CA2139654A1

CA2139654A1 - Molded polyurethane foams

Info

Publication number: CA2139654A1
Application number: CA002139654A
Authority: CA
Inventors: Yoshiaki Miyazaki; Kazuo Mizumura
Original assignee: Individual
Current assignee: Dow Chemical Co
Priority date: 1993-05-12
Filing date: 1994-05-10
Publication date: 1994-11-24
Also published as: EP0650501A1; BR9405366A; AU6829794A; WO1994026800A1; CN1110877A; AU679997B2

Abstract

This invention relates to molded polyurethane foams prepared by reacting a specific polyisocyanate with a specific polyol in the presence of water as a blowing agent and a catalyst, wherein (a) the polyisocyanate comprises a mixture of (i) a specified amount of polymethylene polyphenyl polyisocyanate and (ii) an NCO-terminated prepolymer prepared from the reaction of an organic polyisocyanate with a specified amount of poly(oxytetramethylene)glycol, or a specific NCO-terminated prepolymer prepared from the reaction of (i) an organic polyisocyanate, (ii) a specified amount of polymethylene polyphenyl polyisocyanate and (iii) a specified amount of poly(oxytetramethylene)glycol, (b) the polyol contains a specified amount of polymer polyol prepared from the reaction of a polyetherpolyol with an ethylenic unsaturated monomer, and (c) the catalyst contains an organotin compound. The molded polyurethane foams can be prepared under good demoldability and have excellent abrasion resistance, and therefore, can be useful for automotive steering wheels, headrests, armrests and the like.

Description

~ wo g4~26800 2 13 9 65 ~

MOLDED POLYURETH~NE FOAMS

RACK(~ROIJNl- OF THF ~NVFNTION

The present invention relates to molded polyu~clhalle foarns having ~-Yc~ nt abrasion ..)r,e useful for ~ o.--~ e material for steering wheels, h~,~.L. and ~llu~.7L~" m5-trn~1 for rul~ululc and the like.

Integral skin polyu,~ c foams having fine skin are well-known to the public and are widely utilized as a~lu-,-u~ e material for steering wheels, headrests and a--,u~;,L~,~ and rnaterial for ru~ulul~ and the like in various fields. The ru, ~ . . of the skin layer in the integral skin foams is based on the function of a blowing agent such as cl~vlvnuolv~bvll ( CFC~) in the e~oth~mic reaction of a polyisocyanate with a polyol. The use of a physical blowing agent such as CFC provides to the foams eYcçll~nt skin p~ul e~Lies which are required to the stated products. On the contrary, the use of a rh~o.nnic~l blowing agent such as water does not usually provide any ~oYr~l It-.nt skin p, Up~,l Lies to the foams.

Some approaches to provide PYr~ nt SKin properties to molded polyurcLha~e foams have inrl~IdeA for example, those des.,,il,cd in J~l"".~e Kokai Patent No. H03-24108, in which a specific catalyst mixture cu,,,,uli~,h,g a u~lhaue catalyst and a ~rl,otl;;l"it1~ catalyst is employed to provide low core density in the l"~,..cnce of a non-reactive physical blowing agent, and J~r~n~se Kokai Patent No. H03-33 120, in which a specific catalyst mixture is employed in the p~cs~l~ce of water as the primary blowing agent. F.creri~lly, the ~ l."ol~gy tIicclosed in the latter patent may be useful as an alternative technology of a CFC based blowing agent under the Freon R~ognl~ti~m Since several years ago, it has been pointing out that CFC destroys the ozone layer of the Earth, and c~nc~ ontly~ the use of CFCisglobally ~ 1 to be ,~ crl or aboli~.L~i in various hlllual~lial fields in present and future. In such si~l~tirn~ some approaches to employ water as the primary blowing agent have been trying. IIow~ in such prior arts, there is a terhnir~l problem that d.o.mr'-lin~ time of the process employing water as a sole blowing agent is longer than the one of the process employing CFC as a blowing agent, and also that the former foams are not better in skin properties and abrasion Irs;~ ,,re than the latter foams prepared by emploving CFC.

SIJMMARY OF THF. INVh`NTION

The iu~v~ Lula lcaea.~ ed to Ov~Wllle~ the stated prior t~chnir~l problems. That is, the purpose of the present invention is to provide molded polyulclha~ foams havi.-.g ~.~r~ .nt ~hr~eion under shorter rllom~l~in~ time The inventors diswvered tl.at the stated purpose of the invention can effectively be achieved by employing a specific polyisocyanate, polyol and catalyst in the ~lCSCl-Cc of water as a blowing agent That is, the present invention provides molded polyu-~,..-ane foams pre~.arcd by reacting a polyisocyanate with a polyol in the pl~a~,-lCe of water as a blowing agent and a catalyst wherein (a) the polyisocyanate CC~ liacS a mixture of (i) from 2 to 30 weight percent polymethylene polyphenyl polyisocyanate ("Poly.neric MDI") and (ii) a NCO-te ",;"~t..1 prepolymer ,vl~a.ccl. from the reaction of an organic polyisocyanate with 20 to 45 weight percent POIY(C~LY~ " ll,ylene)glycwl ("PTMG"), said weight "~ ,cllL~ being based on t'-e tota. weight of organic pOlyiso~;y~ulaLc, poly(oxylrl~,~ ,,rll,ylene)glycwl and poly",eLllyl~,.,e polyphenyl polvisocvanate, and (b) the polyol wntains at least 30 weight percent polymer polyol ,vlc~a.ecl from the reaction of a polyetherpolyol with an ethylenic ll~ d ",. l~."~, and (c) the cata.yst cwntains an Ol~ anoLu~ compound. The present invention a.so provides molded polyul~,L.,ane foams pl~,~ar~,d by reacting a polyisocyanate with a polyol in the pl~,i,ellce of water as a blowing agent and a catalyst wherein (a) the polyisocyanate culll~uliaes a NCO-L~..l.Lu~atcd prepolymer prepared from the reaction of (i) an organic polyisocyanate, (ii) from 2 to 30 weight percent polymethylene polyphenyl polyisocyanate and (iii) from 20 to 45 weight percent poly(o~yLcLld~,,tLl,ylene)glycol, said weight percents based on the total weight of the polyisocycu~Le~
polymethylene polyphenvl polyisocyanate and POIY(~"LY~ ,ylene)glycol, and (b) the polyol contains at least 30 weight percent polvmer polyol pl~ d from`the reaction of a polyetherpolyol with an ethylenic ullaaLulaL~,d l"~ . l rl, and the catalyst contains an o~ uLul coll.~.ou"d.

IlFTAT~,Fl) T)F!~CRlPTION OF T~F INVh NTION

Suitable polyisocyanates useful in the present invention include, for example, a mixture of a polymeric MDI and a NCO-LclllLLIlaL~ prepolymer ~ Jal~ from the reaction of an organic polyisocyanate with PTMG, or a NCO-t~ prepolymer p~ JcU~,d from the reaction of an organic polyisocyanate ~,,I~;~; ,g a polymeric MDI with PTMG.

Suitable organic polyisocy~L~ useful in the present invention include, for e~c~mrle, ~liphz.ti~ polyiso~;ya-LaLes, alicyclic polyiso~;ya,~Lta, al~".~Lic polyisocyanates or hetrocyclic polyisocyanates which are well-known to the public in polyulcLl~c or polvurea illduallial field. More specifi~lly, suitable organic polyisocyanates include, for exarnple, l,6-h ~ ,rl~,ylene diisocyanate, cyrlohPY~n~ 4 diisocvanate, 1,4-xylilene diisocyanate, 2,4-toluene diisocvanate. 2,6-toluene WO 94/26800 3 2 1 3 9 ~ ~ ~ PCT/US94/05173 diisocyanate, 4,4'-diphenyl,.. ~lh~ liiso~;yauaLe ("MDI"), 2,4~iphen~,1.. lh~.. P diisocyanate, Polymeric MDI and mo lifiPd polyisocyanates having a group such as u~cll~ c group, urea group, biuret group, carbo~iimi~ group or isocyanurate group, and the mixture thereof. Among the polyisocyanates, preferable polyisocyanates are aromatic polyisocyanates such as MDI, a polyrneric MDI, m~ifi~d polyisocyanates thereof and the mixture thereof.

Suitable poiy(oxylcl,~.lcLLylene)glycol ("PTMG") is a linear POIYG1L~OIYOI having a primary hydroxy group in its both t~rmin~lC and has an weight average -'^c~ r weight of about 300 to about 3,000. The preferable m~lo~ l~r weight of PTMG to be employed in the pl~J~ aLion of the NCO-L~...;..,.I~d prepolvrner ofthe present invention is from about 500 to about 2.400.

The NCO-~c,lllh,dled prepolymer is p~cl~a~ by reacting PTMG with an excess amount of an organic polyisocvanate in the range of Lelnpcldlulc of about 40 to about 1 00C. The NCO content of the prepolymer is from about 14 to about 28 weight percent ("wt%") and the PTMG
content of the prepolymer is from about 10 to about 50 wt%, ~ .ably~ about 20 to about 45 wt%.

One of the polyisGcyculdLGs useful in the present invention is a mixture of a polymeric MDI and the stated PTMG-based prepolymer. The polymeric MDI content of the poly- isocyanate mixture is from about 1 to about 40 wt%, preferably, about 2 to about 30 wt%, more preferably, about 5 to about 20 wt%. The another polyisocyanate useful in the present invention is a prepolymer I"~a,~ from the reaction of an organic poly~so~,yarlalc c~ .g a polymeric MDI with PTMG.
The NCO content of the prepolymer is from about 14 to about 28 wt% and the PTMG content of the prepolymer is from about 10 to about 50 wt%, preferably, about 20 to about 45 wt%. The polymeric MDI content in the prepolvmer is from about 1 to about 40 wt/4 preferably, about 2 to about 30 wt%, more p,GrG,dbly, about 5 to about 20 wt%.

Suitable polyols useful in the present invention include, for example, polyetherpolyols al~,d from the reaction of alkylpnp~yit1p~ such as ethylP.nP~xi-iP~, propylPnPoxide and butylPnPoxi~iP, with low - 'ec~ r weight polyols such as ethyle"cgly~,ol, propyleneglycol, glycerol, l~ul.~llly-~l,ul~duc, L,;~ minP., penta~.yLl"iLol, sorbitol and sucrose, or polyamines such as ethylP~ e, xy1il~ ..;..e, pipc.~;"e and N-N-dimethylamino alkylamine, polymer polyols p,cpa,.,d from the reaction of the stated polyetherpolyols with ethylenic urlsdLuldLed ...ol..~ such as acrylonitrile, styrene, b--t~fiiPn~, methyl met'nacrylate, acrylic amide and vinyl acetate, or polyesthers plc~al~ from the reaction of the stated low ~1~ ' weight polyols with poly~l,oxylic acids such as succiric acid, maleic acid, sebacic acid, adipic acid, furnaric acid, phthalic acid and dimeric acid.

2~39~S ~ 4 The inventors discovered that a polymer polyol is l~,cc~ d to use as a polyol in order to improve abrasion reeiet~nce of molded polyu.cLl,aule foams of the present invention. Suitable polymer polyols include, for example, polyrner polyols plcpi~cd from the reaction of a polyetherpolyol with acrylonitrile only or a mixture of acrylonitrile and other ethylenic ullsaLul dLcd ~ l IOl l ~l such as styrene. However, though the use of such polymer polyols is of good advantage to improvement of abrasion ~c~ of molded polyulcL}ldlle foarns, the amount employed of the polvmer polyol should be ~lrl' ~ r-~ under col~ldclaLion of other plU~,l Lies such as processability since the polymer polyols have generally high viscosity. The amount employed of the polymer polyol in the total polyol is at least 3û wt/4 preferably, about 3û to about 7û wt%, more ,u~ bly, about 35 to about 60 wt%.

Suitable blowing agents useful in the present invention include, for PY~mrle7 water, chlorofluo,ucd,l.o" ("CFC") or a mixture thereof. The suitable blowing agent is water only or a blowing agent c-."l;~;,.;"g water as primary cc",po.,c"L. The amount employed of uater is from about O.û5 to about 5 parts by weight ("pbw") based on the total polyol, preferably, about 0. l to about 3 pbw, more preferably, about 0.3 to about 2 pbw. Solvents, having low boiling point. such as pentane, methylPnP~hloride, dichlo~o",f~ n~ and 4,4'~i~minrrlirhP~nyl"~cl~n~ can optionally bc cmployed as a blowing agent together with water.

In the present invention, it is reernti, I to employ an Ol~ ~lULi" co---~ùu,-d as a catalyst. Suitable Ol~dll~ Li" catalysts include, for rY~mrle~ ol~SdlluLill cC~"~l~o~ e such as dibutyltin dilaurate, dibutyltin ~ rf~ te~ dihexyltin ~ r~1 dimethyltin du~æ~cd~Lide, dibuthyltin .li",~,lcd~Lide, diocthyltin du~e~cd,uLide, di-2-ethylhexyltin oxide~
."c octoate and st~nnoue oleate. Among the stated Ol~,d~lOlill ~.,l,oou-ldsr more preferable compound is a ~c~id~Lide type ol~,dlluLiul compound such as dibuLyllill di~c~cd~Lide, having good hydrolysis lr.~ r~. The amount employed of the olgdlloLill catalyst is less than 0.5 pbw, preferably about O.O l to about 0.5 pbw, more preferably about 0.03 to about 0. l pbw, based on the total polyol of l 00 pbw.

Suitable other catalysts to be optionally employed in the present invention include, for eY~mrlP~ tertiary amine cu",l,uu"ds such as triaLkylamines like trimethylamine and Ll;c1llyldl~illc~
heterocyclic amines like N-alkylmorpholine, ethers like 2,2'-bis -(dimethylamino)diethvlether, ~lirh~tic polyarnines like 1.4~imethyl~ c,~i,le, triethyl~- ,r-~ ,;"P., N,N,N',N'- Irl~i.lllrLhyl-l,3-l)l,li.n~.l;,..";"r.
and N-methylrli~ nol~" ,;"r, or a mixture thereof. The amount employed of the amine type catalyst is usually within the range well-known to the public in the polyu,cll-a-,e ~Lc",i~ly.

~ wo 94,26800 2~ 3 9 ~ ~ PCT/US94/05173 Suitable cross-linking agents to be optionally ~ ,lo~e;l in the present i,~ ,..Lion include7 for example, amine-based low mole~ r weight polyols such as tri~th~nol~min~ and lliP,th~n~ minl-, and low mr-lec~ r weight polyols such as ethylc.,egly~,ol, diethyle,l~ly-;ol, buL~ulediol, L~ ,Lhyl~ lu~Jdlle and glycerol, or a mixture thereof.
The amount employed of the cross-linking agent is usually from about 2 to about 20 pbw based on the total polyol, preferably, about 3 to about 10 pbw.

in addition to the stated col"l ol,~,.,L~, other additives such as emulsifying agent7 stabilizing agent7 surfactant, filler, pigment and ~ ;u,.;~ t can optionally be employed in the present invention. Tnr~ nt~lly, molded poiyul~LLalle foams ofthe present invention can be IllAlll~ ,d in acco,dallce with prior making Jn~th~c such as open-mold process or closed-mold process.

T~XAMPT F~

The present invention is des.;,il~ed more sreçifi~lly in the following Examples and CcJ~.lpa-dLi-~, FX~I "plF ~ It is to be ull~..7Lood, however, that the invention is not to be limited by the emborlim~nt~ described in the following Examples. Reactive components employed in Examples and Col--pd~dLive Examples are as follows. The term "pbw" or "%" is on the basis of weight unless there is specific des~ Lion.

( 1 ) Polyiso~d.~t~,s:
Three polyiso.,yd,~L~;" dipll~ yl...~ diiso~.ydl~L~ ("MDI") (I-125; NCO
ç-)nt~nt 33.6 wt%), a mol~ified MDI (I-143; NCO c nt~.nt 29.4 wt%) and Poly neric MDI (PAPI-135;
NC0 cont~-nt 31.0 wt%) were selected as organic polyisocyanate component. Three PTMGs having di~l~,.,L average molec ll~r weight of 700, 1,000 and l,500 (,~;" e~,Li.~ely "PTMG700", "PTMG1000"
and "PTMGl500") were selected as polyol colllpoil~,llL In ~d~liti- n a polyetherpolyol having an average equivalent weight of 1,600 and capped ethylen~-oxi~l~. (EO) content of 14 wt% ("Polyol Pl"), p.~pa~d from the reaction of glycerol as an initiator with propyleneoxide (PO), was selected as another polyol cu,..pc,..~,..L. Various NCO-I~ ed prepolymers were pl~lJd~d employing the stated polyis~yai~L~ cu~ oll~ and polyols c ~ po~ ,l; The composition of each ~ Joly.l.~" and polyisocyanate mixture is shown in Table 1, Table 2 and Table3.

(2) Polyols:
Polyol P2: A ~ul~yl~ le ("PO")-added polyetherpolyol initiated with glycerol n~tion~lity:3, Average equivalent weight ("EW"): 1,600, PO content:83 wt%, Capped EO content: 17 wt%) This polyetherpolyol was p-..pdl~d capping EO after the reaction of glycerol as an initiator with PO in the presence of potassium hydroxide as a catalyst.
Polyol CPPl: A polymer polyol (F-lnr.tionAIity:3, OH value:28. solid cnntFnt ~0 wt%) This polymer polyol was prepared pol~..u;..~u.g the stated Polyol P2 with acrylonitrile.
Polyol CPP2: A polymer polyol (Fl-nctirJnAlity:3, OH value:28. solid confF;nt ~0 wt%) This polymer polyol was prepared po~ llel lsillg the stated Polyol P2 with a .... n~ mixture of acrylonitrile/styrene (70/30 weight ratio).

(3)Additives:
Catalyst:
O.~UL -- type catalyst: Dibutyltin di~ ,Lide (FOMREZ UL-l:Witco) Amine type catalyst 1: Triethyl~..F;~ ...;..F (dipropyleneglycol 33 % solution) (Dabco 33LV: Air Products) Arnine type catalyst 2: Bis(dimethyl~ .yl)ether (NL~X A-l: Union Carbide) Cross-linking agent: .~o~ hyleneglycol (MEG) Blowing agent: Water; Trichlorofluu.u...~-;h~ (CFC-l 1) F.~A~PT.F~ 1 TO 35 AND COMP.Al~ATIV~ FXAMPT.F.~ 1 TO 4 Accù.Jil.g to the forml~lAtinnc shown in Table 4, 5, 6, 7 8, 9 and 10, various molded pol~ulc~ e foams (steering wheels) were prepared based on the following manner.

A polyol and other additives except a polyisocyanate were mixed for 10 seconds at 3,000 r.p.m. Next, the polyisocyanate ",easul~ was mixed with the polyol mixture fûr 3 seconds at 3,000 r.p.m. and c~Jl.l;l.. Ally the mixture was injected into an iron-made mold being mAintAinyl under 50 C. After curing for certain time (e.g. 180 secr)n~lc 150 sec~n~lc 120 seCon~lc~ 90 seconds and 60 seconds), a polyu~ c foam was ~ from the mold. The surface ,oropel~ies such as bli~t~,.h,g and skin (1~ l ;nn of the foam obt~in~d were ~ J I;~ lr-ly obse, v~d as an evaluation of ~.m~ hility. The results are shown in each Table. The l~eAI~;llg of each mark is as follows. "A"
means "good", "B" means "almost good" and "C" means "not good". Some samples for abrAeinn test were pl~l,al~d from the nûrmal foam obtained. The abrasion test was carried out in the follûwing marmer. The results of the abrasion test are shown in each Table.

Evaluation of Abrasion ]~e;~ c: Testing sarnples having outer pe. il.h~l dl length of about 80 mm were cut and prepared from a foam mo~ linge (steering wheel) obtained as stated above. The foam ~wo g4,26800 2 1 3 !}! 6 5 ~ PCT/US94/05173 mo' ~ ~ was plv~ vd cO~v~ g an iron-made pipe (outside ~ . t~ . 14 mm) with polyuletll~lc foarn (shape of a cross section to the vi~llv.vl-direction: ellipse having a 28 mm long tiiz~mPter and a 23 mm short 1; . .~1~. ). The abrasion resictz~nr~ of the testing sample was evaluated using a testing mztrhine for abrasion l~ ce, 'ISUGA FR-2-S Type" (produced by Suga Test ~ LlUlllv~ in Japan). The testing sample was set in the machine as the outer surface of the sample contztrted a white cloth (Canvas Cloth No. 10) having a 100 g ~. ~,;gl.li.,~ in its one end. The surface of the sample was rubbed against the cloth for certain times (3 x 104, 5 x 104 and 10 x 104 times) under the stated ccn~-l;l ;.~"c, The abrasion test was evaluated by visual ob ,v. villioll and the ranking of 1 to 5 was given to each result. The ...- t~ .g of each rank shown as "5", "4" and "3" in each Table is as follows.

5: no abrasion (no chmge) 4: slight 7tbr~cion with polish 3: more abrasion As evident from results shown in each Table, all lnvention Fxztrnrles show better r~rnol ' bility even in the use of water as a sole blowing agent and also show eYr~-llrnt abrasion properties than Co-~ e F~ les Accc,ld~l~;ly, the molded pOIyul~iLal~ foams of the present invention can be ploluced under very cycle times and can be useful for zi~o..~ e material such as steering wheels, h~ and ~ll~l~tS, material for rullJiLul~ and the like, in which abrasion ~ X
is required.

2~39~ ~ 8 Table 1 Polyisocyanates (Examples) Il rTT IV V Vl VII
(Prepolyrner) Isocyanate Polyol (Polyisocyanate) Total NCO% of20.621.5 22.4 22.520.6 19.8 20.5 the rnixture 2 I 3 9 6 5 ~ PCT/USg4/05173 Table 2 Polyisocvanates (Examples) VIII ~X X XI XTT XTTT
(Prepolymer) Isocyanate Polyol Total NCO% of22.5 20.6 21.5 22.4 20.6 19.8 the Prepolvmer Table 3 Polyisocyanates (Co~ ~aLi~e Examples) XTX XV
(Prepolvmer) Isocyanate Polyol Polvol Pl14 35 Total NC0%of24.5 20.2 ~e Prepolymer WO 94/26800 ~ 65 4 1 o PCTIUS94/05173 Table 4 Fo~m.l~tiot ~ and Properhes (Examples 1 to 7) No. 1 2 3 4 5 6 7 POlyiso~ ~laL~ I 100 - - - - - -Polyisocyanate II - 100 POlyiso~;yallaL~ III - - 100 POlyiso~yallaLe IV - - - 100 - - -Polyisocyanate V - - - - 100 Polyisocyanate VI - - - - - 100 Polyisocyanate VII - - - - - - 100 Polyol P2 60 60 60 60 60 60 60 Polyol CPPl 40 40 40 40 40 40 40 Fornrez UL-l 0.07 0.07 0.07 0.07 0.07 0.07 0.07 Dabco 33LV 1.5 1.5 1.5 1.5 1.5 1.5 1.5 NIAX A-l 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Water 0.5 0.5 0.5 0.5 0.5 0.5 0.5 D~ n I J ~ hility) 180 seconds A A A A A A A
150 seconds A A A A A A A
120 seconds A A A A A A A
90 seconds A A A B A A B
60 seconds B B B C B A C
(Abrasion P~
at 3x104 times 5 5 5 5 5 5 5 at 5x104 tirnes 5 5 5 5 5 5 5 at lOx104 times 4.5 4.5 4.5 4.5 4.5 4.5 4.5 (Note)Arnounternployed: pbw(Polyisocyanate: NCOIndex~

WO g4/26800 Table Forrmll~tionc and Properties (Examples 8 to 15) No. 8 9 10 11 12 13 14 15 Polyisocyanate II 100 100 100 100 100 100 100 100 Polyol P2 30 50 70 lOO 60 60 60 60 Polyol CPPl 70 50 30 - 40 40 40 Polyol CPP2 40 Fomrez UL-l 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 Dabco33LV 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 NIAX A-l 0.3 0.3 0.3 0.3 0.3 0.3 0 3 0 3 Water 0.5 0.5 0.5 0.5 0.3 0.8 0.2 0.5 CFC-ll 5 rDemolcl~bility) 180 seconds A A A A A A A A
150 seconds A A A A A A A A
120 seconds A A A B A A A A
90 seconds A A B C A A B A
60 seconds B B C C B B C B
(Abrasion R~
at 3x104 tirnes 5 5 5 4.5 5 5 5 5 at 5x104 times 5 5 5 4 5 5 5 5 at lOxlO4tirnes 4.5 4.5 4.5 3.5 4.5 4.5 4.5 4.5 (Note) Arnount employed: pbw (Pol~iso.;~cu.at~; NCO Index) 2~39~ ~ 12 Table 6 Fonm-l~tion~ and Properties (Examples 16 to 18) No. 16 17 18 Polyisocvanate II lO0 100 100 Polyol P2 60 60 60 Polyol CPPl 40 40 40 Fomrez UL-l 0.03 0.05 0.1 Dabco33LV 1.5 1.5 1.5 NIAX A-l 0.4 0.4 0 4 Water 0.5 0.5 0.5 (D~.m- kl~bility) 180 seconds A A A
150 seconds A A A
120 seconds A A A
90seconds B A A
60 seconds C B A
(Abrasion P~ æ) at 3x104 times 5 5 5 at 5x104 times 5 5 5 at lOx104 times 4.5 4.5 4.5 (Note) Amount employed: pbw (Polyisocyanate: NCO Index) 21 :~: 9 6 5 ~ PCT/US94/05173 Table 7 Form~ tion~ and Properties (Examples 19 to 24) No. 19 20 21 ~ 23 24 Polyisocyanate VIII 100 Polyisocyanate LX - 100 - - - -Polyisocyanate X - - 100 Polyisocyate XI - - - 100 Poly,s~/d,~L~ XII - - - - 100 Polyisocyanate XIII - - - - - 100 Polyol P2 60 60 60 60 60 60 Polyol CPPl 40 40 40 40 40 40 Fomrez UL-l 0.07 0.07 0.07 0.07 0.07 0.07 Dabco 33LV 1.5 1.5 1.5 1.5 1.5 1.5 NIAX A-l 0.4 0.4 0.4 0.4 0 4 0.4 Water 0.5 05 05 05 05 05 (D~ -'' bility) 180 seconds A A A A A A
150 seconds A A A A A A
120 seconds A A A A A A
90 seconds B A A A A A
60 seconds C B B B B A
(Abrasion R~
at 3x104 times 5 5 5 5 5 5 at 5x104 tirnes 5 5 5 5 5 5 at lOxlO4times 4.5 4.5 4.5 4.5 4.5 4.5 (Note) Amount employed: pbw (Polyisocyanate: NCO Index) PCT/US94/05173 _~
WO 94/26800 ~ _ 3 ~3 6~ ~ 14 Table 8 Forrmll~tinn.~ and P,upe-Lies (F.Y;~...ples 25 to 32) Nû. 25 26 27 28 29 30 31 32 Pûlyisocyanate X 100 100 100 100 100 100 100 100 Pûlyol P2 30 50 70 100 60 60 60 60 Polyûl CPPl 70 50 30 - 40 40 40 Pûlyol CPP2 - - - - ~ ~ ~ 40 Fûmrez UL-l 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 Dabco 33LV 1.5 1.5 1.5 1.51.5 1.5 1.5 1.5 NIAX A-l 0.4 0.4 0.4 0.40.4 0.4 0.4 0.4 Water 0.5 0.5 0.5 0.50.3 0.8 0.2 O.S

(Demoldability) 180 seconds A A A A A A A A
150 seconds A A A A A A A A
120 seconds A A A B A A A A
90seconds A A B C A A B A
60 seconds B B C C B B C B
(Abrasion R~ .ce) at 3x104 times 5 5 5 4.5 5 5 5 5 at 5x104 times 5 5 5 4 5 5 5 5 at lOx104 times 4.5 4.5 4.5 3.5 , 4.5 4.5 4.5 4.5 (Note) Amountemployed: pbw(Polyiso~,ya~ t. NCO Index) n PCT/US94/05173 Table 9 Form~ tion~ and Propertics (Examples 33 to 35) No. 33 34 35 Polyisocyanate X 100 100 100 Polyol P2 60 60 60 Polyol CPPl 40 40 40 Fornrez UL-l 0.03 0.05 0.1 Dabco33LV 1.5 1.5 1.5 NIAX A-l 0.4 0.4 0.4 Water 0.5 0.5 0.5 (D~ - "' hility) 180 seconds A A A
150 seconds A A A.
120 seconds A A A
90 seconds B A A
60 seconds C B A
(Abrasion ~ nce) at 3x104 times 5 5 5 at 5x104 times 5 5 5 at lOx104 times 4.5 4.5 4.5 (Note) Amount employed: pbw (Polyisocyanate: NCO Index) Table 10 Fonn..i~tion~ and Properties (C-...p ~ ;ve Examples 1 to 4) No. 1 2 3 4 PolyisocyanateXIV 100 - - -Polyisocyanate XV - 100 Polyisocyanate II - - 100 Polyisocyanate X - - - 100 Polyol P2 100 100 60 60 Polyol CPP I - - 40 40 Dabco 33LV 2.5 2.52.5 2.5 NIAX A-l 0.4 0.40.4 0.4 Water - 0.50.5 0 5 CFC-l I 15 (D~ility) 180 seconds A B A A
150 seconds A C A A
120 seconds A C B B
90 seconds B C C C
60 seconds B C C C
(Abrasion ~S;~ -r~ ) at 3x104 times 5 3.5 5 5 at 5x104 times 5 3 5 5 at lOx104 times 4.5 - 4.5 4.5 (Note) Amountemploved: pbw(Polyisocyanate: NCO Index)

Claims

WHAT IS CLAIMED IS:

1. Molded polyurethane foams prepared reacting a polyisocyanate with a polyol in the presence of water as a blowing agent and a catalyst, wherein (a) the polyisocyanate comprises a mixture of (i) from about 1 to about 40 weight percent polymethylene polyphenyl polyisocyanate and (ii) a NCO-terminated prepolymer prepared from the reaction of an organic polyisocyanate with from about 10 to about 50 weight percent poly(oxytetramethylene)glycol, said weight percents being based on the total weight of organic polyisocyanate, poly(oxytetramethylene)glycol and polymethylene polyphenyl polyisocyanate, (b) the polyol contains at least 30 weight percent polymer polyol prepared from the reaction of a polyetherpolyol with an ethylenic unsaturated monomer, and (c) the catalyst contains an organotin compound.

2. Molded polyurethane foams prepared by reacting a polyisocyanate with a polyol in the presence of water as a blowing agent and a catalyst, wherein (a) the polyisocyanate comprises a NCO-terminated prepolymer prepared from the reaction of (i) an organic polyisocyanate, (ii) from about 1 to about 40 weight percent polymethylene polyphenyl polyisocyanate and (iii) from about 10 to about 50 weight percent poly(oxytetramethylene)glycol, said weight percents based on the total weight of the polyisocyanate, polymethylene polyphenyl polyisocyanate and poly(oxytetramethylene)glycol, (b) the polyol contains at least 30 weight percent polymer polyol prepared from the reaction of a polyetherpolyol with an ethylenic unsaturated monomer, and (c) the catalyst contains an organotin compound.

3. The molded polyurethane foams of Claim 1 wherein the organic polyisocyanate is 4,4'-diphenylmethane diisocyanate or a modified 4,4'-diphenylmethane diisocyanate.

4. The molded polyurethane foams of Claim 1 wherein the weight average molecularweight of the poly(oxytetramethylene)glycol is from about 500 to about 2,400, the polymethylene polyphenyl polyisocyanate and poly(oxytetramethylene)glycol contents are from about 2 to 30 weight percent and from about 20 to 45 weight percent respectively, based on the total weight of polyisocyanate component (a), and the polyol contains from about 30 to about 70 weight percent polymer polyol based on the total weight of polyol component (b).

5. The molded polyurethane foams of Claim 1 wherein the ethylenic unsaturated monomer is acrylonitrile.

6. The molded polyurethane foams of Claim 1 wherein the water content is from about0.3 to about 2 parts by weight based on the total weight of the polyol component.

7. The molded polyurethane foams of Claim 1 wherein the organotin compound is a mercaptide type organotin compound.

8. The molded polyurethane foams of Claim 7 wherein the mercaptide type organotin compound is dimethyltin dimercaptide, dibutyltin dimercaptide or dioctyltin dimercaptide.

9. The molded polyurethane foams of Claim 2 wherein the organic polyisocyanate is 4,4'-diphenylmethane diisocyanate or a modified 4,4'-diphenylmethane diisocyanate.

10. The molded polyurethane foams of Claim 2 wherein the weight average molecular weight of the poly(oxytetramethylene)glycol is from about 500 to 2,400, the polymethylene polyphenyl polyisocyanate and poly(oxytetramethylene)glycol contents are from about 2 to 30 weight percent and from about 20 to 45 weight percent respectively, based on the total weight of polyisocyanate component (a), and the polyol contains from about 30 to about 70 weight percent polymer polyol based on the total weight of the polyol component (b).

11. The molded polyurethane foams of Claim 2 wherein the ethylenic unsaturated monomer is acrylonitrile.

12. The molded polyurethane foams of Claim 2 wherein the water content is from about 0.3 to about 2 parts by weight based on the total polyol component (b).

13. The molded polyurethane foams of Claim 2 wherein the organotin compound is amercaptide type organotin compound.

14. The molded polyurethane foams of Claim 2 wherein the mercaptide type organotin compound is dimethyltin dimercaptide, dibutyltin dimercaptide or dioctyltin dimercaptide.