Composition for one-component polyurethane foams having low free monomeric MDI content
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08G-018/08
C08G-018/10
C08G-018/76
C08K-005/521
C08G-101/00
출원번호
US-0981303
(2012-01-26)
등록번호
US-9796808
(2017-10-24)
우선권정보
EP-11152422 (2011-01-27)
국제출원번호
PCT/EP2012/051245
(2012-01-26)
§371/§102 date
20131104
(20131104)
국제공개번호
WO2012/101220
(2012-08-02)
발명자
/ 주소
De Schrijver, Aster
Bordado, Joao Moura
Georigev, Georgi
출원인 / 주소
De Schrijver, Aster
대리인 / 주소
Levy & Grandinetti
인용정보
피인용 횟수 :
0인용 특허 :
13
초록▼
A one component precursor for the polymeric foam (OCF) composition comprising a very low amount of free monomeric MDI. The present OCF composition may be obtained without any free MDI removal step, and without the addition of extra solvent to compensate for the substantially lower amount of free MDI
A one component precursor for the polymeric foam (OCF) composition comprising a very low amount of free monomeric MDI. The present OCF composition may be obtained without any free MDI removal step, and without the addition of extra solvent to compensate for the substantially lower amount of free MDI, compared with traditional compositions. The present composition comprises a source of free NCO of functionality of at least 2.6, a tri- or higher functional alcohol, all polyols being characterized by a rather low molecular weight and at least a specific mono-functional alcohol as well as an isocyanate end-capped prepolymer of toluene diisocyanate (=end capped TDI). The OCF composition is suitable for being dispensed from a pressurized can with a blowing agent.
대표청구항▼
1. A one component isocyanate prepolymer mixture for the production of a polyurethane product, said one component isocyanate prepolymer mixture having a content of free monomeric diphenylmethane diisocyanate (MDI) of not more than 4 wt. %, with respect to the total weight of the one component isocya
1. A one component isocyanate prepolymer mixture for the production of a polyurethane product, said one component isocyanate prepolymer mixture having a content of free monomeric diphenylmethane diisocyanate (MDI) of not more than 4 wt. %, with respect to the total weight of the one component isocyanate prepolymer mixture, and being obtained by mixing in the absence of moisture at least: (A) an isocyanate component, or mixture of isocyanate components, having a functionality of at least 2.6;(B) a tri- or higher functional polyol; and(C) a catalyst and optional additives; and wherein said one component isocyanate prepolymer mixture further (a) a mono-functional alcohol having a molecular weight of at least about 130 g/mol, and(b) an isocyanate end-capped prepolymer of toluene diisocyanate. 2. The one component isocyanate prepolymer mixture according to claim 1, wherein said isocyanate component or mixture of isocyanate components comprises crude diphenyl methane diisocyanate (crude MDI), and optionally any one or more of diphenyl methane diisocyanate (MDI), toluene diisocyanate (TDI), crude toluene diisocyanate (crude TDI), poly-phenyl methane poly-isocyanate (PMDI), and any mixture thereof having a functionality of at least 2.6. 3. The one component isocyanate prepolymer mixture according to claim 2, wherein the tri- or higher functional polyol has a molecular weight of not more than 2000, and comprises one or more of (i) an ester with three or more esterified hydroxy functional fatty acid groups, wherein the closest hydroxyl group on each hydrocarbon chain is separated from the respective ester group by at least seven carbons; and(ii) a hydroxy functional polyether oligomer having an overall hydroxy functionality comprised between 3 and 8. 4. The one component isocyanate prepolymer mixture according to claim 3, wherein the tri- or higher functional polyol comprises (i) the ester with three or more esterified hydroxy functional fatty acid groups and wherein the three or more esterified hydroxy functional fatty acid groups are selected from the group consisting of ricinoleic acid, avenoleic acid, strophantus acid, lesquerolic acid, 14-hydroxy-11-eicosenoic acid, densipolic acid, and auricolic acid. 5. The one component isocyanate prepolymer mixture according to claim 4, further comprising a bi-functional alcohol having a molecular weight not greater than about 110 g/mol, wherein said bi-functional alcohol is a member selected from the group consisting of monoethylene glycol (MEG), diethylene glycol (DEG), propylene glycol, 1,3-propylene glycol, 1,3-butane diol, 1,4-butane diol, neopentyl glycol, and mixtures thereof. 6. The one component isocyanate prepolymer mixture according to claim 5, wherein the content of free monomeric MDI is not more than 3 wt. % with respect to the total weight of the one component isocyanate prepolymer mixture. 7. The one component isocyanate prepolymer mixture according to claim 1 for the preparation of a polyurethane foam, further comprising a blowing agent, which is a member selected from the group consisting of propane, butane, i-butane, dimethyl ether (DME), carbon dioxide (CO2), and mixtures thereof. 8. The one component isocyanate prepolymer mixture according to claim 1, comprising one or more additives selected from the group consisting of monochlorinated mono-methyl ester of castor oil, (1-choro-2-proply) phosphate, a Lewis base catalyst, a Lewis acid catalyst, dimethyl aminoethoxyethanol, di-morpholino diethyl ether, a surfactant, a cell structure regulator, a filler, pigment, and a dye. 9. The one component isocyanate prepolymer mixture according to claim 1, wherein the molar ratio, NCO/OH, of isocyanate to hydroxyl groups in the one component isocyanate prepolymer mixture is between 2.6 and 5.0. 10. The one component isocyanate prepolymer mixture according to claim 1, comprising: between 15 and 25 wt. % of diphenyl methane diisocyanate (MDI) or poly-phenyl methane poly-isocyanate (PMDI) prepolymers as the isocyanate component, or mixture of isocyanate components, having a functionality of at least 2.6,between 20 and 75 wt. %, of isocyanate end-capped TDI;between 5 and 15 wt. % of the mono-functional alcohol;between 0 and 15 wt. % of a bi-functional alcohol;between 8 and 20 wt. % of castor oil; all weight fractions being calculated with respect to the total weight of the one component isocyanate prepolymer mixture. 11. A method for preparing a one component isocyanate prepolymer mixture for the production of polyurethane, said one component isocyanate prepolymer mixture having a content of free monomeric diphenylmethane diisocyanate (MDI) of not more than 4 wt. % with respect to the total weight of the one component isocyanate prepolymer mixture, said method comprising preparing in a closed, hermetic vessel protected from moisture a one component isocyanate prepolymer mixture comprising: (a) an isocyanate component, or mixture of components, having a functionality of at least 2.6;(b) a tri- or higher functional polyol;(c) a catalyst and additives;(d) an isocyanate end-capped prepolymer of toluene diisocyanate (TDI); and(e) a mono-functional alcohol having a molecular weight of at least about 130 g/mol. 12. The method according to claim 11, further comprising the following steps: (a) stabilizing the one component isocyanate prepolymer mixture in a short path wiped film evaporator to form a stabilized mixture, and(b) reducing the amount of free monomeric MDI by distillation of the stabilized mixture. 13. The method according to claim 11 for preparing a one component polyurethane foam precursor comprising the additional steps: optionally transferring the one component isocyanate prepolymer mixture a dispensing container, while shielding the one component isocyanate prepolymer mixture from moisture; andhermetically closing the vessel or dispensing container containing the one component isocyanate prepolymer mixture and introducing therein a blowing agent under pressure through a valve. 14. The one component isocyanate prepolymer mixture according to claim 1, wherein the tri- or higher functional polyol has a molecular weight of not more than 2000, and comprises one or more of (i) an ester with three or more esterified hydroxy functional fatty acid groups, wherein the closest hydroxyl group on each hydrocarbon chain is separated from the respective ester group by at least seven carbons; and(ii) a hydroxy functional polyether oligomer having an overall hydroxy functionality comprised between 3 and 8. 15. The one component isocyanate prepolymer mixture according to claim 14, wherein the tri-or higher functional polyol comprises (i) the ester with three or more esterified hydroxy functional fatty acid groups and wherein the three or more esterified hydroxy functional fatty acid groups are selected from the group consisting of ricinoleic acid, avenoleic acid, strophantus acid, lesquerolic acid, 14-hydroxy-11-eicosenoic acid, densipolic acid, and auricolic acid. 16. The one component isocyanate prepolymer mixture according to claim 1, further comprising a bi-functional alcohol having a molecular weight not greater than about 110 g/mol, wherein said bi-functional alcohol is a member selected from the group consisting of monoethylene glycol (MEG), diethylene glycol (DEG), propylene glycol, 1,3-propylene glycol, 1,3-butane diol, 1,4-butane diol, neopentyl glycol, and mixtures thereof. 17. The one component isocyanate prepolymer mixture according to claim 1, wherein the content of free monomeric MDI is not more than 3 wt. % with respect to the total weight of the one component isocyanate prepolymer mixture.
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