CA2218104A1 - Low-viscosity polyurethane prepolymer - Google Patents
Low-viscosity polyurethane prepolymer Download PDFInfo
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- CA2218104A1 CA2218104A1 CA002218104A CA2218104A CA2218104A1 CA 2218104 A1 CA2218104 A1 CA 2218104A1 CA 002218104 A CA002218104 A CA 002218104A CA 2218104 A CA2218104 A CA 2218104A CA 2218104 A1 CA2218104 A1 CA 2218104A1
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- oxazolidine
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
- C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6461—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/26—Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/28—Non-macromolecular organic substances
Abstract
The invention concerns a low-viscosity polyurethane prepolymer consisting of: a) organic polyisocyanates; b) polyols selected from the group comprising hydroxypolyester polyols, hydroxylpolyetherpolyols and their mixed polyols; c) organic natural substances with at least one hydroxyl group, a carboxyl group, an ester group or a conjugatable double bond; d) phosphoric acid ester as marker; d) viscosity stabilizers; and f) acceleration catalysts for hardening the prepolymer selected from the group comprising organic and organometallic amines.
Description
LOW VIS~OSIIY POLYI~RETEk~E PREPOLY~IER ~OHPOSI~IO~i T~e i~ve~tio~ ~elates to a ~ow viscosity polyuretha~e prepclymer compQSi~iOn~
Polyuretha~e prepoly~ers are e~g. used as edge ~nd surf ace fi~ishi~g -age~ts for materials~ part~ulz~ly those havi~g a oertal~ ~at~ral da~pnes~ or ab$orb molsture fra~ t~e enviro~ent~ Typic~l exzmples are mould~nss, boar~s7 etc. made from w~od, ~ooden ma~erials or other natural ~brous ma~-erials. In order tc avoid solvent ~aste a~d e~ssions increasi~g use is bein~ made of polymer systems cont~tuiug li~tle or ~o solTJen~. Such poly-~ers are ge~erally kno~Tn aud are described ~n the l~terature.
O~e of the vital prereq~isites for the seall~ or ~ishin~ (also Prim~n~ or grou~ding) i~ a~ ~dequately good ~Te~ab~llty and Pe~etr~tabiilty via the pores into the substrate ~ the par~lcul~r ma~erlal. AS a functio~ of the a~m and p~rpose of t~e sealing or finish~ng, a polymer viscosity of 50 to 120 mPas ~e 20~~ ~s expected. H~therto use has been ~ade of one-component pol~rethane ~o~ g masses ~DE 33 39 683 Al? EP 0 076 956 Al, US 5 126 4~1 Cl)7 ~h1oh are diluted dow~ ~a the desired ~-lsoosity with s~ghtly polar to ~polar solve~uts, e.~ a~lphatic es~ers, such as 571ycOl or ethyl acetate a~d arom~t~c ~y~rocar~ons, such as tolue~le, ~ylene, etC. It is also known (E~ 0 0~7 195 Al) ~o ~nc~rporate l~to a prepolymer a ~on-vol~ile ~oLve~, na2ely a Cpecif~c l~ctone, in order to red~c~ the vlscosity~
sol~ds COhce~tration of 30 to 7~, mAi~ly 60Z is sought.
Such one-co~ponent polyuIethane adhesives cont~n ~er~inal ~CO groups and a~e gene~ally called isocyanztopolyurethanes ~ Such isocyana~opo~yu~ethanes, also E~now~ as prepolymers or preadducts, can be prep~ed ~th a s~oLchlo-metric polyisocyanate e~cess, startlng ~oth ~ram lo~- ahd also hi h molecular hydro~yl polyeste~ polyol~, as well as the correspondl~ hydroxyl polyether p~lyols. The poly~ socyanate excess a~d f~nctlonality o~ ~he star~in~ ~at-erlals mus~ be such th2t the ~ealing o~ f~nls~;ng of the material edges or surfaces leads to a s~tlsf~ctory strength, durab~lity and elastlclty and i~
particular an adequate stora~e ~ability o~ at lea~t s~x months al e.g. Z0~C, w~hilst still ensur~g a rapid curi~g of the isocyan~opolyuret~ane followi~g applicztio~ 3igadva~tages ~lth ~c~ solvent-diluted Lsocya~te polyure~h-ane prepolymers are the unpleasant~ smell, the toxicolo~ical ob~e~tio~-abillty, the solve~t e~issions, the curi~g reaceio~ delayed by the solve~ts Amended sheet ~k~o~ and proble~ti~l e.~. in the edge sealing of ehipboards by solvent retention ~ the wood materi~l~ a~d the r~latively high e~ergy ~hich ~ust be used in orde~ t~ dry znd further process such ~inished ch~pboards w~ln an e~ouomlc time period. ~he ¢u~ing reaceion takes pla~e in t~o stages, on the one ha~d by evapor2ting t~e sol~e~t and on t~e other by t~e action of at~os-pheric humidity~ ~he curi~ speed is essentially depe~den~ on the mo~sture coLtent of the m~terial ~d the ambient air. ~2 is produced as a byproduct and as the end p~oduct ~re obtained crossli~ed polvurethane ~iurets. Fl~-ally, the t~us finishet surfaces ~st be workable, e. g. ~y gr~nding, polis~ing, etc.
~he proble~ of the inve~tion i~ to for~ulate a Co~positiOn for a solve~t-free, lo~- vl~cosity ~50 to 120 m~asl2a~C~, maisture-curln~ isocyanatopoly-uretha~e prepol~mer, which has an opti~u~ ~e~ting and penetration behaviour with respect to wood and ~ther porous materials with a rela~ively short curing time and i~p~oved ~t~rage st~bility. It ts a ~urther pr~blem of the in~ention ~o impro~e the ~ech~i~ai characteristies of the thus ~reated ~a~er~als, such as the sh~l~kage a~d swelling cha~acterlsti~s under the actio~ of moisture, transverse teusile, compressive, be~ding ~d tenslle st~ength, ~hi~st creatîng an ad~esive ~ase for adhesives, coatlng ma~erlals, etc. o~ ~e thus t~ea~ed ~aterials. ~s a f~ctlon of the lntended use, the s~face ~ished ~t~ the prepo~ymer ~ust be -water diffusion-tl~ht or wa~er dif ~usibLe.
According to the inventlon, this prob~em l$ solved by a polyurethane p~e-polymer ~ompos~tio~ ~lth the ~ollow~n~ formulation a polyuret~ane prepoly~er of a) organlc polylsocya~ates.
b) polyols from the group of hydroxyl polyester polyols, hydroxyl polyether pol~ols or t~ei~ m~xed polyo~s, s~ch as hydroxyl polyester polyether polyol, c) orga~c natural subs~ances wi~4 at least one hydroxyl group, a carboxyl group, an e . te~ group or at least o~e conjugatable double band7 and as ~urther compone~ts d~ phosph~tes as marklng agents, Amended she et e) v~cosity sta~ilizers~
~) accelera~ng ca~alysts for ~u~ing the prepolymer from the ~oup of or~a~iC a~d metallorganic ~ml~es~
A~ ~olyiso~yanates accord~ng to feature a~ are ~n partieular sui~able aliphatic, cyclozliphatic and ~rcm~tic dii~ocyan~tes. ~re~erence is ~iven to tke use of those of genera' formula X(~C0)2, ~n ~hich X ~ta~ds for a~
allphatic hydroca~bon radical with 4 to ~ C-atoms ~ cycloalip~atic hydro-carbo~ radical w~t4 6 to 15 C-ato~ or an aro~atic ~y~rocarbon ~th 6 to 15 G-2so~s .
Pre~erred aromatic~ ~liphatic or cyclo~llphatic diisocy~na~es are 2,4 and 2,~-toluyle~e dilsocyana~es or their isomer ~ixtures, 4,4'-d~phe~yl methane d~lsocyanate and 2,4'-diphcnyl methane diisocyanate~ tetra~e~yl xylylene, di~socy~te, isophorone dlisocYanate, 1~6-he~ane di~socyanate, ~1Z~4 and Z,4,~-trl~ethyl he~e~ylene di-socy~nate, ~yclohexane diisocyanate.
methyl ~yclohe~ane d~isoc~n~te, preferably 4,4'-dip~enyl me~hane diisocy-anate wl~h up to 80h 2~4'-diphenyl methane d~isocyanate Such a ~lxture ca~ have a density o~ 1.0~ to 1.20 ~/cm . Prefere~ce ls ~iven to che use of a~ lso~er ~lxture o~ diphenyl methane-4,L'-dl~socyanate a~d dlphenyl me~ha~e-Z, 4~ -~iisocyanate wt th a free ~1~0 content of approxi~ately 30,0 .
As polyols according to feature b~ ~re suitable ~o~ or high molecul~r weight polyester ~dlor polyether polyols of ~olecul~r ~eight 200 to 1000. For specif~c applications po~yether es~er or polyecter ether polyols have proved satisfactory to a li~ited egte~t and are obtalne~ by the alkox~latio~ of carbo~ylic acids or Polyesters or by the c~dens~tlo~ of polye~hers with polyfu~ctional carboxylic acl~s. ~o~e~er, s~id formul~tions only m~intzin t~eir low YiSCosit~ state for a rela~i~-ely short time (4~ ~o 1~4 hours), ~o t~at ~peedy proees~i~g is "ecessary. P~eference is given to polyols ~ith molecular weight betwee~ 700 and 3000. They are prepared by reacting epoxides ~h alcohols. ~lcohcls w~hich can be used are e.g. ethylene glycol, diethy~ene glycol, propyle~e glycol, g~ycerol, trl~ethyl propane ~nd pentae~ ritol. ~s epoxides are suitabie e.g. e~y}ene ox~de, propylene ~xlde, ~ut~l o~d~, sty~ene o~lde, cyclohe~ane oxide or epichlorohydr~n.
~e~ra~ydrofuran c~ ~e used i~ place of an epo~ide.
A~ended sheet . . . _ . _ _ . . , , _ 3 (A) Besides polyols, according to feature c~ use is ~ade of ~atural substa~ces w~th a~ leas~ one hyd~oxide ~roup, a carbo~yl group, an escer group or a ¢onjugat~41e dou41e bond, such as e.~. rosins a d castcr oil. P~efere~ce ls given to ros1ns ~i~h a~ least one methyl ester gr~up wlth 1 to 5 conjugat-able double bords, ~hich can be used durl~g Che additio~ reactio~. The acld nu~ber of suc~ compo~ds is ldeally bèt~ee~ 0.5 a~d 50, prefe~ably bet~een 2 and 20 mg ~OH/g.
~e~ded sheet As ~arklng ~gents accord~ng to feature d~ hich prevent a sudden viscosl~y ri~e durlng t~e Polyaddi~ion reaction o~ diisocyanate ~mth the polyhydroxyl compound to the lsocya atopoly~retha~e prepolymer, but do not i~alr ~he polyaddltion reaction, use is made of es~ers of phosp~o~ic 2cid, preferably h~vl~g a refraetive index of 1400 to 1~20 and a bolll~g po~n~ of 75 to 85~C
a~ 5 mbar. ~rlet~yl phosp~ate i5 partlcularly effeotiYe. ~hese addltives ~o ~ot prevent t~e polyaddition re~ion and are characterized by thei~
flame-retard~ng ~aracteristics.
Fa~ t~e viscoslty stabilization of the prepolymer (~eature e), ~an be used on the one hand bif~nctional, aro~tic dilsocyanates, p~eferzbly Z,4 and 2,6-toluylene dlisocyanates. a~ well as thelr lsomer mixtures and on the other addlt~ves of organic compounds ~uch a~ 4-methyl dloxola~-(2)-one o~
n-al~yl be~ze~e, ~hich co~tribute to v~scos~ty ~tabil~zatlon for several months.
To accelerate the ~eaction of the d- lsoeyanates lt ls p~ssible to use co~-ventioual, ~O~L ca~a~ysts ~fe~ture .~, suc~ as dibu~yl till dilau~ate~ tin-II-o~toate or ~mines of the gcneral emp~rical form~la C12~24~203 or those of t~e gene~al empiri~l fonmula C5~14N2 or C6~10N2. ~refera~ly use ls m~de of n~etallic a~lne eurin~ a~e~s. namely o~ a mlxture o~ 60 ~o ~0~ of the hî~her valence and 4~ to lOX of the lower vale4ce ammne. Good resul~s have llso 4~e~ obtzi~ed wlth ~ixtures of the aforemen~ioned me~alorganic com-pounds 2nd organic ~mines.
A fi~al viscoslty between 2S a~d 70 m~as is obtai~ed ~lt~ the aforeme~ioned ~ompo~l~io~. ~u m2~y other aPPlications, partlcularly ~or the appl~ca~ion, coat~, e~¢., a higher final viscosity is desi~ed~ I~ order to illcre~se the ~is~oslty e.g. to 120 m~asl~0~C, i~ is possible to bi~d isocya~ate sem~-prepolymers ~ith a free ~C0 content of 5 to 20 and preferably 7 to 12~ ln the polyaddltlo~ reacticn. ~he viscositY re~i~s stable for 6 to 18 month~
w~th a m~ di~e~enoe o~ 10~.
Ad~-antageously flame-re~rding agent~ ~re added to ~he prepoly~er and ~s .
such have proved p~rticula~ly satisfactory p~o~phoric acld polyols ~ith a phosp~orus ~raction of 5 to 3~ (m~m~, prefer2bly 10 to 20 ~mlm~.
_ . . . . . .... . . . _ _ _ _ _ ... . . ... . _ _ Il order to reduce o~ preve~t moisture a'osorptlon, preferably ~ols~ure trap-p-ng agen~s sre added, Mo~oeyclic, bifunctional o~azolldine has proved particularly ~uitable. Oxazolidi~e also ser~eS as an a~tifoa~1n~ agent and as such h~s g~eat signif1cance withi~ the scope of the ~rese~t i~ventio~.
lt prevents ~he fo~ f~rmatio~ ~hich i~ ot~eFwlse observed on ~pply~ng P~R
prepoly~ers ~aking ~t necessary ~o scraPe the appl7' ca~ion several ~i~es, w~ich leads to a correspo~ m g mater1al loss. ~rough the suppresslon of foam format~on and co~sequently bubble formatio~, the oxazo~ldi~7e simul-taneously has a flame-retard~g a~ion Co~vent1o~al polyur~~~ane prePol~er5 are d~ff1cult to ~-~r~ ~ollo~ng curin~, because ~elr el 2~tic~ is e~cessive and the work7ng ~ools, e.g. a~rasive paper~, gr~ding ~-heels or Polishing devices ve~y rapldly become clogged and ineffectlve. Accordin~ to the inve~tio~ th~s is avoided i~ tna~ metal-organ~c ~alts are ~d~ed to t~e prepolYmer, nzmely tho~e of ~ar.boxylic acids o~ empirical formula C~0~0~2 to C22H~4~2' P 18 ~6 2 ~e lo~ Viscosl;y polyurethane ~o~ul~tions accordi~g ~o the l~vention are s.l~able ~0t o~ly for the fi~ls~ or ~ealing o~ ~orous sur~a~e~ ~ut al~o 25 adhe~ives, as reactlve ~hinners or dllue~ts for t~e most ~aried Poly-ure~hane ~ompo~nds or ~orm~la~icns and as pri~ers far dye~, v~nLshes, lacq~ers, plastics a~d ~ther materl~ls.
hxample~
The followil~ ~eaniugs are attributed to the a~breviations ~sed ln the ~ollo~ing examples~
p~T 4,4' or ~4'-diphenyl melhane dlisocyana~e P~ polyetherpoLyol with a molecul~r ~eight of 700 to 3C00 ~atural resan ~ased on rosin e~ter of acld nu~ber 5 to ~ mg ~OH/g KA~ Am~ne acceler~tor MARX Phosphate a~ ~ar~ing agent STAB1 ~oluylene diiso~yanate ~DI) as sta~ilizer STAB2 ~-a}kyl benze~e ~s stabillzer SEMI Polyure~hane semiPrePol}~er ~ith a visco~lty of 70G0 to 1200 ~Pas as a viscos~ty regnl2~Qr far sett~g a hi~her vlscoslty.
Exa~ple ~ ~lo~ viscosi~y P~R prepo,y~er ~rth a ~iscosity ~f 50 mPas/20~C) MDI 5~A~00 P~D 16.620 ~
N~ 8.310 g ~AT 0~008 g MA~Y~ 8.31~ g SL~B1 0.2~ g AB 2 8.21~ g ~he ~I is placed ~ a do~le-~alled, rool2ble reactor, the ra~ material-te~perature ~ot exceedi~g 22~C or droppin$ bela~- 18~C In a premlxi~g con-tainer premlxl~g takes plaee of the de~atere~ ~ED (~-ate~ c~nten~ m~x 500 ppm~
and the ~ 150 de~atered to ~he same ~imum w~ter content) unt11 a st~eak-free, homogeneous polyol m~ss is obtai~ed. The polyol ~ass, which should be ~n ~he s~e temperature ran~e as t~e ~P~ is t~en added slo~ly, acco~pa~ed ~y const2nt ~tirring a~d te~perature co~trol tc the isocya~te. The mlxl~g reactor is advantageously e~acuatèd to approximately 150 m~ar. After m~ing the polyol Lraction into the isoc~anate~ ehe acceler~tor is a~ ed.
As soo~ as a~ exothér2ic te~perature of max 35~~ is reached, the ~ar~ng ~e~t is added to the wi~ure. wsich is ~ooled to belo~- 2~'C. I~mediately znd wh~lst e~clud~ng at~osp~erlc h~ dity, the ~tab~liz2r 1 CTDI) is added, ~xed in in stre~k-free ~an~er a~d l~m~ tely subseque~tly 2ixed with the st~bl I ~ 7-~r 2 a~d thoroughly ~tirred ~r at lea t 5 to 10 minutes. The vl~o~ity ~o~trol ~ust ~ive 3S t~ 3~ mPas/20~C and a sueoessful reaction ls reve~led by a pale yellow, stre~k--'ree, flake-f~ee, transpare~t soiution.
~he ~hus o~ai~ed ~R prepolymer is le~t to s~an~ 'ar 2h h, ~hllst ex~lud~ng a~mosphexic humidi~ and at a storage ~e~perature of approxi~tely 20~C.
~he subseque~t ~lseos~ty meaSure~eht must give apFro~mately 50 ~Pas/20~C.
E~ample 2 ~DI 46.000 ~
P~D13 150 g 6.~70 g ~T 0 0~6 g ~ARK 7.670 ~I 19.755 ~ABZ 6.570 S~AB1 ~.21~ ~
I~ add~tion to example 1, 2n ~ socyznate semipolymer (SEMI) is added toincrease the f~nal vlscosltv. As in exa~ple 1, the MbI ls placed ~ a double-~alled, coolable re~eor and the r~w ~2~erial tempera~ure must ~at d~op below 18~C and must ~ot axceed ~2~C. I~ a pre~ixing container pre-mix~g takes pl~e o~ ~he dewatered PE~ ~ater coRte~t max 500 ppm) and the lso de~atered ~o t~e same ~zter co~tent) u~ll a s~reak-free, homogen-eolls polyol mass ~s obtai~ed. ~ubsequently the pclyol ~as~ is slo~Tly added to the isocyana~e accompa2led by con~t~nt s~irri~g and maint~in~ the afore~entioued ranga. ~d-vTantageously the mi~ing reactor is evacua~ed ~o zpproxl~ately 150 ~a~. As soo~ as the po~yo1 fraction is intermlxed ~n the isocyanaee, the acceler~tor is added, ~ut only i~ a m~ nm exothermlc state of 35~C is ~ot reached wlt~l~ 20 minutes. Other~ise the accelerator quan-~ity ca~ be added. If the accelerator suppl~ lead~ to the exothe~mlc temp~
erature of approxl~ately 35~~ ediate mlxin~ with the m~king z~ent ta~es place ~nd t~e mlxture is cooled to below 2~~C. Accompanled by slaw stirring~
the semipoly~er wit~ a viscositY o~ 7000 to 12000 ~Past20~~l prefera~ly 10000 mPas +/- 5~0 mP~ ~S stirred in. As soo~ as a mLxture v~scosity rise is Lndicated by the process ~iscosimeter installed in or o~ the reac~o~.
i~me~tely mas~ing take~ place w~th the stabilizer 2. On re~ing a homo-ge~eou6 ~lx~ure ~he T~ can be ~dded, ~h~lst e~cludlng a~mospheric ~u~idlty.
A~ter 10 min -~irri~g a visco~y C~sta~cY o~ approxl~ately 120 mPas~20~G
is re~c~ed. ~ny vis~o~ity correctlo~s a~e performed after 24 h. I~ the cas~ o~ inadequate viscosity ret~cke~n~ can ~a~e place ~t4 ~he se~i-polymer, whereas lf the ~iSCosLty is too high the mlxthre ls diluted a~ i~
example 1. The correc~io~s sho~ld ~ot ~e more t~an 5 ~t.~ ~ased o~ ~e ~otal ~xture, ~eeause other~se the vmscosity stabilitv decreas~s.
~isCosit~ as a function of tl~e at a tes~ te~pe~ature of 20~C:
~e~t tlme 2xample i Exa2ple 2 l~medi~tely after p~eparation 30 ~0 AIter 3h 33 120 After 5 h 37 120 After 24 h 50 120 After 43 h 50 120 After 144 h 50 123 ~fter 432 h 50 125 Af~e~ ~5~0 h SS 125 A~ter 10000 h 55 13~
0~ c~ecklng the cu~i~g time the fol~o~g results were o~ e~ compared wi~h a one-compone4t, msistUre-curl~ ~ol~lreth2ne prepolymer di~uted ~t~
solve2t ~toluene) wi~ a s~milz~ accele~aeion and a solids co~tent of ~0 (herei~after called LM-P~R):
Ex~ple 1: Af~er 12 to 24 h 80~ of the ~i~al s~reng.h and a~er 72 h 10~ of the fi~al strength is rea~hed. ~o~ever, the pro~nct ca~ be mecha~
i~ally further worked after 1~ to 24 1 (ac a fu~ctiou OL the atmospherlc and ~aterlal moisture co~ten~, ~s ~e~ as tne ProcessLng temperature~, e.g. by grlnd~g, calibrating~ ~rl~mi~g the sealed chipboard or coating ~he fi~ished materlal surface.
~X-~R; Only a~ter 18 days ls 80~ of the final stren~th and after Z8 days lOOX of the f~nal strength reached. The storage te~perature i~ ~ 20~, emp~rica~ly 35 to 40~C.
A ~ate~ia~, such as e.~. ~h~pbcards with a bul~ densi~y bet~een 400 and _ 9 _ 800 kg/m3, directly after the c~ring of the polyureth~e prepolyme~ accord-ing to example 1 on ~he chipbo~rd ~ave neit~er a swel~ing nor a shri~kage effect. Thus~ tnere is no ~eed to su~sequen~ly callbrate such a chipboard.
A~ opposed to this, a ~ s~stem ~as described herein~efore~ has ~ ~hrlnk-age effect of on average Z~ o~ the board thick~ess. In addit~on~ a co~mer-~i~lly available ~ter glass ~yste~ has a swell~ng effec~ of on avera~e 11~. Such baards must be reworked, ~-h~ch Lnvolves additional costs.
Example 3 M~I 60.940 pb~ (p2rts b~ weight) PEP 14.320 NE 5.730 FS 1.430 0.010 ~AR~ 8.Q50 ST~Bl 0.2~0 ST~B3 0~40Q
S~AB~ 7.160 FF L.720 Total lOQ.OOQ pb~- (parts ~ elght~
~he followlng meanlngs are used:
FS fireproofi~g a~ent phospho~us pol~ol STAB~ fiame-~etarding stabi~izer ~polyslloxane) FF ~ois~ure trappi~g agen~ and antifoam~ng age~t MCS carboxylîc acid metal salt ~he sa~e procedure as i~ e~ample 1 i adop~ea, but the FS is siowly added, aceompanled by st~rr~n~, at a low speed o~ the polyol mass (compr~si~g PE~
and ~H), in s~ch a way that ~o streaks are ~ormed. If the ~S is added too rapidly, a2 nndesired ir~compatibllity with the rem~ining polyol mass ~hust be e~p~cted. In t~s case the polyQl m~ture must be reprePared.
~he STAB3 is externally prem1~ed ~n th~ STAB2 and together, following the addition of STABl and after a correspond~T stirring tlme are subseouently mixed. After a sti~ring tl~e of 5 to 10 m~nutes, the FF is supplied, ~hil~ e~cludi~ atmospheric h~mi dl~T~ and o~ce a~aln ~tlrring e~kes place at z ~lo~ speed for min 10 m~nu~es. It must be ens~red tha~
excessi~ely vigorous stirri~g does not ~ntroduce bubbles.
The same process procedure ~lth the parameters af e~ample 2 leads eo a hlghe~ ~inal viscosity.
E~a~le 4 prepol;mer accordl~g to example 1 98 pbw ~CS 2 pb~T
Total 100 p~
MCS ~n ~he form of a ~i~e po~der, at the e~ of the pro~ess is dispersed ln a hlgh-speed dissol~er until a lump-free, ~omo~eneous, f~nely dispersed mlx~ure is obtai~ed, w~h ~as a mil~y colo~r.
~e prepoLymer obtained ca~ be mechanica~Ly re~-orked extremely ~ell, e.g. by gri~din8 or polishin~.
~he same proces~ procedure ~ith the para~eters of e~amples 2 and 4 leads to a prepolymer with a~ l~creased flnal ~iscosity.
Polyuretha~e prepoly~ers are e~g. used as edge ~nd surf ace fi~ishi~g -age~ts for materials~ part~ulz~ly those havi~g a oertal~ ~at~ral da~pnes~ or ab$orb molsture fra~ t~e enviro~ent~ Typic~l exzmples are mould~nss, boar~s7 etc. made from w~od, ~ooden ma~erials or other natural ~brous ma~-erials. In order tc avoid solvent ~aste a~d e~ssions increasi~g use is bein~ made of polymer systems cont~tuiug li~tle or ~o solTJen~. Such poly-~ers are ge~erally kno~Tn aud are described ~n the l~terature.
O~e of the vital prereq~isites for the seall~ or ~ishin~ (also Prim~n~ or grou~ding) i~ a~ ~dequately good ~Te~ab~llty and Pe~etr~tabiilty via the pores into the substrate ~ the par~lcul~r ma~erlal. AS a functio~ of the a~m and p~rpose of t~e sealing or finish~ng, a polymer viscosity of 50 to 120 mPas ~e 20~~ ~s expected. H~therto use has been ~ade of one-component pol~rethane ~o~ g masses ~DE 33 39 683 Al? EP 0 076 956 Al, US 5 126 4~1 Cl)7 ~h1oh are diluted dow~ ~a the desired ~-lsoosity with s~ghtly polar to ~polar solve~uts, e.~ a~lphatic es~ers, such as 571ycOl or ethyl acetate a~d arom~t~c ~y~rocar~ons, such as tolue~le, ~ylene, etC. It is also known (E~ 0 0~7 195 Al) ~o ~nc~rporate l~to a prepolymer a ~on-vol~ile ~oLve~, na2ely a Cpecif~c l~ctone, in order to red~c~ the vlscosity~
sol~ds COhce~tration of 30 to 7~, mAi~ly 60Z is sought.
Such one-co~ponent polyuIethane adhesives cont~n ~er~inal ~CO groups and a~e gene~ally called isocyanztopolyurethanes ~ Such isocyana~opo~yu~ethanes, also E~now~ as prepolymers or preadducts, can be prep~ed ~th a s~oLchlo-metric polyisocyanate e~cess, startlng ~oth ~ram lo~- ahd also hi h molecular hydro~yl polyeste~ polyol~, as well as the correspondl~ hydroxyl polyether p~lyols. The poly~ socyanate excess a~d f~nctlonality o~ ~he star~in~ ~at-erlals mus~ be such th2t the ~ealing o~ f~nls~;ng of the material edges or surfaces leads to a s~tlsf~ctory strength, durab~lity and elastlclty and i~
particular an adequate stora~e ~ability o~ at lea~t s~x months al e.g. Z0~C, w~hilst still ensur~g a rapid curi~g of the isocyan~opolyuret~ane followi~g applicztio~ 3igadva~tages ~lth ~c~ solvent-diluted Lsocya~te polyure~h-ane prepolymers are the unpleasant~ smell, the toxicolo~ical ob~e~tio~-abillty, the solve~t e~issions, the curi~g reaceio~ delayed by the solve~ts Amended sheet ~k~o~ and proble~ti~l e.~. in the edge sealing of ehipboards by solvent retention ~ the wood materi~l~ a~d the r~latively high e~ergy ~hich ~ust be used in orde~ t~ dry znd further process such ~inished ch~pboards w~ln an e~ouomlc time period. ~he ¢u~ing reaceion takes pla~e in t~o stages, on the one ha~d by evapor2ting t~e sol~e~t and on t~e other by t~e action of at~os-pheric humidity~ ~he curi~ speed is essentially depe~den~ on the mo~sture coLtent of the m~terial ~d the ambient air. ~2 is produced as a byproduct and as the end p~oduct ~re obtained crossli~ed polvurethane ~iurets. Fl~-ally, the t~us finishet surfaces ~st be workable, e. g. ~y gr~nding, polis~ing, etc.
~he proble~ of the inve~tion i~ to for~ulate a Co~positiOn for a solve~t-free, lo~- vl~cosity ~50 to 120 m~asl2a~C~, maisture-curln~ isocyanatopoly-uretha~e prepol~mer, which has an opti~u~ ~e~ting and penetration behaviour with respect to wood and ~ther porous materials with a rela~ively short curing time and i~p~oved ~t~rage st~bility. It ts a ~urther pr~blem of the in~ention ~o impro~e the ~ech~i~ai characteristies of the thus ~reated ~a~er~als, such as the sh~l~kage a~d swelling cha~acterlsti~s under the actio~ of moisture, transverse teusile, compressive, be~ding ~d tenslle st~ength, ~hi~st creatîng an ad~esive ~ase for adhesives, coatlng ma~erlals, etc. o~ ~e thus t~ea~ed ~aterials. ~s a f~ctlon of the lntended use, the s~face ~ished ~t~ the prepo~ymer ~ust be -water diffusion-tl~ht or wa~er dif ~usibLe.
According to the inventlon, this prob~em l$ solved by a polyurethane p~e-polymer ~ompos~tio~ ~lth the ~ollow~n~ formulation a polyuret~ane prepoly~er of a) organlc polylsocya~ates.
b) polyols from the group of hydroxyl polyester polyols, hydroxyl polyether pol~ols or t~ei~ m~xed polyo~s, s~ch as hydroxyl polyester polyether polyol, c) orga~c natural subs~ances wi~4 at least one hydroxyl group, a carboxyl group, an e . te~ group or at least o~e conjugatable double band7 and as ~urther compone~ts d~ phosph~tes as marklng agents, Amended she et e) v~cosity sta~ilizers~
~) accelera~ng ca~alysts for ~u~ing the prepolymer from the ~oup of or~a~iC a~d metallorganic ~ml~es~
A~ ~olyiso~yanates accord~ng to feature a~ are ~n partieular sui~able aliphatic, cyclozliphatic and ~rcm~tic dii~ocyan~tes. ~re~erence is ~iven to tke use of those of genera' formula X(~C0)2, ~n ~hich X ~ta~ds for a~
allphatic hydroca~bon radical with 4 to ~ C-atoms ~ cycloalip~atic hydro-carbo~ radical w~t4 6 to 15 C-ato~ or an aro~atic ~y~rocarbon ~th 6 to 15 G-2so~s .
Pre~erred aromatic~ ~liphatic or cyclo~llphatic diisocy~na~es are 2,4 and 2,~-toluyle~e dilsocyana~es or their isomer ~ixtures, 4,4'-d~phe~yl methane d~lsocyanate and 2,4'-diphcnyl methane diisocyanate~ tetra~e~yl xylylene, di~socy~te, isophorone dlisocYanate, 1~6-he~ane di~socyanate, ~1Z~4 and Z,4,~-trl~ethyl he~e~ylene di-socy~nate, ~yclohexane diisocyanate.
methyl ~yclohe~ane d~isoc~n~te, preferably 4,4'-dip~enyl me~hane diisocy-anate wl~h up to 80h 2~4'-diphenyl methane d~isocyanate Such a ~lxture ca~ have a density o~ 1.0~ to 1.20 ~/cm . Prefere~ce ls ~iven to che use of a~ lso~er ~lxture o~ diphenyl methane-4,L'-dl~socyanate a~d dlphenyl me~ha~e-Z, 4~ -~iisocyanate wt th a free ~1~0 content of approxi~ately 30,0 .
As polyols according to feature b~ ~re suitable ~o~ or high molecul~r weight polyester ~dlor polyether polyols of ~olecul~r ~eight 200 to 1000. For specif~c applications po~yether es~er or polyecter ether polyols have proved satisfactory to a li~ited egte~t and are obtalne~ by the alkox~latio~ of carbo~ylic acids or Polyesters or by the c~dens~tlo~ of polye~hers with polyfu~ctional carboxylic acl~s. ~o~e~er, s~id formul~tions only m~intzin t~eir low YiSCosit~ state for a rela~i~-ely short time (4~ ~o 1~4 hours), ~o t~at ~peedy proees~i~g is "ecessary. P~eference is given to polyols ~ith molecular weight betwee~ 700 and 3000. They are prepared by reacting epoxides ~h alcohols. ~lcohcls w~hich can be used are e.g. ethylene glycol, diethy~ene glycol, propyle~e glycol, g~ycerol, trl~ethyl propane ~nd pentae~ ritol. ~s epoxides are suitabie e.g. e~y}ene ox~de, propylene ~xlde, ~ut~l o~d~, sty~ene o~lde, cyclohe~ane oxide or epichlorohydr~n.
~e~ra~ydrofuran c~ ~e used i~ place of an epo~ide.
A~ended sheet . . . _ . _ _ . . , , _ 3 (A) Besides polyols, according to feature c~ use is ~ade of ~atural substa~ces w~th a~ leas~ one hyd~oxide ~roup, a carbo~yl group, an escer group or a ¢onjugat~41e dou41e bond, such as e.~. rosins a d castcr oil. P~efere~ce ls given to ros1ns ~i~h a~ least one methyl ester gr~up wlth 1 to 5 conjugat-able double bords, ~hich can be used durl~g Che additio~ reactio~. The acld nu~ber of suc~ compo~ds is ldeally bèt~ee~ 0.5 a~d 50, prefe~ably bet~een 2 and 20 mg ~OH/g.
~e~ded sheet As ~arklng ~gents accord~ng to feature d~ hich prevent a sudden viscosl~y ri~e durlng t~e Polyaddi~ion reaction o~ diisocyanate ~mth the polyhydroxyl compound to the lsocya atopoly~retha~e prepolymer, but do not i~alr ~he polyaddltion reaction, use is made of es~ers of phosp~o~ic 2cid, preferably h~vl~g a refraetive index of 1400 to 1~20 and a bolll~g po~n~ of 75 to 85~C
a~ 5 mbar. ~rlet~yl phosp~ate i5 partlcularly effeotiYe. ~hese addltives ~o ~ot prevent t~e polyaddition re~ion and are characterized by thei~
flame-retard~ng ~aracteristics.
Fa~ t~e viscoslty stabilization of the prepolymer (~eature e), ~an be used on the one hand bif~nctional, aro~tic dilsocyanates, p~eferzbly Z,4 and 2,6-toluylene dlisocyanates. a~ well as thelr lsomer mixtures and on the other addlt~ves of organic compounds ~uch a~ 4-methyl dloxola~-(2)-one o~
n-al~yl be~ze~e, ~hich co~tribute to v~scos~ty ~tabil~zatlon for several months.
To accelerate the ~eaction of the d- lsoeyanates lt ls p~ssible to use co~-ventioual, ~O~L ca~a~ysts ~fe~ture .~, suc~ as dibu~yl till dilau~ate~ tin-II-o~toate or ~mines of the gcneral emp~rical form~la C12~24~203 or those of t~e gene~al empiri~l fonmula C5~14N2 or C6~10N2. ~refera~ly use ls m~de of n~etallic a~lne eurin~ a~e~s. namely o~ a mlxture o~ 60 ~o ~0~ of the hî~her valence and 4~ to lOX of the lower vale4ce ammne. Good resul~s have llso 4~e~ obtzi~ed wlth ~ixtures of the aforemen~ioned me~alorganic com-pounds 2nd organic ~mines.
A fi~al viscoslty between 2S a~d 70 m~as is obtai~ed ~lt~ the aforeme~ioned ~ompo~l~io~. ~u m2~y other aPPlications, partlcularly ~or the appl~ca~ion, coat~, e~¢., a higher final viscosity is desi~ed~ I~ order to illcre~se the ~is~oslty e.g. to 120 m~asl~0~C, i~ is possible to bi~d isocya~ate sem~-prepolymers ~ith a free ~C0 content of 5 to 20 and preferably 7 to 12~ ln the polyaddltlo~ reacticn. ~he viscositY re~i~s stable for 6 to 18 month~
w~th a m~ di~e~enoe o~ 10~.
Ad~-antageously flame-re~rding agent~ ~re added to ~he prepoly~er and ~s .
such have proved p~rticula~ly satisfactory p~o~phoric acld polyols ~ith a phosp~orus ~raction of 5 to 3~ (m~m~, prefer2bly 10 to 20 ~mlm~.
_ . . . . . .... . . . _ _ _ _ _ ... . . ... . _ _ Il order to reduce o~ preve~t moisture a'osorptlon, preferably ~ols~ure trap-p-ng agen~s sre added, Mo~oeyclic, bifunctional o~azolldine has proved particularly ~uitable. Oxazolidi~e also ser~eS as an a~tifoa~1n~ agent and as such h~s g~eat signif1cance withi~ the scope of the ~rese~t i~ventio~.
lt prevents ~he fo~ f~rmatio~ ~hich i~ ot~eFwlse observed on ~pply~ng P~R
prepoly~ers ~aking ~t necessary ~o scraPe the appl7' ca~ion several ~i~es, w~ich leads to a correspo~ m g mater1al loss. ~rough the suppresslon of foam format~on and co~sequently bubble formatio~, the oxazo~ldi~7e simul-taneously has a flame-retard~g a~ion Co~vent1o~al polyur~~~ane prePol~er5 are d~ff1cult to ~-~r~ ~ollo~ng curin~, because ~elr el 2~tic~ is e~cessive and the work7ng ~ools, e.g. a~rasive paper~, gr~ding ~-heels or Polishing devices ve~y rapldly become clogged and ineffectlve. Accordin~ to the inve~tio~ th~s is avoided i~ tna~ metal-organ~c ~alts are ~d~ed to t~e prepolYmer, nzmely tho~e of ~ar.boxylic acids o~ empirical formula C~0~0~2 to C22H~4~2' P 18 ~6 2 ~e lo~ Viscosl;y polyurethane ~o~ul~tions accordi~g ~o the l~vention are s.l~able ~0t o~ly for the fi~ls~ or ~ealing o~ ~orous sur~a~e~ ~ut al~o 25 adhe~ives, as reactlve ~hinners or dllue~ts for t~e most ~aried Poly-ure~hane ~ompo~nds or ~orm~la~icns and as pri~ers far dye~, v~nLshes, lacq~ers, plastics a~d ~ther materl~ls.
hxample~
The followil~ ~eaniugs are attributed to the a~breviations ~sed ln the ~ollo~ing examples~
p~T 4,4' or ~4'-diphenyl melhane dlisocyana~e P~ polyetherpoLyol with a molecul~r ~eight of 700 to 3C00 ~atural resan ~ased on rosin e~ter of acld nu~ber 5 to ~ mg ~OH/g KA~ Am~ne acceler~tor MARX Phosphate a~ ~ar~ing agent STAB1 ~oluylene diiso~yanate ~DI) as sta~ilizer STAB2 ~-a}kyl benze~e ~s stabillzer SEMI Polyure~hane semiPrePol}~er ~ith a visco~lty of 70G0 to 1200 ~Pas as a viscos~ty regnl2~Qr far sett~g a hi~her vlscoslty.
Exa~ple ~ ~lo~ viscosi~y P~R prepo,y~er ~rth a ~iscosity ~f 50 mPas/20~C) MDI 5~A~00 P~D 16.620 ~
N~ 8.310 g ~AT 0~008 g MA~Y~ 8.31~ g SL~B1 0.2~ g AB 2 8.21~ g ~he ~I is placed ~ a do~le-~alled, rool2ble reactor, the ra~ material-te~perature ~ot exceedi~g 22~C or droppin$ bela~- 18~C In a premlxi~g con-tainer premlxl~g takes plaee of the de~atere~ ~ED (~-ate~ c~nten~ m~x 500 ppm~
and the ~ 150 de~atered to ~he same ~imum w~ter content) unt11 a st~eak-free, homogeneous polyol m~ss is obtai~ed. The polyol ~ass, which should be ~n ~he s~e temperature ran~e as t~e ~P~ is t~en added slo~ly, acco~pa~ed ~y const2nt ~tirring a~d te~perature co~trol tc the isocya~te. The mlxl~g reactor is advantageously e~acuatèd to approximately 150 m~ar. After m~ing the polyol Lraction into the isoc~anate~ ehe acceler~tor is a~ ed.
As soo~ as a~ exothér2ic te~perature of max 35~~ is reached, the ~ar~ng ~e~t is added to the wi~ure. wsich is ~ooled to belo~- 2~'C. I~mediately znd wh~lst e~clud~ng at~osp~erlc h~ dity, the ~tab~liz2r 1 CTDI) is added, ~xed in in stre~k-free ~an~er a~d l~m~ tely subseque~tly 2ixed with the st~bl I ~ 7-~r 2 a~d thoroughly ~tirred ~r at lea t 5 to 10 minutes. The vl~o~ity ~o~trol ~ust ~ive 3S t~ 3~ mPas/20~C and a sueoessful reaction ls reve~led by a pale yellow, stre~k--'ree, flake-f~ee, transpare~t soiution.
~he ~hus o~ai~ed ~R prepolymer is le~t to s~an~ 'ar 2h h, ~hllst ex~lud~ng a~mosphexic humidi~ and at a storage ~e~perature of approxi~tely 20~C.
~he subseque~t ~lseos~ty meaSure~eht must give apFro~mately 50 ~Pas/20~C.
E~ample 2 ~DI 46.000 ~
P~D13 150 g 6.~70 g ~T 0 0~6 g ~ARK 7.670 ~I 19.755 ~ABZ 6.570 S~AB1 ~.21~ ~
I~ add~tion to example 1, 2n ~ socyznate semipolymer (SEMI) is added toincrease the f~nal vlscosltv. As in exa~ple 1, the MbI ls placed ~ a double-~alled, coolable re~eor and the r~w ~2~erial tempera~ure must ~at d~op below 18~C and must ~ot axceed ~2~C. I~ a pre~ixing container pre-mix~g takes pl~e o~ ~he dewatered PE~ ~ater coRte~t max 500 ppm) and the lso de~atered ~o t~e same ~zter co~tent) u~ll a s~reak-free, homogen-eolls polyol mass ~s obtai~ed. ~ubsequently the pclyol ~as~ is slo~Tly added to the isocyana~e accompa2led by con~t~nt s~irri~g and maint~in~ the afore~entioued ranga. ~d-vTantageously the mi~ing reactor is evacua~ed ~o zpproxl~ately 150 ~a~. As soo~ as the po~yo1 fraction is intermlxed ~n the isocyanaee, the acceler~tor is added, ~ut only i~ a m~ nm exothermlc state of 35~C is ~ot reached wlt~l~ 20 minutes. Other~ise the accelerator quan-~ity ca~ be added. If the accelerator suppl~ lead~ to the exothe~mlc temp~
erature of approxl~ately 35~~ ediate mlxin~ with the m~king z~ent ta~es place ~nd t~e mlxture is cooled to below 2~~C. Accompanled by slaw stirring~
the semipoly~er wit~ a viscositY o~ 7000 to 12000 ~Past20~~l prefera~ly 10000 mPas +/- 5~0 mP~ ~S stirred in. As soo~ as a mLxture v~scosity rise is Lndicated by the process ~iscosimeter installed in or o~ the reac~o~.
i~me~tely mas~ing take~ place w~th the stabilizer 2. On re~ing a homo-ge~eou6 ~lx~ure ~he T~ can be ~dded, ~h~lst e~cludlng a~mospheric ~u~idlty.
A~ter 10 min -~irri~g a visco~y C~sta~cY o~ approxl~ately 120 mPas~20~G
is re~c~ed. ~ny vis~o~ity correctlo~s a~e performed after 24 h. I~ the cas~ o~ inadequate viscosity ret~cke~n~ can ~a~e place ~t4 ~he se~i-polymer, whereas lf the ~iSCosLty is too high the mlxthre ls diluted a~ i~
example 1. The correc~io~s sho~ld ~ot ~e more t~an 5 ~t.~ ~ased o~ ~e ~otal ~xture, ~eeause other~se the vmscosity stabilitv decreas~s.
~isCosit~ as a function of tl~e at a tes~ te~pe~ature of 20~C:
~e~t tlme 2xample i Exa2ple 2 l~medi~tely after p~eparation 30 ~0 AIter 3h 33 120 After 5 h 37 120 After 24 h 50 120 After 43 h 50 120 After 144 h 50 123 ~fter 432 h 50 125 Af~e~ ~5~0 h SS 125 A~ter 10000 h 55 13~
0~ c~ecklng the cu~i~g time the fol~o~g results were o~ e~ compared wi~h a one-compone4t, msistUre-curl~ ~ol~lreth2ne prepolymer di~uted ~t~
solve2t ~toluene) wi~ a s~milz~ accele~aeion and a solids co~tent of ~0 (herei~after called LM-P~R):
Ex~ple 1: Af~er 12 to 24 h 80~ of the ~i~al s~reng.h and a~er 72 h 10~ of the fi~al strength is rea~hed. ~o~ever, the pro~nct ca~ be mecha~
i~ally further worked after 1~ to 24 1 (ac a fu~ctiou OL the atmospherlc and ~aterlal moisture co~ten~, ~s ~e~ as tne ProcessLng temperature~, e.g. by grlnd~g, calibrating~ ~rl~mi~g the sealed chipboard or coating ~he fi~ished materlal surface.
~X-~R; Only a~ter 18 days ls 80~ of the final stren~th and after Z8 days lOOX of the f~nal strength reached. The storage te~perature i~ ~ 20~, emp~rica~ly 35 to 40~C.
A ~ate~ia~, such as e.~. ~h~pbcards with a bul~ densi~y bet~een 400 and _ 9 _ 800 kg/m3, directly after the c~ring of the polyureth~e prepolyme~ accord-ing to example 1 on ~he chipbo~rd ~ave neit~er a swel~ing nor a shri~kage effect. Thus~ tnere is no ~eed to su~sequen~ly callbrate such a chipboard.
A~ opposed to this, a ~ s~stem ~as described herein~efore~ has ~ ~hrlnk-age effect of on average Z~ o~ the board thick~ess. In addit~on~ a co~mer-~i~lly available ~ter glass ~yste~ has a swell~ng effec~ of on avera~e 11~. Such baards must be reworked, ~-h~ch Lnvolves additional costs.
Example 3 M~I 60.940 pb~ (p2rts b~ weight) PEP 14.320 NE 5.730 FS 1.430 0.010 ~AR~ 8.Q50 ST~Bl 0.2~0 ST~B3 0~40Q
S~AB~ 7.160 FF L.720 Total lOQ.OOQ pb~- (parts ~ elght~
~he followlng meanlngs are used:
FS fireproofi~g a~ent phospho~us pol~ol STAB~ fiame-~etarding stabi~izer ~polyslloxane) FF ~ois~ure trappi~g agen~ and antifoam~ng age~t MCS carboxylîc acid metal salt ~he sa~e procedure as i~ e~ample 1 i adop~ea, but the FS is siowly added, aceompanled by st~rr~n~, at a low speed o~ the polyol mass (compr~si~g PE~
and ~H), in s~ch a way that ~o streaks are ~ormed. If the ~S is added too rapidly, a2 nndesired ir~compatibllity with the rem~ining polyol mass ~hust be e~p~cted. In t~s case the polyQl m~ture must be reprePared.
~he STAB3 is externally prem1~ed ~n th~ STAB2 and together, following the addition of STABl and after a correspond~T stirring tlme are subseouently mixed. After a sti~ring tl~e of 5 to 10 m~nutes, the FF is supplied, ~hil~ e~cludi~ atmospheric h~mi dl~T~ and o~ce a~aln ~tlrring e~kes place at z ~lo~ speed for min 10 m~nu~es. It must be ens~red tha~
excessi~ely vigorous stirri~g does not ~ntroduce bubbles.
The same process procedure ~lth the parameters af e~ample 2 leads eo a hlghe~ ~inal viscosity.
E~a~le 4 prepol;mer accordl~g to example 1 98 pbw ~CS 2 pb~T
Total 100 p~
MCS ~n ~he form of a ~i~e po~der, at the e~ of the pro~ess is dispersed ln a hlgh-speed dissol~er until a lump-free, ~omo~eneous, f~nely dispersed mlx~ure is obtai~ed, w~h ~as a mil~y colo~r.
~e prepoLymer obtained ca~ be mechanica~Ly re~-orked extremely ~ell, e.g. by gri~din8 or polishin~.
~he same proces~ procedure ~ith the para~eters of e~amples 2 and 4 leads to a prepolymer with a~ l~creased flnal ~iscosity.
Claims (42)
1. Low viscosity polyurethane prepolymer composition up to 120 mPas at 20°C, comprising a polyurethane prepolymer of mPas a) organic polyisocyanates, b) polyols from the group of hydroxyl polyester polyols, hydroxyl polyether polyols and their mixed polyols, c) organic natural substances with at least one hydroxyl group, a carboxyl group, an ester group of a conjugatable double bond, and as further components d) phosphates as marking agents, e) viscosity stabilizers, f) accelerating catalysts fur curing the prepolymer from the group of organic amines and metallorganic compounds.
2. Composition according to claim 1, characterized in that it additionally contains an isocyanate semipreolymer for controlling the final viscosity.
3. Composition according to claim 1, characterized in that it contains flame-retarding agents.
4. Composition according to one of the claims 1 to 3, characterized in that it contains monocyclic, bifunctional oxazolidine as an antifoaming agent and reactive moisture trapping agent.
5. Composition according to one of the claims 1 to 4, characterized in that it contains metallorganic salts.
6. Composition according to claim 1. characterized in that the polyisocyanates are chosen from the group of aliphatic, cycloaliphatic and aromatic diisocyanates of empirical formula X(NCO)2, in which X stands for an aliphatic radical with 4 to 12 C-atoms, a cyclcaliphatic radical with 6 to 15 C-atoms or an aromatic radical with 6 to 15 C-atoms.
7. Composition according to claim 6, characterized in that the polyisocyanate is an isomer mixture of diphenyl methane-4,4'-diisocyanate and diphenyl methane-2,4'-diisocyanate with a NCO content of approximately 30%.
8. Composition according to claim 7, characterized in that the isomer mixture has a NCO content between 30 and 32%.
9. Composition according to claim 7 or 8, characterized in that the isomer mixture has a density of 1.08 to 1.20 g/cm3.
10. Composition according to claim 1, characterized in that polyols are chosen from the group of polyester, polyether, polyetherester and polyesteresther polyols of molecular weight 200 to 10,000.
11. Composition according to claim 10, characterized in that the selected polyols have a molecular weight of 700 to 3000.
12. Composition according to claim 1, characterized in that the natural substance is rosin.
13. Composition according to claim 1, characterized in that the natural substance is castor oil.
14. Composition according to claim 1, characterized in that the phosphate has a refractive index of 1400 to 1420 and a boiling point of 75 to 85°C
at 5 mbar.
at 5 mbar.
15. Composition according to claim 1 and 14, characterized in that the phosphate is triethyl phosphate.
16. Composition according to claim 1, characterized in that the viscosity stabilizer is a bifunctional, aromatic diisocyanate or an isomer mixture thereof.
17. Composition according to claim 15, characterized in that the viscosity stabilizer is an isomer mixture of 2,4-toluylene diisocyanate and 2,6-toluylene diisocyanate.
18. Composition according to claim 1, characterized in that the viscosity stabilizer is 4-methyl-dioxolan-(2)-one.
19. Composition according to claim 1, characterized in that the viscosity stabilizer is n-alkyl benzene.
20. Composition according to claim 1 and 2, characterized in that the isocyanate semiprepolymer has a free NCO content of 5 to 20%.
21. Composition according to claim 20, characterized in that the isocyanate prepolymer has a free NCO content of 7 to 12%.
22. Composition according to claim 1, characterized in that the accelerating catalyst is an organic amine of empirical formula C12H24N2O3.
23. Compostion according to claim 1, characterized in that the accelerating catalyst an organic amine of empirical formula C5H14N2 or C6H10N2.
24. Composition according to claim 22 and 23, characterized in that the accelerating catalyst is a mixture of 60 to 90% C12H24O3 and 40 to 10%
C5H14N2 or C6H10N2.
C5H14N2 or C6H10N2.
25. Composition according to claim 1, characterized in that the accelerating catalyst is an organic tin compound.
26. Composition according to claim 35, characterized in that the accelerating catalyst is dibutyl tin dilaurate.
27. Composition according to claim 25, characterized in that the accelerating catalyst is tin-II-octoate.
28. Composition according to claim 1 and 3, characterized in that the flame-retarding agent is a phosphoric acid polyol, namely phosphoric acid ethylene glycol polyester with alkyl ester and hydroxyl alkyl ester groups and a phosphorus fraction of 5 to 30% (m/m).
29. Composition according to claim 28, characterized in that the phosphoric acid polyol has a phosphorus fraction of 10 to 20% (m/m).
30. Composition according to claim 27 and 28, characterized in that the phosphoric acid polyol has a hydroxyl number of 60 to 80 mg KOH/g and an acid number >2mg KOH/g.
31. Composition according to claim 28 and 29, characterized in that the phosphoric acid polyol has a hydroxyl number of 100 to 140 mg KOH/g and an acid number > 1 mg KOH/g.
32. Composition according to claim 1 and 3, characterized in that the flame-retarding agent is a halogenated or phosphated polyol with a hydroxyl number of 50 to 200 mg KOH/g.
33. Composition according to claim 1 to 3, characterized in that additional polymethyl siloxane is provided as flame-retarding stabilizing additive.
34. Composition according to one of the claims 28 to 32, characterized in that the flame-retarding stabilizing additive is present in a proportion of 0.5 to 3 parts for 100 parts of flame-retarding agent.
35. Composition according to claim 34, characterized in that the flame-retarding stabilizing additive is present with a proportion of 1 to 2 parts for 100 parts of flame-retarding agent.
36. Composition according to claim 1 and 4, characterized in that the oxazolidine has blocked amino and/or kydroxyl groups activatable by water or moisture.
37. Composition according to claim 36, characterized in that the oxazolidine has a functionality of 2 and an equivalent weight of 90 to 140.
38. Composition according to claim 37, characterized in that the oxazolidine has a functionality of 100 to 120.
39. Composition according to claim 37 or 38, characterized in that more than 90% of the oxazolidine is mono-oxazolidine.
40. Composition according to claim 39, characterized in that more that 98%
of the oxazolidine is mono-oxazolidine.
of the oxazolidine is mono-oxazolidine.
41. Composition according to claim 1 and 5, characterized in that the metallorganic salts are those of carboxylic acids of empirical formula C10H20O2 to C22H44O2.
42. Composition according to claim 41, characterized in that the metallorganic salts are those of carboxylic acids of empirical formula C18H36O2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19513442.7 | 1995-04-13 | ||
| DE19513442 | 1995-04-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2218104A1 true CA2218104A1 (en) | 1996-10-17 |
Family
ID=7759302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002218104A Abandoned CA2218104A1 (en) | 1995-04-13 | 1996-04-14 | Low-viscosity polyurethane prepolymer |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0820480A1 (en) |
| CA (1) | CA2218104A1 (en) |
| WO (1) | WO1996032431A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017166005A1 (en) * | 2016-03-28 | 2017-10-05 | Dow Global Technologies Llc | Two-component solventless adhesive compositions and methods of making same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1120638A (en) * | 1978-07-12 | 1982-03-23 | Edward L. Hagen | Polyurethane spray composition containing lactone viscosity modifier |
| DE3139967A1 (en) * | 1981-10-08 | 1983-04-28 | Bayer Ag, 5090 Leverkusen | NEW MIXTURES OF NCO PREPOLYMERS HAVING TERTIAL NITROGEN WITH AUXILIARIES AND ADDITIVES, AND THEIR USE AS ADHESIVE OR. COATING AGENTS |
| DE3339683A1 (en) * | 1983-11-02 | 1985-05-15 | BGB-Gesellschaft Reinmar John, Rainer-Leo Meyer & Olga Meyer geb. Klöpfer, 7580 Bühl | COATING MEASUREMENT FOR FLEXIBLE SUBSTRATES, THEIR USE, AND METHOD FOR PRODUCING A PROTECTIVE COATING |
| DE4006248A1 (en) * | 1990-02-28 | 1991-08-29 | Bayer Ag | MIXTURES OF PRAEPOLYMERS AND DIISOCYANATOTOLUOLES CONTAINING URETHANE GROUPS AND THEIR USE |
| US5126421A (en) * | 1990-04-27 | 1992-06-30 | 501 Tremco Ltd. | Curing system for isocyanate prepolymers |
-
1996
- 1996-04-14 EP EP96913501A patent/EP0820480A1/en not_active Withdrawn
- 1996-04-14 CA CA002218104A patent/CA2218104A1/en not_active Abandoned
- 1996-04-14 WO PCT/EP1996/001571 patent/WO1996032431A1/en not_active Application Discontinuation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017166005A1 (en) * | 2016-03-28 | 2017-10-05 | Dow Global Technologies Llc | Two-component solventless adhesive compositions and methods of making same |
| CN108884207A (en) * | 2016-03-28 | 2018-11-23 | 陶氏环球技术有限责任公司 | Bi-component adhesive for solvent-free use composition and preparation method |
| RU2736512C2 (en) * | 2016-03-28 | 2020-11-17 | Дау Глоубл Текнолоджиз Ллк | Two-component adhesive compositions which do not contain a solvent, and methods for production thereof |
| US11015093B2 (en) | 2016-03-28 | 2021-05-25 | Dow Global Technologies Llc | Two-component solventless adhesive compositions and methods of making same |
| CN108884207B (en) * | 2016-03-28 | 2021-09-10 | 陶氏环球技术有限责任公司 | Two-component solvent-free adhesive composition and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1996032431A1 (en) | 1996-10-17 |
| EP0820480A1 (en) | 1998-01-28 |
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