CA2037715C - Rigid foams using blends of chlorofluorocarbons and hydrocarbons as blowing agent - Google Patents
Rigid foams using blends of chlorofluorocarbons and hydrocarbons as blowing agent Download PDFInfo
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- CA2037715C CA2037715C CA002037715A CA2037715A CA2037715C CA 2037715 C CA2037715 C CA 2037715C CA 002037715 A CA002037715 A CA 002037715A CA 2037715 A CA2037715 A CA 2037715A CA 2037715 C CA2037715 C CA 2037715C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
- Y10S264/05—Use of one or more blowing agents together
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S521/91—Plural blowing agents for producing nonpolyurethane cellular products
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention is directed to the use of a mixture of (i) from 30 to 95 % by wt. of 2,2-dichloro-1,1,1-trifluoroethane and/or 1,1-dichloro-1-fluoroethane and (ii) from 5 to 70 % by wt. of n-pentane, 2-methylbutane, hexane, position isomers of hexane and mixtures thereof in the production of rigid, closed cell foams.
Description
~~ Mo3401 RIGID FOAMS USING BLENDS OF CHLOROFLUOROCARBONS
AND HYDROCARBONS AS BLOWING AGENT
BACKGROUND OF THE INDENTION
The use of trichloromonofluoromethane ("CFC-11") in the production of closed cell, rigid polyurethane and polyiso-cyanurate foams is well known (see, e.g., U.S. Patents 3,072,582; 3,091,551; 3,153,002; 3,524,825; 3,846,347; and 4,248,975). Recently, the urethane foam industry has been investigating methods for reducing the amount of CFC-11 used in to producing rigid foams.
U.S. Patent 3,745,203 describes the production of polyurethane moldings using a mixture of two volatile blowing agents. The least volatile of the blowing agents has a boiling point of from 30°F to 120°F, while the more volatile blowing agent in the mixture has a boiling point of from -50°F to 500F.
The difference between the boiling points of the two blowing agents in the mixture is from 30°F to 150°F.
German Auslegeschrift 1,288,312 describes the use of an azeotrope of CFC-11 and isopentane as a blowing agent (U. S.
2o Patent 3,249,546 describes the azeotrope itself).
U.S. Patent 4,055,521 describes a blowing agent which is a mixture of CFC-11, isopentane, and methylene chloride.
U.S. Patent 3,391,093 describes the use of halogenated blowing agents which generally have boiling points below about 80°F for producing polyurethane foams. The reference does indicate that low molecular weight hydrocarbon gases can be used with the halogenated blowing agents. U.S.
Patent 4,795,763 broadly indicates that mixtures of 3o halohydrocarbons and hydrocarbons can be used as blowing agents for polyurethane foams.
It has also been suggested that 2,2-dichloro-1,1,1-trifluoroethane ("HCFC-123") and 1,1-dichloro-1-fluoroethane ("HCFC-141 b") can be used as blowing agents for rigid polyurethane foams (See, e.g., Dishart et al, "The DuPont Program on Fluorocarbon Alternative Blowing Agents for Polyurethane Foams," POLYURETHANES
WORLD CONGRESS 1987 - SEPTEMBER 29-OCTOBER 2, 1987, pages 59-66, and U.S. Patent 4,076,644).
The use of a mixture of a chlorofluorocarbon having an atmospheric boiling point of from about 74°F to about 120°F and an alkyl alkanoate having a molecular weight of no more than about 88 as a blowing agent has been described in U.S. Patent 4,960,804. Among the chlorofluoro-carbons described are HCFC 123 and HCFC 141 b. Among the alkyl alkanoates described is methyl formate.
Finally, various compositions based on halogenated hydrocarbons are known for use as cleaning solvents. For example, U.S. Patent 4,055,507 describes the use of an azeotropic mixture of 1,2-dichloro-1,1-difluoroethane and 3-methylpentane. Japanese 1,141,995 (abstract only) describes an azeotropic mixture of 67 to 87 % by weight of HCFC-123 and 13 to 33 % by weight of 2-methylbutane. Japanese 1,141,996 (abstract only) describes an uzeotropic mixture of HCFC-141 b and a member selected from the group n-pentane, 2-methylbutane and 2,2-dimethyl-butane.
DESCRIPTION OF THE INVENTION
The present invention is directed to the discovery that a mixture of specific hydrochlorofluorocarbons with specific hydrocarbons is eminently suitable for the production of closed cell, rigid foams. The resultant foams are substantially lovfver in density than foams produced from trichloromono-fluoromethane alone, yet still have relatively low K-factors. Additionally, since the hydrocarbons will have no ozone depletion potential, the ozone depletion potential of the hydrochlorofluorocarbons used herein will be lowered. More particularly, the present invention is directed to an improved process for the preparation of closed cell rigid foams. The process broadly cc:~;~prises reacting a) a polyol component having Mo3401 a hydroxyl number of from about 200 to about 650, and b) an organic polyisocyanate, in the presence of c) a catalyst, d) a foam stabilizer, and e) a blowing agent. The improvement resides in the use of a mixture of i) from 30 to 95 percent by s weight, and preferably from 60 to 90 percent by weight, of a hydrochlorofluorocarbon selected from the group consisting of 2,2-dichlor-1,1,1-trifluoroethane (b.p about 82°F) and 1,1-dichloro-1-fluoroethane (b.p. about 90°F) and ii) from 5 to 70 percent by weight, and preferably from 10 to 40 percent by to weight, of a hydrocarbon selected from the group consisting of n-pentane, 2-methylbutane, hexane, the position isomers of hexane and mixtures thereof. The most preferred mixture consists of 2,2-dichloro-1,1,1-trifluoroethane and n-pentane.
If desired, the blowing agent can also contain water.
15 The polyols, isocyanates, catalysts, and foam stabilizers useful herein and the various methods of combining them to produce closed cell, rigid foams are generally known in the art.
The invention is further illustrated but is not 2o intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
EXAMPLES
In the examples which follow, the following materials were used:
2s POLYOL A: a 460 OH number polyol prepared by sequentially reacting 1 mole of an 80/20 mixture of 2,4- and 2,6-toluene diamine with about 3.7 moles of ethylene oxide and then about 3.3 moles of propylene oxide.
3o POLYOL B: a 395 OH number polyol prepared by sequentially reacting 1 mole of a mixture of 2,3- and 3,4-toluene diamine with about 3.5 moles of ethylene oxide and then with about 4.5 moles of propylene oxide.
Mo3401 ~G3 '~~5 JPOLYOL CC: Stepanol*PS-2502, a 250 OH number aromatic polyester polyol commercially available from Stepan Company.
HCFC123:123: 1,1-dichloro-2,2,2-trifluoroethane.
s HCFC-141b: 1,1-dichloro-1-fluoroethane.
2-MB: 2-methylbutane.
n-pentane.
~-5440* a polyalkyleneoxidedimethylsiloxane copolymer, cortmercially available from 1o Union Carbide.
PMDTA: pentamethyldiethylenetriamine.
C-~: Dabco*K-15 catalyst, a potassium based catalyst commercially available from Air Products.
is MR- : Dabco*TMR-30 catalyst, an amine catalyst commercially available from Air Products.
DC-193* a siloxane surfactant commercially available from Dow Corning Corporation.
TM A: tetramethylethylenediamine.
20 ISO A: Mondur*MR isocyanate, a commercially available polymethylene polyphenyl polyisocyanate from Mobay Corporation, having an NCO content of about 32%.
ISO B: Mondur*489 isocyanate, a commercially 2s available polymethylene polyphenyl polyisocyanate from Mobay Corporation, having an NCO content of about 31%.
In t he examples, the HCFC-123 and HCFC-141b were first mixed wi th the hydrocarbon noted. The ingredients listed 3o in the Tables under B-side were then blended. The isocyanate was then mixed in a mixing vessel using an air stirrer.
After the mix times noted in the Tables, the reaction mixtures were poured into a polyethylene lined 10~" x 10~" x 2~~
cardboard box. The cream times, gel times, densities and K-factors of 35 the systems were as reported in the Tables. In the Tables, MO~~~~ mark A
J
..
_5-Table 2 representsisocyanurate groupcontaining foams.
Finally, Examples 1, 7 and were comparative 4, 10 examples.
POLYOL A,pbw 33.533.5 33.5 36.4 36.4 36.4 POLYOL B,pbw 33.533.5 33.5 36.4 36.4 36.4 L-5440,pbw 1.5 1.5 1.5 1.5 1.5 1.5 PMTDA,pbw 2.2 2.2 2.2 2.2 2.2 2.2 1o TMEDA,pbw 1.1 1.1 1.1 1.1 1.1 1.1 HCFC-123,pbw 28.222.38 22.38-- -- --HCFC-141b,pbw -- -- -- 22.4 18.83 18.83 2-MB,pbw -- 2.49 __ __ 2.09 __ n-P,pbw -- -- 2.49 -- -- 2.09 ISO-A,pbw 70.070.0 70.0 76.0 76.0 76.0 RESULTS
Mix time,sec. 4 4 4 4 4 4 20 Cream time,sec. 14 11 12 10 9 9 Gel time, sec. 39 37 39 33 33 33 Density,pcf. 1.871.84 1.87 1.84 1.81 1.80 K-factor {BTU-in 0.1200.126 0.1270.122 0.127 0.128 2s hr-ft2) Mo3401 ., POLYOL C,pbw 100.0 100.0 100.0 100.0 100.0 100.0 K-l5,pbw 3.0 3.0 3.0 3.0 3.0 3.0 TMR-30,pbw 0.6 0.6 0.6 0.6 0.6 0.6 DC-193,pbw 1.5 1.5 1.5 1.5 1.5 1.5 HCFC-123,pbw 45.4 36.09 36.09 -- -- --HCFC-141b,pbw -- -- -- 33.4 28.08 28.08 l0 2-MB,pbw -- 4.01 -- -- 3.12 --n-P,pbw -- -- 4.01 -- -- 3.12 A-SIDE
ISO-B,pbw 158.5 158.5 158.5 158.5 158.5 158.5 Mix time,sec. 4 4 4 4 4 4 Cream time,sec. 21 17 20 16 16 16 Gel time, sec. 35 36 35 30 31 30 Density,pcf. 1.97 1.94 1.95 1.88 1.82 1.82 2o K-factor (BTU-in 0.130 0.128 0.131 0.133 0.134 0.134 hr-ft2) Mo3401 _7_ POLYOL A,pbw 33.5 36.4 33.5 36.4 POLYOL B,pbw 33.5 36.4 33.5 36.4 L-5440,pbw 1.5 1.5 1.5 1.5 PMTDA,pbw 2.2 2.2 2.2 2.2 TMEDA,pbw 1.1 1.1 1.1 1.1 HCFC-123,pbw 17.74 -- 24.39 --to HCFC-141b,pbw -- 15.59 -- 16.44 2-MB,pbw 10.46 6.81 -- --n-P,pbw -- -- 3.81 5.96 A-SIDE
1s ISO-A,pbw 70.0 76.0 70.0 76.0 RESULTS
Mix time,sec. 5 5 5 5 Cream time,sec. 11 9 13 7 2o Gel time, sec. 38 37 38 29 Density,pcf. 1.34 1.27 1.69 1.63 K-factor (BTU-in 0.152 0.162 0.130 0.132 hr-ft2) 2s Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention so except as it may be limited by the claims.
Mo3401
AND HYDROCARBONS AS BLOWING AGENT
BACKGROUND OF THE INDENTION
The use of trichloromonofluoromethane ("CFC-11") in the production of closed cell, rigid polyurethane and polyiso-cyanurate foams is well known (see, e.g., U.S. Patents 3,072,582; 3,091,551; 3,153,002; 3,524,825; 3,846,347; and 4,248,975). Recently, the urethane foam industry has been investigating methods for reducing the amount of CFC-11 used in to producing rigid foams.
U.S. Patent 3,745,203 describes the production of polyurethane moldings using a mixture of two volatile blowing agents. The least volatile of the blowing agents has a boiling point of from 30°F to 120°F, while the more volatile blowing agent in the mixture has a boiling point of from -50°F to 500F.
The difference between the boiling points of the two blowing agents in the mixture is from 30°F to 150°F.
German Auslegeschrift 1,288,312 describes the use of an azeotrope of CFC-11 and isopentane as a blowing agent (U. S.
2o Patent 3,249,546 describes the azeotrope itself).
U.S. Patent 4,055,521 describes a blowing agent which is a mixture of CFC-11, isopentane, and methylene chloride.
U.S. Patent 3,391,093 describes the use of halogenated blowing agents which generally have boiling points below about 80°F for producing polyurethane foams. The reference does indicate that low molecular weight hydrocarbon gases can be used with the halogenated blowing agents. U.S.
Patent 4,795,763 broadly indicates that mixtures of 3o halohydrocarbons and hydrocarbons can be used as blowing agents for polyurethane foams.
It has also been suggested that 2,2-dichloro-1,1,1-trifluoroethane ("HCFC-123") and 1,1-dichloro-1-fluoroethane ("HCFC-141 b") can be used as blowing agents for rigid polyurethane foams (See, e.g., Dishart et al, "The DuPont Program on Fluorocarbon Alternative Blowing Agents for Polyurethane Foams," POLYURETHANES
WORLD CONGRESS 1987 - SEPTEMBER 29-OCTOBER 2, 1987, pages 59-66, and U.S. Patent 4,076,644).
The use of a mixture of a chlorofluorocarbon having an atmospheric boiling point of from about 74°F to about 120°F and an alkyl alkanoate having a molecular weight of no more than about 88 as a blowing agent has been described in U.S. Patent 4,960,804. Among the chlorofluoro-carbons described are HCFC 123 and HCFC 141 b. Among the alkyl alkanoates described is methyl formate.
Finally, various compositions based on halogenated hydrocarbons are known for use as cleaning solvents. For example, U.S. Patent 4,055,507 describes the use of an azeotropic mixture of 1,2-dichloro-1,1-difluoroethane and 3-methylpentane. Japanese 1,141,995 (abstract only) describes an azeotropic mixture of 67 to 87 % by weight of HCFC-123 and 13 to 33 % by weight of 2-methylbutane. Japanese 1,141,996 (abstract only) describes an uzeotropic mixture of HCFC-141 b and a member selected from the group n-pentane, 2-methylbutane and 2,2-dimethyl-butane.
DESCRIPTION OF THE INVENTION
The present invention is directed to the discovery that a mixture of specific hydrochlorofluorocarbons with specific hydrocarbons is eminently suitable for the production of closed cell, rigid foams. The resultant foams are substantially lovfver in density than foams produced from trichloromono-fluoromethane alone, yet still have relatively low K-factors. Additionally, since the hydrocarbons will have no ozone depletion potential, the ozone depletion potential of the hydrochlorofluorocarbons used herein will be lowered. More particularly, the present invention is directed to an improved process for the preparation of closed cell rigid foams. The process broadly cc:~;~prises reacting a) a polyol component having Mo3401 a hydroxyl number of from about 200 to about 650, and b) an organic polyisocyanate, in the presence of c) a catalyst, d) a foam stabilizer, and e) a blowing agent. The improvement resides in the use of a mixture of i) from 30 to 95 percent by s weight, and preferably from 60 to 90 percent by weight, of a hydrochlorofluorocarbon selected from the group consisting of 2,2-dichlor-1,1,1-trifluoroethane (b.p about 82°F) and 1,1-dichloro-1-fluoroethane (b.p. about 90°F) and ii) from 5 to 70 percent by weight, and preferably from 10 to 40 percent by to weight, of a hydrocarbon selected from the group consisting of n-pentane, 2-methylbutane, hexane, the position isomers of hexane and mixtures thereof. The most preferred mixture consists of 2,2-dichloro-1,1,1-trifluoroethane and n-pentane.
If desired, the blowing agent can also contain water.
15 The polyols, isocyanates, catalysts, and foam stabilizers useful herein and the various methods of combining them to produce closed cell, rigid foams are generally known in the art.
The invention is further illustrated but is not 2o intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
EXAMPLES
In the examples which follow, the following materials were used:
2s POLYOL A: a 460 OH number polyol prepared by sequentially reacting 1 mole of an 80/20 mixture of 2,4- and 2,6-toluene diamine with about 3.7 moles of ethylene oxide and then about 3.3 moles of propylene oxide.
3o POLYOL B: a 395 OH number polyol prepared by sequentially reacting 1 mole of a mixture of 2,3- and 3,4-toluene diamine with about 3.5 moles of ethylene oxide and then with about 4.5 moles of propylene oxide.
Mo3401 ~G3 '~~5 JPOLYOL CC: Stepanol*PS-2502, a 250 OH number aromatic polyester polyol commercially available from Stepan Company.
HCFC123:123: 1,1-dichloro-2,2,2-trifluoroethane.
s HCFC-141b: 1,1-dichloro-1-fluoroethane.
2-MB: 2-methylbutane.
n-pentane.
~-5440* a polyalkyleneoxidedimethylsiloxane copolymer, cortmercially available from 1o Union Carbide.
PMDTA: pentamethyldiethylenetriamine.
C-~: Dabco*K-15 catalyst, a potassium based catalyst commercially available from Air Products.
is MR- : Dabco*TMR-30 catalyst, an amine catalyst commercially available from Air Products.
DC-193* a siloxane surfactant commercially available from Dow Corning Corporation.
TM A: tetramethylethylenediamine.
20 ISO A: Mondur*MR isocyanate, a commercially available polymethylene polyphenyl polyisocyanate from Mobay Corporation, having an NCO content of about 32%.
ISO B: Mondur*489 isocyanate, a commercially 2s available polymethylene polyphenyl polyisocyanate from Mobay Corporation, having an NCO content of about 31%.
In t he examples, the HCFC-123 and HCFC-141b were first mixed wi th the hydrocarbon noted. The ingredients listed 3o in the Tables under B-side were then blended. The isocyanate was then mixed in a mixing vessel using an air stirrer.
After the mix times noted in the Tables, the reaction mixtures were poured into a polyethylene lined 10~" x 10~" x 2~~
cardboard box. The cream times, gel times, densities and K-factors of 35 the systems were as reported in the Tables. In the Tables, MO~~~~ mark A
J
..
_5-Table 2 representsisocyanurate groupcontaining foams.
Finally, Examples 1, 7 and were comparative 4, 10 examples.
POLYOL A,pbw 33.533.5 33.5 36.4 36.4 36.4 POLYOL B,pbw 33.533.5 33.5 36.4 36.4 36.4 L-5440,pbw 1.5 1.5 1.5 1.5 1.5 1.5 PMTDA,pbw 2.2 2.2 2.2 2.2 2.2 2.2 1o TMEDA,pbw 1.1 1.1 1.1 1.1 1.1 1.1 HCFC-123,pbw 28.222.38 22.38-- -- --HCFC-141b,pbw -- -- -- 22.4 18.83 18.83 2-MB,pbw -- 2.49 __ __ 2.09 __ n-P,pbw -- -- 2.49 -- -- 2.09 ISO-A,pbw 70.070.0 70.0 76.0 76.0 76.0 RESULTS
Mix time,sec. 4 4 4 4 4 4 20 Cream time,sec. 14 11 12 10 9 9 Gel time, sec. 39 37 39 33 33 33 Density,pcf. 1.871.84 1.87 1.84 1.81 1.80 K-factor {BTU-in 0.1200.126 0.1270.122 0.127 0.128 2s hr-ft2) Mo3401 ., POLYOL C,pbw 100.0 100.0 100.0 100.0 100.0 100.0 K-l5,pbw 3.0 3.0 3.0 3.0 3.0 3.0 TMR-30,pbw 0.6 0.6 0.6 0.6 0.6 0.6 DC-193,pbw 1.5 1.5 1.5 1.5 1.5 1.5 HCFC-123,pbw 45.4 36.09 36.09 -- -- --HCFC-141b,pbw -- -- -- 33.4 28.08 28.08 l0 2-MB,pbw -- 4.01 -- -- 3.12 --n-P,pbw -- -- 4.01 -- -- 3.12 A-SIDE
ISO-B,pbw 158.5 158.5 158.5 158.5 158.5 158.5 Mix time,sec. 4 4 4 4 4 4 Cream time,sec. 21 17 20 16 16 16 Gel time, sec. 35 36 35 30 31 30 Density,pcf. 1.97 1.94 1.95 1.88 1.82 1.82 2o K-factor (BTU-in 0.130 0.128 0.131 0.133 0.134 0.134 hr-ft2) Mo3401 _7_ POLYOL A,pbw 33.5 36.4 33.5 36.4 POLYOL B,pbw 33.5 36.4 33.5 36.4 L-5440,pbw 1.5 1.5 1.5 1.5 PMTDA,pbw 2.2 2.2 2.2 2.2 TMEDA,pbw 1.1 1.1 1.1 1.1 HCFC-123,pbw 17.74 -- 24.39 --to HCFC-141b,pbw -- 15.59 -- 16.44 2-MB,pbw 10.46 6.81 -- --n-P,pbw -- -- 3.81 5.96 A-SIDE
1s ISO-A,pbw 70.0 76.0 70.0 76.0 RESULTS
Mix time,sec. 5 5 5 5 Cream time,sec. 11 9 13 7 2o Gel time, sec. 38 37 38 29 Density,pcf. 1.34 1.27 1.69 1.63 K-factor (BTU-in 0.152 0.162 0.130 0.132 hr-ft2) 2s Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention so except as it may be limited by the claims.
Mo3401
Claims (3)
1. In a process for the preparation of closed cell, rigid foams by reacting a) a polyol component having a hydroxyl number of from about 200 to about 650, and b) an organic polyisocyanate, in the presence of c) a catalyst, d) a foam stabilizer, and e) a blowing agent, the improvement wherein the blowing agent comprises a mixture of i) from 30 to 95 percent by weight of a hydrochlorofluorocarbon selected from the group consisting of 2,2-dichlor-1,1,1-trifluoroethane and 1,1-dichloro-1-fluoroethane and ii) from 5 to 70 percent by weight of a hydrocarbon selected from the group consisting of n-pentane, 2-methylbutane, hexane, the position of isomers of hexane and mixtures thereof.
2. The process of Claim 1, wherein said blowing agent comprises a mixture of i) from 60 to 90 percent by weight of said hydrochlorofluorocarbon and ii) from 10 to 40 percent by weight of said hydrocarbon.
3. The process of Claim 1 wherein said hydrochlorofluorocarbon is 2,2-dichlor-1,1,1-trifluoroethane and 1,1-dichloro-1-fluoroethane and said hydrocarbon is n-pentane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/505,867 US5057547A (en) | 1990-04-06 | 1990-04-06 | Rigid foams using blends of chlorofluorocarbons and hydrocarbons as blowing agent |
| US07/505,867 | 1990-04-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2037715A1 CA2037715A1 (en) | 1991-10-07 |
| CA2037715C true CA2037715C (en) | 2001-10-16 |
Family
ID=24012206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002037715A Expired - Fee Related CA2037715C (en) | 1990-04-06 | 1991-03-07 | Rigid foams using blends of chlorofluorocarbons and hydrocarbons as blowing agent |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US5057547A (en) |
| CA (1) | CA2037715C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5124064A (en) * | 1990-12-19 | 1992-06-23 | Allied-Signal Inc. | Azeotrope-like compositions of 1,1-dichloro-1-fluoroethane; dichlorotrifluoroethane; ethanol; and alkane having 5 or 6 carbon atoms |
| US5124063A (en) * | 1990-12-20 | 1992-06-23 | Allied-Signal Inc. | Azeotrope-like compositions of 1,1-dichloro-1-fluoroethane; dichlorotrifluoroethane; methanol; and alkane having 5 or 6 carbon atoms |
| US5336696A (en) * | 1993-12-10 | 1994-08-09 | Nisshinbo Industries, Inc. | Halogen-free blowing agents that include cycloaliphatic hydrocarbons and are suitable for isocyanate-based polymeric foams |
| US5840212A (en) * | 1996-10-23 | 1998-11-24 | Bayer Corporation | Rigid foams with improved insulation properties and a process for the production of such foams |
| US20040126564A1 (en) * | 2000-11-15 | 2004-07-01 | Atlas Roofing Corporation | Thermosetting plastic foams and methods of production thereof using adhesion additives |
| US6866923B2 (en) * | 2000-11-15 | 2005-03-15 | Atlas Roofing Corporation | Thermosetting plastic foams and methods of production thereof using adhesion additives |
| US20040082675A1 (en) * | 2002-10-28 | 2004-04-29 | Schilling Steven L. | Rigid foams and a process for the production of such foams |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2524825A (en) * | 1945-09-14 | 1950-10-10 | Socony Vacuum Oil Co Inc | Metal cleaning composition |
| US3072582A (en) * | 1955-10-20 | 1963-01-08 | Gen Tire & Rubber Co | Polyether-urethane foams and method of making same |
| US3091551A (en) * | 1959-01-26 | 1963-05-28 | Wyandotte Chemicals Corp | Process of spraying a polyether-based polyurethane foam |
| US3391093A (en) * | 1959-04-01 | 1968-07-02 | Gen Tire & Rubber Co | Polyester-polyurethane foams and method of making same |
| NL254612A (en) * | 1959-08-12 | |||
| US3249546A (en) * | 1963-10-30 | 1966-05-03 | Du Pont | Azeotrope refrigerant compositions |
| US3846347A (en) * | 1967-11-15 | 1974-11-05 | Witco Chemical Corp | Rigid foams from polyurethane and methods and compositions for use in their preparation |
| US3745203A (en) * | 1971-08-19 | 1973-07-10 | Cincinnati Milling Machine Co | Process for molding polyurethane utilizing a mixture of two blowing agents |
| US4055521A (en) * | 1975-10-08 | 1977-10-25 | Allied Chemical Corporation | Constant boiling ternary compositions and the process for using such compositions in the preparation of polyurethane foam |
| US4055507A (en) * | 1975-12-31 | 1977-10-25 | E. I. Du Pont De Nemours And Company | Methylpentane/CClF2 CH2 Cl azeotropic mixtures |
| US4076644A (en) * | 1976-01-08 | 1978-02-28 | E. I. Du Pont De Nemours And Company | Storage stabile polyol-chlorofluoroalkane composition |
| US4248975A (en) * | 1978-03-22 | 1981-02-03 | Witco Chemical Corporation | Rigid shrink stable polyurethane foam derived from an adduct of an alkylene oxide having at least three carbon atoms and a polyol having at least four hydroxy groups and blown with a fluorinated-chlorinated alkane |
| JPH01141996A (en) * | 1987-11-30 | 1989-06-02 | Asahi Glass Co Ltd | Fluorinated hydrocarbon-based azeotropic mixture |
| JPH01141995A (en) * | 1987-11-30 | 1989-06-02 | Asahi Glass Co Ltd | Fluorinated hydrocarbon-based azeotropic mixture |
| US4795763A (en) * | 1988-04-18 | 1989-01-03 | The Celotex Corporation | Carbon black-filled foam |
-
1990
- 1990-04-06 US US07/505,867 patent/US5057547A/en not_active Expired - Lifetime
-
1991
- 1991-03-07 CA CA002037715A patent/CA2037715C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US5057547A (en) | 1991-10-15 |
| CA2037715A1 (en) | 1991-10-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |