CA1245225A - Polyether polyols, their manufacture and use in polyurethanes production - Google Patents
Polyether polyols, their manufacture and use in polyurethanes productionInfo
- Publication number
- CA1245225A CA1245225A CA000512920A CA512920A CA1245225A CA 1245225 A CA1245225 A CA 1245225A CA 000512920 A CA000512920 A CA 000512920A CA 512920 A CA512920 A CA 512920A CA 1245225 A CA1245225 A CA 1245225A
- Authority
- CA
- Canada
- Prior art keywords
- parts
- polyol
- polyether
- polyether polyol
- manufacture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- 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
- C08G18/48—Polyethers
- C08G18/487—Polyethers containing cyclic groups
- C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
Abstract
ABSTRACT
The invention relates to polyether polyols having an average hydroxyl value in the range of 100 to 250 mgKOH/g, which are alkoxylated derivatives of a polyhydric alcohol being a mixture of compounds according to formula (I) or/and (II) ( I ) or (II)
The invention relates to polyether polyols having an average hydroxyl value in the range of 100 to 250 mgKOH/g, which are alkoxylated derivatives of a polyhydric alcohol being a mixture of compounds according to formula (I) or/and (II) ( I ) or (II)
Description
E. 33559 The present invention rslates to new alkoxylated derivativ~s of certain polyhydric alcohols and their use as compatibi-lising agent in the manufacture of polyurethanes, more particularly rigid polyurethane foams.
When the components of rigid polyurethane foam are mixed there is a tendency for the polyol component to separate from the isocyanate component, pol~meric MDI for example, due to physical incompatibility. Under conditions of high mixing efficiency (i.e. impingement under high pressure, 200 bar for example, or mixing under high shear) polymerisation and foaming occurs before separation can take place~
However, under conditions of low mixing eficiency (i.e. low shear) often encountered in laxge scale production, the rigid foams produced have areas rich in polyol and areas rich in isocyanate. Under very low shear with badly mixing components the actual polymerisation reaction may be impaired.
Using a laboratory variable shear mixer the behaviour of commercial systems may be investigated and the above conclu-sions can be substantia~ed.
It has now been observed, quite surprisingly, tha~ the addition of a small amount of a defined polyether polyol derived from the polyalkoxylation of a by-product of penta-~S~25 erythritol manufacture, from formaldehyde and acetaldehyde, behaves as a compatibilising agent for certain polyols with polyisocyanatesc Known compatibilising agents are based on expensive glycerol derivatives.
The cheap and readily available pentaerythritol residues are a mixture of pentaeryth.ritol and pentaerythritol derivatives comprising formaldehyde derived acetals according to the general formula tI) C/ \ C
Rl O - CH / CH20R2 ~5 or ~
C /
where Rl is ~, -C~3 or -OCH3 R2 is -H, -CH2OH or -CH2C(CH2OH)3 R3 and R4, which may be the same ~r different, are -H
CH2OH~ OCH2C(CH2H)3 .. _ _ _ , . ....
These pentaerythritol by-products and alkoxylated derivatives thereof are Eurther described in Canadian Patent 1,223,599.
This patent discloses polyether polyol having an average hydroxyl value in the range 400-650 mgKOH/g which i5 a mixture of alkoxylated derivatives of compounds of formula I and II.
Canadian Patent Application 500,78~ describes polyester polyols derived from such polyether polyol.
The polyhydric alcohol according to formula tI) and (II) is used as an initiator or alkoxylation with an alkylene oxide, such as propylene oxide, ethylene oxide, butylene oxide or mixtures of two or more alkylene oxides. Alkoxylation may take place sequentially with different alkylene oxides.
The preferred polyether polyols of the invention are derived ~rom propylene oxide and ethylene oxlde.
A method o oxalkylation to afford the defined polyether polyol of the invention is known and is described in detail in the examples 1 and S. Other methods well-known to the man skilled in the art may also be used. The above mentioned by-products should be oxyalkylated to a hydroxyl value in . ~
~":
When the components of rigid polyurethane foam are mixed there is a tendency for the polyol component to separate from the isocyanate component, pol~meric MDI for example, due to physical incompatibility. Under conditions of high mixing efficiency (i.e. impingement under high pressure, 200 bar for example, or mixing under high shear) polymerisation and foaming occurs before separation can take place~
However, under conditions of low mixing eficiency (i.e. low shear) often encountered in laxge scale production, the rigid foams produced have areas rich in polyol and areas rich in isocyanate. Under very low shear with badly mixing components the actual polymerisation reaction may be impaired.
Using a laboratory variable shear mixer the behaviour of commercial systems may be investigated and the above conclu-sions can be substantia~ed.
It has now been observed, quite surprisingly, tha~ the addition of a small amount of a defined polyether polyol derived from the polyalkoxylation of a by-product of penta-~S~25 erythritol manufacture, from formaldehyde and acetaldehyde, behaves as a compatibilising agent for certain polyols with polyisocyanatesc Known compatibilising agents are based on expensive glycerol derivatives.
The cheap and readily available pentaerythritol residues are a mixture of pentaeryth.ritol and pentaerythritol derivatives comprising formaldehyde derived acetals according to the general formula tI) C/ \ C
Rl O - CH / CH20R2 ~5 or ~
C /
where Rl is ~, -C~3 or -OCH3 R2 is -H, -CH2OH or -CH2C(CH2OH)3 R3 and R4, which may be the same ~r different, are -H
CH2OH~ OCH2C(CH2H)3 .. _ _ _ , . ....
These pentaerythritol by-products and alkoxylated derivatives thereof are Eurther described in Canadian Patent 1,223,599.
This patent discloses polyether polyol having an average hydroxyl value in the range 400-650 mgKOH/g which i5 a mixture of alkoxylated derivatives of compounds of formula I and II.
Canadian Patent Application 500,78~ describes polyester polyols derived from such polyether polyol.
The polyhydric alcohol according to formula tI) and (II) is used as an initiator or alkoxylation with an alkylene oxide, such as propylene oxide, ethylene oxide, butylene oxide or mixtures of two or more alkylene oxides. Alkoxylation may take place sequentially with different alkylene oxides.
The preferred polyether polyols of the invention are derived ~rom propylene oxide and ethylene oxlde.
A method o oxalkylation to afford the defined polyether polyol of the invention is known and is described in detail in the examples 1 and S. Other methods well-known to the man skilled in the art may also be used. The above mentioned by-products should be oxyalkylated to a hydroxyl value in . ~
~":
2~
the range of 100 to 2S0 mg KOH/g, most preferably 125 to 175 mg KOH/g. The amount of the polyether polyol of the present invention to be added to the main polyol blend is in the range of 1 ~o 20 parts on 100 parts of polyol, most prefe-rably 5 to 15 parts. The use of the resulting polyol blend for rigid foam manufacture i5 given in the examples A to E
and the benefits are described.
The main polyol blend to which the polyol of the invention is added preferably consists of one or more polyether polyol based for example on sucro~e, sorbitol, glycerol, bisphenol A, alkanolamine, toluene diamine, polyalkylene-polyamine or mixtures thereof, oxyalkylated to a hydroxyl value ranging ~rom 200 to Ç00 mgKOH/g. The polyol blend may also be a polyester polyol or a mixture of polyether and polyester polyols.
The present invention includes the manufacture of polyure-thane products, for example polyurethane foams, in known manner, from the polyether and polyester polyols described above to which the polyol of the invention has been added, and also includes polyure~hane products so prepared.
Polyurethane products are made by reacting a di- or poly-isocyanate with the described polyether and polyester polyols. The nature of the polyurethane product, for example the polyurethane foam may ~e varied depending on a ~52;~5 variety of factors such as the func~ionali~y of the reactants and the presence of active ingredients.
The organic di~ or polyisocyanates may be any o. the isocyanates known to be useful for the formation o~ poly-urethane products such as polyurethane foams~ Of parti-cular interest are aromatic di- or polyisocyanates, for example tolylene diisocyanate and especially diphenylmethane diisocyanate (MDI) which are commercialy available in a variety of forms. Suitable diphenylmethane di-isocyanates include :
(a) diphenylmethane 4,4' diisocyanate and mixtures thereof with other isomers of diphenylmethane diisocyanate;
~b) methylene bridged polyphenylpolyisocyanates prepared by phosgenation of mixtures of appropriate polyamines obtained by the condensation of aniline and formaldehyde and known as 'polymeric ' MDI, the composition of which may subsequently be varied by distillation, crystallisation or other separation techniques ~o give products with a weight average functionality in the range 2 to at least 3.3 ;
c) polymers and oligomers obtained by reacting diphenylmethane dii~ocyana~es or polymeric MDI with a monomeric glycol or polyhydric alcohol (or mixtures thereof) or with a hydroxyl-ended polyester or polyether and known as 'MDI prepolymers'; and ~L2~ 5 d) modified diphenylmethane diisocyanates or 'polymeric MDI' in which a proportion of the isocyanate groups are converted into other groups such as carbodi-imide, uretoneimine, biuret or allophanate groups, or in which a proportion of the isocyanate groups are re~c~ed with an isocyanate-reactive compound.
The prepara~ion of the foamed polyurethane materials may be carried out by the general methods fully described elsewhereO Thus ~he foam forming components may be mixed continuously or discontinuously in the presence of the gas generating agent to give a foam. The foam forming gas may be generated by a variety of methods. For example the gas may be carbon dioxide generated by the reaction of a propor~ion of the organic isocyanate wlth water incorporated in the reaction mixture. Gas may also be generated by lncorporating in the reaction mixture an inert liguid of low boiling point which vaporises during the exothermic polyurethane foaming reaction . Mixtures of water with inert low boiling point liquids may be used if desired.
Suitable inert low-boiling point li~uids are liquids that are inert towards the polyurethane foam forming ingredients and have boiling point not exceeding 75 deg C at atmospheric pressure and preferably between -40 deg C and 50 deg C.
Ex~mples of such liquids are halogenated hydrocarbons such ..... .. ...... _ . ... ~.. .. _ .. _ _, .. . . _. . .. .. . . . .. .... . . .
~Z~5Z;;~5;
as methylene chloride, trichloromonofluoromethane, dichloro-difluoromethane, dichloromonofluoromethane, monochlorodifluoro-methane, dichlorotetrarluoroethane, l,1,2-trichlor-1,2,2-tri-fluoroe~hane, dibromofluoromethane and monobromotrifluoro-e~hans. Mixtures of these low boiling liquids one withanother and/or with other substituted or unsubstituted hydrocarbons may also be used. Such li~uids are usually employed in amounts of from 1% to 100%, preferably 5% ~o 35%
by weight of the polyol.
It is ~enerally preferred to carry out the foam prep~ration in a single stage reaction of the organic polyisocyanate with the polyol in the presence of gas-generating asent.
If desired there may also be included in the polyurethane forming reaction mixture a c~talyst. Suitable catalysts are well known in the art and inalude basic compounds of all types but particularly tertiary amines. Examples of suitable tertiary amines include triethylamine, dimethyl cycohexyl-amine~ dimethylbenzylamine, dimethylphenylethylamine,tetramethyl-1,3-butanediamine, triethylene diamine, N-alkyl morpholines, N-alkylpyrrolidines and fully N-substituted 4-aminopyridines such as 4-dimethylaminopyridine, and bis (2~dimethylaminoethyl)ether.
Other suitable catalysts include basic and non-basic organic . , . .. _ . .. _ _ _ .__ _ . ,. _ . . . _ . . ....
2~i compounds of metals, for example dibutyltin dilaurate, manganese acetylacetonate, stannous carboxylates such as stannous octoate. Mixtures of catalysts are often particu-larly advantageous. As described in the prior axt, the general methods of preparation of foamed polyurethane ma include the incorporation in the polyurethane forming mixture of various additives such as ~urface-active agents.
Suitable surace active agPnts include silicone fluids and particularly siloxane-oxyalkylene block copolymers. Oxy-ethylated phenols, oxyethylated fatty alcohols and block copolymers of ethylene and propylene oxides are examples of other surface-active agents which may be emploved.
The polyurethane forming reaction may further be modified by the inclusion of known addi~ives such as fillers, plasticisers, flame-retardants such as tris(beta-chloroethyl)phosphate, tris(beta-chloroisopropyl)phosphate or antimony oxide and antioxidants.
The resulting polyurethane foams and articles made thereof are also within the scope of the present invention.
The invention is illustrated bu~ not limited by the following examples in which all parts and percentages are by weight.
~2~
g _ _ Production of the polyether polyol of the invention. X
parts of pentaerythritol residues having a hydroxyl value of 796 mgKOH/g and containing 0.24 % sodium formate is charged to a stainless steel reactor and purged well with nitrogen.
This residue is a mixture of polyhydric alcohols as follows :
5-(5-hydroxy methyl-1,3-dioxane)-methanol 58.6~
5-(5-hydroxy methyl-1,3-dioxane)-methoxy-methanol 8.1 %
pentaerythritol 9.4 %
pentaerythritol monohydroxymethylether 8.7 %
other polyhydric alcohols according to either of formula I
and II each individually present at less than 3% totalling, 15.2%
Water and other volatiles are removed by heating to 150 deg C with agitation under reduced pressure. Y parts of propylene oxide is added over 7 hours, maintaining the temperature at 150-160 deg C and allowing the pressure to rise to a maximum of 4.5 bar absolute. On completion of the addition the reaction is allowed to continue until the pressure remains constant. The residual propylene oxide is removed by applying vacuum, and maintaining the temperature at 150-160 deg C for 30 min.
9100 parts of the resulting polyol A cooled to 40 deg C is treated with 1000 parts of water, and passed through an acid ion-exchange resin at 40 deg C . The water is then removed under reduced pressure at 110 deg C untill the water content is less than 0O1 %
The obtained produc~s la, lb, lc and ld have a hydroxyl value, an acid value and a viscosity at 25 deg. Celsius as stated in Table I.
10Table I.
Example Y hydroxy~ acid valxe viscocity _ _ _ mgKOHg mo centistokec 1 a 3501 15886 155 0.1 384 l b 2870 7130 245 ___ ___ 1 c 2870 21,639 105 0.1 354 I ~ ~343 7654 205 0.03 410 EXAM~7LE 2 8198 parts of untreated polyol product 1 a of example 1 is neutralised with 11.4 parts of 85 % phosphoric acid solution diluted with 425 parts of water, at 80 deg C . The water is removed slowly under reduced pressure allowing the temperature ~2gL~2~
to rise to 120 deg c . When th~ water content is less than 0.1 % the material is passed through a heated Calmic filter to remove the precipitated phosphate salt. The product has a hydroxyl value of 152 mg KOH/g , an acid value of 0~26 mgKOH/g, a water content of 0.025 %, a viscosity at 25 deg C
of 356 centistokes and a sodium content of 4 ppmO
5497 parts of the un~reated polyol product lb of example 1 having a hydroxyl value of 24S mgKOHg 1 is charged to a stainless s~eel reactor and purged well with nitrogen. A
nitrogen pressure of 1 bar gauge is applied to the reaction vessel. The temperature is raised to 120 deg. Celsius and 3603 parts of ethylene oxide are added with agitation, over a period of 4 hours. On completion of the addition the reaction is allowed to continue un~il the pressure remains constant. The residual ethylene oxide is ramoved by applying vacuum at 120 deg. Celsius for 30 min.
8100 parts of the resultiny polyol cooled to 40 deg. Celsius is treated with 1000 parts of water, and passed through an acid ion exchange resin at 40 degO Celsius. The water is then removed under reduced pressure at 110 deg. Celsius until the water content is less than 0O1 %.
52%~
-12~
The product 3 has a hydroxyl value of 150 mg KOHg 1, a water contsnt of 0.02 %, an acid value or 0.07 mgKO'dg 1 and a viscosity of 267 centistokes.
~X~MPL~ 4 2912 parts of the pentaerythritol residues of example 1 is charged to a stainless steel reactor and purged with nitrogen. Water and other volatiles are removed by heating to 120 deg. Celsius with agitation under reduced pressure for 1 hour. A~ a temperature of 120 deg. Celsius a pressure of 1 bar gauge of nitrogen is applied to the reac~or and e~hylene oxide is added. 13,545 parts of ethylene oxide is added with agitation in 6 1/2 hours. On completion of the addition the reaction is allowed to continue until the pressure remains constant. The residual ethylene oxide is removed by applying vacuum at 120 deg. Celsius for 30 min.
8100 parts of the resulting polyol cooled to 40 de~. Celsius is treated with 1000 parts of water and passed through as acid lon exchange resin at 40 deg. Celsius. The wat.er is then removed under ~educed pressure at 110 deg. Celsius until the water content is less than 0.1 %. The product 4 has a hydroxyl value of 150 mgKOHg 1l a water content of 0.02 %, an acid value of 0.06 mgKOHq 1 and a viscosity of 305 centistokes.
~2~ 5 2912 parts of tne pentaerythritol residues of example 1 is charged to a stainless steel reactor and purged with nitrogen. Water and other volatiles are removed by hea~ing to 120 deg. Celsius with agitation under reduced pressure for 1 hour. At a tempera~ure of 120 deg. Celsius, a pressure of 1 bar gauge of nitrogen is applied to the reaction and ethylene oxide is added. 6872 parts of ethylene oxide is added with agitation in 6 1/2 hours. On completion of the addition the reaction is allowed to continue until the pressure remains cons~ant. The residual ethylene oxide is removed by applying vacuum at 120 deg.
Celsius for 30 min. 6674 parts of propylene oxide is added over 7 hours, maintaining the temperature at 150 - 160 deg.
Celsius and allowing the pressure to rise to a maximum of 4.5 bar absolute. On completion of the addition the reaction is allowed to continue until the pressure remains constant. 'rhe residual propylene oxide is removed by applying vacuum, and maintaining the ~emperature at 150 -160 deg Celsius for 30 min.
9100 parts of the resulting polyol cooled to 40 deg. Celsius is treated with 1000 parts of water and passed through an acid ion exchange resin at 40 deg. Celsius. The water is then removed under reduced pressure at 110 deg. Celsius until the water content is less than 0.1%. The product S has a hydroxyl value of 150 mg KOHg 1, a water content of 0.02% and a viscosity of 305 centistokes.
Ex~le A
__ __ .
A polyol blend consisting of 100 parts of a sorbitol based polyol of hydroxyl value 490 mgKO~/g, 15 parts of a fire retardant based on tris(beta~chloroisopropyl)phosphate, 2.5 parts of a catalyst based on N,N dimethylcyclohexylamine, 1.5 part of water, 1.5 parts of a oxyalkylene block copolymer surfactant, 0.1 part of alpha methyl styrene and 42.5 parts of 'Arcton' 11 fluorocarbon, was reacted with 148.9 parts of 'Suprasec' DNR methylene diphenyl diisocyanate ('Arcton' and 'Suprasec' are trademarks of Imperial Chemical Industries PLC).
The polyol and isocyanate components were mixed with a variable shear mixer. At low shear and hence low mixing efficiency the above system produced poor quality foam w;th both isocyanate rich and polyol rich areas and large cells. The addition, to the polyol blend, of 10 parts of the polyol product 1 a as described in example 1 and the commensurate increase in isocyanate amount to 153.4 parts in order to maintain the index and the increase in fluorocarbon 'Arcton' All* to 46.2 parts in order to maintain the blowing ratio, resulted in better mixing under low shear as exemplified by better ~uality foam and a decrease in the heterogeneity of the constituents and a decrease in the visible cell size.
Exam~le B
___ _ The addition, to the polyol blend used in example A/ of ll.S
parts of the polyol product as described in example 1 c and the commensurate increase in isocyanate amount to 151.8 parts in * Trademark ~, 2~5Z~5 order to maintain the index and the increase in fluorocarbon 'Arcton' All* to 46 parts in order to maintain the blowing ratio, resulted in better mixing under low shear as exemplified by better quality foam and a decrease in the heterogeneity of the constituents and a decrease in the visible cell size.
Exam~le C
____ ____ The addition, to the polyol used in example A, of 10 parts of the polyol products as described in example 3 and the commensurate increase in isocyanate amount to 153.4 parts in order to maintain the index and the increase in fluorocarbon 'Arcton' All* to 46.2 parts in order to mai.ntain the blowing * Trademark /
/
. . . .. . _ _ 2~225;
ra~io, result~d in better mixing under low shear as exemplified by better ~uality foam and a decrease in the heterogeneity of the constltuents and a decrease in ~he visible cell si~e.
ExamPle D
A polyol blend consisting of 25 parts of a glycerol based polyol of hydroxyl value 540 mg KOH/g, 75 parts of a toluene diamine based polyol of hydroxyl value 390 mg KOE/g, 2 parts of a catalyst based on N,N-dimethylcyclohexylamine, 2 parts of water, 1.5 parts of a siloxane oxyalkylene block copolymer surfactant, and 37.5 parts of 'Arcton'll ~trademark) flu~rocarbon, was reacted with 142.8 parts of 'Suprasec'DNR
(trademark) polymeric MDIo The polyol and isocyanate components were mixed with a variable shear mixer. At low shear the system as described produced poor quality foam. The addition of 10 parts of the polyol o~ example 1 a and the commensurate increase of isocyanate and fluorocarbon A 11 to 145.3 parts and 41 parts respectively! resulted in better mixing under low shear as exemplified by better quality foam. In addition a marked decrease in surface friability was observed in that the adhesion of the ~oam coverings were much enhanced.
~Z~Z2S
Example E
In addition to the polyol blend used in exa~ple D of 10 parts of the polyol of example 5 and the commensurate increase of isocyanate and fluorocarbon All to 145.3 parts and 41 parts respectively, resulted in better mixing under low shPar as exemplified by better quality foam ~
A polyol blend consisting of 53 parts of a sorbitol based polyol of hydroxyl value 555 mg KOH/~, 66 parts of a sucrose . based polyol of hydroxyl value 440 mg KOH/g, 13 parts of a toluene diamine/alkanolamine based polyol of hydroxyl value.
502 mg/KOH/g, 2.6 parts of wa~er, 2.6 parts of a catalyst based on N,N-dime~hylcyclohexylamine, 2.0 parts of a silo-xane oxyalkylene block copolymeric surfactant and 50.4 parts of 'Arcton' 11 fluorocarbon (trademar~) , was reacted with 209 parts of 'Suprasec DNR' ttrademark) polymeric MDI. As in the previous examples , at low shear bad ~uality ~oams were obtained. The addition of 9.7 parts of the polyol of the invention of examples la or 2 and the commensurate increase of the polyisocyanate and blowing agent to respec-tively 214.2 parts and 55.5 parts resulted in better mixing at low shear and hence better quality foam and reduction in the visible cell sizes.
~2~L~2Z~
Example G
The addition to the polyol blend used in example F of 9.7 parts of the polyol of example 4 and the commensurate increase of the polyisocyanate and blowing âgent to respectively 214.2 par~s and 55.5 parts resulted in better mixing at low shear and better quality foams and reduction in the visible cell size.
Example H
The addition to the polyol blend used in example F of 13.2 parts of the polyol of example 1 c and the commensurate increase of the polyisocyanate and blowing agent to respectively 211.5 parts and 55.5 parts resulted in ~etter mixing at low shear and better quality foam and reduction in the visible cell sizes.
Example I
A polyol blend consisting of 100 parts of a sucrose based polyol of hydxoxyl value 440 mg KOH/gr 2 parts of water, 3 parts of a mixture of catalysts based on N,N-dimethylcyclohexylamine ~z~%~
and bis(2-dimethylaminoethyl)ether, 2 parts of a mixture of siloxane oxyalkylene surfactants ('Tegostab' ttrademark) B8404 and B1903 ,trademaxks of Goldschmidt AG) and 37~6 parts of fluorocarbon 'Arcton' 11 ttrademark) was reacted with 141.8 part~ of 'Suprasec' (~rademark) D~R polymeric MDI. As in the previous examples , at low shear bad quality foams were obtained. The addition of 10 parts of the polyol of the invention of example 1 a or 3, and the commensurate increase of the polyisocyanat and blowing agent to respectively 141.9 parts and 39O9 parts resulted in better mixing a~ low shear and hence better quality foam and reduction in the visible cell size.
ExamPle J
A polyol blend consisting of 50 parts of a sucrose based polyol of hydroxyl value 310 mg KOHg 1, 30 parts of a toluene diamine based polyol of hydroxyl value 390 mgKOHg 1, 10 parts of glycerol based polyol of hydroxyl value 540 mgKOHg 1, 10 parts of a glycerol based polyol of hydroxyl value 1120 mgKOHg 1, 1.9 parts of water, 2~5 parts of a catalyst based o~ N,N~dimethylcyclohexylamine, 2.0 parts of a mixture of siloxane oxyalkylene block copolymeric surfactants and 31~9 parts of 'Arcton' 11 fluorobarcon (~rade mark~, was reacted wi~h 135 parts of 'Suprasec DND' (trade mark) polymeric MDI~
~2~ 25 As in the previous examples, at low shear bad quality foams were obtained. The addition of 10 parts of the polyol of the invention of example la and the commensurate increase of polyisocyanate and blowing agent to respectively 151.9 parts and 34O9 parts resulted in better mixing at low shear and hence better quality foam and reduction in the visible cell sizes.
the range of 100 to 2S0 mg KOH/g, most preferably 125 to 175 mg KOH/g. The amount of the polyether polyol of the present invention to be added to the main polyol blend is in the range of 1 ~o 20 parts on 100 parts of polyol, most prefe-rably 5 to 15 parts. The use of the resulting polyol blend for rigid foam manufacture i5 given in the examples A to E
and the benefits are described.
The main polyol blend to which the polyol of the invention is added preferably consists of one or more polyether polyol based for example on sucro~e, sorbitol, glycerol, bisphenol A, alkanolamine, toluene diamine, polyalkylene-polyamine or mixtures thereof, oxyalkylated to a hydroxyl value ranging ~rom 200 to Ç00 mgKOH/g. The polyol blend may also be a polyester polyol or a mixture of polyether and polyester polyols.
The present invention includes the manufacture of polyure-thane products, for example polyurethane foams, in known manner, from the polyether and polyester polyols described above to which the polyol of the invention has been added, and also includes polyure~hane products so prepared.
Polyurethane products are made by reacting a di- or poly-isocyanate with the described polyether and polyester polyols. The nature of the polyurethane product, for example the polyurethane foam may ~e varied depending on a ~52;~5 variety of factors such as the func~ionali~y of the reactants and the presence of active ingredients.
The organic di~ or polyisocyanates may be any o. the isocyanates known to be useful for the formation o~ poly-urethane products such as polyurethane foams~ Of parti-cular interest are aromatic di- or polyisocyanates, for example tolylene diisocyanate and especially diphenylmethane diisocyanate (MDI) which are commercialy available in a variety of forms. Suitable diphenylmethane di-isocyanates include :
(a) diphenylmethane 4,4' diisocyanate and mixtures thereof with other isomers of diphenylmethane diisocyanate;
~b) methylene bridged polyphenylpolyisocyanates prepared by phosgenation of mixtures of appropriate polyamines obtained by the condensation of aniline and formaldehyde and known as 'polymeric ' MDI, the composition of which may subsequently be varied by distillation, crystallisation or other separation techniques ~o give products with a weight average functionality in the range 2 to at least 3.3 ;
c) polymers and oligomers obtained by reacting diphenylmethane dii~ocyana~es or polymeric MDI with a monomeric glycol or polyhydric alcohol (or mixtures thereof) or with a hydroxyl-ended polyester or polyether and known as 'MDI prepolymers'; and ~L2~ 5 d) modified diphenylmethane diisocyanates or 'polymeric MDI' in which a proportion of the isocyanate groups are converted into other groups such as carbodi-imide, uretoneimine, biuret or allophanate groups, or in which a proportion of the isocyanate groups are re~c~ed with an isocyanate-reactive compound.
The prepara~ion of the foamed polyurethane materials may be carried out by the general methods fully described elsewhereO Thus ~he foam forming components may be mixed continuously or discontinuously in the presence of the gas generating agent to give a foam. The foam forming gas may be generated by a variety of methods. For example the gas may be carbon dioxide generated by the reaction of a propor~ion of the organic isocyanate wlth water incorporated in the reaction mixture. Gas may also be generated by lncorporating in the reaction mixture an inert liguid of low boiling point which vaporises during the exothermic polyurethane foaming reaction . Mixtures of water with inert low boiling point liquids may be used if desired.
Suitable inert low-boiling point li~uids are liquids that are inert towards the polyurethane foam forming ingredients and have boiling point not exceeding 75 deg C at atmospheric pressure and preferably between -40 deg C and 50 deg C.
Ex~mples of such liquids are halogenated hydrocarbons such ..... .. ...... _ . ... ~.. .. _ .. _ _, .. . . _. . .. .. . . . .. .... . . .
~Z~5Z;;~5;
as methylene chloride, trichloromonofluoromethane, dichloro-difluoromethane, dichloromonofluoromethane, monochlorodifluoro-methane, dichlorotetrarluoroethane, l,1,2-trichlor-1,2,2-tri-fluoroe~hane, dibromofluoromethane and monobromotrifluoro-e~hans. Mixtures of these low boiling liquids one withanother and/or with other substituted or unsubstituted hydrocarbons may also be used. Such li~uids are usually employed in amounts of from 1% to 100%, preferably 5% ~o 35%
by weight of the polyol.
It is ~enerally preferred to carry out the foam prep~ration in a single stage reaction of the organic polyisocyanate with the polyol in the presence of gas-generating asent.
If desired there may also be included in the polyurethane forming reaction mixture a c~talyst. Suitable catalysts are well known in the art and inalude basic compounds of all types but particularly tertiary amines. Examples of suitable tertiary amines include triethylamine, dimethyl cycohexyl-amine~ dimethylbenzylamine, dimethylphenylethylamine,tetramethyl-1,3-butanediamine, triethylene diamine, N-alkyl morpholines, N-alkylpyrrolidines and fully N-substituted 4-aminopyridines such as 4-dimethylaminopyridine, and bis (2~dimethylaminoethyl)ether.
Other suitable catalysts include basic and non-basic organic . , . .. _ . .. _ _ _ .__ _ . ,. _ . . . _ . . ....
2~i compounds of metals, for example dibutyltin dilaurate, manganese acetylacetonate, stannous carboxylates such as stannous octoate. Mixtures of catalysts are often particu-larly advantageous. As described in the prior axt, the general methods of preparation of foamed polyurethane ma include the incorporation in the polyurethane forming mixture of various additives such as ~urface-active agents.
Suitable surace active agPnts include silicone fluids and particularly siloxane-oxyalkylene block copolymers. Oxy-ethylated phenols, oxyethylated fatty alcohols and block copolymers of ethylene and propylene oxides are examples of other surface-active agents which may be emploved.
The polyurethane forming reaction may further be modified by the inclusion of known addi~ives such as fillers, plasticisers, flame-retardants such as tris(beta-chloroethyl)phosphate, tris(beta-chloroisopropyl)phosphate or antimony oxide and antioxidants.
The resulting polyurethane foams and articles made thereof are also within the scope of the present invention.
The invention is illustrated bu~ not limited by the following examples in which all parts and percentages are by weight.
~2~
g _ _ Production of the polyether polyol of the invention. X
parts of pentaerythritol residues having a hydroxyl value of 796 mgKOH/g and containing 0.24 % sodium formate is charged to a stainless steel reactor and purged well with nitrogen.
This residue is a mixture of polyhydric alcohols as follows :
5-(5-hydroxy methyl-1,3-dioxane)-methanol 58.6~
5-(5-hydroxy methyl-1,3-dioxane)-methoxy-methanol 8.1 %
pentaerythritol 9.4 %
pentaerythritol monohydroxymethylether 8.7 %
other polyhydric alcohols according to either of formula I
and II each individually present at less than 3% totalling, 15.2%
Water and other volatiles are removed by heating to 150 deg C with agitation under reduced pressure. Y parts of propylene oxide is added over 7 hours, maintaining the temperature at 150-160 deg C and allowing the pressure to rise to a maximum of 4.5 bar absolute. On completion of the addition the reaction is allowed to continue until the pressure remains constant. The residual propylene oxide is removed by applying vacuum, and maintaining the temperature at 150-160 deg C for 30 min.
9100 parts of the resulting polyol A cooled to 40 deg C is treated with 1000 parts of water, and passed through an acid ion-exchange resin at 40 deg C . The water is then removed under reduced pressure at 110 deg C untill the water content is less than 0O1 %
The obtained produc~s la, lb, lc and ld have a hydroxyl value, an acid value and a viscosity at 25 deg. Celsius as stated in Table I.
10Table I.
Example Y hydroxy~ acid valxe viscocity _ _ _ mgKOHg mo centistokec 1 a 3501 15886 155 0.1 384 l b 2870 7130 245 ___ ___ 1 c 2870 21,639 105 0.1 354 I ~ ~343 7654 205 0.03 410 EXAM~7LE 2 8198 parts of untreated polyol product 1 a of example 1 is neutralised with 11.4 parts of 85 % phosphoric acid solution diluted with 425 parts of water, at 80 deg C . The water is removed slowly under reduced pressure allowing the temperature ~2gL~2~
to rise to 120 deg c . When th~ water content is less than 0.1 % the material is passed through a heated Calmic filter to remove the precipitated phosphate salt. The product has a hydroxyl value of 152 mg KOH/g , an acid value of 0~26 mgKOH/g, a water content of 0.025 %, a viscosity at 25 deg C
of 356 centistokes and a sodium content of 4 ppmO
5497 parts of the un~reated polyol product lb of example 1 having a hydroxyl value of 24S mgKOHg 1 is charged to a stainless s~eel reactor and purged well with nitrogen. A
nitrogen pressure of 1 bar gauge is applied to the reaction vessel. The temperature is raised to 120 deg. Celsius and 3603 parts of ethylene oxide are added with agitation, over a period of 4 hours. On completion of the addition the reaction is allowed to continue un~il the pressure remains constant. The residual ethylene oxide is ramoved by applying vacuum at 120 deg. Celsius for 30 min.
8100 parts of the resultiny polyol cooled to 40 deg. Celsius is treated with 1000 parts of water, and passed through an acid ion exchange resin at 40 degO Celsius. The water is then removed under reduced pressure at 110 deg. Celsius until the water content is less than 0O1 %.
52%~
-12~
The product 3 has a hydroxyl value of 150 mg KOHg 1, a water contsnt of 0.02 %, an acid value or 0.07 mgKO'dg 1 and a viscosity of 267 centistokes.
~X~MPL~ 4 2912 parts of the pentaerythritol residues of example 1 is charged to a stainless steel reactor and purged with nitrogen. Water and other volatiles are removed by heating to 120 deg. Celsius with agitation under reduced pressure for 1 hour. A~ a temperature of 120 deg. Celsius a pressure of 1 bar gauge of nitrogen is applied to the reac~or and e~hylene oxide is added. 13,545 parts of ethylene oxide is added with agitation in 6 1/2 hours. On completion of the addition the reaction is allowed to continue until the pressure remains constant. The residual ethylene oxide is removed by applying vacuum at 120 deg. Celsius for 30 min.
8100 parts of the resulting polyol cooled to 40 de~. Celsius is treated with 1000 parts of water and passed through as acid lon exchange resin at 40 deg. Celsius. The wat.er is then removed under ~educed pressure at 110 deg. Celsius until the water content is less than 0.1 %. The product 4 has a hydroxyl value of 150 mgKOHg 1l a water content of 0.02 %, an acid value of 0.06 mgKOHq 1 and a viscosity of 305 centistokes.
~2~ 5 2912 parts of tne pentaerythritol residues of example 1 is charged to a stainless steel reactor and purged with nitrogen. Water and other volatiles are removed by hea~ing to 120 deg. Celsius with agitation under reduced pressure for 1 hour. At a tempera~ure of 120 deg. Celsius, a pressure of 1 bar gauge of nitrogen is applied to the reaction and ethylene oxide is added. 6872 parts of ethylene oxide is added with agitation in 6 1/2 hours. On completion of the addition the reaction is allowed to continue until the pressure remains cons~ant. The residual ethylene oxide is removed by applying vacuum at 120 deg.
Celsius for 30 min. 6674 parts of propylene oxide is added over 7 hours, maintaining the temperature at 150 - 160 deg.
Celsius and allowing the pressure to rise to a maximum of 4.5 bar absolute. On completion of the addition the reaction is allowed to continue until the pressure remains constant. 'rhe residual propylene oxide is removed by applying vacuum, and maintaining the ~emperature at 150 -160 deg Celsius for 30 min.
9100 parts of the resulting polyol cooled to 40 deg. Celsius is treated with 1000 parts of water and passed through an acid ion exchange resin at 40 deg. Celsius. The water is then removed under reduced pressure at 110 deg. Celsius until the water content is less than 0.1%. The product S has a hydroxyl value of 150 mg KOHg 1, a water content of 0.02% and a viscosity of 305 centistokes.
Ex~le A
__ __ .
A polyol blend consisting of 100 parts of a sorbitol based polyol of hydroxyl value 490 mgKO~/g, 15 parts of a fire retardant based on tris(beta~chloroisopropyl)phosphate, 2.5 parts of a catalyst based on N,N dimethylcyclohexylamine, 1.5 part of water, 1.5 parts of a oxyalkylene block copolymer surfactant, 0.1 part of alpha methyl styrene and 42.5 parts of 'Arcton' 11 fluorocarbon, was reacted with 148.9 parts of 'Suprasec' DNR methylene diphenyl diisocyanate ('Arcton' and 'Suprasec' are trademarks of Imperial Chemical Industries PLC).
The polyol and isocyanate components were mixed with a variable shear mixer. At low shear and hence low mixing efficiency the above system produced poor quality foam w;th both isocyanate rich and polyol rich areas and large cells. The addition, to the polyol blend, of 10 parts of the polyol product 1 a as described in example 1 and the commensurate increase in isocyanate amount to 153.4 parts in order to maintain the index and the increase in fluorocarbon 'Arcton' All* to 46.2 parts in order to maintain the blowing ratio, resulted in better mixing under low shear as exemplified by better ~uality foam and a decrease in the heterogeneity of the constituents and a decrease in the visible cell size.
Exam~le B
___ _ The addition, to the polyol blend used in example A/ of ll.S
parts of the polyol product as described in example 1 c and the commensurate increase in isocyanate amount to 151.8 parts in * Trademark ~, 2~5Z~5 order to maintain the index and the increase in fluorocarbon 'Arcton' All* to 46 parts in order to maintain the blowing ratio, resulted in better mixing under low shear as exemplified by better quality foam and a decrease in the heterogeneity of the constituents and a decrease in the visible cell size.
Exam~le C
____ ____ The addition, to the polyol used in example A, of 10 parts of the polyol products as described in example 3 and the commensurate increase in isocyanate amount to 153.4 parts in order to maintain the index and the increase in fluorocarbon 'Arcton' All* to 46.2 parts in order to mai.ntain the blowing * Trademark /
/
. . . .. . _ _ 2~225;
ra~io, result~d in better mixing under low shear as exemplified by better ~uality foam and a decrease in the heterogeneity of the constltuents and a decrease in ~he visible cell si~e.
ExamPle D
A polyol blend consisting of 25 parts of a glycerol based polyol of hydroxyl value 540 mg KOH/g, 75 parts of a toluene diamine based polyol of hydroxyl value 390 mg KOE/g, 2 parts of a catalyst based on N,N-dimethylcyclohexylamine, 2 parts of water, 1.5 parts of a siloxane oxyalkylene block copolymer surfactant, and 37.5 parts of 'Arcton'll ~trademark) flu~rocarbon, was reacted with 142.8 parts of 'Suprasec'DNR
(trademark) polymeric MDIo The polyol and isocyanate components were mixed with a variable shear mixer. At low shear the system as described produced poor quality foam. The addition of 10 parts of the polyol o~ example 1 a and the commensurate increase of isocyanate and fluorocarbon A 11 to 145.3 parts and 41 parts respectively! resulted in better mixing under low shear as exemplified by better quality foam. In addition a marked decrease in surface friability was observed in that the adhesion of the ~oam coverings were much enhanced.
~Z~Z2S
Example E
In addition to the polyol blend used in exa~ple D of 10 parts of the polyol of example 5 and the commensurate increase of isocyanate and fluorocarbon All to 145.3 parts and 41 parts respectively, resulted in better mixing under low shPar as exemplified by better quality foam ~
A polyol blend consisting of 53 parts of a sorbitol based polyol of hydroxyl value 555 mg KOH/~, 66 parts of a sucrose . based polyol of hydroxyl value 440 mg KOH/g, 13 parts of a toluene diamine/alkanolamine based polyol of hydroxyl value.
502 mg/KOH/g, 2.6 parts of wa~er, 2.6 parts of a catalyst based on N,N-dime~hylcyclohexylamine, 2.0 parts of a silo-xane oxyalkylene block copolymeric surfactant and 50.4 parts of 'Arcton' 11 fluorocarbon (trademar~) , was reacted with 209 parts of 'Suprasec DNR' ttrademark) polymeric MDI. As in the previous examples , at low shear bad ~uality ~oams were obtained. The addition of 9.7 parts of the polyol of the invention of examples la or 2 and the commensurate increase of the polyisocyanate and blowing agent to respec-tively 214.2 parts and 55.5 parts resulted in better mixing at low shear and hence better quality foam and reduction in the visible cell sizes.
~2~L~2Z~
Example G
The addition to the polyol blend used in example F of 9.7 parts of the polyol of example 4 and the commensurate increase of the polyisocyanate and blowing âgent to respectively 214.2 par~s and 55.5 parts resulted in better mixing at low shear and better quality foams and reduction in the visible cell size.
Example H
The addition to the polyol blend used in example F of 13.2 parts of the polyol of example 1 c and the commensurate increase of the polyisocyanate and blowing agent to respectively 211.5 parts and 55.5 parts resulted in ~etter mixing at low shear and better quality foam and reduction in the visible cell sizes.
Example I
A polyol blend consisting of 100 parts of a sucrose based polyol of hydxoxyl value 440 mg KOH/gr 2 parts of water, 3 parts of a mixture of catalysts based on N,N-dimethylcyclohexylamine ~z~%~
and bis(2-dimethylaminoethyl)ether, 2 parts of a mixture of siloxane oxyalkylene surfactants ('Tegostab' ttrademark) B8404 and B1903 ,trademaxks of Goldschmidt AG) and 37~6 parts of fluorocarbon 'Arcton' 11 ttrademark) was reacted with 141.8 part~ of 'Suprasec' (~rademark) D~R polymeric MDI. As in the previous examples , at low shear bad quality foams were obtained. The addition of 10 parts of the polyol of the invention of example 1 a or 3, and the commensurate increase of the polyisocyanat and blowing agent to respectively 141.9 parts and 39O9 parts resulted in better mixing a~ low shear and hence better quality foam and reduction in the visible cell size.
ExamPle J
A polyol blend consisting of 50 parts of a sucrose based polyol of hydroxyl value 310 mg KOHg 1, 30 parts of a toluene diamine based polyol of hydroxyl value 390 mgKOHg 1, 10 parts of glycerol based polyol of hydroxyl value 540 mgKOHg 1, 10 parts of a glycerol based polyol of hydroxyl value 1120 mgKOHg 1, 1.9 parts of water, 2~5 parts of a catalyst based o~ N,N~dimethylcyclohexylamine, 2.0 parts of a mixture of siloxane oxyalkylene block copolymeric surfactants and 31~9 parts of 'Arcton' 11 fluorobarcon (~rade mark~, was reacted wi~h 135 parts of 'Suprasec DND' (trade mark) polymeric MDI~
~2~ 25 As in the previous examples, at low shear bad quality foams were obtained. The addition of 10 parts of the polyol of the invention of example la and the commensurate increase of polyisocyanate and blowing agent to respectively 151.9 parts and 34O9 parts resulted in better mixing at low shear and hence better quality foam and reduction in the visible cell sizes.
Claims (8)
1. A polyether polyol having an average hydroxyl value in the range of 100 to 250 mgKOH/g which is an alkoxylated derivative of a polyhydric alcohol obtained as by-product in pentaerythritol manufacture & consisting essentially of a mixture of compounds according to formula (I).
(I) and (II) (II) wherein R1 is H, CH3 or OCH3 R2 is H, CH2OH or CH2 C(CH2OH)3 R3 and R4 which may be the same or different are H, CH2OH,CH2OCH3 provided that only one of R3 or R4 may be CH2OCH3
(I) and (II) (II) wherein R1 is H, CH3 or OCH3 R2 is H, CH2OH or CH2 C(CH2OH)3 R3 and R4 which may be the same or different are H, CH2OH,CH2OCH3 provided that only one of R3 or R4 may be CH2OCH3
2. A polyether polyol in accordance with claim 1 wherein the alkoxylated derivative is a propoxylated derivative.
3. A polyether polyol blend comprising a polyether polyol according to claim 1.
4. A compatibilising additive comprising a polyether polyol according to claim 1.
5. A composition comprising 1 to 20 parts by weight of a polyether polyol according to claim 1 and 100 parts of a polyol blend.
6. A composition comprising 5 to 15 parts by weight of a polyether polyol according to claim 1 and 100 parts of a polyol blend.
7. A polyol blend comprising a polyether polyol according to claim 1 in addition to one or more catalysts, blowing agents, flame-retardant, surfactants, fillers and other usual ingredients used in polyurethane manufacture.
8. A process to manufacture rigid polyurethane foams comprising reacting a polyether and/or polyol and a polylsocyanate in the presence of 1 to 20% parts by weight, for 100 parts of said polyether/or polyester polyol, of a polyether polyol according to claim 1.
9. A polyurethane product made according to the process of
8. A process to manufacture rigid polyurethane foams comprising reacting a polyether and/or polyol and a polylsocyanate in the presence of 1 to 20% parts by weight, for 100 parts of said polyether/or polyester polyol, of a polyether polyol according to claim 1.
9. A polyurethane product made according to the process of
claim 8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8516618 | 1985-07-01 | ||
| GB858516618A GB8516618D0 (en) | 1985-07-01 | 1985-07-01 | Polyether polyols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1245225A true CA1245225A (en) | 1988-11-22 |
Family
ID=10581612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000512920A Expired CA1245225A (en) | 1985-07-01 | 1986-07-02 | Polyether polyols, their manufacture and use in polyurethanes production |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4703069A (en) |
| EP (1) | EP0213697A3 (en) |
| JP (1) | JPS6213434A (en) |
| AR (1) | AR241908A1 (en) |
| AU (1) | AU579739B2 (en) |
| CA (1) | CA1245225A (en) |
| DK (1) | DK307786A (en) |
| GB (1) | GB8516618D0 (en) |
| NZ (1) | NZ216595A (en) |
| ZA (1) | ZA864559B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8410480D0 (en) * | 1984-04-24 | 1984-05-31 | Bp Chem Int Ltd | Preparation of polymer polyols |
| US4943626A (en) * | 1988-07-29 | 1990-07-24 | The Dow Chemical Company | Primary polyether active hydrogen compounds which are prepared from linked, protectively initiated polyalkyleneoxides |
| US5591446A (en) * | 1989-04-04 | 1997-01-07 | Beiersdorf, A.G. | Methods and agents for the prophylaxis of atopy |
| US5091438A (en) * | 1989-07-14 | 1992-02-25 | Takeda Chemical Industries, Ltd. | Method of producing rigid urethane foam |
| CA2066503A1 (en) * | 1991-04-22 | 1992-10-23 | Joseph S. Sollers | Polyurethane foam based on combination of polyester resin and polyether polyol |
| US5484820A (en) * | 1994-08-05 | 1996-01-16 | The Dow Chemical Company | Polyurethane foam for packaging applications |
| US5698213A (en) * | 1995-03-06 | 1997-12-16 | Ethicon, Inc. | Hydrogels of absorbable polyoxaesters |
| US5962023A (en) * | 1995-03-06 | 1999-10-05 | Ethicon, Inc. | Hydrogels containing absorbable polyoxaamides |
| US5844017A (en) * | 1995-03-06 | 1998-12-01 | Ethicon, Inc. | Prepolymers of absorbable polyoxaesters containing amines and/or amido groups |
| US5859150A (en) * | 1995-03-06 | 1999-01-12 | Ethicon, Inc. | Prepolymers of absorbable polyoxaesters |
| US5597579A (en) * | 1995-03-06 | 1997-01-28 | Ethicon, Inc. | Blends of absorbable polyoxaamides |
| US5700583A (en) * | 1995-03-06 | 1997-12-23 | Ethicon, Inc. | Hydrogels of absorbable polyoxaesters containing amines or amido groups |
| US6147168A (en) | 1995-03-06 | 2000-11-14 | Ethicon, Inc. | Copolymers of absorbable polyoxaesters |
| US6100346A (en) * | 1995-03-06 | 2000-08-08 | Ethicon, Inc. | Copolymers of polyoxaamides |
| US6403655B1 (en) | 1995-03-06 | 2002-06-11 | Ethicon, Inc. | Method of preventing adhesions with absorbable polyoxaesters |
| DE19639121A1 (en) † | 1996-09-24 | 1998-03-26 | Basf Ag | Process for the production of rigid polyurethane foams |
| US6074660A (en) * | 1998-04-20 | 2000-06-13 | Ethicon, Inc. | Absorbable polyoxaesters containing amines and/ or amido groups |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2866774A (en) * | 1953-09-23 | 1958-12-30 | Univ Notre Dame | Polyether polyurethane rubber |
| US3290387A (en) * | 1961-05-08 | 1966-12-06 | Exxon Research Engineering Co | Oxyalkylated dimethylol and trimethylol alkanes |
| FR2269550A1 (en) * | 1974-05-03 | 1975-11-28 | Progil Bayer Ugine | Cold, one-shot prepn. of polyurethane foams - using unmodified diisocyanate and specific polyether polyols |
| JPS6029368B2 (en) * | 1976-06-28 | 1985-07-10 | 理研ビタミン株式会社 | Process for producing polyoxyethylene adducts of pentaerythritol and dipentaerythritol |
| DE3267968D1 (en) * | 1981-03-13 | 1986-01-30 | Goldschmidt Ag Th | Method for the preparation of polymers containing polyoxyalkylene side chains |
| GB2106506B (en) * | 1981-07-04 | 1985-05-09 | Univ Manchester | Production of polymeric polyols |
| US4581470A (en) * | 1983-09-27 | 1986-04-08 | Union Carbide Corporation | Novel polyols and uses thereof |
| GB8404022D0 (en) * | 1984-02-15 | 1984-03-21 | Ici Plc | Polyether polyols |
-
1985
- 1985-07-01 GB GB858516618A patent/GB8516618D0/en active Pending
-
1986
- 1986-06-18 ZA ZA864559A patent/ZA864559B/en unknown
- 1986-06-19 NZ NZ216595A patent/NZ216595A/en unknown
- 1986-06-24 AU AU59146/86A patent/AU579739B2/en not_active Ceased
- 1986-06-24 EP EP86304857A patent/EP0213697A3/en not_active Ceased
- 1986-06-27 US US06/879,435 patent/US4703069A/en not_active Expired - Fee Related
- 1986-06-27 DK DK307786A patent/DK307786A/en not_active Application Discontinuation
- 1986-07-01 AR AR86304414A patent/AR241908A1/en active
- 1986-07-01 JP JP61154949A patent/JPS6213434A/en active Pending
- 1986-07-02 CA CA000512920A patent/CA1245225A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU579739B2 (en) | 1988-12-08 |
| EP0213697A3 (en) | 1988-11-02 |
| EP0213697A2 (en) | 1987-03-11 |
| DK307786A (en) | 1987-01-02 |
| NZ216595A (en) | 1989-01-27 |
| DK307786D0 (en) | 1986-06-27 |
| AR241908A1 (en) | 1993-01-29 |
| GB8516618D0 (en) | 1985-08-07 |
| US4703069A (en) | 1987-10-27 |
| JPS6213434A (en) | 1987-01-22 |
| AU5914686A (en) | 1987-01-08 |
| ZA864559B (en) | 1987-05-27 |
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