CA1263494A - Polyester polyols, their manufacture and use in polyurethane production - Google Patents
Polyester polyols, their manufacture and use in polyurethane productionInfo
- Publication number
- CA1263494A CA1263494A CA000500785A CA500785A CA1263494A CA 1263494 A CA1263494 A CA 1263494A CA 000500785 A CA000500785 A CA 000500785A CA 500785 A CA500785 A CA 500785A CA 1263494 A CA1263494 A CA 1263494A
- Authority
- CA
- Canada
- Prior art keywords
- polyester polyol
- weight
- formula
- polyester
- polyhydric
- 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
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
Abstract
ABSTRACT
Polyester Polyols, Their Manufacture and Use in Polyurethane Production A polyester polyol derived from a polyalkoxylated by-product of pentaerythritol manufacture and polycarboxylic acids, the latter being themselves by-products from the production of adipic acid or terephthalic acid or derivatives thereof, useful for the manufacture of rigid foam.
Polyester Polyols, Their Manufacture and Use in Polyurethane Production A polyester polyol derived from a polyalkoxylated by-product of pentaerythritol manufacture and polycarboxylic acids, the latter being themselves by-products from the production of adipic acid or terephthalic acid or derivatives thereof, useful for the manufacture of rigid foam.
Description
~.2~;3~
POLYESTER P~LYOLS , THEIR HANUFACTURE AND USE I~
POLYUR~TIIANE PROOUCTIO~J
The ~vention relates to polyester polyols of a defined type, to their manu~acture by esterificatlan or transester~cat~on of polyether polyols also of a defined type, with certain polybas~c acid species an~ their con~ersion to polyurethanes by reactton w;th polyisocyanates.
The starting polyether polyols to be used in the inYention are describe~l in European Patent Application EP 153031 A2. This Patent Apptication di5closes ?olyether polyols having an average hydrcxyl value in the range 40Q - GSO mg KOH/g, and preferably 490 - 575 mg KOH/g, which is an alkoxylated derivative of a polyhydric alcohol itself being a single compound or a mixture of compounds according to the general formula (I) below :
~C8~ ~ ~C~20~
ca2 / ~ C~20R2 where~n Rl is -H, -CII3, or -OC~I3 R2 is -H, -C1l201l, or -CII2C~CII20H)3 Uhe~ polyether polyol co~position~ according eo EP 153031 A2 ~re prepared by blendlng alko~ylated co~pounds, preferably at least 10 Z by weight of the co~pouents u~ed in the blend ls an.alko~ylated deri~ative of one or ~ore polyhydric alcohols according to for~ula (I).
g ~ ~
~634g4 The polyether co~p~6itlo~s de~cribed abo~e ~ay be blended with 5 to 9S Z
by ueight of hydro~yl terminatet polyesters or polyester~1des.
Ad~ustmentR to achieve the deslred level ~f func~ionallty and hydro~yl value may be made by selection of the polyhydric alcohoIs aud control of the degree of alko~ylation respectively.
~here a polyhydric alcohol is present, other than one cf the type defined above, it is pre~erably incorporated into the composition such that after alkoxylation the alkoxylated derivatiYe forms at least 5 Z by weight of the polyether polyol composftion and the polyhydric alcohol has the general formula (II) or i5 a mixture of compounds of that formula, ~3 C~ 0 (II) \ / 2 ~4 \ C~2 - ~S
wherein R3 and R4, which may be the same or different, are selected from -H, -CH20H and -CH20CH3 provided that only one of R3 or R4 may be -CH20CH3, R5 is -OH,-OCH20H or -OCH2C(CH20H~3.
Thus a preferred polyether polyol comprises 10 to g5 X of oxyalkylated polyhydric alcohols according to fo~mula I and 5 to 50 % of oxyalkylated polyhydric alcohols according to formula (II).
The alkoxylation agent could be propylene oxide, ethylene oxide or butylene oxide or mixtures thereof.
It has now been found unexpectedly that some polyester derivatives of the above polyols provide new polyols of improved processability suitable for the manufacture of rigid polyurethane foams of fine cell-structure.
Economy has also become a critical factor in rigid foam business and accordingly, another main advantage resulting rrom the present invention is that the polyols are manufactured from two readily available starting components. The latter are indeed waste by-products from the manufacture of pentaerythritol on one side and adipic acid or terephthalic acid or derivatives thereof on the other side.
The polybàsic acid species used in the preparation of the polyester polyols of the invention include :
a) aliphatic dibasic acids or esters of the type 200C (CH2)n COOR
wherein n ~ 2 to 8 and R is H, methyl or ethyl or mixtures thereof, preferably mixtures of adipic, glutaric and succinic acids or derivatives thereof, b) aromatic dibasic acids of the general formula COOR
ROOC
wherein R is H , methyl or ethyl and the carboxyl groups are in the ortho, meta or para positions relative to each other or mixtures thereof, preferably dimethyl terephthalate or distillation residues therefrom, residues from poly-thylene ~ 'ID
~E~
_ 4 _ ~ Z 6 ~ 4 terephthalate tPET) manufacture or product from the recycle of P~T
waste, c) other aromatic polybasic acids such as benzenetricarboxylic acids or polycarboxy substituted diphenyls and polyphenyls and the corresponding methyl esters.
Tetrabutyl-o-titanate was used for this invention and is a known catalyst for esterification/transesterification reactions ; other catalysts could include stannous octoate or p-toluene sulphonic acid.
The polyester polyol of the present invention, with an average hydroxyl value in the range 250 to 400 mgKOH/g, and with a weight average functionality of 2.3 to 5.0, may be used in admixture with known polyether polyols, polyester polyols or polyesteramide polyols.
The present invention includes also the manufacture of polyurethane products, for example polyurethane foams, in known manner, from the polyester polyols described above, and also ~ncludes polyurethanes product so prepared.
Polyurethanes products are made by re~cting a di- or polyisocyanate with the described polyester polyol . The nature of the polyurethane product, for example the polyurethane foam may be varied depending on a variety of factors such as the functionality of the reactants and the presence of active ingredients.
The organic di- or polyisocyanates may be any of the isocyanates known to be useful for the formation of polyurethane products such as polyurethane foams. Of particular interest are aromatic di- or ~A~
~Jv~j3-~3~
polyisocyanates, for example tolylene diisocyanate and especially diphenylmethane di1socyanate (MDI) which are commercialy available in a Yariety of forms. Suitable diphenylmethane di-isocyanates include (a) diphenylmethane 4,4' diisocyanate and mixtures thereof with other isomers of diphenylmethane diisocyanate;
(b) methylene bridged polyphenylpqlyisocyanates prepared by phosgenation of mixtures of appropriate polyamines obtalned 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 to give products with a weight average functionality in the range 2 to at least 3.3 ;
c) polymers and oligomers obtained by reacting diphenylmethane lS diisocyanates or polymeric M0~ with a monomeric glycol or polyhydric alcohol (or mixtures thereof) or with a hydroxyl-ended polyester or polyether and known as 'MOI prepolymers'; and d) modified diphenylmethane diisocyanates or 'polymeric MDI' in which a proportion o the isocyanate groups are conYerted into other groups such as carbodiimide, uretoneimine, biuret or allophanate groups, or in which a proportion of the isocyanate groups are reacted with an isocyanate-reactive compound.
The preparation of the foamed polyurethane materials may be carried out by the general methods fully described elsewhere.
Thus the foam forming components may be mixed continuously or discontinuously in the presence of the gas generating agent to give a foam.
- 6 - ~ i34g4 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 proportion of the organic isocyanate with water incorporated in the reaction mixture. Gas may also be generated by incorporatinq in the reaction mixture an inert liquid 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. Examples of such liquids are halogenated hydrocarbons such as methylene chloride, halomethanes and haloethanes.
Mixtures of these low boiling point liquids one with another and/or with other substituted or unsubstituted hydrocarbons may also be used. Such liquids are usually employed in amounts of from 5 Z to 50X by weight of the polyester polyol.
Water is usually employe~ in amounts oF from 1 % to 10 Z by we~ght of the polyester when used as a gas generating agent.
Catalysts for the polyurethane forming reaction may also be included, especially tertiary-amines, basic compounds and metal compounds. Foam stabilisers such as siloxane alkoxy-ether copolymers may be present, together with additives suoh as pigments, flame retardants, fillers, chain extenders, cross-linking agents, plasticisers and anti-oxldants, each being used a10ne or in combination with the other additiYes.
A preferxed process for making a rigid polyurethane foam is to react a polyester polyol derived from formula I with a polyisocyanate of weight average functionality in the range
POLYESTER P~LYOLS , THEIR HANUFACTURE AND USE I~
POLYUR~TIIANE PROOUCTIO~J
The ~vention relates to polyester polyols of a defined type, to their manu~acture by esterificatlan or transester~cat~on of polyether polyols also of a defined type, with certain polybas~c acid species an~ their con~ersion to polyurethanes by reactton w;th polyisocyanates.
The starting polyether polyols to be used in the inYention are describe~l in European Patent Application EP 153031 A2. This Patent Apptication di5closes ?olyether polyols having an average hydrcxyl value in the range 40Q - GSO mg KOH/g, and preferably 490 - 575 mg KOH/g, which is an alkoxylated derivative of a polyhydric alcohol itself being a single compound or a mixture of compounds according to the general formula (I) below :
~C8~ ~ ~C~20~
ca2 / ~ C~20R2 where~n Rl is -H, -CII3, or -OC~I3 R2 is -H, -C1l201l, or -CII2C~CII20H)3 Uhe~ polyether polyol co~position~ according eo EP 153031 A2 ~re prepared by blendlng alko~ylated co~pounds, preferably at least 10 Z by weight of the co~pouents u~ed in the blend ls an.alko~ylated deri~ative of one or ~ore polyhydric alcohols according to for~ula (I).
g ~ ~
~634g4 The polyether co~p~6itlo~s de~cribed abo~e ~ay be blended with 5 to 9S Z
by ueight of hydro~yl terminatet polyesters or polyester~1des.
Ad~ustmentR to achieve the deslred level ~f func~ionallty and hydro~yl value may be made by selection of the polyhydric alcohoIs aud control of the degree of alko~ylation respectively.
~here a polyhydric alcohol is present, other than one cf the type defined above, it is pre~erably incorporated into the composition such that after alkoxylation the alkoxylated derivatiYe forms at least 5 Z by weight of the polyether polyol composftion and the polyhydric alcohol has the general formula (II) or i5 a mixture of compounds of that formula, ~3 C~ 0 (II) \ / 2 ~4 \ C~2 - ~S
wherein R3 and R4, which may be the same or different, are selected from -H, -CH20H and -CH20CH3 provided that only one of R3 or R4 may be -CH20CH3, R5 is -OH,-OCH20H or -OCH2C(CH20H~3.
Thus a preferred polyether polyol comprises 10 to g5 X of oxyalkylated polyhydric alcohols according to fo~mula I and 5 to 50 % of oxyalkylated polyhydric alcohols according to formula (II).
The alkoxylation agent could be propylene oxide, ethylene oxide or butylene oxide or mixtures thereof.
It has now been found unexpectedly that some polyester derivatives of the above polyols provide new polyols of improved processability suitable for the manufacture of rigid polyurethane foams of fine cell-structure.
Economy has also become a critical factor in rigid foam business and accordingly, another main advantage resulting rrom the present invention is that the polyols are manufactured from two readily available starting components. The latter are indeed waste by-products from the manufacture of pentaerythritol on one side and adipic acid or terephthalic acid or derivatives thereof on the other side.
The polybàsic acid species used in the preparation of the polyester polyols of the invention include :
a) aliphatic dibasic acids or esters of the type 200C (CH2)n COOR
wherein n ~ 2 to 8 and R is H, methyl or ethyl or mixtures thereof, preferably mixtures of adipic, glutaric and succinic acids or derivatives thereof, b) aromatic dibasic acids of the general formula COOR
ROOC
wherein R is H , methyl or ethyl and the carboxyl groups are in the ortho, meta or para positions relative to each other or mixtures thereof, preferably dimethyl terephthalate or distillation residues therefrom, residues from poly-thylene ~ 'ID
~E~
_ 4 _ ~ Z 6 ~ 4 terephthalate tPET) manufacture or product from the recycle of P~T
waste, c) other aromatic polybasic acids such as benzenetricarboxylic acids or polycarboxy substituted diphenyls and polyphenyls and the corresponding methyl esters.
Tetrabutyl-o-titanate was used for this invention and is a known catalyst for esterification/transesterification reactions ; other catalysts could include stannous octoate or p-toluene sulphonic acid.
The polyester polyol of the present invention, with an average hydroxyl value in the range 250 to 400 mgKOH/g, and with a weight average functionality of 2.3 to 5.0, may be used in admixture with known polyether polyols, polyester polyols or polyesteramide polyols.
The present invention includes also the manufacture of polyurethane products, for example polyurethane foams, in known manner, from the polyester polyols described above, and also ~ncludes polyurethanes product so prepared.
Polyurethanes products are made by re~cting a di- or polyisocyanate with the described polyester polyol . The nature of the polyurethane product, for example the polyurethane foam may be varied depending on a variety of factors such as the functionality of the reactants and the presence of active ingredients.
The organic di- or polyisocyanates may be any of the isocyanates known to be useful for the formation of polyurethane products such as polyurethane foams. Of particular interest are aromatic di- or ~A~
~Jv~j3-~3~
polyisocyanates, for example tolylene diisocyanate and especially diphenylmethane di1socyanate (MDI) which are commercialy available in a Yariety of forms. Suitable diphenylmethane di-isocyanates include (a) diphenylmethane 4,4' diisocyanate and mixtures thereof with other isomers of diphenylmethane diisocyanate;
(b) methylene bridged polyphenylpqlyisocyanates prepared by phosgenation of mixtures of appropriate polyamines obtalned 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 to give products with a weight average functionality in the range 2 to at least 3.3 ;
c) polymers and oligomers obtained by reacting diphenylmethane lS diisocyanates or polymeric M0~ with a monomeric glycol or polyhydric alcohol (or mixtures thereof) or with a hydroxyl-ended polyester or polyether and known as 'MOI prepolymers'; and d) modified diphenylmethane diisocyanates or 'polymeric MDI' in which a proportion o the isocyanate groups are conYerted into other groups such as carbodiimide, uretoneimine, biuret or allophanate groups, or in which a proportion of the isocyanate groups are reacted with an isocyanate-reactive compound.
The preparation of the foamed polyurethane materials may be carried out by the general methods fully described elsewhere.
Thus the foam forming components may be mixed continuously or discontinuously in the presence of the gas generating agent to give a foam.
- 6 - ~ i34g4 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 proportion of the organic isocyanate with water incorporated in the reaction mixture. Gas may also be generated by incorporatinq in the reaction mixture an inert liquid 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. Examples of such liquids are halogenated hydrocarbons such as methylene chloride, halomethanes and haloethanes.
Mixtures of these low boiling point liquids one with another and/or with other substituted or unsubstituted hydrocarbons may also be used. Such liquids are usually employed in amounts of from 5 Z to 50X by weight of the polyester polyol.
Water is usually employe~ in amounts oF from 1 % to 10 Z by we~ght of the polyester when used as a gas generating agent.
Catalysts for the polyurethane forming reaction may also be included, especially tertiary-amines, basic compounds and metal compounds. Foam stabilisers such as siloxane alkoxy-ether copolymers may be present, together with additives suoh as pigments, flame retardants, fillers, chain extenders, cross-linking agents, plasticisers and anti-oxldants, each being used a10ne or in combination with the other additiYes.
A preferxed process for making a rigid polyurethane foam is to react a polyester polyol derived from formula I with a polyisocyanate of weight average functionality in the range
2. 7 to 3.3 in the presence of a blowing agent.
!
tB
_ 7 _ 3L263494 Examples of the polyester polyols prepared accordlng to the present invention are given below but could also include use of adipic acid, d;methyl terephthalate and the starting polyether polyols could also be prepared solely using ethylene oxide or m;xture of ethylene-oxide~propylene ox;de both by sequent;al or concurrent addition.
The inYention is thus illustrated but not limited by the ~ollo~ng examples.
Example 1 5555 parts by weight of a propoxylated polyether polyol A prepared from residues of pentaerythritol manufacture as defined for the example s 1-3 o~ European Patent Application EP 153031 A2 and propy1ene oxide to a hydroxyl value of 604 mg K0H/g , the res1dual catalyst being removed by ion exchange before dehydration, ~ere charged to a 7.7 1 stainless steel reactor with 1777 parts by weight of mixed dimethyl ester of adipic, glutaric and succinic acids (in the ratio A:G:S of 20:60:20). 0.29 parts by weight of tetrabutyl-o-titanate were also added. A nitrogen sparge was established through the reactor contents at a rate of 62 l/h with agitation. The reactor was fitted with a reflux/rractionation column packed with 5 mm ceramic Raschig rings. Vapour from the top of the column passed through an air/water condenser system to a suitable calibratPd recei~er.
The reactor contents were heated to 200 - 210 deg C at which temperature, methanol commenced disti11ing from the column top.
~ 650 parts total distillate were recovered over 6 h during which Lu~
- 8 - ~2634g~
time the reactor ccntents had reached 230 des C ; the column head temperature remained constant at 60-65 deg C. When the column tops temperature fell to ~ 30 deg C , the column was re~oved from the reactor and sparging continued via a side arm on the reactor top at a reactor temperature of 230 deg C for 30 min and any distillate traces collected via a water condenser. The product (C) was then cooled to ~ 100 deg C by applying cooling water to the reactor coil and discharged from the reactor. The product had the analysis : hydroxyl value 325 mg KOH/g, acid value 0.17 mg KOH/g, viscosity at 100 deg C of 145 centistokes and a methoxyl content of 0.52Z as methanol.
Example 2 G3Z9 parts by weigllt of a polyether polyol (B) prepared from pent~erythritol residues alld propylene oxide (see European Patent Application EP 153031 ~2) to a hydroxyl value of 545 mg KOH/g, the residual catalyst being removed by ~on exchange before dehydration, were charged to a 7.7 1 stainless steel reactor with 1805 parts by weight of mixed dimethyl esters as in Example 1 and 0.320 parts by weight of tetra butyl-o-titanate. The experimental procedure followed that as in Example 1. 700 parts total distillate was collected over 6 h. The final product (O) hours on side arm distillation, had the following analysis hydroxyl value 290 mg KOII/g, acid value 0.15 mg KOH~g, viscosity at 100 deg C of 69 centistokes and methoxyl content of 0.37 Z as methanol.
.
;3~g4 - 8a -Examples 3-7 (see Table ) The prepared polyester polyols from Examples 1 and 2 aboYe (C,O) were co-blended with (a) their based polyether polyols (A and ~) respectiYely or (b) polyether polyol (E), a h;gh functional sucrdse amine product of hydroxyl Yalue 575 mg ~OH/g or ~c) a combination of (a) or (b) as detailed in the Table .
The average hydroxyl vdlue oF the polyol blend is ment~oned.
The polyurethane rigid foams , made from the polyester polyol blends with their parent polyether polyol or sucrose-amine polyether or nlixtures thereof, are also descr;bed in Examples 3 to 7 in the Table.
- 9 ~
TABLE
Polyether Polyol A Ex.1 18.98 13.61 Polyether Polyol B Ex.2 14.12 Polyester C
Ex.1 18.98 18.99 13.61 Polyester D
Ex.2 19.27 14.12 Polyether polyol E 18.99 9.07 19.27 9.41 OH value 465 450 490 430 460 DMMP 3.00 3.00 3.00 3.00 3.00 Silicone B8406 O.SQ O.SO O.SO O.SO O.SO
Catalyst SFC 0.55 0.90 0.60 l.SO 1.25 DBTOL 0.005 0.010 0.0075 O.Q15 0.010 Arcton II 13.00 13.00 13.00 13.00 13.00 Suprasec DNR 45.04 44.61 46.60 43,45 44.59 Index 105 105 105 105 105 Cream Time sec 17 13 16 12 14 Str1ng Time 37 32 36 31 34 Tack Free Time 46 42 46 40 44 End of rise 80 65 75 60 75 Core dens~ty kg/m3 32 34 32 34 34 10X compres-sive strength KPa 296 279 265 220 223 Dimensional stability (X change in length and width,1 day) - lS deg C -2 -0.3 -0.1 0.0 -4 + 100 deg C +2 +3 +4 +4 +5 Chemical compositions are expressed in parts by weight.
;3~ 94 Proprietary materials or abbreviations used in the formulations are listed below; names marked by asterik are trademarks.
Name Composition Company ; Catalyst SFC N,N-dimethylcyclohexylamine ICI
Surfactant B8406 siloxane copolymerised with Coldschmidt polyether Laboratories Arcton* 11 trichloromonofluoromethane ICI
Suprasec* DNR polymeric MOI ICI
OMMP dimethyl methylphosphonate Stauffer /Tenneco DBTDL - dibutyltin dilaurate
!
tB
_ 7 _ 3L263494 Examples of the polyester polyols prepared accordlng to the present invention are given below but could also include use of adipic acid, d;methyl terephthalate and the starting polyether polyols could also be prepared solely using ethylene oxide or m;xture of ethylene-oxide~propylene ox;de both by sequent;al or concurrent addition.
The inYention is thus illustrated but not limited by the ~ollo~ng examples.
Example 1 5555 parts by weight of a propoxylated polyether polyol A prepared from residues of pentaerythritol manufacture as defined for the example s 1-3 o~ European Patent Application EP 153031 A2 and propy1ene oxide to a hydroxyl value of 604 mg K0H/g , the res1dual catalyst being removed by ion exchange before dehydration, ~ere charged to a 7.7 1 stainless steel reactor with 1777 parts by weight of mixed dimethyl ester of adipic, glutaric and succinic acids (in the ratio A:G:S of 20:60:20). 0.29 parts by weight of tetrabutyl-o-titanate were also added. A nitrogen sparge was established through the reactor contents at a rate of 62 l/h with agitation. The reactor was fitted with a reflux/rractionation column packed with 5 mm ceramic Raschig rings. Vapour from the top of the column passed through an air/water condenser system to a suitable calibratPd recei~er.
The reactor contents were heated to 200 - 210 deg C at which temperature, methanol commenced disti11ing from the column top.
~ 650 parts total distillate were recovered over 6 h during which Lu~
- 8 - ~2634g~
time the reactor ccntents had reached 230 des C ; the column head temperature remained constant at 60-65 deg C. When the column tops temperature fell to ~ 30 deg C , the column was re~oved from the reactor and sparging continued via a side arm on the reactor top at a reactor temperature of 230 deg C for 30 min and any distillate traces collected via a water condenser. The product (C) was then cooled to ~ 100 deg C by applying cooling water to the reactor coil and discharged from the reactor. The product had the analysis : hydroxyl value 325 mg KOH/g, acid value 0.17 mg KOH/g, viscosity at 100 deg C of 145 centistokes and a methoxyl content of 0.52Z as methanol.
Example 2 G3Z9 parts by weigllt of a polyether polyol (B) prepared from pent~erythritol residues alld propylene oxide (see European Patent Application EP 153031 ~2) to a hydroxyl value of 545 mg KOH/g, the residual catalyst being removed by ~on exchange before dehydration, were charged to a 7.7 1 stainless steel reactor with 1805 parts by weight of mixed dimethyl esters as in Example 1 and 0.320 parts by weight of tetra butyl-o-titanate. The experimental procedure followed that as in Example 1. 700 parts total distillate was collected over 6 h. The final product (O) hours on side arm distillation, had the following analysis hydroxyl value 290 mg KOII/g, acid value 0.15 mg KOH~g, viscosity at 100 deg C of 69 centistokes and methoxyl content of 0.37 Z as methanol.
.
;3~g4 - 8a -Examples 3-7 (see Table ) The prepared polyester polyols from Examples 1 and 2 aboYe (C,O) were co-blended with (a) their based polyether polyols (A and ~) respectiYely or (b) polyether polyol (E), a h;gh functional sucrdse amine product of hydroxyl Yalue 575 mg ~OH/g or ~c) a combination of (a) or (b) as detailed in the Table .
The average hydroxyl vdlue oF the polyol blend is ment~oned.
The polyurethane rigid foams , made from the polyester polyol blends with their parent polyether polyol or sucrose-amine polyether or nlixtures thereof, are also descr;bed in Examples 3 to 7 in the Table.
- 9 ~
TABLE
Polyether Polyol A Ex.1 18.98 13.61 Polyether Polyol B Ex.2 14.12 Polyester C
Ex.1 18.98 18.99 13.61 Polyester D
Ex.2 19.27 14.12 Polyether polyol E 18.99 9.07 19.27 9.41 OH value 465 450 490 430 460 DMMP 3.00 3.00 3.00 3.00 3.00 Silicone B8406 O.SQ O.SO O.SO O.SO O.SO
Catalyst SFC 0.55 0.90 0.60 l.SO 1.25 DBTOL 0.005 0.010 0.0075 O.Q15 0.010 Arcton II 13.00 13.00 13.00 13.00 13.00 Suprasec DNR 45.04 44.61 46.60 43,45 44.59 Index 105 105 105 105 105 Cream Time sec 17 13 16 12 14 Str1ng Time 37 32 36 31 34 Tack Free Time 46 42 46 40 44 End of rise 80 65 75 60 75 Core dens~ty kg/m3 32 34 32 34 34 10X compres-sive strength KPa 296 279 265 220 223 Dimensional stability (X change in length and width,1 day) - lS deg C -2 -0.3 -0.1 0.0 -4 + 100 deg C +2 +3 +4 +4 +5 Chemical compositions are expressed in parts by weight.
;3~ 94 Proprietary materials or abbreviations used in the formulations are listed below; names marked by asterik are trademarks.
Name Composition Company ; Catalyst SFC N,N-dimethylcyclohexylamine ICI
Surfactant B8406 siloxane copolymerised with Coldschmidt polyether Laboratories Arcton* 11 trichloromonofluoromethane ICI
Suprasec* DNR polymeric MOI ICI
OMMP dimethyl methylphosphonate Stauffer /Tenneco DBTDL - dibutyltin dilaurate
Claims (13)
1. A polyester polyol having an average hydroxyl value in the range 250 to 400 mg ROH/g which comprises the reaction product of i) a polyhydric alkoxylated derivative which is itself a reaction product of a polyhydric alcohol of the general formula (I) wherein R1 is -H, -CH3 or -OCH3 and R2 is -H, CH2OH or CH2C(CH2OH)3 with one or several alkylene oxides, and ii) a polycarboxylic acid selected from the group consisting of dicarboxylic acids or esters of the formula ROOC(CH2)nCOOR
or of the formula where n is 2 to 8 and R is hydrogen, methyl or ethyl, or benzenetricarboxylic acid, polycarboxy substituted diphenyl or polyphenyls or the corresponding methyl csters.
or of the formula where n is 2 to 8 and R is hydrogen, methyl or ethyl, or benzenetricarboxylic acid, polycarboxy substituted diphenyl or polyphenyls or the corresponding methyl csters.
2. A polyester polyol composition comprising a polyester polyol according to claim 1 which also contains at least 5 % by weight of a reaction product selected from the group consisting of an alkoxylated polyydric derivative of a compound of the formula (II) or the polyhydric compound of the formula II
wherein R3 and R4 are the same or different and are selected from the group consisting of -H, -CH2OH and -CH2OCH3 provided that only one of R3 or R4 may be -CH2OCH3, and R5 is -OH, -CH2OH or -OCH2C(CH2OH)3 with a polycarboxylic acid as defined in claim 1.
wherein R3 and R4 are the same or different and are selected from the group consisting of -H, -CH2OH and -CH2OCH3 provided that only one of R3 or R4 may be -CH2OCH3, and R5 is -OH, -CH2OH or -OCH2C(CH2OH)3 with a polycarboxylic acid as defined in claim 1.
3. A polyester polyol composition comprising at least 10 percent by weight of a polyester polyol according to claim 1.
4. A polyester polyol composition according to claim 2, comprising at least 10 percent by weight of a polyester polyol of Claim 1 and at least 5 percent by weight of an alkoxylated derivative of a polyhydric compound of the formula (II) or a mixture thereof.
5. A polyester polyol or a polyester polyol composition according to any one of the claims l to 3 in which the alkoxylated derivatives are propoxylated derivatives.
6. A polyester polyol according to claim 1 in which the polyhydric alkoxylated derivative has an average hydroxyl value in the range of from 490 to 575 mg KOH/g.
7. A polyester polyol according to claim 1 in which the weight average functionality is in the range of 2.3 to 5Ø
8. A polyester polyol composition comprising a polyester polyol according to claim 1 in which there is also present 5 to 95 percent by weight of a hydroxy-terminated polyether, polyester or polyester amide.
9. A process for making a polyurethane product by reaction of a polyol according to claim 1 with a polyisocyanate.
10. A process for making a rigid polyurethane foam in which a polyol according to claim 1 is reacted with a polyisocyanate of weight average functionality in the range 2.7 to 3.3 in the presence of a blowing agent.
11. A process according to any one of claims 9 and 10 in which the polyisocyanate comprises methylene bridged polyphenyl-polyisocyanates.
12. A polyurethane product made according to the process of claim 9.
13. A polyester polyol composition according to claim 2 in which the alkoxylated polyhydric derivative of a compound of the formula (II) has an average hydroxyl value in the range of 490 to 575 mg KOH/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000500785A CA1263494A (en) | 1985-02-18 | 1986-01-30 | Polyester polyols, their manufacture and use in polyurethane production |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8504096 | 1985-02-18 | ||
| GB858504096A GB8504096D0 (en) | 1985-02-18 | 1985-02-18 | Polyester polyols |
| CA000500785A CA1263494A (en) | 1985-02-18 | 1986-01-30 | Polyester polyols, their manufacture and use in polyurethane production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1263494A true CA1263494A (en) | 1989-11-28 |
Family
ID=10574646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000500785A Expired CA1263494A (en) | 1985-02-18 | 1986-01-30 | Polyester polyols, their manufacture and use in polyurethane production |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4758606A (en) |
| EP (1) | EP0192325B1 (en) |
| JP (1) | JPS61192726A (en) |
| AT (1) | ATE47411T1 (en) |
| AU (1) | AU578513B2 (en) |
| CA (1) | CA1263494A (en) |
| DE (1) | DE3666445D1 (en) |
| DK (1) | DK70186A (en) |
| GB (1) | GB8504096D0 (en) |
| ZA (1) | ZA86488B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1277997B1 (en) * | 1995-05-10 | 1997-11-12 | Coim Spa | POLYESTERS POLYOLS, ESPECIALLY FOR THE PRODUCTION OF RIGID POLYURETHANE FOAMS. |
| US5998568A (en) * | 1999-01-14 | 1999-12-07 | Reichhold, Inc. | Polyesters prepared from alkoxylated intermediates |
| US5969056A (en) * | 1999-01-14 | 1999-10-19 | Reichhold, Inc. | Process for preparing esterification products from cyclic organic carbonates using catalysts comprising quaternary ammonium salts |
| US20080108719A1 (en) * | 1999-10-25 | 2008-05-08 | Geiger Eric J | Phthalic Anhydride Based Polyester-Ether Polyols and Double Metal Cyanide Catalyst System for Preparing Same |
| US6569352B1 (en) | 1999-10-25 | 2003-05-27 | Stepan Company | Phthalic anhydride based polyester-ether polyols and urethane prepolymers produced therefrom |
| US20050085658A1 (en) * | 1999-10-25 | 2005-04-21 | Geiger Eric J. | Phthalic anhydride based polyester-ether polyols and double metal cyanide catalyst system for preparing same |
| DE10009295A1 (en) * | 2000-02-28 | 2001-08-30 | Mitsubishi Polyester Film Gmbh | White, biaxially-oriented, fire-resistant polyester film, used e.g. for packaging light- or air-sensitive food, has at least one layer containing cyclo-olefin copolymer and fire retardant |
| US6954253B2 (en) * | 2000-07-25 | 2005-10-11 | Scientific Solutions, Inc. | Optical multiplexer and cross-switch using etched liquid crystal fabry-perot etalons |
| US20090082483A1 (en) * | 2007-09-20 | 2009-03-26 | Petrovic Zoran S | Polyglycerol based polyols and polyurethanes and methods for producing polyols and polyurethanes |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2945008A (en) * | 1956-08-23 | 1960-07-12 | Eastman Kodak Co | Condensation polymers derived from spiroglycols |
| NL291967A (en) * | 1962-04-25 | |||
| US3267084A (en) * | 1962-05-23 | 1966-08-16 | Gulf Oil Corp | Polymerizable 5-alkylene-m-dioxanyl acrylic esters |
| US3287419A (en) * | 1962-08-16 | 1966-11-22 | Eastman Kodak Co | 3, 3'-oxybis |
| US3412069A (en) * | 1966-05-20 | 1968-11-19 | Celanese Corp | Polyesters with spiro structure |
| US3860611A (en) * | 1972-01-19 | 1975-01-14 | Du Pont | Macrocyclic polyether polyols and condensation polymers derived therefrom |
| AU509884B2 (en) * | 1977-05-25 | 1980-05-29 | Monsanto Company | Process for preparing polyester resins |
| AU510971B2 (en) * | 1977-05-25 | 1980-07-24 | Monsanto Company | Polyester process |
| GB2106506B (en) * | 1981-07-04 | 1985-05-09 | Univ Manchester | Production of polymeric polyols |
| GB8404022D0 (en) * | 1984-02-15 | 1984-03-21 | Ici Plc | Polyether polyols |
-
1985
- 1985-02-18 GB GB858504096A patent/GB8504096D0/en active Pending
-
1986
- 1986-01-15 AT AT86300244T patent/ATE47411T1/en not_active IP Right Cessation
- 1986-01-15 DE DE8686300244T patent/DE3666445D1/en not_active Expired
- 1986-01-15 EP EP86300244A patent/EP0192325B1/en not_active Expired
- 1986-01-22 ZA ZA86488A patent/ZA86488B/en unknown
- 1986-01-24 US US06/822,132 patent/US4758606A/en not_active Expired - Fee Related
- 1986-01-24 AU AU52718/86A patent/AU578513B2/en not_active Ceased
- 1986-01-30 CA CA000500785A patent/CA1263494A/en not_active Expired
- 1986-02-13 DK DK070186A patent/DK70186A/en not_active Application Discontinuation
- 1986-02-18 JP JP61033681A patent/JPS61192726A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| ATE47411T1 (en) | 1989-11-15 |
| US4758606A (en) | 1988-07-19 |
| DK70186D0 (en) | 1986-02-13 |
| AU578513B2 (en) | 1988-10-27 |
| EP0192325A3 (en) | 1987-10-21 |
| GB8504096D0 (en) | 1985-03-20 |
| EP0192325A2 (en) | 1986-08-27 |
| DE3666445D1 (en) | 1989-11-23 |
| JPS61192726A (en) | 1986-08-27 |
| DK70186A (en) | 1986-08-19 |
| AU5271886A (en) | 1986-08-21 |
| EP0192325B1 (en) | 1989-10-18 |
| ZA86488B (en) | 1986-11-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |