CA2346806A1 - Polyethylene naphthalate polyester polyol and rigid polyurethane foams obtained therefrom - Google Patents
Polyethylene naphthalate polyester polyol and rigid polyurethane foams obtained therefrom Download PDFInfo
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- CA2346806A1 CA2346806A1 CA002346806A CA2346806A CA2346806A1 CA 2346806 A1 CA2346806 A1 CA 2346806A1 CA 002346806 A CA002346806 A CA 002346806A CA 2346806 A CA2346806 A CA 2346806A CA 2346806 A1 CA2346806 A1 CA 2346806A1
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- polyester polyol
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- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
- C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
- C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene 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
- 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
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
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- 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
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Process for preparing a poly(alkylene polyaromatic dicarboxylate)ester based polyester polyol comprising the steps of a) depolymerising poly(alkylene polyaromatic dicarboxylate) in the presence of a glycol and b) transesterifying the obtained product by addition of polycarboxylic acids, anhydrides or esters and/or polyhydric alcohols and use of the thus obtained polyester polyol in the manufacture of rigid polyurethane and urethane- modified polyisocyanurate foams.
Description
DESCRIPTION
POLYETHYLENE NAPHTHALATE POLYESTER POLYOL AND RIGID POLYURETHANE FOAMS
OBTAINED THEREFROM
This invention relates to the preparation of poly(alkylene polyaromatic dicarboxylate) ester based polyester polyols and the use thereof in the preparation of rigid polyurethane and polyisocyanurate foams.
The invention more specifically relates to polyester polyols produced from reacting polyethylene naphthalate.
l0 The preparation of a rigid polyurethane (PUR) and polyisocyanurate (PIR) foam by the reaction of a polyisocyanate, a polyol and a blowing agent in the presence of a catalyst is well known. A wide variety of polyols have been used as one of the components in the preparation of rigid polyurethane foams, including polyols from different waste streams.
The polyols are usually polyether alcohols or polyester alcohols, or a mixture of the two. Both aliphatic and f 5 aromatic polyester polyalcohols are in use. They are the reaction products of an esterification of a dicarboxylic acid or an anhydride with glycols (primary/secondary). More often a transesterification process is used. Aromatic polyester polyols used in rigid PUR/PIR foams are typically based on production waste streams of dimethyl terephtalate (DMT;>. Polyethylene terephtalate (PET) scrap is also a source of aromatic carboxylates. Depolymerization of production waste streams or post consumer waste from e.g. PET bottles is 20 a known method in the preparation of a polyester polyol.
Presently available polyols made from scrap PET or DMT process residue suffer from a variety of disadvantages such as the lack of compatibility with blowing agents commonly used in the manufacture of rigid PUR/PIR foams. Foams prepared from these polyols are sometimes deficient in compressive strength and/or thermal insulation capacity and/or flame resistance.
:! 5 It has now been found that poly(ethyiene naphthalate) (PEN) can easily be depolymerized and that a polyester polyol with high aromatic content can be made based on this depolymerization product. Rigid polyurethane or polyisocyanurate foams made using this polyester polyol show excellent mechanical stability, good fire performance and low smoke generation together with a low thermal conductivity.
?~0 The poly(alkylene polyaromatic dicarboxylate) ester preferably used in the present invention is polyethylene 2,6-naphthalate). Other isomers of this polymer, or copolymers with e.g.
poly(ethylene terephtalate) (PET), poly(butylene terephthalate) (PBT) or poly(butylene naphthalate) can also be employed, as well as the polyesters based on dicarboxylates with a multi ring structure (e.g.
anthracene, phenantrene) and their ? 5 copolymers.
The polyester polyol is prepared by a two step process.
In a first step. the polyester is depolymerised in the presence of a glycol.
This can be, for example, 1,4-butanediol, diethyleneglycol (DEG) or dipropyleneglycol (DPG). Most suitable as the diol is DEG and it is 40 preferably used in an amount in excess of that required for digestion.
Although the reaction takes place in the absence of catalysts, the reaction times are significantly shortened by use of the appropriate catalysts. The preferred catalyst is tetra-N-butyltitanatc; (TBT). Zinc oxide or mangane acetate can also be employed.
The depolymerization is carried out at such temperature that the polyester dissociates and the core units are obtained. This is typically in the temperature range of 150 to 350°C, preferably about 240°C. The process is typically carried out at atmospheric pressure. However, it will be obvious that pressures higher than atmospheric can be used. At higher prcasures the reaction temperature can be increased significantly, thus shortening the reaction time. The obtained reaction mixture contains the esterification product from the polyaromatic dicarboxylate and the used glycol, together with the diol of the alkylene chain between the aromatic rings. Very often, excess glycols are present. When starting with PEN, the product from this first l0 step contains naphthalate polyols, unreacted glycols and ethylene glycol from the PEN. During the depolymerisation and esterification, removal of the formed ethylene glycol by vacuum distillation is possible.
This normally results in a lower OH value of the final polyester polyol, together with a reduction of fhe aliphatic content, which is reflected in the fire performance of the obtained foam. In the present invention the ethylene glycol was not removed, with no detrimental effects on the final rigid foam properties.
In a second step, the mixture is further transesterified by addition of other polycarboxylic acids, anhydrides or esters and a polyhydric alcohol. This further esterification brings the final polyester polyol in the desired viscosity range. The total content of polyester polymer used in the synthesis of the polyester polyol is typically in the range 5 to 50 wt%, prE;ferably 10 to 40 wt%. The polycarboxylic acid and the polyhydric 2.0 alcohol are added at a temperature in the range of 80 to 240°C, preferably 100 to 180°C.
Suitable examples of the polycarboxylic; acid component or its derivatives are adipic acid, glutaric acid and anhydride, succinic acid, oxalic acid, malonic acid, suberic acid, azelaic acid, sebacic acid, phtalic acid, phtalic anhydride, pyromellitic anhydride. As polyfunetional alcohol, glycols are preferred. They can be a simple glycol of general formula CnH2n(OH)2 or polyglycols with intervening ether linkages, as represented in the general formula CnH2nOx(OH)2. They also may contain heteroatoms.
The polycarboxylic component and polyhydric alcohol may include substituents which are inert in the reaction, e.g. chlorine and bromine substituents, and/or may be unsaturated.
Examples of suitable polyhydric alcohols are alkylene glycols and oxyalkylene glycols, such as ethylene glycol, diethylene glycol and higher polyethylene glycols, propylene glycol, dipropyleneglycol and higher propylene glycols, glycerol, pentaerythritol, trimethylolpropane, sorb~itol and mannitol.
The two steps described above can also be carried out in a single step process. The depolymerisation of the polyester polymer is more complete and faster when using a two step process.
The final polyo) mixture for use in the present invention has an average functionality of 1.5 to 8, preferably 2 to 3. The hydroxyl number is generally between 200 and 550 mg KOH/g polyol.
The molecular weight ofthe polyesters is generally in the range 200 to 3000, preferably 200 to 1000, most preferably 200 to 800.
The term polyester polyol as used herein includes. any minor amounts of unreacted polyol remaining after the preparation of the polyester polyol and/or unesterified polyol.
The polyester polyol according to the present invention is used to make polyurethane-based rigid foam. In the processing of polyurethane and polyisocyanurate foams, the polyisocyanates and the mixture of isocyanate-reactive components are generally mixed in a one-shot method. Both high and low-pressure techniques can be employed in the mixing step. The ratio of the NCO/OH groups generally falls within the range 0.85 to 1.40, preferably 0.95 to 1.2 for polyurethane foam, and within the range 50 to 1, preferably 8 to 1 for polyisocyanurate foam.
Besides the PEN based polyester polyol of the present invention other isocyanate-reactive compounds can be used in the process for making rigid polyurethane or urethane-modified polyisocyanurate foams. Suitable isocyanate-reactive compounds include any of that known in the art for the production of rigid polyurethane foam, especially polyether polyols and other types of polyester polyols.
In general the PEN based polyester polyol of the present invention constitutes between 60 and 100 % by weight of total isocyanate-reactive compounds.
IS
The isocyanate-reactive mixture generally contains the polyhydric alcohols and other optional additives such as blowing agents, fire retardants, fillers, stabilizers, catalysts and surfactants. Preferred catalysts for the polyurethane formation are amines, most preferably tertiary amines. Dibutyl tin dilaurate is an example of a non-amine based polyurethane catalyst. Preferred polyisocyanurate catalysts are alkali metal carboxylates and quaternary ammonium carboxylat:es.
Any of the blowing agents known in the art for the preparation of rigid polyurethane or urethane-modified polyisocyanurate foams can be used in the process of the present invention.
Both physical and chemical blowing agents can be used, singly or in mixtures.
Z~ Suitable physical blowing agents are. for example, hydrocarbons, dialkyl ethers, alkyl alkanoates, aliphatic and cycloaliphatic hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorine-containing ethers and carbon dioxide. Examples of preferred blowing agents are isomers of pentane such as cyclopentane, n-pentane and isopentane, and mixtures thereof, 1,1-dichloro-2-fluoroethane (HCFC
141b), I,1,1-trifluoro-2-fluoroethane (HFC 134a), chlorodifluoromethane (HCFC
22), I,1-difluoro-3,3,3-trifluoropropane (HFC 245fa).
Carbon dioxide releasing products can be used as chemical blowing agent.
Water, which releases carbon dioxide upon reaction with isocyanate, .is widely known as a chemical blowing agent.
The total quantity of blowing agent is typically from 0.1 to 25% by weight based on the total reaction system.
Both aliphatic and aromatic poiyisocyanates can be used. Preferred are the aromatic polyisocyanates such as diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI) or prepolymers thereof. Mixtures of isomers and oligomers can be employed. Most preferred is the polymeric form of MDI.
The polyisocyanate can be uretonimine or carbodiimide modified.
POLYETHYLENE NAPHTHALATE POLYESTER POLYOL AND RIGID POLYURETHANE FOAMS
OBTAINED THEREFROM
This invention relates to the preparation of poly(alkylene polyaromatic dicarboxylate) ester based polyester polyols and the use thereof in the preparation of rigid polyurethane and polyisocyanurate foams.
The invention more specifically relates to polyester polyols produced from reacting polyethylene naphthalate.
l0 The preparation of a rigid polyurethane (PUR) and polyisocyanurate (PIR) foam by the reaction of a polyisocyanate, a polyol and a blowing agent in the presence of a catalyst is well known. A wide variety of polyols have been used as one of the components in the preparation of rigid polyurethane foams, including polyols from different waste streams.
The polyols are usually polyether alcohols or polyester alcohols, or a mixture of the two. Both aliphatic and f 5 aromatic polyester polyalcohols are in use. They are the reaction products of an esterification of a dicarboxylic acid or an anhydride with glycols (primary/secondary). More often a transesterification process is used. Aromatic polyester polyols used in rigid PUR/PIR foams are typically based on production waste streams of dimethyl terephtalate (DMT;>. Polyethylene terephtalate (PET) scrap is also a source of aromatic carboxylates. Depolymerization of production waste streams or post consumer waste from e.g. PET bottles is 20 a known method in the preparation of a polyester polyol.
Presently available polyols made from scrap PET or DMT process residue suffer from a variety of disadvantages such as the lack of compatibility with blowing agents commonly used in the manufacture of rigid PUR/PIR foams. Foams prepared from these polyols are sometimes deficient in compressive strength and/or thermal insulation capacity and/or flame resistance.
:! 5 It has now been found that poly(ethyiene naphthalate) (PEN) can easily be depolymerized and that a polyester polyol with high aromatic content can be made based on this depolymerization product. Rigid polyurethane or polyisocyanurate foams made using this polyester polyol show excellent mechanical stability, good fire performance and low smoke generation together with a low thermal conductivity.
?~0 The poly(alkylene polyaromatic dicarboxylate) ester preferably used in the present invention is polyethylene 2,6-naphthalate). Other isomers of this polymer, or copolymers with e.g.
poly(ethylene terephtalate) (PET), poly(butylene terephthalate) (PBT) or poly(butylene naphthalate) can also be employed, as well as the polyesters based on dicarboxylates with a multi ring structure (e.g.
anthracene, phenantrene) and their ? 5 copolymers.
The polyester polyol is prepared by a two step process.
In a first step. the polyester is depolymerised in the presence of a glycol.
This can be, for example, 1,4-butanediol, diethyleneglycol (DEG) or dipropyleneglycol (DPG). Most suitable as the diol is DEG and it is 40 preferably used in an amount in excess of that required for digestion.
Although the reaction takes place in the absence of catalysts, the reaction times are significantly shortened by use of the appropriate catalysts. The preferred catalyst is tetra-N-butyltitanatc; (TBT). Zinc oxide or mangane acetate can also be employed.
The depolymerization is carried out at such temperature that the polyester dissociates and the core units are obtained. This is typically in the temperature range of 150 to 350°C, preferably about 240°C. The process is typically carried out at atmospheric pressure. However, it will be obvious that pressures higher than atmospheric can be used. At higher prcasures the reaction temperature can be increased significantly, thus shortening the reaction time. The obtained reaction mixture contains the esterification product from the polyaromatic dicarboxylate and the used glycol, together with the diol of the alkylene chain between the aromatic rings. Very often, excess glycols are present. When starting with PEN, the product from this first l0 step contains naphthalate polyols, unreacted glycols and ethylene glycol from the PEN. During the depolymerisation and esterification, removal of the formed ethylene glycol by vacuum distillation is possible.
This normally results in a lower OH value of the final polyester polyol, together with a reduction of fhe aliphatic content, which is reflected in the fire performance of the obtained foam. In the present invention the ethylene glycol was not removed, with no detrimental effects on the final rigid foam properties.
In a second step, the mixture is further transesterified by addition of other polycarboxylic acids, anhydrides or esters and a polyhydric alcohol. This further esterification brings the final polyester polyol in the desired viscosity range. The total content of polyester polymer used in the synthesis of the polyester polyol is typically in the range 5 to 50 wt%, prE;ferably 10 to 40 wt%. The polycarboxylic acid and the polyhydric 2.0 alcohol are added at a temperature in the range of 80 to 240°C, preferably 100 to 180°C.
Suitable examples of the polycarboxylic; acid component or its derivatives are adipic acid, glutaric acid and anhydride, succinic acid, oxalic acid, malonic acid, suberic acid, azelaic acid, sebacic acid, phtalic acid, phtalic anhydride, pyromellitic anhydride. As polyfunetional alcohol, glycols are preferred. They can be a simple glycol of general formula CnH2n(OH)2 or polyglycols with intervening ether linkages, as represented in the general formula CnH2nOx(OH)2. They also may contain heteroatoms.
The polycarboxylic component and polyhydric alcohol may include substituents which are inert in the reaction, e.g. chlorine and bromine substituents, and/or may be unsaturated.
Examples of suitable polyhydric alcohols are alkylene glycols and oxyalkylene glycols, such as ethylene glycol, diethylene glycol and higher polyethylene glycols, propylene glycol, dipropyleneglycol and higher propylene glycols, glycerol, pentaerythritol, trimethylolpropane, sorb~itol and mannitol.
The two steps described above can also be carried out in a single step process. The depolymerisation of the polyester polymer is more complete and faster when using a two step process.
The final polyo) mixture for use in the present invention has an average functionality of 1.5 to 8, preferably 2 to 3. The hydroxyl number is generally between 200 and 550 mg KOH/g polyol.
The molecular weight ofthe polyesters is generally in the range 200 to 3000, preferably 200 to 1000, most preferably 200 to 800.
The term polyester polyol as used herein includes. any minor amounts of unreacted polyol remaining after the preparation of the polyester polyol and/or unesterified polyol.
The polyester polyol according to the present invention is used to make polyurethane-based rigid foam. In the processing of polyurethane and polyisocyanurate foams, the polyisocyanates and the mixture of isocyanate-reactive components are generally mixed in a one-shot method. Both high and low-pressure techniques can be employed in the mixing step. The ratio of the NCO/OH groups generally falls within the range 0.85 to 1.40, preferably 0.95 to 1.2 for polyurethane foam, and within the range 50 to 1, preferably 8 to 1 for polyisocyanurate foam.
Besides the PEN based polyester polyol of the present invention other isocyanate-reactive compounds can be used in the process for making rigid polyurethane or urethane-modified polyisocyanurate foams. Suitable isocyanate-reactive compounds include any of that known in the art for the production of rigid polyurethane foam, especially polyether polyols and other types of polyester polyols.
In general the PEN based polyester polyol of the present invention constitutes between 60 and 100 % by weight of total isocyanate-reactive compounds.
IS
The isocyanate-reactive mixture generally contains the polyhydric alcohols and other optional additives such as blowing agents, fire retardants, fillers, stabilizers, catalysts and surfactants. Preferred catalysts for the polyurethane formation are amines, most preferably tertiary amines. Dibutyl tin dilaurate is an example of a non-amine based polyurethane catalyst. Preferred polyisocyanurate catalysts are alkali metal carboxylates and quaternary ammonium carboxylat:es.
Any of the blowing agents known in the art for the preparation of rigid polyurethane or urethane-modified polyisocyanurate foams can be used in the process of the present invention.
Both physical and chemical blowing agents can be used, singly or in mixtures.
Z~ Suitable physical blowing agents are. for example, hydrocarbons, dialkyl ethers, alkyl alkanoates, aliphatic and cycloaliphatic hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorine-containing ethers and carbon dioxide. Examples of preferred blowing agents are isomers of pentane such as cyclopentane, n-pentane and isopentane, and mixtures thereof, 1,1-dichloro-2-fluoroethane (HCFC
141b), I,1,1-trifluoro-2-fluoroethane (HFC 134a), chlorodifluoromethane (HCFC
22), I,1-difluoro-3,3,3-trifluoropropane (HFC 245fa).
Carbon dioxide releasing products can be used as chemical blowing agent.
Water, which releases carbon dioxide upon reaction with isocyanate, .is widely known as a chemical blowing agent.
The total quantity of blowing agent is typically from 0.1 to 25% by weight based on the total reaction system.
Both aliphatic and aromatic poiyisocyanates can be used. Preferred are the aromatic polyisocyanates such as diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI) or prepolymers thereof. Mixtures of isomers and oligomers can be employed. Most preferred is the polymeric form of MDI.
The polyisocyanate can be uretonimine or carbodiimide modified.
The invention is illustrated by, but not limited to. the following examples.
Example 1-3: Synthesis of the polyester.
s In a two-liter flask equipped with an efficient agitator, thermocouple and distillation set-up, diethylene glycol and polyethylene 2,6-naphthalate was charged. 10 ppm of TBT was added. The content was heated to 240°C
under efficient stirring and a nitrogen atmosphere. After 2 to 3 hours, the temperature was towered to 160°C
and adipic acid and glycerol were charged (quantities see table 1 ), together with 10 ppm TBT . The mixture was heated slowly to 180°C and water was removed by distillation. To complete the esterification, the I 0 temperature was further increased to 200°C until the theoretical stoichiometric amount of water was removed by distillation under vacuum. When the distillation rate flattened out, an acid value titration was performed.
Acid values of 2 mg KOHlgram are acceptable.
The specifications of the obtained polyesters are shown in Table I .
15 Table 1 Example 1: Example 2: Example 3:
polyol A polyol B polyol C
PEN (gram) 311.00 420.00 532.00 DEG (gram) 583.00 538.00 492.00 glycerol (gram) 133.00 134.00 136.00 adipic acid (gram)473.00 407.00 340.00 OH value 351.00 357.00 363.00 (mg KOH/gram) Viscosity (cPs 2100.00 4100.00 12900.00 at 25C) Free glycois MEG (%) 1.10 1.60 1.90 DEG (%) 8.30 7.30 6.30 glycerol (%) 3.30 6.60 3.50 Example 4-7 Rigid urethane-modified polyisocyanurate foams were prepared from the polyesters made according to examples 1 to 3 above. The formulation components (400 gram) were mixed at 5000 rpm with a small-scale iab mixing unit and poured into a 20x20x30 cm open mould. HCFC 141b was used as blowing agent. After standing at room temperature for at least 24 hours, physical properties of the foams were tested. Ingredients ?~ amounts in parts by weight) and foam physical properties obtained with polyols A. B and C and a comparative example based on a PET polyol are listed in Table 2.
PET polyol: polyester polyol based on scrap PET, OH value 350 mg KOH/gram.
Tegostab B 8406: silicone based surfactant available from Goldschmidt.
Example 1-3: Synthesis of the polyester.
s In a two-liter flask equipped with an efficient agitator, thermocouple and distillation set-up, diethylene glycol and polyethylene 2,6-naphthalate was charged. 10 ppm of TBT was added. The content was heated to 240°C
under efficient stirring and a nitrogen atmosphere. After 2 to 3 hours, the temperature was towered to 160°C
and adipic acid and glycerol were charged (quantities see table 1 ), together with 10 ppm TBT . The mixture was heated slowly to 180°C and water was removed by distillation. To complete the esterification, the I 0 temperature was further increased to 200°C until the theoretical stoichiometric amount of water was removed by distillation under vacuum. When the distillation rate flattened out, an acid value titration was performed.
Acid values of 2 mg KOHlgram are acceptable.
The specifications of the obtained polyesters are shown in Table I .
15 Table 1 Example 1: Example 2: Example 3:
polyol A polyol B polyol C
PEN (gram) 311.00 420.00 532.00 DEG (gram) 583.00 538.00 492.00 glycerol (gram) 133.00 134.00 136.00 adipic acid (gram)473.00 407.00 340.00 OH value 351.00 357.00 363.00 (mg KOH/gram) Viscosity (cPs 2100.00 4100.00 12900.00 at 25C) Free glycois MEG (%) 1.10 1.60 1.90 DEG (%) 8.30 7.30 6.30 glycerol (%) 3.30 6.60 3.50 Example 4-7 Rigid urethane-modified polyisocyanurate foams were prepared from the polyesters made according to examples 1 to 3 above. The formulation components (400 gram) were mixed at 5000 rpm with a small-scale iab mixing unit and poured into a 20x20x30 cm open mould. HCFC 141b was used as blowing agent. After standing at room temperature for at least 24 hours, physical properties of the foams were tested. Ingredients ?~ amounts in parts by weight) and foam physical properties obtained with polyols A. B and C and a comparative example based on a PET polyol are listed in Table 2.
PET polyol: polyester polyol based on scrap PET, OH value 350 mg KOH/gram.
Tegostab B 8406: silicone based surfactant available from Goldschmidt.
5 TEP: triethylphosphate fire retardant.
DMEA: dimethylethanolamine catalyst.
Niax A I : bis(dimethylamino ethylether) catalyst.
Dabco KIS: potassium octoate cataly;~t.
SUPRASEC 2085: polymeric MDl available from Huntsman Polyurethanes (SUPRASEC
is a trademark of Huntsman ICI Chemicals LLC}.
CT: cream time, which is the time from mixing to the change of appearance of the mixed chemicals, which indicates the onset of the expansion.
ST: string time, which is the time from mixing to the instant at which it is possible to pull a string of polymer from the reacting mixture using a spatula.
ER: end-of rise time, which is the time from mixing to the end of expansion of the foam.
TF: tack-free time which is the time; from mixing to when the surface of the foam no longer sticks to a spatula when light pressure is applied.
Density was measured according to standard DIN 53420.
Thermal conductivity was measured according to standard ISO 2581.
Compression strength was measured according to standard DIN 53421.
Kieinbrenner values were determined according to standard D1N 4102.
Limited 02 index was determined according to standard ASTM 2863.
NBS Smoke values were determined according to standard ASTM E 662.
Example 8-11 Rigid wethane-modified polyisocyatturate foams were prepared from the polyesters made according to examples 1 to 3 above. The formulation components (400 gram) were mixed at 5000 rpm and poured into a 20x20x30 cm open mould. lsopentane was used as blowing agent. After standing at room temperature for at least 24 hours, the physical properties of the obtained foams were tested.
Ingredients (amounts in parts by weight) and foam physical properties obtained using polyols A, B and C and a comparative PET based polyol are listed in Table 3.
DMEA: dimethylethanolamine catalyst.
Niax A I : bis(dimethylamino ethylether) catalyst.
Dabco KIS: potassium octoate cataly;~t.
SUPRASEC 2085: polymeric MDl available from Huntsman Polyurethanes (SUPRASEC
is a trademark of Huntsman ICI Chemicals LLC}.
CT: cream time, which is the time from mixing to the change of appearance of the mixed chemicals, which indicates the onset of the expansion.
ST: string time, which is the time from mixing to the instant at which it is possible to pull a string of polymer from the reacting mixture using a spatula.
ER: end-of rise time, which is the time from mixing to the end of expansion of the foam.
TF: tack-free time which is the time; from mixing to when the surface of the foam no longer sticks to a spatula when light pressure is applied.
Density was measured according to standard DIN 53420.
Thermal conductivity was measured according to standard ISO 2581.
Compression strength was measured according to standard DIN 53421.
Kieinbrenner values were determined according to standard D1N 4102.
Limited 02 index was determined according to standard ASTM 2863.
NBS Smoke values were determined according to standard ASTM E 662.
Example 8-11 Rigid wethane-modified polyisocyatturate foams were prepared from the polyesters made according to examples 1 to 3 above. The formulation components (400 gram) were mixed at 5000 rpm and poured into a 20x20x30 cm open mould. lsopentane was used as blowing agent. After standing at room temperature for at least 24 hours, the physical properties of the obtained foams were tested.
Ingredients (amounts in parts by weight) and foam physical properties obtained using polyols A, B and C and a comparative PET based polyol are listed in Table 3.
Table 2 Example Exam le Exam Exam 4 S le 6 le 7 PET of of 100.00 of of A 100.00 of of B 100.00 of of C 100.00 Teeostab B 8406 2.00 2.00 2.00 2.00 TEP I 5.00 15.00 15.00 15.00 DMEA 2.40 2.50 2.50 2.50 Niax A 1 U.13 0.13 0.13 0.13 Dabco K 15 1.80 I .90 1.90 1.90 water 2.30 2.30 2.30 2.30 HCFC 141 b 21.00 25.00 25.00 25.00 SUPRASEC 2085 312.00 312.00 312.00 312.00 Index (%) 250.00 25(1.00 250.00 250.00 Reaction rofile CT (sec) 14.00 14.00 14.00 14.00 ST (sec) 35.00 40.00 40.00 40.00 ER (sec) 50.00 75.00 75.00 75.00 TF (sec) 60.00 75.00 75.00 75.00 Densi k m3) 35,00 33.00 33.00 34.00 Thermal conductivi (mW/m K
initiall 22.70 22.10 21.40 21.20 1 week 28.70 27.80 27.10 26.70 3 weeks 29.80 29.40 28.40 28.50 weeks 29:70 29:80 29.30 28.70 Com ression stren th (kPa) arallel to rise 312.00 270.00 270.00 299.00 a endicular to rise 97.00 87.60 82.70 94.30 Isotro is 33 k m3 130..00 127.00 122.00 131.00 Kleinbrenner _ Ext. time (s) 15.00 15.00 15.00 15.00 Flame Hei ht (cm) 9.00 8.00 7.00 7.00 Limited 02 index (%) 28.0 28.1 28.1 28.1 NBS Smoke mass loss (%) ___ 49.00 44.00 44.00 43.00 ~
optical densitV~ 126.00 106.00 93.00 119.00 Table 3 Exam le Exam Exam le Exam le 8 le 9 10 11 PET 7 of 10_0.00 ~
of of A 100.00 _ _ of of B 100.00 of of C _ 100.00 Te ostab B 8406 2.00 2.00 2.00 2.00 TEP 15.00 15.00 15.00 15.00 __ DMEA 2.40 2.40 2.40 2.40 Niax A1 0.13 0.13 0.13 0.13 Dabco K 15 1.80 _ 1.80 1.80 1.80 water 2.30 2.30 2.30 2.30 i- entane 15.00 15.00 15.00 15.00 SUPRASEC 2085 312.00 312.00 312.00 312.00 lndex (% 250.00 250.00 250.00 250.00 Reaction rofile _ CT (sec) 10.00 11.00 10.00 10.00 ~
ST (sec) 42.00 40.00 42.00 40.00 Densi (k m3) 32.00 31.00 32.50 33.00 Thermal conductivity (mWlm K
initiall 24.00 23.60 24.30 23.60 1 week 27.10 26.50 27.50 26.50 3 weeks 29.00 28.60 28.40 28.40 _ weeks 28.30 27.70 28.60 28.30 Com ression Stren h (kPa arallel to rise 241.00 270.00 269.00 309.00 a endicular to 74.50_ 79.90 91.40 96.10 rise Isotro is 33 k 116.70 132.00 134.00 142.00 m3 Limited 02 index 25.6 26.2 26.2 26.2 (%) Kleinbrenner Ext. time (sec) 15.00 15.00 15.00 15.00 Flame Hei ht (cm 11.00 11.00 12.00 11.00 NBS Smoke _ mass loss (% 49.00 44.00 44.00 43.00 o tical densi __ 63.00 57.00 71.00 71.00
initiall 22.70 22.10 21.40 21.20 1 week 28.70 27.80 27.10 26.70 3 weeks 29.80 29.40 28.40 28.50 weeks 29:70 29:80 29.30 28.70 Com ression stren th (kPa) arallel to rise 312.00 270.00 270.00 299.00 a endicular to rise 97.00 87.60 82.70 94.30 Isotro is 33 k m3 130..00 127.00 122.00 131.00 Kleinbrenner _ Ext. time (s) 15.00 15.00 15.00 15.00 Flame Hei ht (cm) 9.00 8.00 7.00 7.00 Limited 02 index (%) 28.0 28.1 28.1 28.1 NBS Smoke mass loss (%) ___ 49.00 44.00 44.00 43.00 ~
optical densitV~ 126.00 106.00 93.00 119.00 Table 3 Exam le Exam Exam le Exam le 8 le 9 10 11 PET 7 of 10_0.00 ~
of of A 100.00 _ _ of of B 100.00 of of C _ 100.00 Te ostab B 8406 2.00 2.00 2.00 2.00 TEP 15.00 15.00 15.00 15.00 __ DMEA 2.40 2.40 2.40 2.40 Niax A1 0.13 0.13 0.13 0.13 Dabco K 15 1.80 _ 1.80 1.80 1.80 water 2.30 2.30 2.30 2.30 i- entane 15.00 15.00 15.00 15.00 SUPRASEC 2085 312.00 312.00 312.00 312.00 lndex (% 250.00 250.00 250.00 250.00 Reaction rofile _ CT (sec) 10.00 11.00 10.00 10.00 ~
ST (sec) 42.00 40.00 42.00 40.00 Densi (k m3) 32.00 31.00 32.50 33.00 Thermal conductivity (mWlm K
initiall 24.00 23.60 24.30 23.60 1 week 27.10 26.50 27.50 26.50 3 weeks 29.00 28.60 28.40 28.40 _ weeks 28.30 27.70 28.60 28.30 Com ression Stren h (kPa arallel to rise 241.00 270.00 269.00 309.00 a endicular to 74.50_ 79.90 91.40 96.10 rise Isotro is 33 k 116.70 132.00 134.00 142.00 m3 Limited 02 index 25.6 26.2 26.2 26.2 (%) Kleinbrenner Ext. time (sec) 15.00 15.00 15.00 15.00 Flame Hei ht (cm 11.00 11.00 12.00 11.00 NBS Smoke _ mass loss (% 49.00 44.00 44.00 43.00 o tical densi __ 63.00 57.00 71.00 71.00
Claims (9)
1. Process for prepping a poly(alkylene polyaromatic dicarboxylate)ester based polyester polyol comprising the steps of a) depolymerising poly(alkylene polyaramatic dicarboaylate) in the presence of a glycol and b) transerifying the obtained product by addition of polycarboxylic acids, anhydrides or esters and polyhydric alcohols.
2. Process according to claim 1 wherein poly(alkylene polyaromatic dicarboxylate) is poly(ethylere 2,6-naphthalate).
3. Process according to claim 2 wherein the polyethylene 2,6-naphthalate) comes from a production waste stream or post-consumer waste.
4. Process according to any one of the preceding claims wherein the glycol used in step a) is diethyleneglycol.
5. Process according to any one of the preceding claims wherein stop a) is carried out is the, presence of tetra-N-botyltitanate as catalyst.
6. Process according to any one of the decoding claims wherein the polyester polyol has an average functionality of 1.5 to 8, a hydroxyl number of 200 to 550 mg KOH/g and a molecular weight of 200 to 3000.
7. Polyester polyol obtainable by the process as deflated in any one of the preceding claims.
8. Process for preparing rigid polyurethane or urethane-modified polyisocyanurate foams by reacting an organic polyisocyanate with a polyfunctional isocyanate-reactive composition in the presence of a blowing agent characterized in that the polyfunctional isocyanate-reactive composition comprises a polyester polyol as defined is claim 7.
9. Process according to claim 8 wherein said polyester polyol constitutes 60 to 100 % by weight of total isocyanate-reactive compounds.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98121285.5 | 1998-11-09 | ||
| EP98121285 | 1998-11-09 | ||
| PCT/EP1999/007520 WO2000027899A1 (en) | 1998-11-09 | 1999-10-07 | Polyethylene naphthalate polyester polyol and rigid polyurethane foams obtained therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2346806A1 true CA2346806A1 (en) | 2000-05-18 |
Family
ID=8232939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002346806A Abandoned CA2346806A1 (en) | 1998-11-09 | 1999-10-07 | Polyethylene naphthalate polyester polyol and rigid polyurethane foams obtained therefrom |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1131367A1 (en) |
| JP (1) | JP2002529558A (en) |
| CN (1) | CN1328583A (en) |
| AU (1) | AU6335499A (en) |
| CA (1) | CA2346806A1 (en) |
| WO (1) | WO2000027899A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100617939B1 (en) | 2005-05-06 | 2006-08-30 | 한밭대학교 산학협력단 | Aromatic polyester polyol and manufacturing method thereof |
| JP5662650B2 (en) * | 2009-04-14 | 2015-02-04 | 太陽ホールディングス株式会社 | Polyol compound and thermosetting composition containing the same |
| EP3183286A4 (en) * | 2014-08-20 | 2018-08-22 | Resinate Materials Group, Inc. | Polyester polyols from recycled polymers and waste streams |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4184022A (en) * | 1978-09-15 | 1980-01-15 | Owens-Corning Fiberglas Corporation | Polyisocyanurate foam comprising reaction product of a polyisocyanate and a polyol mixture comprising a carboxylic ester polyol and a resole polyether polyol using a catalyst comprising dimethylethanolamine and an alkali metal salt of a carboxylic acid |
| US5008299A (en) * | 1988-12-09 | 1991-04-16 | The Dow Chemical Company | Rigid polyurethane foams with low thermal conductivities |
| US5539078A (en) * | 1994-12-14 | 1996-07-23 | Shell Oil Company | Process for manufacturing polyester copolymers |
| EP0854130A1 (en) * | 1997-01-15 | 1998-07-22 | Eastman Kodak Company | Recovery of monomers from polyethylene naphthalate |
| EP0857714A1 (en) * | 1997-01-31 | 1998-08-12 | Eastman Kodak Company | Recovery of monomers from polyethylene naphthalate |
| US5895807A (en) * | 1997-11-19 | 1999-04-20 | Shell Oil Company | Process for manufacturing polyester copolymers |
-
1999
- 1999-10-07 JP JP2000581075A patent/JP2002529558A/en not_active Withdrawn
- 1999-10-07 WO PCT/EP1999/007520 patent/WO2000027899A1/en not_active Application Discontinuation
- 1999-10-07 CA CA002346806A patent/CA2346806A1/en not_active Abandoned
- 1999-10-07 AU AU63354/99A patent/AU6335499A/en not_active Abandoned
- 1999-10-07 CN CN99812856A patent/CN1328583A/en active Pending
- 1999-10-07 EP EP99950662A patent/EP1131367A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002529558A (en) | 2002-09-10 |
| EP1131367A1 (en) | 2001-09-12 |
| AU6335499A (en) | 2000-05-29 |
| WO2000027899A1 (en) | 2000-05-18 |
| CN1328583A (en) | 2001-12-26 |
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