WO2000027899A1 - Polyethylene naphthalate polyester polyol and rigid polyurethane foams obtained therefrom - Google Patents
Polyethylene naphthalate polyester polyol and rigid polyurethane foams obtained therefrom Download PDFInfo
- Publication number
- WO2000027899A1 WO2000027899A1 PCT/EP1999/007520 EP9907520W WO0027899A1 WO 2000027899 A1 WO2000027899 A1 WO 2000027899A1 EP 9907520 W EP9907520 W EP 9907520W WO 0027899 A1 WO0027899 A1 WO 0027899A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyester polyol
- poly
- process according
- alkylene
- polyaromatic
- Prior art date
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
- C08G63/02—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
-
- 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
-
- 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
Definitions
- the invention more specifically relates to polyester polyols produced from reacting polyethylene naphthalate.
- Aromatic polyester polyols used in rigid PUR/PIR foams are typically based on production waste streams of dimethyl terephtalate (DMT).
- DMT dimethyl terephtalate
- PET polyethylene terephtalate
- Depolymerization of production waste streams or post consumer waste from e.g. PET bottles is a known method in the preparation of a polyester polyol.
- PEN poly(ethylene naphthalate)
- PEN poly(ethylene naphthalate)
- PEN poly(ethylene naphthalate)
- 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.
- the poly(alkylene polyaromatic dicarboxylate) ester preferably used in the present invention is poly(ethylene 2,6-naphthalate).
- Other isomers of this polymer, or copolymers with e.g. polyethylene 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 copolymers.
- the polyester is depolymerised in the presence of a glycol.
- a glycol can be, for example, 1,4- butanediol, diethyleneglycol (DEG) or dipropyleneglycol (DPG).
- DEG diethyleneglycol
- DPG dipropyleneglycol
- Most suitable as the diol is DEG and it is preferably used in an amount in excess of that required for digestion.
- the preferred catalyst is tetra-N-butyltitanate (TBT). Zinc oxide or mangane acetate can also be employed.
- TBT tetra-N-butyltitanate
- 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.
- the process 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 pressures 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.
- the product from this first 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.
- the mixture is further transesterified by addition of other polycarboxyhc 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%, preferably 10 to 40 wt%.
- the polycarboxyhc acid and the polyhydric alcohol are added at a temperature in the range of 80 to 240°C, preferably 100 to 180°C.
- polycarboxyhc 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.
- polyfunctional alcohol glycols are preferred. They can be a simple glycol of general formula C n H2 n (OH)2 or polyglycols with intervening ether linkages, as represented in the general formula C n H2 n O x (OH)2. They also may contain heteroatoms.
- the polycarboxyhc component and polyhydric alcohol may include substituents which are inert in the reaction, e.g. chlorine and bromine substituents, and/or may be unsaturated.
- 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, sorbitol and mannitol.
- the final polyol 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 of the polyesters is generally in the range 200 to 3000, preferably 200 to 1000, most preferably 200 to 800.
- polyester polyol as used herein includes any minor amounts of unreacted polyol remaining after the preparation of the polvester polyol and/or uneste ⁇ fied polyol
- the polyester polyol according to the present invention is used to make polyurethane-based rigid foam
- the polyisocyanates and the mixture of lsocyanate- 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
- 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
- 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 tm dilaurate is an example of a non-amine based polyurethane catalyst
- Preferred polyisocyanurate catalysts are alkali metal carboxylates and quaternary ammonium carboxylates
- aromatic polyisocyanates such as diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI) or prepolvmers thereof Mixtures of isomers and o gomers can be employed Most preferred is the polymeric form of MDI
- the polyisocvanate can be uretonimine or carbodnmide modified
- the invention is illustrated by, but not limited to. the following examples.
- DMEA dimethylethanolamine catalyst
- Niax A 1 bis(dimethylamino ethylether) catalyst.
- Dabco K15 potassium octoate catalyst.
- 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.
- Thermal conductivity was measured according to standard ISO 2581. Compression strength was measured according to standard DIN 53421.
Landscapes
- 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
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000581075A JP2002529558A (en) | 1998-11-09 | 1999-10-07 | Polyethylene naphthalate polyester polyol and rigid polyurethane foam obtained therefrom |
AU63354/99A AU6335499A (en) | 1998-11-09 | 1999-10-07 | Polyethylene naphthalate polyester polyol and rigid polyurethane foams obtained therefrom |
CA002346806A CA2346806A1 (en) | 1998-11-09 | 1999-10-07 | Polyethylene naphthalate polyester polyol and rigid polyurethane foams obtained therefrom |
EP99950662A EP1131367A1 (en) | 1998-11-09 | 1999-10-07 | Polyethylene naphthalate polyester polyol and rigid polyurethane foams obtained therefrom |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98121285.5 | 1998-11-09 | ||
EP98121285 | 1998-11-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000027899A1 true WO2000027899A1 (en) | 2000-05-18 |
Family
ID=8232939
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/007520 WO2000027899A1 (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) |
Cited By (1)
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 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Citations (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 |
EP0717060A2 (en) * | 1994-12-14 | 1996-06-19 | Shell Internationale Researchmaatschappij B.V. | Process for manufacturing polyester copolymers containing terephthalate and naphthalate units |
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
Patent Citations (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 |
EP0717060A2 (en) * | 1994-12-14 | 1996-06-19 | Shell Internationale Researchmaatschappij B.V. | Process for manufacturing polyester copolymers containing terephthalate and naphthalate units |
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 |
Cited By (1)
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 |
Also Published As
Publication number | Publication date |
---|---|
JP2002529558A (en) | 2002-09-10 |
EP1131367A1 (en) | 2001-09-12 |
CA2346806A1 (en) | 2000-05-18 |
AU6335499A (en) | 2000-05-29 |
CN1328583A (en) | 2001-12-26 |
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