CA2181079A1 - Preparation of polyols containing isocyanurate groups - Google Patents
Preparation of polyols containing isocyanurate groupsInfo
- Publication number
- CA2181079A1 CA2181079A1 CA 2181079 CA2181079A CA2181079A1 CA 2181079 A1 CA2181079 A1 CA 2181079A1 CA 2181079 CA2181079 CA 2181079 CA 2181079 A CA2181079 A CA 2181079A CA 2181079 A1 CA2181079 A1 CA 2181079A1
- Authority
- CA
- Canada
- Prior art keywords
- mixture
- reaction
- polyols
- pir
- polyol
- 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.)
- Abandoned
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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5054—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/5063—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl 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
- 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
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
In a process for preparing polyols containing isocyanurate groups by reacting PIR with short-chain, hydroxyl-containing compounds, the reaction of the PIR is carried out in the presence of carrier polyols having an OH number of at most 500 mg KOH/g and a molecu-lar mass of at least 450 g/mol.
The polyols containing isocyanurate groups prepared by this pro-cess can be used for producing PUR and PIR.
The polyols containing isocyanurate groups prepared by this pro-cess can be used for producing PUR and PIR.
Description
2~81079 Preparation of polyols containing isocyanurate groups The invention relates to a process f or preparing polyols contain-ing isocyanurate groups by reacting polyi~ yeu-uL.ltes (PIR) with short-chain, hydroxyl-containing , '- in the presence of carrier polyols. The invention further relates to the use o~ the polyols thus obtained for producing polyurethanes (PUR) and PIR.
10 PIR are produced as cellular or cell-free plastics by the poly-addition process, in which c~talysts which allow isocyanate groups to trimerize into isocyanurate groups are added to a mix-ture of isocyanates, in particular one based on polymethylene diisocyanate, and polyols, in which mixture the isocyanates are ==
present in a large excess. Catalyst9 of this type are specifi-cally phosphines, phospholin derivatives, amines, alkali metal salts, metal compounds and Mannich bases. The process i8 de-scribed in detail in Becker/Braun, Kunststoffhandbuch, Volume 7, Polyurethane, Carl-Hanser-Verlag, 3rd Edition, Munich, Vienna 20 1993. The ob~ect of the PIR ~ormation is the development of particular properties such as, for example, high hardness, flame resistance and an increase in the thermal stability. For this purpo6e, isocyanates are incorporated into the system comprising polyol component and isocyanate in an amount ~oLL__p~JIlding to an i~ocyanate index of at least 1,0, but usually from 200 to 800.
This excess of isocyanate groups reacts virtually quantitatively and irreversibly to form isocyanurate.
In the patent and specialist literature, processes for the chemi-30 cal recycling of PIR are mentioned rather rarely in comparison with PUR and PUR/polyureas. In most cases, PIR is mentioned in addition to PUR, but no concrete examples are given. An example of this is DE-A-29 02 509 in which catalysts based on titanium and ~irconium are claimed for the glycolysis of PUR and PIR, but only PUR is used in the examples.
H. Ulrich et al. in Polymer Engineering and Science lB (1978) 11, pp. 844 to B4B and in SPE Tech. Papers 35, Conf., Montreal, Vol-ume 23, 1977, pp. 41 to 43, describQ a process for the glycolysis of PIR ~o~ms which was patented in 1973 by US-A-3 70B 440. If the 40 procedure of this process is repeated, the result is not the ex-pected homogeneous glycolysate which can be used for new PUR and/
or PIR syntheses. It instead gives black, coke-like lumps which make further processing impossible.
218107~
Ei. Ulrich discusses a reaction -hsln; ~`m according to which the glycolysis glycol cleaves the isocyanurate ring to form short-chain urethane and aromatic amine.
The glycolysis processes frequently described in the literature are also unsuccessful in the case of PIR. In each case, the PIR
are not converted into a liguid, but c'~ ~ to form coke-like lumps. Examples of such glycolysi~ processes which can be used for PUR but not for PIR are described in the patents US-A-4 110 266, EP-A-0 601 596, EP-Ei-0 542 806, DB-A-43 24 156, DE--A-42 15 014, DE-A-41 40 967 and DE--A--41 28 588.
This list is far from complete.
The glycolysis described in DE-A-42 34 335 also does not lead to the objective in the case of PIR~ Although it gives liquid prod-ucts, these contain a high level of black, crumbly impurities.
It is an object of the present invention to develop a simple and economical process for the glycolysis of PIR which leads to a re-cycled poly~1 whose amine content is below the characteristic value of 0.1 ~ by weight and which can immediately be used as such for producing PUR and PIR.
We have found that this object i8 achieved by the preparation of polyols containing isocyanurate groups being carried out by reacting PIR with short-chain, hydroxyl-containing compounds in the presence of carrier polyols having an OH number of at most 500 mg KOH/g and a molecular mass of at least 450 g/mol.
The invention accordingly provides a process for preparing poly-ols containing isocyanurate groups by reacting PIR with short-chain, hydroxyl-containing, ~ r wherein the reaction of the 40 PIR is carried out in the presence of carrier polyols having an OH number of at most 500 mg XOH/g and a molecular mass of at least 450 g/mol.
The invention further provides the po1yols containing isocyanu-rate groups which are prepared by this process, and also provides ~or their use for producing PUR and PIR.
218107~
To carry out the process of the inver~tion, the PIR, usually in comminuted form, 18 reacted with a mixture of short-chain, hy-droxyl-containing ~- ' used znd carrier polyol.
According to a particularly advantageous embodiment, the process of the invention is carried out in such a way that the mixture of short-chain, hydroxyl-containing c. '- used and carrier poly-ol is heated to from 190 to 240 C, preferably from 210 to 230 C, before addition of the PIR and the temperature is lowered by from 10 10 to 40 C after addition of the PIR. At thiD temperature, the reaction iB carried out over a period of from 1.5 to 3 hour6, preferably from 2 to 2.5 hours, with continual stirriDg. After the reaction is complete, the reaction mixture is cooled to from 50 to 150 C, preferably from 80 to 130 C, and a hydroxide of an alkali metal or an alkaline earth metal is added to the reaction mixture in an amount of at most 5 ~ by weiqht, based on the total mixture. The mixture i8 stirred for from 0.5 to 1.5 hours at this t. , clLUL~:.
20 Preference is given to using sodium hydroxide or potassium hy-droxide f or this purpose .
According to a further advantagéous embodiment, the reaction mix-ture is, after the reaction is complete, cooled to from 100 to 160 C, a glycidyl ether is added to the reaction mixture in an amount of at most 10 ~ by weight, based on the total mixture, and the mixture is st~rred for ~rom 0.5 to 1.5 hours at this tempera-ture .
30 The glycidyl ether used is preferably a monofunctional glycidyl ether, particularly preferably 2-ethylhexyl glycidyl ether.
If desired, this can be followed by a work-up of the recycled polyol, for example by filtration.
The ratio of the short-chain, hydroxyl-containing compounds used to the carrier polyol is generally ~5-20) :1, the ratio of the mixture of short-chain, hydroxyl-containing compounds used and carrier polyol to the PIR is ( 1-5 ) :1.
The reaction of PIR with 3hort--chain, hydroxyl-containing com-pounds is, according to the invention, carried out usin~ carrier polyols having an O~ number of at most 500 mg ~COE~g and a molecu-lar mass of at least 450 g/mol. Suitable carrier polyols are, for example, polyols prepared by polyaddition of propylene oxide to trihydric alcohols. Preference is given to using polyols based on glycerol and/or trimethylolpropane.
The short-chain, hydroxyl-containing compounds can in principle be any dihydric or higher-functional alcohols.
Dihydric alcohol3 are particularly advantageous ~or the process of the invention. The alcohols can be u3ed individually or a6 a mixture .
Preference is given to using ethylene glycol and lta higher homo-logs, in particular diethylene glycol, snd propylene glycol and it3 higher homologs, in particular dipropylene glycol, individu-ally or in admixture with one another.
The process can be carried out in the presence of customary poly-urethane catalysts. Preference i8 given to u3ing organic tin and titanium compounds for this purpose.
20 The PIR used can be scrap, for example from the production of PIR
block foams, PIR moldings or sandwich elements.
It was surprising that the glycolysis to give liquid products leads to no significant content of solid products if it is carried out according to the invention using a carrier polyol.
It was also surprising that the glycolysis polyols prepared by this process have an aromatic amine content of below 0.1 ~, which dispenses with the need for complicated deamination. It would 30 have been expected that amines would have been formed to a greater extent by hydrolysis and urea cleavage during the glyco-lysi3 .
It was also surprising that the IR spectra 3how the i30cyanurate structure3 virtually unchanged in the glycolysate, thus refuting the abovementioned theory of H . Ulrich ( attack on and breaking up of the isocyanurate rings ) .
The glycolysis polyols prepared by this process can, without fur-40 ther treatment, be again ~L~:es6ed to give PU~ or PIR.
For this purpose, they are reacted alone, but preferably in ad-mixture with other hydroxyl-containing '~, with polyiso-cyanates in the presence of customary blowing agents, catalyst3, auxiliaries and additives.
.
, ~. 2181079 Since the glycolysis polyols of the invention have very low vis-cosities, they can also be advantageously used for CFC-free rigid foam systems.
The invention is illustrated by the following examples.
Example 1 (comparison) 120 g of diethylene glycol were admixed with 0.15 9~ by weight, 10 based on the total mixture, of titanium tetrabutoxide and heated to 220 C. 50 g of PI}~ foam (NCO index 350) were then added at such a rate that the mass remained stirrable. The mixture was stirred for 3 hours. The product contained black pieces which still showed the foam ~lu.1 u~.
The product was unusable.
Example 2 ( comparison ) 20 ~he ~ e.lU~ was as in Example 1, but 20 e by weight, based on the total mixture, of 2-ethylhexyl glycidyl ether were added dropwise over the reaction time~ similar to the method described in DE-A 42 34 335. Here too the product was; nhl j~ne.u~ and un-usable .
Example 3 55 g of a PIR foam (NCO index 350 ) were introduced at from 215 to 225 C into a mixture of 100 g of diethylene glycol, 15.5 g of a 30 polyol based on glycerol and propylene oxide (PO) (1 mol of glyc-erol: 8.5 mol of PO, Lupranol 3300 from BASF Aktiengesellschaft) and 0.15 ~ by weight, based on the total mixture, of titanium tetrabutoxide in such a way that the contents of the flask re-mained stirrable. After the addition was complete, the tempera-ture was lowered to from 190 to 200 C and the mixture was left stirring for 2 hours. The temperature was then lowered further to 100 C, 2 g of solid NaO~ were added and the mixture was stirred for a further hour. This gave a homogeneous black-brown liquid having the following properties:
OE~ number : 638 mg ROH/g Acid number : O . 22 mg ROE~/g Viscosity at 25 C : 3520 mPa- s MDA content : O . 089 ~ by weigh 2~81079 Example 4 The procedure was as in Example 3, but the NaOE~ treatment was not carried out. The glycolysate had the following properties:
OH number : 625 mg }COH/g Acid number : 11. 4 mg ICOH/g Visco~ity at 25-C : 3844 mPa-s MDA content : 0 . 071 % by weight lo Examplo S
The ~ e~uL~ wa~ as in Example 3, but a PIR foam having an NCO
index of 600 was used. The glycolysate had the following proper-ties:
OH number : 734 mg ~OH/g Acid number : 0 . 05 mg KO~/g Viscosity at 25 C : 3174 mPa s 20 MDA content : 0 . 030 ~ by weight Example 6 80 g of a PIR foam based on a polyethylene terephthalate polyol (NCO index 450) and containing ~bout 20 ~ by weight of glass fibres were added at from 215 to 225 C to a mixture of 100 g of diethylene diglycol and 32 g of Lupranol 3300 and 0.1 % by weight, based on the total mixture, of tin(II) octoate in such a way that the contents of the flask remained stirrable. The tem-30 perature was then lowered to from 190 to 200 C and maintained for2 hours while stirring. The mixture was then cooled further to 150 C and 9 g of 2-ethylhexyl glycidyl ether were added and the mixture was stirred for a further hour at this temperature. This gave a homogeneous dark brown liquid having the following proper-ties:
OH number : 610 mg KOH/g Acid number : 0 . 6 mg ~OH/g Vi6cosity at 25-C : 3180 mPa-s 40 MDA content : 0 . 042 % by weight
10 PIR are produced as cellular or cell-free plastics by the poly-addition process, in which c~talysts which allow isocyanate groups to trimerize into isocyanurate groups are added to a mix-ture of isocyanates, in particular one based on polymethylene diisocyanate, and polyols, in which mixture the isocyanates are ==
present in a large excess. Catalyst9 of this type are specifi-cally phosphines, phospholin derivatives, amines, alkali metal salts, metal compounds and Mannich bases. The process i8 de-scribed in detail in Becker/Braun, Kunststoffhandbuch, Volume 7, Polyurethane, Carl-Hanser-Verlag, 3rd Edition, Munich, Vienna 20 1993. The ob~ect of the PIR ~ormation is the development of particular properties such as, for example, high hardness, flame resistance and an increase in the thermal stability. For this purpo6e, isocyanates are incorporated into the system comprising polyol component and isocyanate in an amount ~oLL__p~JIlding to an i~ocyanate index of at least 1,0, but usually from 200 to 800.
This excess of isocyanate groups reacts virtually quantitatively and irreversibly to form isocyanurate.
In the patent and specialist literature, processes for the chemi-30 cal recycling of PIR are mentioned rather rarely in comparison with PUR and PUR/polyureas. In most cases, PIR is mentioned in addition to PUR, but no concrete examples are given. An example of this is DE-A-29 02 509 in which catalysts based on titanium and ~irconium are claimed for the glycolysis of PUR and PIR, but only PUR is used in the examples.
H. Ulrich et al. in Polymer Engineering and Science lB (1978) 11, pp. 844 to B4B and in SPE Tech. Papers 35, Conf., Montreal, Vol-ume 23, 1977, pp. 41 to 43, describQ a process for the glycolysis of PIR ~o~ms which was patented in 1973 by US-A-3 70B 440. If the 40 procedure of this process is repeated, the result is not the ex-pected homogeneous glycolysate which can be used for new PUR and/
or PIR syntheses. It instead gives black, coke-like lumps which make further processing impossible.
218107~
Ei. Ulrich discusses a reaction -hsln; ~`m according to which the glycolysis glycol cleaves the isocyanurate ring to form short-chain urethane and aromatic amine.
The glycolysis processes frequently described in the literature are also unsuccessful in the case of PIR. In each case, the PIR
are not converted into a liguid, but c'~ ~ to form coke-like lumps. Examples of such glycolysi~ processes which can be used for PUR but not for PIR are described in the patents US-A-4 110 266, EP-A-0 601 596, EP-Ei-0 542 806, DB-A-43 24 156, DE--A-42 15 014, DE-A-41 40 967 and DE--A--41 28 588.
This list is far from complete.
The glycolysis described in DE-A-42 34 335 also does not lead to the objective in the case of PIR~ Although it gives liquid prod-ucts, these contain a high level of black, crumbly impurities.
It is an object of the present invention to develop a simple and economical process for the glycolysis of PIR which leads to a re-cycled poly~1 whose amine content is below the characteristic value of 0.1 ~ by weight and which can immediately be used as such for producing PUR and PIR.
We have found that this object i8 achieved by the preparation of polyols containing isocyanurate groups being carried out by reacting PIR with short-chain, hydroxyl-containing compounds in the presence of carrier polyols having an OH number of at most 500 mg KOH/g and a molecular mass of at least 450 g/mol.
The invention accordingly provides a process for preparing poly-ols containing isocyanurate groups by reacting PIR with short-chain, hydroxyl-containing, ~ r wherein the reaction of the 40 PIR is carried out in the presence of carrier polyols having an OH number of at most 500 mg XOH/g and a molecular mass of at least 450 g/mol.
The invention further provides the po1yols containing isocyanu-rate groups which are prepared by this process, and also provides ~or their use for producing PUR and PIR.
218107~
To carry out the process of the inver~tion, the PIR, usually in comminuted form, 18 reacted with a mixture of short-chain, hy-droxyl-containing ~- ' used znd carrier polyol.
According to a particularly advantageous embodiment, the process of the invention is carried out in such a way that the mixture of short-chain, hydroxyl-containing c. '- used and carrier poly-ol is heated to from 190 to 240 C, preferably from 210 to 230 C, before addition of the PIR and the temperature is lowered by from 10 10 to 40 C after addition of the PIR. At thiD temperature, the reaction iB carried out over a period of from 1.5 to 3 hour6, preferably from 2 to 2.5 hours, with continual stirriDg. After the reaction is complete, the reaction mixture is cooled to from 50 to 150 C, preferably from 80 to 130 C, and a hydroxide of an alkali metal or an alkaline earth metal is added to the reaction mixture in an amount of at most 5 ~ by weiqht, based on the total mixture. The mixture i8 stirred for from 0.5 to 1.5 hours at this t. , clLUL~:.
20 Preference is given to using sodium hydroxide or potassium hy-droxide f or this purpose .
According to a further advantagéous embodiment, the reaction mix-ture is, after the reaction is complete, cooled to from 100 to 160 C, a glycidyl ether is added to the reaction mixture in an amount of at most 10 ~ by weight, based on the total mixture, and the mixture is st~rred for ~rom 0.5 to 1.5 hours at this tempera-ture .
30 The glycidyl ether used is preferably a monofunctional glycidyl ether, particularly preferably 2-ethylhexyl glycidyl ether.
If desired, this can be followed by a work-up of the recycled polyol, for example by filtration.
The ratio of the short-chain, hydroxyl-containing compounds used to the carrier polyol is generally ~5-20) :1, the ratio of the mixture of short-chain, hydroxyl-containing compounds used and carrier polyol to the PIR is ( 1-5 ) :1.
The reaction of PIR with 3hort--chain, hydroxyl-containing com-pounds is, according to the invention, carried out usin~ carrier polyols having an O~ number of at most 500 mg ~COE~g and a molecu-lar mass of at least 450 g/mol. Suitable carrier polyols are, for example, polyols prepared by polyaddition of propylene oxide to trihydric alcohols. Preference is given to using polyols based on glycerol and/or trimethylolpropane.
The short-chain, hydroxyl-containing compounds can in principle be any dihydric or higher-functional alcohols.
Dihydric alcohol3 are particularly advantageous ~or the process of the invention. The alcohols can be u3ed individually or a6 a mixture .
Preference is given to using ethylene glycol and lta higher homo-logs, in particular diethylene glycol, snd propylene glycol and it3 higher homologs, in particular dipropylene glycol, individu-ally or in admixture with one another.
The process can be carried out in the presence of customary poly-urethane catalysts. Preference i8 given to u3ing organic tin and titanium compounds for this purpose.
20 The PIR used can be scrap, for example from the production of PIR
block foams, PIR moldings or sandwich elements.
It was surprising that the glycolysis to give liquid products leads to no significant content of solid products if it is carried out according to the invention using a carrier polyol.
It was also surprising that the glycolysis polyols prepared by this process have an aromatic amine content of below 0.1 ~, which dispenses with the need for complicated deamination. It would 30 have been expected that amines would have been formed to a greater extent by hydrolysis and urea cleavage during the glyco-lysi3 .
It was also surprising that the IR spectra 3how the i30cyanurate structure3 virtually unchanged in the glycolysate, thus refuting the abovementioned theory of H . Ulrich ( attack on and breaking up of the isocyanurate rings ) .
The glycolysis polyols prepared by this process can, without fur-40 ther treatment, be again ~L~:es6ed to give PU~ or PIR.
For this purpose, they are reacted alone, but preferably in ad-mixture with other hydroxyl-containing '~, with polyiso-cyanates in the presence of customary blowing agents, catalyst3, auxiliaries and additives.
.
, ~. 2181079 Since the glycolysis polyols of the invention have very low vis-cosities, they can also be advantageously used for CFC-free rigid foam systems.
The invention is illustrated by the following examples.
Example 1 (comparison) 120 g of diethylene glycol were admixed with 0.15 9~ by weight, 10 based on the total mixture, of titanium tetrabutoxide and heated to 220 C. 50 g of PI}~ foam (NCO index 350) were then added at such a rate that the mass remained stirrable. The mixture was stirred for 3 hours. The product contained black pieces which still showed the foam ~lu.1 u~.
The product was unusable.
Example 2 ( comparison ) 20 ~he ~ e.lU~ was as in Example 1, but 20 e by weight, based on the total mixture, of 2-ethylhexyl glycidyl ether were added dropwise over the reaction time~ similar to the method described in DE-A 42 34 335. Here too the product was; nhl j~ne.u~ and un-usable .
Example 3 55 g of a PIR foam (NCO index 350 ) were introduced at from 215 to 225 C into a mixture of 100 g of diethylene glycol, 15.5 g of a 30 polyol based on glycerol and propylene oxide (PO) (1 mol of glyc-erol: 8.5 mol of PO, Lupranol 3300 from BASF Aktiengesellschaft) and 0.15 ~ by weight, based on the total mixture, of titanium tetrabutoxide in such a way that the contents of the flask re-mained stirrable. After the addition was complete, the tempera-ture was lowered to from 190 to 200 C and the mixture was left stirring for 2 hours. The temperature was then lowered further to 100 C, 2 g of solid NaO~ were added and the mixture was stirred for a further hour. This gave a homogeneous black-brown liquid having the following properties:
OE~ number : 638 mg ROH/g Acid number : O . 22 mg ROE~/g Viscosity at 25 C : 3520 mPa- s MDA content : O . 089 ~ by weigh 2~81079 Example 4 The procedure was as in Example 3, but the NaOE~ treatment was not carried out. The glycolysate had the following properties:
OH number : 625 mg }COH/g Acid number : 11. 4 mg ICOH/g Visco~ity at 25-C : 3844 mPa-s MDA content : 0 . 071 % by weight lo Examplo S
The ~ e~uL~ wa~ as in Example 3, but a PIR foam having an NCO
index of 600 was used. The glycolysate had the following proper-ties:
OH number : 734 mg ~OH/g Acid number : 0 . 05 mg KO~/g Viscosity at 25 C : 3174 mPa s 20 MDA content : 0 . 030 ~ by weight Example 6 80 g of a PIR foam based on a polyethylene terephthalate polyol (NCO index 450) and containing ~bout 20 ~ by weight of glass fibres were added at from 215 to 225 C to a mixture of 100 g of diethylene diglycol and 32 g of Lupranol 3300 and 0.1 % by weight, based on the total mixture, of tin(II) octoate in such a way that the contents of the flask remained stirrable. The tem-30 perature was then lowered to from 190 to 200 C and maintained for2 hours while stirring. The mixture was then cooled further to 150 C and 9 g of 2-ethylhexyl glycidyl ether were added and the mixture was stirred for a further hour at this temperature. This gave a homogeneous dark brown liquid having the following proper-ties:
OH number : 610 mg KOH/g Acid number : 0 . 6 mg ~OH/g Vi6cosity at 25-C : 3180 mPa-s 40 MDA content : 0 . 042 % by weight
Claims (10)
1. A process for preparing polyols containing isocyanurate groups by reacting polyisocyanurates with short-chain, hy-droxyl-containing compounds, wherein the reaction of the polyisocyanurates is carried out in the presence of carrier polyols having an OH number of at most 500 mg XOH/g and a molecular mass of at least 450 g/mol.
2. A process as claimed in claim 1, wherein the carrier polyols used are polyols based on glycerol and/or trimethylolpropane.
3. A process as claimed in claim 1 or 2, wherein the ratio of the short-chain, hydroxyl-containing compounds used to the carrier polyol is (5-20):1.
4. A process as claimed in any one of claims 1 to 3, wherein the ratio of the mixture of short-chain, hydroxyl-containing com-pounds used and carrier polyol to the polyisocyanurate is (1-5):1.
5. A process as claimed in any one of claims 1 to 4, wherein the mixture of short-chain, hydroxyl-containing compounds used and carrier polyol is heated to from 190 to 240°C before addition of the polyisocyanurate, the temperature is lowered by from 10 to 40°C after addition of the polyisocyanurate and the reaction is carried out at this temperature for from 1.5 to 3 hours with continual stirring.
6. A process as claimed in any one of claims 1 to 5, wherein the reaction mixture is, after completion of the reaction, cooled to from 50 to 150°C, a hydroxide of an alkali metal or alka-line earth metal is added to the reaction mixture in an amount of at most 5 % by weight, based on the total mixture, and the mixture is stirred for from 0.5 to 1.5 hours at this temperature.
7. A process as claimed in any one of claims 1 to 5, wherein the reaction mixture is, after the reaction is complete, cooled to from 100 to 160°C, a monofunctional glycidyl ether is added to the reaction mixture in an amount of at most 10 % by weight, based on the total mixture, and the mixture is stirred for from 0.5 to 1.5 hours at this temperature.
8. A polyol containing isocyanurate groups, which can be pre-pared by the process claimed in any one of claims 1 to 7.
9. Use of the polyol containing isocyanurate groups as claimed in claim 8 for producing polyurethanes.
10. Use of the polyol containing isocyanurato groups as claimed in claim 8 for producing polyisocyanurates.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19525301.9 | 1995-07-12 | ||
| DE19525301A DE19525301A1 (en) | 1995-07-12 | 1995-07-12 | Process for the preparation of polyols containing isocyanurate groups |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2181079A1 true CA2181079A1 (en) | 1997-01-13 |
Family
ID=7766580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2181079 Abandoned CA2181079A1 (en) | 1995-07-12 | 1996-07-11 | Preparation of polyols containing isocyanurate groups |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0753535B1 (en) |
| JP (1) | JPH09118737A (en) |
| KR (1) | KR970006343A (en) |
| AT (1) | ATE165382T1 (en) |
| CA (1) | CA2181079A1 (en) |
| DE (2) | DE19525301A1 (en) |
| DK (1) | DK0753535T3 (en) |
| ES (1) | ES2115412T3 (en) |
| MX (1) | MX9602586A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2591750B2 (en) * | 1986-06-26 | 1997-03-19 | オ−ソ・ダイアグノステイツク・システムズ・インコ−ポレ−テツド | Immunoassay system |
| WO2023208946A1 (en) | 2022-04-27 | 2023-11-02 | Covestro Deutschland Ag | Method for recovering raw materials from isocyanurate-containing polyurethane products |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3708440A (en) * | 1972-02-14 | 1973-01-02 | Upjohn Co | Reclaiming scrap polyisocyanurate foam with an aliphatic diol and a dialkanolamine |
| US4110266A (en) * | 1976-07-09 | 1978-08-29 | Mcdonnell Douglas Corporation | Process for converting the decomposition products of polyurethane and novel compositions thereby obtained |
| DE2902509A1 (en) * | 1979-01-23 | 1980-07-31 | Apprich Johannes | Liq. poly:ol prepn. from polyurethane and/or polyisocyanurate waste - by heating foam with diol using gp=iv metal cpd. catalyst |
-
1995
- 1995-07-12 DE DE19525301A patent/DE19525301A1/en not_active Withdrawn
-
1996
- 1996-07-02 DE DE59600162T patent/DE59600162D1/en not_active Expired - Fee Related
- 1996-07-02 EP EP19960110653 patent/EP0753535B1/en not_active Expired - Lifetime
- 1996-07-02 AT AT96110653T patent/ATE165382T1/en not_active IP Right Cessation
- 1996-07-02 ES ES96110653T patent/ES2115412T3/en not_active Expired - Lifetime
- 1996-07-02 DK DK96110653T patent/DK0753535T3/en active
- 1996-07-03 MX MX9602586A patent/MX9602586A/en not_active Application Discontinuation
- 1996-07-09 KR KR1019960027561A patent/KR970006343A/en not_active Application Discontinuation
- 1996-07-10 JP JP18057596A patent/JPH09118737A/en not_active Withdrawn
- 1996-07-11 CA CA 2181079 patent/CA2181079A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| DK0753535T3 (en) | 1998-10-07 |
| MX9602586A (en) | 1997-01-31 |
| JPH09118737A (en) | 1997-05-06 |
| EP0753535B1 (en) | 1998-04-22 |
| EP0753535A1 (en) | 1997-01-15 |
| DE59600162D1 (en) | 1998-05-28 |
| ATE165382T1 (en) | 1998-05-15 |
| DE19525301A1 (en) | 1997-01-16 |
| KR970006343A (en) | 1997-02-19 |
| ES2115412T3 (en) | 1998-06-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |
Effective date: 20040712 |