viscosity of the slurry used in the production of the porous material showed extremely high viscosity.
;~ - 1 0 ~246817 . T~ble 1 _ flller pa ~ cla S~ > 50% 5~ ~ 30~
-~\ epoxy _ _.... _ ._ ~ .~ _ .. , \~ ~ sin EP828 EPB15 EP8 ~ ~P~ 15 \~ .
f ~ none ~x~t 10~ none about 10~
. .__ ~ _ _ .. .___ . _ , __ ~~slu~m3a~ 81u~ ~~ ~lllrry mea~l 5111rry pO~ ~!5509it~ pc~e v~ ~7 pore Vi~ 3it~t pore vi~
81~ ~CD5 at ~iæ (cps at siæ (cps at size ~cps at O~) ~oo~) ~/~) 30C) (t~) 3~C) (t~) 30~C) , .. __ . .... _ 1.2 n~7 73,000 1.0 ~6,000 1.1 55,000 103 6Q,000 . _ . . _ .. . . . .
1.~ O.fi 5~,000 lo.9 40,000 100 ,000 1.3 39,000 Note) i) EP828 and EP815 (trademarks) are bisphenol-type epoxy resin produced by Yuka Cell Epoxy Company.
ii) ~f~ mean~ he volume ratio of filler to sum of re~infi .
iii) Water content i6 41% ln terms of volume ratio.
iv) The reactive diluent 15 butylglycldylether.
v) The mean pore size is shown in term of the least diameter of pores which are filled with mercury, when 50% of the total pore volume is filled with mercury, as measured by a mercury press-feeding porosimeter.
vi) The filler is produced by pulverizing a silica sand for glass produced in Seto district (manufactured by . ~-:lZ4681~
Nippo Keisa Kogyo K.K.) into a desired particle size.
vii) The slurry viscosity was measured with the slurry prepared in accordance with the method of Japanese Patent Publication No. 2464/1978, using a B-type viscosi-meter with No. 4 rotor at 6RPM.
In contrast to the above, in the method of the invention an oleic acid, NNA 35 (trademark; produced by Nippon Ushi K.K ) was used as the monomeric fatty acid, while the VERSADYME V216 (produced by ~enkel Japan) was used as the polymeric fatty acid. At the same time, tetraethylene-pentamine was used as the ethyleneamine. A porous material was produced in accordance with the method of the invention, using the reaction mixture of these three substances as the hardener. As will be seen from Table 2, the mean pore size is increased as the content of the amide compound of the monomeric fatty acid is increased, so that the mean pore size is controllable within the range of between 1 and 8 microns even when the kinds and the contents of the materials other than the hardener are unchanged. From Table 2, it will be seen also that the viscosity of the slurry becomes lower as the content of the amide compound of monomeric fatty acid is increased.
~,.
~24~ 17 Tabl~ 2 ~ __, , _ ~ _ m~XJe ~ I f W filler dl~ter ccntrac~on ~lurry fatty acl~ ~ p~cle æ~ze ~.~) (~3 ~3CPogc~t _ __ ~ _ _ __ 0 1~2 41 5,L~ > 3~6 1D3 Q~ll 4!~,~10D
~i .. u o~ 1.~ o~ 11 4~000 ~ R 1 ~ ~i O~ 13 32~ OOtl
3 ~ 1~1 # N l . g 0 .16 25~ 0 ~i 0 n ~ 1~ ;2~ 0 3,~13 21 ~, ~ 100 iSO ~ ~t ~ ~o;~ 0~20 16,500 ~;6 u 1~ u 3~9 0~;~2 15~500 ~ ~1 ~ 5~3. 0O30 15~00 ~ D~ _ ~ ~55 15~000 . _ .
Note) 1) The mixiny ratio or content of the monomeric fatty acid amide i~ determln~d as follow~. Tetr~ethyl~nepentamine 20 18 added to the ~ixture of monomeric f~tty acid and poly~leric fatty acid at a ratio ~f 1 mol for one carboxyl yroup existing in the m~xture. The mixture with the addition of tetraethylenepentamine i~ heated up to 230C over 2 hour~ in N~ atmosphere and then maintained at 230 to 240C for 2 hours to become the hardener. The mixing ratio of the monol~ric fatty acid amide i8 the ratio of ~mount of the in~t~al monomeric f~tty acid before the ~ixiny to the ~um of the a~ount~ o~ this monomer~c fatty ac~d and the polymeric fatty -- 13 ~
68~
acid.
i~) "f~ i8 the volume rat~o of the filler to the sum of resins.
iii) ~W~ iB the volume rat1o of water to the whole of the prepare~ material.
iv~ The mean pore size i~ the mean diameter vf pores in the porous material produced by th~ method of the invention.
v~ The contraction rate is ~xpreased as the contraction rate ln the hei~htwiae direction of a hardened body and i~ measured as follow~. A ~lurry is ca3t in an FRP
case haivng a ~ize of 50 (length) x 50 ~wldth) x 500 (height) mm and is cured for 24 hours in a room of an ~ir temperature controlled at 45C under ~ drylng prevention (the ca6e ia sealed). ~fter the harden~ng, the porou~ material is taken out of the ca3~, and the helghtwlse lineAr contra~tion rate i8 ~ea~ured from the contraction mark~ form~d at 450mm intervai in the FRP c~se and the marks left on the hardened porous mater1al.
vi) Silica s~nd for glass produced in Seto district ~manufactured by Nippo Keisa Kogyo K.R~) pulverized into size of 5 m~crons ~30% wa~ used as the filler mater~
vil~ EP815 produced by Yu~a Cell ~poxy Company was used aa the bisphenol-type epoxy resin.
viil) The 81urry Yi~Cosity i8 the viscosity of the alurry prepared in accord~nce with the lnvention~ as meaaured by a B-type v i scometer.
It may appear that the chang~ of the mean pore aize from 6~:~1L7 the order as shown ln Table 1 to that shown ln Tabl~ 2 1~ only mlnor and, hence, no ~ubstantlal effect is produce~ by ~uch a change. A8 a matter of fact however, this 6mall change in the pore 5ize offers a great advantaqe a~ explained S hereinbelow.
~ ttention mu~t be drawn to the following formula which i~
known as Poiseuille'~ eguation.
g 5 ~ , h where, Q representæ the amount of tran3mission through por~
per unit time, ~r~ represents a pore diameter, ~ represent the vl~cosity of fluid, ~h~ represents the pressure difference, and ~.0~ represent~ th~ pore leng h. A-~ will ba under~tood from thi~ iEormula, the veloc~ty o~ 3 fluld flow~ng through ~he pore iB proportion~l to the fourth power of the pore ~iameter. Thus, a remarkable practical advantage is produced even by a s~nall change or adjustment of the above mean pore ize.
Porou~ material~ were produced ln accordance with the method of the invention, u~ing pentaethylenehexamine as the ethyleneamine, wlth various hardener compo~itions without ch~nging the klnds and amounts of the materials other than the hardener. Table 3 show the mean pore ~ize6 and contraction rates a measured wlth these porous materials. From thi~
Table, lt w~ll be understood that the mean pore size i5 lncrea~ed, while the vi~co~ity of the &lurry 1B decre~ed, a~
the content of the amiae compound of monomeric fatty acid is increased.
681~
. ~
C~ Q Ul ~ O W ~ 3 ~o~ r ~ ~1 ~'D D
r-- ~ ~ W ~ V~ Cr ~ ~ ~ ~l D' O ~ Vl ~ o o ~J ~ ~ ~
___ Y ~ ~ ~b . _. _ _ _ . ~.
~1~ s s:~ ~ ~ dP :~:
. ~ t~--~ ai t~D
~ 8 ~ a~ ~
X ~:
~ .
~ d ~ ~
~ ~. ~ ~ ~ w r h ~ ~_ VJ1~ 2 ~ P~ ~ t . ~ . , ~ ~
~æ
, - - - ~ ~ a o ~ 7 ;~ O ~ 1~ ~V
~ o 2 ~ ~ ~
. . . . _ _. ; ~ ;r o o o o o o~ o ~g ~ dP
. . . _ ._ ~ _--_ o o o o _ . _ ., , It , r~ ~, G~ ~ 0~
~ Uol 'o o o ~ ~ ~
6~
~ote) i) The ratio between the monomeric fatty acid amide and the polymeric at~y acld poly~mide is determined a~ follow~.
In the case of the mixture obtained after independent reactions, the harden~r is prepared by a proces~ comprising the steps ofs (a~ adding 1 mol of pentaethylenehexamine to 1 mol of the monomeric fatty acid to conduct a ~ynthesis under the following condition to orm an amide compound of monomeric fatty acid, and (b) mixing a polymeric fatty acid and pentaethylene-hexaoine which i~ added at a ratio of 1 mol for 1 ~one~ carboxylic group existing in t~e polymer~c fatty acid to effect a ~ynthesi~ under the following condition to form a polymerlc fatty acid polyamide, ancl ~c~ mixing the thus formed ~mide compound of monomeric fatty a~id ~) and polymeric fa~ty a~id polyamlde ~b) ~t ratios shown ~n Tabl~ 3. The r~tio between the a~ount of the ~nitial amid~ compound of monomeric fatty acid ~nd th~ amount of the initlal pol~meric fatty acid polyamide beforoe they arQ ~.ixed 1~ dete}mined a~ the ratio between monomerlc fatty acld amide and the polym~ric fatty acld polyamide in the hardener~ '~t should be noted that the amide compound of monomeric fatty acid which may exi~t in the polymeric fatty a~id polyamide i excluded from the above-mentiGned in~tial amide compound of monomeric fatty acid.
In the ca~e where the reaction mixture ls used as the hardener, the ~onomeric fatty acid and the polymeric atty acid ~re mixed at the ratios ~hown ln Table 3. After addin~
pentaethylenehe~amine to thi~ mixtur~ ~t a ratio of 1 mol for 1 ~one~ carboxyllc group ln the mixture, the mixture i~ heated 6~
up to 23~ C over 2 hours and then 1~ maintained at 230 to 2~0C
for 2 hour~ in ~2 gag atmo~phere to cause a reaction thereby to synthesize ~he hardener. In thi~ case, the ratlo between the monomeric fatty acid and the polymeri~ f~tty acid beore the ~xlng i~ determined ~ the ratio between ~onomerlc fa~ty acid amide and poly~eric fatty acid polyamlde in the hardener.
f~ repre~ents the volume ratio of filler to the ~u~ of re~ins.
iii) ~W~ repre~ents the ~olu~e ~ of water in the prepared material.
iv) The mean pore s~ze ~hows the mean diameter of pores in th~ porou~ material produced by the ~.ethod of the in~ention.
7) ~he contract~on r~ ~B the rate of ccntraction in the heigh~w~$e direction of a hardened body and i8 measured as follo~. A slurry is c~st in an FRP case havlng a size of 50 (length) ~ S0 (width) x S00 ~he~ght) nu~ ~nd i~ cured for 24 hours in ~ room of an air temperature controlled at 4SC under a dr~ing prevention ('che case is sealed). Af~er the 20 hardening, the porou~ material i~ taken out of the c~se, and the heightwise linear contraction rate ~ 9 measured from the cor.traction marks formed at 450mm interval in the FRP case and ~he marks left on the hardened porous material.
vi~ An oleic acid (NNA35 manufactured by Nippon Yushi 25 R.E~ used a3 the monomeric fatty ~lcid.
vii) VERSADYME V216 produced by E~enkel Japan is used as the polymer ic fatty acid .
viii) Pulverized ~llica ~and for gla85 produced 1n Seto 1~ -~, ....
i ~r=
. ,. ~ .
6~
district (manufactured by Nippo ~eisa Kogyo ~.K.) is used as the filler.
ix) ~PB15 manufacturæ by Yuka Cell Epo~y Company is u~ed as the bisphenol-type epoxy resln.
x) The slurry viscoslty is the vi6cosity of the slurry prepared in accordance with the metho~ of the invention, as measured ~y a B-type visco~eter.
As ~tated before~ the monomeric fatty ~cid as used in the method of the invention can include 10 to 22 carbon atoms per molecule. Fatty acids havlng carbon atom numbers exceeding 22 cannot be u~ed adequately b~cause of too high melting point, while the fatty acid~ having c~rbon atom numher~ less than 10 cause a problem that the amide compound produced through reaction with the ethyleneamine shows only a small surfactant effect sc that the slurry is made un~table to allow a ~arge contraction during ~he hardening.
Generally, iatty acids produced from animal and vegetable oils and fat~ are constituted by a nixture of mainly lauric acid, myri~tic acid, palmitic acid, stearic acid, oleic acid an~/or linolic acid, as well as other fatty acids having carbon atom number~ r~nging between 10 and 22. Theae mixed fatty acids from natural mater ials can be used for tbe monomeric fatty acid in this invention. Among the mixed fatty acids, those containiny oleic acid, linoleic acid and/or eruCic acid as the maior constituent are prefeable from the vie~points of the properties of the hardener o~tained and the contraction during the hardening.
.~ '' ~6~
Table 4 ~how~ the v~ ~cosl~ies ~t ~8C of harden~3r~ which were prep~red ~y mixlng Yariou~ monomeric atty a::~ds wlth the polyme~ic fatty Acid at mol~ ratlo of 50s50, ~ddlng thereto tetrae'chylenepentamine (~) of a ratio of 1 mol for one 5 carboxyl group e~isting in the mixed fatty acids, heating the mixture up ~o 230~C over 2 hour~ and then maintaining ~he ~ame at 230 to 240C ~or an ad~itional 2 hour~ to sbtain the hardener. The table al~o shows th~ ratlo of c~ntraction during the hardening ln the case where tbe ;?orous ~a~erlal was 10 produced b~ using the absve hardeners.
Tab le klnd of h~er Filler particl~ C~ltract~on fat~r ~ld (cps at 25C~ f ~ si2e ha~ening~
. ~ ~ __ ~
olelc acld 3500 1.~ 41 5 f~ > 30~ 0.13 l~ lc a~:ld 3000 ~ .. .. 0.,15 stearic acld ~el ., n ~ 0~17 palJIlltic acld g~l u ~ n 0. 49 rr~ tlc acld gel .. n u 0~31 ].aurlc acld 5500 . a _ 0~67 ~IL2~68~7 Note) i) The ~onomeric fat~y acld~ other than oleic acid ~re reagents produced by ~okyo Kasei K.~.
~1) Oleic acid ifi NNA35 manufactured by Nippon Yu~hi K.R.
iii) V~RSADY~E V216 produced by ~enkel Japan is used a~
the polymeric fatty acit3.
iv) "f~ repre~ents ~he volu~e ratio of filler to the sum of resin~. `
Y~ ~W" represents the volume % of water in the prepared material.
vi) Pulverized silica 6an~ for gla~s produced ln Seto distr~t (manufactured by Nippo Keisa Rogyo X.R.~ i8 used a9 the f~ller.
vii) EP815 ~anufactured by Yuka Cell Epoxy Gompany is UBed ~5 the bisphenol-type epo~y resin.
viil) The contraction rate is the rate of contraction in the he~ghtwlse dlrection of a hardened body and i8 ~;ea~ured a~
follows. A slurry is cast ln an FRP case h&ving a size of 50 20 (len~'ch) x 50 (wldth) x 500 (height) m~n and is cured for 24 hours in a room of an ~ir temperature controlled at 45C under A drying prevention (the case ls sealed). After the hardening, the porous mater ial ifi taken out of the case, and the heightwise llnear contraction rate i~ measured from the ~5 contraction ~arks ~ormed at 450~ interval ln the FRP case and the mark~ left on the hardened porous materlal~
~ 21 -~ .
~L24~
In the ethy~eneamine ~N-tC~C~-N~ a~ u6ed, the nunlber ~n~ ~s sele~ted ~o be 3 to S for the followlng reason.
Namely, B slurry ¢o~pr t sing the hardener prepared from th~
ethylenediamine or ~iethylene~riamine having the number "n~ of 1 or 2 e~hib~t~ a hi~h cohesion fo~ce, a8 well as a large contrac~ion; an~, therefore, the hardener cannot be u~ed pract~cally i~ the production of the porou~ materlal.
Triethylen~tetramine having ~he number ~n~ o~ 3 al80 ~ends to exllibit a ~o~ewhat large cohe~ion ana contraction. For th~se rea60ns, it i8 preferred to use tetraethylerlepentamine and pentaet~ylenehexamine having the nu~her~ ~n~ o~ 4 and 5, re~pectively.
As a ~atter of fac~, howe~er, it i6 diff~cult to co~merclally obtain ~ pure ~thyl~ne~ine having ~ ~lngle compo~ition. ~he ethyleneam~ne as used ~n the i~vent~on, therefor~, ~ay be such R ~ixture a~ the ~ommercially available goods.
In the mel:hod of the invention, ebe ratio between the amide compound of monomer~c ratty acid and the polymeric fatty acid polyamide in the hardener is ~elect~d ~referably to range between 90210 an~ 5:95 by welght. A8 wlll ~e ~een from Table~
2 and 3, a~ the content of the amide compound of the ~,onomeric f~tty acid iB increa~e~, the r~te of hardening contr~ction is lncrea~ed to impair the production of porou6 materlal at high dimensional precision. For this reason, the content of the ~id~ compound of monomeric f~tty ~cid ~hould be ~electe~ not to exceed 90~ This content i5 preferably up to 80~, when the product has a l~rge ~ize end complcatea fihape.
- 2~ -'7 On the oth~r hand, ;~he~s lt is degired to produce ~ porou~
m~terial havlng open pores o ~ pore dla~neter of abou~ 90 5 micron, the conterlt o~ the am~ de compound of the monomer ic fatty acid may be smaller ~:has~ 59~. ~owever, the production of S 'che p~rous material having mean pore size not smaller than 1.5 micron encoun~er~ ~ d~fficulty when ~he ~bove-mentioned content i~ smaller than 5%. For thi~ reason, the preerred lower limi t of the content of amide compound of monomer ic ~atty acid i~ selec'ced to be 5%.
In the method of the invention, the ~mide comp3und of monomeric fat'cy ~cid and the polymeric fatty ac~d polyamide are synthe~lzed w~th the addition of ethyleneamine at a ratio of about 0. 8 to about 2. 0 mol~ per 1 tone) carboxyl gLQUp.
When the ethyleneallline 1~ increaseB beyond 1.0 mol, the 31urry 15 tend~ to make a cohe~lon c~on raction during hardening~ el8 ~
re3ul'c of the pre~nce of free or ~eparated ethylene~mine. On the other h~n~, when t~e ethyleneamine i8 decreased below 1. 0 mol, the NH2 radicals at ~:>oth ends of the ethyleneam~ ne react with COO~. The slurry comprir~ing the hardener obtained showed 20 an increa ed tendency of cohe~ior~ contraction at the time of hardenins. ~he ethyleneamine content ranging between about 0. 8 an~l about 2. 0 mol~ per 1 ~one) carboxyl group, however, can produce a ~enerally acceptable result.
A reactive diluent SUCII as butyl ~lycidyl ether, allyl glycldyl ether, phenyl glycidyl ether, terti2ry carboxylic acid glycidyl ester, secondary pentyl phenol ~,onoglycidyl ether or the like may b~ added to the b~sph2nol-type epo~y re~in. As a r~sult of sdd~tion of suc~ a diluent, the ~lurry -- 23 ~
~2~6~
visco$1ty i5 decrea~ed and the pore si~e ln the porou~ product i8 increa~ed. A too la~e ~ount of ~dd~tion o~ such ~
diluent, howev~r, unde~irably causes ~ contraction during the hardenln~. The li~lit~ o Anlount of addition of the re~ctive diluent depends on the kind of the diluent. I~ is preferred to u~e the diluent of not more than 25 parts by ~eight for 100 part~ by weight of the bi6phenol-type epoxy resin.
In the method of the in~ention, lt i~ preferable to add a hsrdening pro~otion ayent, in order to incre~se the rate of 1~ h~rden1ng and, hence, to enhance the strength of the hardened body. Vsually, ~ubstances such as phenol, triethanola~ine, hexamethylenetetramine, benzyldimethylamine, tri dimethyl-amin~ethylphe~ol or the like ~re u~able as the hardening promotion a~ent in combLnation wit~ a polyamid~ hardener~ In 15 the m~thod of the invention, a super~or effect i~ obtained p~rtlcul~rly by the use of a har~ening promotion ~gent of a tertiary amine of aromatic group such a3 b~nzyldimethylamin~, trl5dlmethylaminomethylphenol and 80 forth. From the viewpoint of the strength of the hardened body, ~t is 'preferred to u~e a hardening promotor in about 7 to 15 parts by weight for 100 parts by ~eight of the hardener.
An ex&~ple of the method of the invention is ~hown below only for the illustratlng purpose.
Example 796g of ~ polymeric fatty acid ( VERSADYME V216, producea by IJenkel Japan), 15919 of oleic acid ~NNA 35 produced by Nippon Yu3hi ~.K.3 and 16139 of tetraethylenepentz~ine ~Z~ 7 (produced by Seitetsu Kagaku K.K.) were put together in a stainless steel reaction vessel having a volume of 5~. The mixture was heated from the normal temperature up to 230C in 2 hours while continuing stirring under a supply of N2 gas and then held at 230 to 240C for 2 hours to synthesize 3790g of hardener.
Thenr 647.9g of bisphenol-type epoxy resin (EP815 produced by Yuka Epoxy K~K.), 218.2g of the above-mentioned hardener, 17.7g of a hardening promotion agent TAP (trademark;
made by Kayaku Noulli K.K.), 2803g of silica sand powder of particle size of 5 microns ~30~ and 1348g of wa~er were put in a a stainless steel vessel having no lid. These materials were vigorously stirred or 10 minutes to make a slurry.
This slurry was cast in an FRP case having a size of 50 (length) x 50 (width) x 500 (height) mm and was cured for 24 hours in a room of an air ~emperature controlled at 45C under a drying prevention ~the case was sealed). Ater the hardening, the porous material was taken out of the case, and the heightwise linear contraction rate was measured from the contraction marks formed at 450mm interval in the FRP case and the marks left on the hardened porous material. The contraction rate thus measured was 0.18%. This hardened porous material was then dried and the pore size distribution was measured by means of a mercury press-feeding type porosimeter. This hardened porous material showed a mean pore size of 4.0 microns.
Test pieces for measurement of bending strength were molded from this slurry. The bending strength in wet cond~tion waB ~ne~ured aft~r a drylng prevention harderllng of ~he ca3~ sll~rry at ~5C~c for 24 bour~ The mean bendlng strengt31 was 70 Rg~cm2. Th~ ~ried test pieCeB ater mea~urement of the wet bendirlg strength ~howed an apparent 5 porosity of 4196.
2~ -
Note) 1) The mixiny ratio or content of the monomeric fatty acid amide i~ determln~d as follow~. Tetr~ethyl~nepentamine 20 18 added to the ~ixture of monomeric f~tty acid and poly~leric fatty acid at a ratio ~f 1 mol for one carboxyl yroup existing in the m~xture. The mixture with the addition of tetraethylenepentamine i~ heated up to 230C over 2 hour~ in N~ atmosphere and then maintained at 230 to 240C for 2 hours to become the hardener. The mixing ratio of the monol~ric fatty acid amide i8 the ratio of ~mount of the in~t~al monomeric f~tty acid before the ~ixiny to the ~um of the a~ount~ o~ this monomer~c fatty ac~d and the polymeric fatty -- 13 ~
68~
acid.
i~) "f~ i8 the volume rat~o of the filler to the sum of resins.
iii) ~W~ iB the volume rat1o of water to the whole of the prepare~ material.
iv~ The mean pore size i~ the mean diameter vf pores in the porous material produced by th~ method of the invention.
v~ The contraction rate is ~xpreased as the contraction rate ln the hei~htwiae direction of a hardened body and i~ measured as follow~. A ~lurry is ca3t in an FRP
case haivng a ~ize of 50 (length) x 50 ~wldth) x 500 (height) mm and is cured for 24 hours in a room of an ~ir temperature controlled at 45C under ~ drylng prevention (the ca6e ia sealed). ~fter the harden~ng, the porou~ material is taken out of the ca3~, and the helghtwlse lineAr contra~tion rate i8 ~ea~ured from the contraction mark~ form~d at 450mm intervai in the FRP c~se and the marks left on the hardened porous mater1al.
vi) Silica s~nd for glass produced in Seto district ~manufactured by Nippo Keisa Kogyo K.R~) pulverized into size of 5 m~crons ~30% wa~ used as the filler mater~
vil~ EP815 produced by Yu~a Cell ~poxy Company was used aa the bisphenol-type epoxy resin.
viil) The 81urry Yi~Cosity i8 the viscosity of the alurry prepared in accord~nce with the lnvention~ as meaaured by a B-type v i scometer.
It may appear that the chang~ of the mean pore aize from 6~:~1L7 the order as shown ln Table 1 to that shown ln Tabl~ 2 1~ only mlnor and, hence, no ~ubstantlal effect is produce~ by ~uch a change. A8 a matter of fact however, this 6mall change in the pore 5ize offers a great advantaqe a~ explained S hereinbelow.
~ ttention mu~t be drawn to the following formula which i~
known as Poiseuille'~ eguation.
g 5 ~ , h where, Q representæ the amount of tran3mission through por~
per unit time, ~r~ represents a pore diameter, ~ represent the vl~cosity of fluid, ~h~ represents the pressure difference, and ~.0~ represent~ th~ pore leng h. A-~ will ba under~tood from thi~ iEormula, the veloc~ty o~ 3 fluld flow~ng through ~he pore iB proportion~l to the fourth power of the pore ~iameter. Thus, a remarkable practical advantage is produced even by a s~nall change or adjustment of the above mean pore ize.
Porou~ material~ were produced ln accordance with the method of the invention, u~ing pentaethylenehexamine as the ethyleneamine, wlth various hardener compo~itions without ch~nging the klnds and amounts of the materials other than the hardener. Table 3 show the mean pore ~ize6 and contraction rates a measured wlth these porous materials. From thi~
Table, lt w~ll be understood that the mean pore size i5 lncrea~ed, while the vi~co~ity of the &lurry 1B decre~ed, a~
the content of the amiae compound of monomeric fatty acid is increased.
681~
. ~
C~ Q Ul ~ O W ~ 3 ~o~ r ~ ~1 ~'D D
r-- ~ ~ W ~ V~ Cr ~ ~ ~ ~l D' O ~ Vl ~ o o ~J ~ ~ ~
___ Y ~ ~ ~b . _. _ _ _ . ~.
~1~ s s:~ ~ ~ dP :~:
. ~ t~--~ ai t~D
~ 8 ~ a~ ~
X ~:
~ .
~ d ~ ~
~ ~. ~ ~ ~ w r h ~ ~_ VJ1~ 2 ~ P~ ~ t . ~ . , ~ ~
~æ
, - - - ~ ~ a o ~ 7 ;~ O ~ 1~ ~V
~ o 2 ~ ~ ~
. . . . _ _. ; ~ ;r o o o o o o~ o ~g ~ dP
. . . _ ._ ~ _--_ o o o o _ . _ ., , It , r~ ~, G~ ~ 0~
~ Uol 'o o o ~ ~ ~
6~
~ote) i) The ratio between the monomeric fatty acid amide and the polymeric at~y acld poly~mide is determined a~ follow~.
In the case of the mixture obtained after independent reactions, the harden~r is prepared by a proces~ comprising the steps ofs (a~ adding 1 mol of pentaethylenehexamine to 1 mol of the monomeric fatty acid to conduct a ~ynthesis under the following condition to orm an amide compound of monomeric fatty acid, and (b) mixing a polymeric fatty acid and pentaethylene-hexaoine which i~ added at a ratio of 1 mol for 1 ~one~ carboxylic group existing in t~e polymer~c fatty acid to effect a ~ynthesi~ under the following condition to form a polymerlc fatty acid polyamide, ancl ~c~ mixing the thus formed ~mide compound of monomeric fatty a~id ~) and polymeric fa~ty a~id polyamlde ~b) ~t ratios shown ~n Tabl~ 3. The r~tio between the a~ount of the ~nitial amid~ compound of monomeric fatty acid ~nd th~ amount of the initlal pol~meric fatty acid polyamide beforoe they arQ ~.ixed 1~ dete}mined a~ the ratio between monomerlc fatty acld amide and the polym~ric fatty acld polyamide in the hardener~ '~t should be noted that the amide compound of monomeric fatty acid which may exi~t in the polymeric fatty a~id polyamide i excluded from the above-mentiGned in~tial amide compound of monomeric fatty acid.
In the ca~e where the reaction mixture ls used as the hardener, the ~onomeric fatty acid and the polymeric atty acid ~re mixed at the ratios ~hown ln Table 3. After addin~
pentaethylenehe~amine to thi~ mixtur~ ~t a ratio of 1 mol for 1 ~one~ carboxyllc group ln the mixture, the mixture i~ heated 6~
up to 23~ C over 2 hours and then 1~ maintained at 230 to 2~0C
for 2 hour~ in ~2 gag atmo~phere to cause a reaction thereby to synthesize ~he hardener. In thi~ case, the ratlo between the monomeric fatty acid and the polymeri~ f~tty acid beore the ~xlng i~ determined ~ the ratio between ~onomerlc fa~ty acid amide and poly~eric fatty acid polyamlde in the hardener.
f~ repre~ents the volume ratio of filler to the ~u~ of re~ins.
iii) ~W~ repre~ents the ~olu~e ~ of water in the prepared material.
iv) The mean pore s~ze ~hows the mean diameter of pores in th~ porou~ material produced by the ~.ethod of the in~ention.
7) ~he contract~on r~ ~B the rate of ccntraction in the heigh~w~$e direction of a hardened body and i8 measured as follo~. A slurry is c~st in an FRP case havlng a size of 50 (length) ~ S0 (width) x S00 ~he~ght) nu~ ~nd i~ cured for 24 hours in ~ room of an air temperature controlled at 4SC under a dr~ing prevention ('che case is sealed). Af~er the 20 hardening, the porou~ material i~ taken out of the c~se, and the heightwise linear contraction rate ~ 9 measured from the cor.traction marks formed at 450mm interval in the FRP case and ~he marks left on the hardened porous material.
vi~ An oleic acid (NNA35 manufactured by Nippon Yushi 25 R.E~ used a3 the monomeric fatty ~lcid.
vii) VERSADYME V216 produced by E~enkel Japan is used as the polymer ic fatty acid .
viii) Pulverized ~llica ~and for gla85 produced 1n Seto 1~ -~, ....
i ~r=
. ,. ~ .
6~
district (manufactured by Nippo ~eisa Kogyo ~.K.) is used as the filler.
ix) ~PB15 manufacturæ by Yuka Cell Epo~y Company is u~ed as the bisphenol-type epoxy resln.
x) The slurry viscoslty is the vi6cosity of the slurry prepared in accordance with the metho~ of the invention, as measured ~y a B-type visco~eter.
As ~tated before~ the monomeric fatty ~cid as used in the method of the invention can include 10 to 22 carbon atoms per molecule. Fatty acids havlng carbon atom numbers exceeding 22 cannot be u~ed adequately b~cause of too high melting point, while the fatty acid~ having c~rbon atom numher~ less than 10 cause a problem that the amide compound produced through reaction with the ethyleneamine shows only a small surfactant effect sc that the slurry is made un~table to allow a ~arge contraction during ~he hardening.
Generally, iatty acids produced from animal and vegetable oils and fat~ are constituted by a nixture of mainly lauric acid, myri~tic acid, palmitic acid, stearic acid, oleic acid an~/or linolic acid, as well as other fatty acids having carbon atom number~ r~nging between 10 and 22. Theae mixed fatty acids from natural mater ials can be used for tbe monomeric fatty acid in this invention. Among the mixed fatty acids, those containiny oleic acid, linoleic acid and/or eruCic acid as the maior constituent are prefeable from the vie~points of the properties of the hardener o~tained and the contraction during the hardening.
.~ '' ~6~
Table 4 ~how~ the v~ ~cosl~ies ~t ~8C of harden~3r~ which were prep~red ~y mixlng Yariou~ monomeric atty a::~ds wlth the polyme~ic fatty Acid at mol~ ratlo of 50s50, ~ddlng thereto tetrae'chylenepentamine (~) of a ratio of 1 mol for one 5 carboxyl group e~isting in the mixed fatty acids, heating the mixture up ~o 230~C over 2 hour~ and then maintaining ~he ~ame at 230 to 240C ~or an ad~itional 2 hour~ to sbtain the hardener. The table al~o shows th~ ratlo of c~ntraction during the hardening ln the case where tbe ;?orous ~a~erlal was 10 produced b~ using the absve hardeners.
Tab le klnd of h~er Filler particl~ C~ltract~on fat~r ~ld (cps at 25C~ f ~ si2e ha~ening~
. ~ ~ __ ~
olelc acld 3500 1.~ 41 5 f~ > 30~ 0.13 l~ lc a~:ld 3000 ~ .. .. 0.,15 stearic acld ~el ., n ~ 0~17 palJIlltic acld g~l u ~ n 0. 49 rr~ tlc acld gel .. n u 0~31 ].aurlc acld 5500 . a _ 0~67 ~IL2~68~7 Note) i) The ~onomeric fat~y acld~ other than oleic acid ~re reagents produced by ~okyo Kasei K.~.
~1) Oleic acid ifi NNA35 manufactured by Nippon Yu~hi K.R.
iii) V~RSADY~E V216 produced by ~enkel Japan is used a~
the polymeric fatty acit3.
iv) "f~ repre~ents ~he volu~e ratio of filler to the sum of resin~. `
Y~ ~W" represents the volume % of water in the prepared material.
vi) Pulverized silica 6an~ for gla~s produced ln Seto distr~t (manufactured by Nippo Keisa Rogyo X.R.~ i8 used a9 the f~ller.
vii) EP815 ~anufactured by Yuka Cell Epoxy Gompany is UBed ~5 the bisphenol-type epo~y resin.
viil) The contraction rate is the rate of contraction in the he~ghtwlse dlrection of a hardened body and i8 ~;ea~ured a~
follows. A slurry is cast ln an FRP case h&ving a size of 50 20 (len~'ch) x 50 (wldth) x 500 (height) m~n and is cured for 24 hours in a room of an ~ir temperature controlled at 45C under A drying prevention (the case ls sealed). After the hardening, the porous mater ial ifi taken out of the case, and the heightwise llnear contraction rate i~ measured from the ~5 contraction ~arks ~ormed at 450~ interval ln the FRP case and the mark~ left on the hardened porous materlal~
~ 21 -~ .
~L24~
In the ethy~eneamine ~N-tC~C~-N~ a~ u6ed, the nunlber ~n~ ~s sele~ted ~o be 3 to S for the followlng reason.
Namely, B slurry ¢o~pr t sing the hardener prepared from th~
ethylenediamine or ~iethylene~riamine having the number "n~ of 1 or 2 e~hib~t~ a hi~h cohesion fo~ce, a8 well as a large contrac~ion; an~, therefore, the hardener cannot be u~ed pract~cally i~ the production of the porou~ materlal.
Triethylen~tetramine having ~he number ~n~ o~ 3 al80 ~ends to exllibit a ~o~ewhat large cohe~ion ana contraction. For th~se rea60ns, it i8 preferred to use tetraethylerlepentamine and pentaet~ylenehexamine having the nu~her~ ~n~ o~ 4 and 5, re~pectively.
As a ~atter of fac~, howe~er, it i6 diff~cult to co~merclally obtain ~ pure ~thyl~ne~ine having ~ ~lngle compo~ition. ~he ethyleneam~ne as used ~n the i~vent~on, therefor~, ~ay be such R ~ixture a~ the ~ommercially available goods.
In the mel:hod of the invention, ebe ratio between the amide compound of monomer~c ratty acid and the polymeric fatty acid polyamide in the hardener is ~elect~d ~referably to range between 90210 an~ 5:95 by welght. A8 wlll ~e ~een from Table~
2 and 3, a~ the content of the amide compound of the ~,onomeric f~tty acid iB increa~e~, the r~te of hardening contr~ction is lncrea~ed to impair the production of porou6 materlal at high dimensional precision. For this reason, the content of the ~id~ compound of monomeric f~tty ~cid ~hould be ~electe~ not to exceed 90~ This content i5 preferably up to 80~, when the product has a l~rge ~ize end complcatea fihape.
- 2~ -'7 On the oth~r hand, ;~he~s lt is degired to produce ~ porou~
m~terial havlng open pores o ~ pore dla~neter of abou~ 90 5 micron, the conterlt o~ the am~ de compound of the monomer ic fatty acid may be smaller ~:has~ 59~. ~owever, the production of S 'che p~rous material having mean pore size not smaller than 1.5 micron encoun~er~ ~ d~fficulty when ~he ~bove-mentioned content i~ smaller than 5%. For thi~ reason, the preerred lower limi t of the content of amide compound of monomer ic ~atty acid i~ selec'ced to be 5%.
In the method of the invention, the ~mide comp3und of monomeric fat'cy ~cid and the polymeric fatty ac~d polyamide are synthe~lzed w~th the addition of ethyleneamine at a ratio of about 0. 8 to about 2. 0 mol~ per 1 tone) carboxyl gLQUp.
When the ethyleneallline 1~ increaseB beyond 1.0 mol, the 31urry 15 tend~ to make a cohe~lon c~on raction during hardening~ el8 ~
re3ul'c of the pre~nce of free or ~eparated ethylene~mine. On the other h~n~, when t~e ethyleneamine i8 decreased below 1. 0 mol, the NH2 radicals at ~:>oth ends of the ethyleneam~ ne react with COO~. The slurry comprir~ing the hardener obtained showed 20 an increa ed tendency of cohe~ior~ contraction at the time of hardenins. ~he ethyleneamine content ranging between about 0. 8 an~l about 2. 0 mol~ per 1 ~one) carboxyl group, however, can produce a ~enerally acceptable result.
A reactive diluent SUCII as butyl ~lycidyl ether, allyl glycldyl ether, phenyl glycidyl ether, terti2ry carboxylic acid glycidyl ester, secondary pentyl phenol ~,onoglycidyl ether or the like may b~ added to the b~sph2nol-type epo~y re~in. As a r~sult of sdd~tion of suc~ a diluent, the ~lurry -- 23 ~
~2~6~
visco$1ty i5 decrea~ed and the pore si~e ln the porou~ product i8 increa~ed. A too la~e ~ount of ~dd~tion o~ such ~
diluent, howev~r, unde~irably causes ~ contraction during the hardenln~. The li~lit~ o Anlount of addition of the re~ctive diluent depends on the kind of the diluent. I~ is preferred to u~e the diluent of not more than 25 parts by ~eight for 100 part~ by weight of the bi6phenol-type epoxy resin.
In the method of the in~ention, lt i~ preferable to add a hsrdening pro~otion ayent, in order to incre~se the rate of 1~ h~rden1ng and, hence, to enhance the strength of the hardened body. Vsually, ~ubstances such as phenol, triethanola~ine, hexamethylenetetramine, benzyldimethylamine, tri dimethyl-amin~ethylphe~ol or the like ~re u~able as the hardening promotion a~ent in combLnation wit~ a polyamid~ hardener~ In 15 the m~thod of the invention, a super~or effect i~ obtained p~rtlcul~rly by the use of a har~ening promotion ~gent of a tertiary amine of aromatic group such a3 b~nzyldimethylamin~, trl5dlmethylaminomethylphenol and 80 forth. From the viewpoint of the strength of the hardened body, ~t is 'preferred to u~e a hardening promotor in about 7 to 15 parts by weight for 100 parts by ~eight of the hardener.
An ex&~ple of the method of the invention is ~hown below only for the illustratlng purpose.
Example 796g of ~ polymeric fatty acid ( VERSADYME V216, producea by IJenkel Japan), 15919 of oleic acid ~NNA 35 produced by Nippon Yu3hi ~.K.3 and 16139 of tetraethylenepentz~ine ~Z~ 7 (produced by Seitetsu Kagaku K.K.) were put together in a stainless steel reaction vessel having a volume of 5~. The mixture was heated from the normal temperature up to 230C in 2 hours while continuing stirring under a supply of N2 gas and then held at 230 to 240C for 2 hours to synthesize 3790g of hardener.
Thenr 647.9g of bisphenol-type epoxy resin (EP815 produced by Yuka Epoxy K~K.), 218.2g of the above-mentioned hardener, 17.7g of a hardening promotion agent TAP (trademark;
made by Kayaku Noulli K.K.), 2803g of silica sand powder of particle size of 5 microns ~30~ and 1348g of wa~er were put in a a stainless steel vessel having no lid. These materials were vigorously stirred or 10 minutes to make a slurry.
This slurry was cast in an FRP case having a size of 50 (length) x 50 (width) x 500 (height) mm and was cured for 24 hours in a room of an air ~emperature controlled at 45C under a drying prevention ~the case was sealed). Ater the hardening, the porous material was taken out of the case, and the heightwise linear contraction rate was measured from the contraction marks formed at 450mm interval in the FRP case and the marks left on the hardened porous material. The contraction rate thus measured was 0.18%. This hardened porous material was then dried and the pore size distribution was measured by means of a mercury press-feeding type porosimeter. This hardened porous material showed a mean pore size of 4.0 microns.
Test pieces for measurement of bending strength were molded from this slurry. The bending strength in wet cond~tion waB ~ne~ured aft~r a drylng prevention harderllng of ~he ca3~ sll~rry at ~5C~c for 24 bour~ The mean bendlng strengt31 was 70 Rg~cm2. Th~ ~ried test pieCeB ater mea~urement of the wet bendirlg strength ~howed an apparent 5 porosity of 4196.
2~ -
Claims (7)
1. A method of producing a porous material having open pores, comprising the steps of preparing a slurry from a mixture comprising a bisphenol-type epoxy resin, a hardener, a filler and water, casting said slurry in a water-impermeable mold, hardening said slurry while it contains the water and dehydrating the hardened body, wherein said hardener is either (a) a mixture of (i) an amide compound which is obtained through a reaction between a monomeric fatty acid having 10 to 22 carbon atoms per molecule and an ethyleneamine expressed by the formula of H2N-(CH2-CH2-NH)n-H where "n" is 3 to 5, and (ii) a polymeric fatty acid polyamide obtained through a reaction of a polymeric fatty acid and said ethyleneamine, or (b) a reaction mixture obtained by mixing reaction of said monomeric fatty acid, said polymeric fatty acid and said ethyleneamine, said amide compound of said monomeric fatty acid, and polymeric fatty acid polyamide and said reaction mixture being formed by reactions which are conducted by adding about 0.8 to about 2.0 moles of ethyleneamine for 1 (one) carboxylic group in said fatty acid, the ratio between said amide compound of said monomeric fatty acid and said polymeric fatty acid polyamide ranging between 90:10 and 5:95 by weight.
2. A method of producing a porous material according to claim 1, wherein said monomeric fatty acid is selected from the group consisting of oleic acid, linoleic acid and erucic acid.
3. A method of producing a porous material according to claims 1 or 2, wherein said ethylene-amine is constituted mainly by tetraethylenepentamine and/or pentaethylenehexamine.
4. A method of producing a porous material according to claim 1, wherein said mixture for producing a slurry further contains a reactive diluent and/or a hardening promotion agent.
5. A method of producing a porous material according to claim 4, wherein said hardening promotion agent is selected from tertiary amines containing an aromatic group.
6. A method of producing a porous material according to claim 5, wherein said hardening promotion agent is benzyldimethylamine or trisdimethylaminomethyl-phenol.
7. A porous material having a mean pore size ranging between about 0.5 and about 10 microns, which is produced in accordance with a method as defined in claims 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000444929A CA1246817A (en) | 1984-01-09 | 1984-01-09 | Hardening slurry of eopxy resin and amide compound of ethylene amine ad fatty acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000444929A CA1246817A (en) | 1984-01-09 | 1984-01-09 | Hardening slurry of eopxy resin and amide compound of ethylene amine ad fatty acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1246817A true CA1246817A (en) | 1988-12-20 |
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ID=4126904
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000444929A Expired CA1246817A (en) | 1984-01-09 | 1984-01-09 | Hardening slurry of eopxy resin and amide compound of ethylene amine ad fatty acid |
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| Country | Link |
|---|---|
| CA (1) | CA1246817A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006053783A1 (en) * | 2004-11-19 | 2006-05-26 | Glaxo Group Limited | Amide and peptide derivatives of tetraalkylenepentamines as transfection agents |
-
1984
- 1984-01-09 CA CA000444929A patent/CA1246817A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006053783A1 (en) * | 2004-11-19 | 2006-05-26 | Glaxo Group Limited | Amide and peptide derivatives of tetraalkylenepentamines as transfection agents |
| JP2008520610A (en) * | 2004-11-19 | 2008-06-19 | グラクソ グループ リミテッド | Amide and peptide derivatives of tetraalkylenepentamine as transfection agents |
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