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
  • C08G18/4829—Polyethers containing at least three hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
• • 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
• • 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3271—Hydroxyamines
• • 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
• • 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
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
  • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
• • 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
  • C08G2101/00—Manufacture of cellular products
• • 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
  • C08G2110/0041—Foam properties having specified density
  • C08G2110/005—< 50kg/m3

Definitions

• the present invention describes a process for the preparation of PIPA polyols and their use for the production of flexible polyurethane foams.
• PUR foams are obtained by reacting polyisocyanates and compounds having at least two reactive hydrogen atoms in the presence of blowing agents and other additives.
• An overview of the production of polyurethanes is given in Kunststoff-Handbuch, volume VE, "Polyurethane", 3rd edition, 1993, by Dr. G. Oertel (Carl Hanser Verlag).
• PMPOs polymer polyols
• PPD polyols polyurea dispersions
• PIPA polyols polyisocyanate polyaddition polyols
• 4,093,569 and GB-A 1,501,172 are prepared by the polyaddition reaction of hydrazines or amines with mono- , Dioder polyisocyanates prepared in polyols and PIPA polyols ("JPIP A-Process for the Future", K.
• Highly elastic foams are not only more elastic than standard foams but show better fire properties.
• One goal of the soft foam manufacturers is the continuous improvement of the fire properties of the foams. Different fire tests are used for different end applications and in different countries. Typical examples are "Califonia 117A”, “California 117D”, “Motor Vehicle Safety System 302” and “3ritish Standard 5852 part 2, Crib V”. In particular, the latter test can usually only be achieved by using a relatively high proportion of expensive flame retardants.
• PIPA polyols The stability and / or viscosity of PIPA polyols is often problematic.
• EP-A 129 977 good PIPA polyols are obtained when a dispersant is used in the preparation. Without the dispersant, the products are coarse, high viscosity or solid pastes.
• One goal of many developments is to increase the solids content to improve the properties of the foams made with the PIPA polyol and to reduce the amount of PIPA polyol to be transported. When increasing the filler content, an unacceptable increase in viscosity must be avoided.
• EP-A 79 115 PIPA polyols are described with 40-80 wt.% Filler. A portion of the isocyanate is retained and added at a later stage.
• viscosity reduction and post-production viscosity stabilization ie, little or no increase in viscosity over time
• a second olamine is added to the reaction mixture of isocyanate and olamine in a second mixing head. Without the addition of the second olamine, the product gels.
• the stabilization of the viscosity is achieved by the addition of 0.05 to 0.5 parts by weight of a mono- or di-carboxylic acid.
• WO 94/20558 the viscosity and stability of the PIPA dispersions are improved by the use of a stabilizer.
• the stabilizer itself is again a PIPA polyol.
• PIPA polyols having a filler content of 30% by weight could be prepared in which the filler does not settle over time.
• DE-A 198 11 471 describes a process for the preparation of stable dispersions. This is achieved by the addition of a monofunctional amine (such as di-N-butylamine).
• a monofunctional amine such as di-N-butylamine
• the comparative examples without di-N-butylamine could either not be processed as a flexible foam polyol or led to a very non-uniform foam structure.
• US-A 4,293,470 is by the Addition of 0.1-1.0 wt.% Of a secondary amine such as dibutylamine avoided a change in the viscosity of the filled polyol and thus achieved an improved storage stability. '
• Viscosity is known. According to US Pat. No. 4,093,569, more than 4% by weight (particularly preferably 10 to 25% by weight) of water is used. The disadvantage, however, is that the high water content must be removed before foaming. Other prior art documents therefore teach using lower levels of water. In US-A 4,497,913 about 0.1 to 0.5 wt .-% are
• WO 2004/099281 describes the preparation of PIPA polyols having filler contents of 1-80% by weight from a short-chain polyol and an MDI-based isocyanate in the presence of 0.1-5% by weight of water ,
• A-polyols tend to inhomogeneity (clumping or agglomeration) or instability (phase separation or viscosity change) and are therefore not suitable for the production of foams.
• the object of the present invention is to provide PIP A polyols having improved homogeneity. It has now been found that an improvement in the homogeneity can be achieved by adding urea in the production of polyol.
• the invention relates to a process for the preparation of polyisocyanate polyaddition polyols (PIPA polyols) in which polyisocyanates are reacted with amines or alkanolamines or mixtures thereof in a polyether polyol in the presence of urea and water.
• PIPA polyols polyisocyanate polyaddition polyols
• Toluene diisocyanate (TDI) is preferably used as the polyisocyanate in the process according to the invention, more preferably in the form of an isomer mixture containing 80% by weight of 2,4-TDI
• the polyisocyanate is diphenylmethane diisocyanate (MDI) used in the form of monomeric MDI, mixtures of MDI and its higher homologues Ho ⁇ (polymeric MDI ”) or mixtures thereof.
• MDI diphenylmethane diisocyanate
• amines having primary, secondary or tertiary amino groups, preferably primary or secondary amino groups.
• Aliphatic, cycloaliphatic or aromatic amines can be used.
• suitable amines are N-methyl-1,3-propanediamine, phenylhydrazine, 1,12-diamino-4,9-dioxadecane, 1,2-propylenediamine and 1,3-propylenediamine, ⁇ -aminodiphenylmethane, N, N triamine dibenzylethylenediamine, amino-terminated polyols (such as Jeffamine ® from.
• Preferred amines are l, 12-diamino-4,9-dioxadecane, 1,2 diamine, -Propy-, ⁇ -aminodiphenylmethane, N, N-dibenzylethylenediamine, difunctional polyoxypropylene lenamin having a number average molecular weight of 230 g / mol (Jeffamine ® D230), 3-dimethylamino-1-propylamine, diethylenetriamine.
• Suitable alkanolamines for the process according to the invention are diethanolamine (DEOA), 3-amino-1-propanol, aminoethylethanolamine, aminoethanol and aminoethoxyethanol.
• Diethanolamine, 3-amino-1-propanol or aminoethylethanolamine are preferred. Particular preference is given to using combinations of diethanolamine with other amines or alkanolamines.
• the mixing ratio DEOA to further amines or alkanolamines is preferably 0.5: 1 to 5: 1.
• the NH number of the mixtures is typically 400 to 700.
• the different reactivities of primary and secondary NH groups are not taken into account here. It is assumed for the formulation calculation that the OH groups in alkanolamines do not react.
• Suitable polyether polyols for the process according to the invention generally have an OH number of 28 to 56, an OH functionality of 2 to 4 and an ethylene oxide content of 15 to 20% by weight.
• an aqueous urea solution is co-used.
• the weight ratio of urea to water is generally 1: 1.
• the solubility of urea in water at 2O 0 C is 1080 g / l, so that significantly concentrated solutions are not possible.
• a more dilute solution can also lead to homogeneous dispersions. In this case, the quantities must be adjusted accordingly.
• very dilute solutions are not of interest if their use means that the PIPA polyols made therewith would contain more than about 3 parts water, typically 3 parts of water are used in foaming and one additional step (distillation to remove excess water) is not desired.
• an antioxidant can be added.
• polyisocyanate and amines or alkanolamines are used in such a ratio that the ratio of the isocyanate groups to the isocyanate-reactive NH or NH 2 groups is 0.90 to 1.1, preferably 0.95 to 1.05, particularly preferred 1: 1.
• the PIPA polyols prepared by the process according to the invention have filler contents of from 1 to 50% by weight, preferably from 10 to 20% by weight.
• the erfmdungswashe process can be carried out by first polyether polyol, amines or alkanolamines, water and urea are mixed and then the polyisocyanate is added. Alternatively, all components can be mixed simultaneously in a mixing head.
• the process according to the invention is generally carried out at room temperature.
• the PIPA polyols prepared by the process according to the invention are notable for their particular homogeneity and can therefore be further processed advantageously into flexible polyurethane foams.
• urea chemically participates in the reaction in such a way as to stabilize the dispersion.
• a polymer usable for polyurethane flexible foams must be a stable dispersion of discrete polymer particles in a base polyether.
• the filled polyol must also show good processing properties: The viscosity must be within an acceptable range, so that the filled polyol can be processed in conventional foam systems. Ideally, this filled polyol should also result in a foam with good cell opening: ie not too much cell opening, otherwise foam collapse occurs and not too little cell opening to avoid shrinkage or poor quality of the resulting foam. Examples
• Polyether A trifunctional polyether polyol of OHZ 35 with an EO content of 17.5 wt .-%.
• Desmodur ® T80 mixture of 2,4- and 2,6-TDI (80:20), having an NCO content of 48
• Irganox ® 1135 antioxidant (Ciba Specialty Chemicals)
• Irganox ® 68b antioxidant (Ciba Specialty Chemicals)
• Tegostab ® B8681 polysiloxane-polyether-based foam stabilizer (Goldschmidt AG).
• Niax ® Al bis (2-dimethylamino) ethyl ether in dipropylene glycol
• Dabco ® 33-LV 33% triethylenediamine, 67% dipropylene glycol (Air Products).
• Levagard PP tris (2-chloroisopropyl) phosphate (Rhein Chemie). Method for Examples 1-9
• Polyether A the amines and / or alkanolamines and an aqueous urea solution (50 wt .-%) were placed in a mixing cup at room temperature. With a Pendraulik stirrer was stirred at -2400 U / min for two minutes. Desmodur ® T80 was added in one portion and stirred at -2400 U / min for another 2 minutes. Due to the exothermic nature of the reaction, the mixture warmed significantly. Once the dispersion was cooled to about 6O 0 C, was added Irganox ® 1135th
• Polyether A the amines and / or alkanolamines and water were placed in a mixing cup at room temperature. With a Pendraulik stirrer was stirred at ⁇ 2400 U / min for two minutes. Desmodur ® T80 was added in one portion and stirred at ⁇ 2400 U / min for another 2 minutes. Due to the exothermic nature of the reaction, the mixture warmed significantly. Once the dispersion was cooled to about 6O 0 C, was added Irganox ® 1135th
• the homogeneous PIPA dispersions 1-9 and 6a were used for the production of flexible foams (Examples 10-19):
• the start time is the period from the beginning of the last mixing operation to a visually perceptible change or a significant increase in the volume of the reaction mixture.
• the rise time is the time between start of mixing and maximum vertical foam expansion.
• the bulk density is determined by determining the volume and mass of a test specimen.
• the flow resistance (open-cell density) is determined by passing air through the test specimen and measuring the resistance of this air flow using a water column on a scale of 0 to 350 mm.
• the apparatus used for this purpose consists of a glass cylinder provided with a millimeter graduation of 0 to 350, whose inner diameter is 36 mm, and an inner tube of 7 mm clear width. This inner tube ends at the top in a T-piece, to which the air supply is connected on one side and the hose with the measuring head on the other side.
• the hose for the measuring head has an inner diameter of 12 mm and a length of 1.80 m.
• the glass cylinder is closed at the bottom and can be filled with water via the funnel at the rear.
• the tester is connected to a compressed air source via two taps, a pressure reducer and a hose of any length and diameter, with the pressure reducer set to approximately 2.0 bar.
• the glass container is filled with distilled water until the lower meniscus edge reaches the H 2 O-hour mark.
• cock 1 is turned on and the flow rate on the cock 2 changed until the lower meniscus edge of the inner column reaches the 0 mm mark and thus a pre-pressure of 100 mm water column is set.
• the measuring head is placed on the sample without pressure and the height of the water column in the inner tube is read off. This is equal to the flow resistance of the sample.
• Dispersions 1-9 made with the aqueous urea solution resulted in acceptable flexible foams.
• Dispersion 6a, prepared without urea resulted in an unacceptable high shrink foam. This shows that the use of an aqueous urea solution in the preparation of the PIPA polyol not only leads to an improvement in the polyol homogeneity, but can also have a positive influence on the foaming.
• Example 20 is directly comparable to Example 9.
• the polyols used in Examples 20 and 9 are both homogeneous, but that
• Example 20 results in foam collapse.
• Example 21 also used a polyol with dibutyl tylzinndilaurat prepared as a catalyst. However, the corresponding filled polyol was not homogeneous.
• Example 22 is a 10% PIPA prepared as in Example 9 except that in this case the PEPA polyol is made via a low pressure mixing head with a mechanical stirrer.
• Comparative Example 23 a standard PIPA based on TEOA and with dibutyltin dilaurate catalysis was also prepared via a low-pressure mixing head with a mechanical stirrer. Both attempts resulted in stable PIPA polyols, which were foamed in Example 24 and Comparative Example 25 on a UBT unit. Although both products pass the Crib V fire test (mass loss ⁇ 60g and firing time ⁇ 10min), the mass loss and burn through time of the foams containing the PIPA polyols of the invention are lower in Example 24 than in Comparative Example 25. This shows that the Fire properties can be improved by optimizing the polyol combinations.

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

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• 2005
  • 2005-10-22 DE DE102005050701A patent/DE102005050701A1/de not_active Withdrawn
• 2006
  • 2006-10-10 CA CA002626470A patent/CA2626470A1/en not_active Abandoned
  • 2006-10-10 JP JP2008535933A patent/JP2009512746A/ja not_active Withdrawn
  • 2006-10-10 BR BRPI0617734-4A patent/BRPI0617734A2/pt not_active Application Discontinuation
  • 2006-10-10 CN CNA2006800393409A patent/CN101291968A/zh active Pending
  • 2006-10-10 RU RU2008119951/04A patent/RU2008119951A/ru not_active Application Discontinuation
  • 2006-10-10 KR KR1020087012115A patent/KR20080072862A/ko not_active Withdrawn
  • 2006-10-10 EP EP06806127A patent/EP1951776A1/de not_active Withdrawn
  • 2006-10-10 WO PCT/EP2006/009750 patent/WO2007045372A1/de not_active Ceased
  • 2006-10-18 US US11/583,492 patent/US20070238796A1/en not_active Abandoned
• 2008
  • 2008-05-09 NO NO20082169A patent/NO20082169L/no not_active Application Discontinuation

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