CA2088521C - Process for the continuous production of polyurethane and polyurethane urea prepolymers - Google Patents
Process for the continuous production of polyurethane and polyurethane urea prepolymers Download PDFInfo
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- CA2088521C CA2088521C CA002088521A CA2088521A CA2088521C CA 2088521 C CA2088521 C CA 2088521C CA 002088521 A CA002088521 A CA 002088521A CA 2088521 A CA2088521 A CA 2088521A CA 2088521 C CA2088521 C CA 2088521C
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0895—Manufacture of polymers by continuous processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/30—Injector mixers
- B01F25/31—Injector mixers in conduits or tubes through which the main component flows
- B01F25/312—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/30—Injector mixers
- B01F25/31—Injector mixers in conduits or tubes through which the main component flows
- B01F25/312—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof
- B01F25/3124—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof characterised by the place of introduction of the main flow
- B01F25/31242—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof characterised by the place of introduction of the main flow the main flow being injected in the central area of the venturi, creating an aspiration in the circumferential part of the conduit
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/30—Injector mixers
- B01F25/31—Injector mixers in conduits or tubes through which the main component flows
- B01F25/314—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced at the circumference of the conduit
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/32—Mixing; Kneading continuous, with mechanical mixing or kneading devices with non-movable mixing or kneading devices
- B29B7/325—Static mixers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The invention relates to the continuous production of polyurethane and polyurethane urea prepolymers by reaction of polyisocyanates with polyhydroxyl compounds in a mixing nozzle.
Description
2~~~~2~
hto3868 LeA 28,883 PROCESS FOR THE CONTINUOUS PRODUCTION OF
POLYURETHANE AND POLYURETHANE UREA PREPOLYMERS
8ackcrround of the Invention The present invention relates to a process for the continuous production of polyurethane and polyurethane urea prepolymers by reaction of polyisocyanates with polyhydroxy compounds or polyamine compounds having molecular weights of 400 to 10,000. It is known that such prepolymers can be produced from polyisocyanates and polyhydroxyl and/or polyamino compounds. Various production processes for such prepolymers are known in the art.
Prepolymer production processes carried out in a reaction vessel of the type described in Ullmann's Encyklopadie der technischen Chemie, Vol. 19, Chap. 9.3, Verlag Chemie, Neinheim (1982) are attended by the disadvantage that 'the chemical and physical properties of the prepolymers (such as reactivity, degree of crosslinking and viscosity) change unfavorably during their reaction to polyurethane elastomers, so that uniform production is not possible.
Continuous production processes using mixing heads are also described in the same reference. However these processes have the disadvantage that mixing can only be carried out to a limited degree and only with starting materials of chemically the same type. Another problem is that it is difficult to seal the places where the shafts of the mixing elements pass through the housing of the mixing head against the internal pressure and the non-lubricating and sealing medium of the poly-isocyanates. Accordingly, relatively high pressures cannot be used.
hto3868 LeA 28,883 PROCESS FOR THE CONTINUOUS PRODUCTION OF
POLYURETHANE AND POLYURETHANE UREA PREPOLYMERS
8ackcrround of the Invention The present invention relates to a process for the continuous production of polyurethane and polyurethane urea prepolymers by reaction of polyisocyanates with polyhydroxy compounds or polyamine compounds having molecular weights of 400 to 10,000. It is known that such prepolymers can be produced from polyisocyanates and polyhydroxyl and/or polyamino compounds. Various production processes for such prepolymers are known in the art.
Prepolymer production processes carried out in a reaction vessel of the type described in Ullmann's Encyklopadie der technischen Chemie, Vol. 19, Chap. 9.3, Verlag Chemie, Neinheim (1982) are attended by the disadvantage that 'the chemical and physical properties of the prepolymers (such as reactivity, degree of crosslinking and viscosity) change unfavorably during their reaction to polyurethane elastomers, so that uniform production is not possible.
Continuous production processes using mixing heads are also described in the same reference. However these processes have the disadvantage that mixing can only be carried out to a limited degree and only with starting materials of chemically the same type. Another problem is that it is difficult to seal the places where the shafts of the mixing elements pass through the housing of the mixing head against the internal pressure and the non-lubricating and sealing medium of the poly-isocyanates. Accordingly, relatively high pressures cannot be used.
3~ _ A continuous process in which the prepolymers are produced in a twin-screw extruder with co-rotating screws and self-cleaning screw geometry at temperatures of 70 to 260°C is described in German Offenlegungsschrift 2,842,806. The disadvantages of this process are that the components are very Le A 28 883 - US
_2_ thinly liquid at the temperatures mentioned, the mixing effect obtained by two co-rotating shafts is not great and the residence time is too short for a complete reaction.
German Offenlegungsschrift 2,302,564 mentions small-volume, stirred mixing chambers and mixing nozzles for mixing for the production of prepolymers. Mixing nozzles are known elements for mixing liquids. Detailed particulars of the geometry of the mixing nozzle and the arrangement of the volume flows or pressure conditions are not provided. In the Examples, to a mix head rather than mixing nozzles is used for the production of prepolymers from po'lyisocyanates and polyol mixtures. A process using a mixing nozzle is not described.
German Offenlegungsschrift 2,823,762 describes a continuous process in which the starting components are passed through a static premixer, in which they are intermixed, the product temperature being so low that a reaction is largely avoided, thus preventing the products from caking. Although thorough mixing is achieved by this process, separation in the reaction zone is not prevented by suppression of 'the reaction 2o at low temperatures. The prepolymer does not have sufficient reaction time in the following step to react out completely and uniformly.
European patent 87,817 describes a process for the production of prepolymers in which the components are introduced into a static mixer comprising internally arranged heat exchangers. Optimal mixing is achieved by internally mounted mixing elements which also provide for a residue-free plug flow in the system. This process is only suitable for low-viscosity prepolymers and only for production runs with no 3o change of raw materials. This is because residues (in some cases even over-crosslinked and brown in color) gradually accumulate in the mixing elements and, after the reaction to thermoplastic elastomers, give rise to contamination of the end product or to infusible particles in extrudates, such as films.
Mo3868 _3_ Accordingly, the problem addressed by the present invention was to pravide a new process for the continuous production of polyurethane and polyurethane urea prepolymers by reaction of polyisocyanates with polyhydroxyl compounds and/or polyamine compounds having molecular weights of 400 to 10,000, in which a) the components would beg mixed and, at the same time, be very finely disperss~d, b) rotating parts would not cause any sealing problems to relative to the outsides environment, c) sufficient reaction time would be available for a complete reaction, i.e. until the prepolymer has reacted with chain extenders, such as short-chain diols or diamines, to the thermoplastic polyurethane, d) the equipment used would be easy to clean and would not lead to any caking of product or blockages in the system.
BRIEF DESCRIPTION OF THE DRAtJINGS
Figure 1 is a longitudinal section through a nozzle useful in the present invention.
Figure 2 is a sectional view on the line A-B of Figure 1.
DESCRIPTION OF THE INVENTION
The present invention resides in combining the poly-isocyanates and the polyhydroxy compounds or the poiyamine compounds in a special nozzle. More particularly, the present invention is directed to a process for the continuous production of polyurethane and polyurethane urea prepolymers by the reaction of A) one or more organic poiyisocyanates, 3o B) one or more isocyanate-reactive compounds having molecular weights of from 400 to 10,000 and being selected from the group consisting of polyhydroxy compounds, polyamine compounds, and mixtures thereof, Mo3868 i I
_2_ thinly liquid at the temperatures mentioned, the mixing effect obtained by two co-rotating shafts is not great and the residence time is too short for a complete reaction.
German Offenlegungsschrift 2,302,564 mentions small-volume, stirred mixing chambers and mixing nozzles for mixing for the production of prepolymers. Mixing nozzles are known elements for mixing liquids. Detailed particulars of the geometry of the mixing nozzle and the arrangement of the volume flows or pressure conditions are not provided. In the Examples, to a mix head rather than mixing nozzles is used for the production of prepolymers from po'lyisocyanates and polyol mixtures. A process using a mixing nozzle is not described.
German Offenlegungsschrift 2,823,762 describes a continuous process in which the starting components are passed through a static premixer, in which they are intermixed, the product temperature being so low that a reaction is largely avoided, thus preventing the products from caking. Although thorough mixing is achieved by this process, separation in the reaction zone is not prevented by suppression of 'the reaction 2o at low temperatures. The prepolymer does not have sufficient reaction time in the following step to react out completely and uniformly.
European patent 87,817 describes a process for the production of prepolymers in which the components are introduced into a static mixer comprising internally arranged heat exchangers. Optimal mixing is achieved by internally mounted mixing elements which also provide for a residue-free plug flow in the system. This process is only suitable for low-viscosity prepolymers and only for production runs with no 3o change of raw materials. This is because residues (in some cases even over-crosslinked and brown in color) gradually accumulate in the mixing elements and, after the reaction to thermoplastic elastomers, give rise to contamination of the end product or to infusible particles in extrudates, such as films.
Mo3868 _3_ Accordingly, the problem addressed by the present invention was to pravide a new process for the continuous production of polyurethane and polyurethane urea prepolymers by reaction of polyisocyanates with polyhydroxyl compounds and/or polyamine compounds having molecular weights of 400 to 10,000, in which a) the components would beg mixed and, at the same time, be very finely disperss~d, b) rotating parts would not cause any sealing problems to relative to the outsides environment, c) sufficient reaction time would be available for a complete reaction, i.e. until the prepolymer has reacted with chain extenders, such as short-chain diols or diamines, to the thermoplastic polyurethane, d) the equipment used would be easy to clean and would not lead to any caking of product or blockages in the system.
BRIEF DESCRIPTION OF THE DRAtJINGS
Figure 1 is a longitudinal section through a nozzle useful in the present invention.
Figure 2 is a sectional view on the line A-B of Figure 1.
DESCRIPTION OF THE INVENTION
The present invention resides in combining the poly-isocyanates and the polyhydroxy compounds or the poiyamine compounds in a special nozzle. More particularly, the present invention is directed to a process for the continuous production of polyurethane and polyurethane urea prepolymers by the reaction of A) one or more organic poiyisocyanates, 3o B) one or more isocyanate-reactive compounds having molecular weights of from 400 to 10,000 and being selected from the group consisting of polyhydroxy compounds, polyamine compounds, and mixtures thereof, Mo3868 i I
C) optionally in the presence of one or more monofunctional compounds, such as monoisocyanates, monoalcohols or monoamines, and D) optionally in the presence of activators, stabilizers, lubricants and other additives.
The present invention comprises combining the components (i.e., A) through D)) in a nozzle which has a constriction wherein a) either the isocyanate-containing components or the isocyanate-reactive components are passed axially through the constriction of the nozzle, thereby forming an axial stream, b) the other components are introduced laterally into the axial stream of components passing through the constriction via several bores distributed over the periphery of and in the walls of said constriction, thereby forming a lateral stream, and c) the resultant mixture comprising the axial stream and the lateral stream passes through a pipe in which the components react to form the prepolymer.
The pipe which provides a dwell zone for reacting the axial and lateral streams preferably has no inside mixing elements.
It has surprisingly been found that this process can be carried out with low pressure losses. In addition, despite short residence times, a high degree of conversion can be obtained through the extremely good mixing effect of the nozzle.
The nozzle used is also called an annular nozzle. The constriction of the first stream may take place suddenly or steadily. Since, in general, a pressure loss of only about 3 bar is necessary for obtaining optimal mixing in the annular nozzle, the pressures of the component streams may generally be kept low. Accordingly, the usual pumps may be used and any existing pipe systems may be retained. However, higher pressure losses Mo3868 -4a-may also be applied providing the disadvantage of higher component pressures is accepted.
Polyisocyanates A) suitable for use in the invention include any of the aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic diisocyanates known in the art.
Mo3868 ~~i~~~~1 Diisocyanates preferably used in accordance with the invention are aromatic diisocyanates such as naphthylene-1,5-diisocyanate; 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TOD D ;
1,4-diisocyanatobenzene and the correspondingly hydrogenated product; tolylene diisocyanates; and, most particularly, the diphenyl methane diisocyanates. It is particularly preferred to use 4,4'-diisocyanatodiphenyl metlhane or its isomer mixtures with up to 5 mol-% and preferably 1 to 4 moi-% 2,4'-di-isocyanatodiphenyl methane, generally accompanied by very small to quantities of the 2,2'-diisocyanatodiphenyl methane isomer.
The diisocyanates may be used with up to about 15 mol-(based on diisocyanate) of a polyisocyanate of higher functionality. However, the quantity in which the higher polyisocyanate is used must be limited to such an extent that a still meltable or thermoplastic polyurethane elastomer is obtained after the prepoiymers according to the invention have been subsequently processed to thermoplastic polymers. A
relatively large quantity of higher isocyanates generally has to be compensated by the use of on average less than difunctional hydroxyl or amino compounds or even mono-isocyanates, so that excessive chemical crosslinking of the product is avoided. Examples of isocyanates of relatively high functionality and monofunctional compounds C) can be found in the prior art cited above.
Monoamines, such as butyl or dibutyl amine, aniline, hydroxyl amine, stearyl amine, piperidine, and N-methyl stearyl amine; and monoalcohols, such as 1-butanol, 2-ethyl-1-hexanol, 1-dodecanol, isobutanol or tertiary butanol, cyclohexanol, ethylene glycol monomethyl ether, 1-octanol and stearyl alcohol 3o are examples of suitable monofunctional components.
When used, the monofunctional compounds are used in relatively small quantities, for example in quantities of O.D1 to 4% by weight, based on the weight of all the reactive components.
Mo3868 ~~i)~r'l Preferred hydroxy functional, relatively high molecular weight compounds 8) are polyester, polyester carbonate and polyether diols, for example polyester diols of linear or branched, aliphatic and/or cycloaliphatic diols and aliphatic dicarboxylic acids, more particularly adipic acid. However, they may also contain small quantities of aromatic dicarboxylic acids, more particularly phthalic acid and even terephthalic acid, and hydrogenation products thereof. Hydroxyl poly-carbonates and hydroxy polycaprolactones are also suitable.
to . Preferr~ are polyesters based on 1.4-butane diol and adipic acid having a molecular weight from 1500-50C0. Also preferred are hydroxyether diols based on ethylene oxide, propyl~nz oxide or mixed polyethers of propylene oxide and/or ethylene oxide and/or tetrahydrofuran, for exa<rple hydroxvether diols based on tetrahvdrofuran having molecular weights of from 1000 to 3000. Suitable polyols are described in details, for 15 example, in German Offenlegungsschriften 2,302,564, 2,402,840, 2,423,764, 2,549,372, 2,854,384, 2,920,501 and 3,405,531, U.S.
patents 3,963,679, 3,984,607, and 4,035,213, and German Auslegeschrift 2,457,387.
Relatively high molecular weight polyamine compounds B), 2o preferably containing primary aromatic amino groups, may also be used. Preferred representatives are obtained, for example, by (preferably basic) hydrolysis of the corresponding isocyanate prepolymers based on relatively high molecular weight poiyhydroxy compounds and excess aromatic diisocyanates.
25 Examples of these polyamines can be found in German Auslegeschriften 2,948,419, 3,039,600, and 3,112,118, and European patents 61,627, 71,132 and 97,869. The '419 reference also mentions other known processes for the production of aromatic amino compounds of relatively high molecular weight 30 (so-called aminopolyethers) which are suitable for use in the process according to the invention. Other production processes are described in French patent 1,415,317, and in German Auslegeschriften 1,694,152 and 1,155,907.
The usual auxiliaries D), such as catalysts, release 35 agents, antistatic agents, flameproofing agents and pigments Mo3868 ~~~~~~1 corresponding to the prior art (see, for example, German Auslegeschrift 2,854,409, German Offenlegungsschrift 2,920,501 and German patent 3,329,775), may of course be added before and/or during and/or after the polyurethane reaction.
Antioxidants and U~ absorbers (light stabilizers) may also be added in accordance with the prior art (see, a.g., German Auslegeschrift 3,405,531). Suitable catalysts include, for example, tertiary amines, organometallic compounds, more particularly organotin compounds, organolead compounds and organotitanium compounds, for example tin(II) acetate, tin(II) ethyl hexoate, dibutyl tin dilaurate or lead acetate. Preferred release agents are waxes and oils and, for example, long-chain compounds containing carboxyl, ester, amide, urethane or urea groups and silicones, for example of the type mentioned as ~5 release agents in German Offenlegungsschrift 2,204,470.
In the process according to the invention, the quantities of reaction components A) to D) for the polyurethane or polyurethane urea prepolymers are generally selected so that the NCO/OH or NCO/NHR ratio of isocyanate to OH compounds or amine compounds is between 11:1 and 1:1 and preferably between 6:1 and 3:1.
The components mentioned may be homogenized in the annular nozzle in pure form, in admixture with one another or in the form of partly reacted mixtures and subsequently reacted.
The larger volume stream is preferably guided through the constriction of the nozzle. Where substantially the same volume streams are used, each of the two components may form the middle stream or sidestream. Observing these measures ensures optimal mixing and, hence, a satisfactory reaction.
. The polyisocyanate-containing component stream is preferably passed through the side bores if the volume stream is smaller than the volume stream of the polyol or polyamine component.
If several prepolymer nozzles according to the invention are arranged in tandem to mix a prepolymer and optionally Mo3868 i -$-polyisocyanate-containing component with other components, such as a polyol or polyamine component or liquid additives, the polyisocyanate-containing component stream may also form the main stream.
In one preferred embodiment, a flow rate of 1 to 10 m/sec. is maintained in the constriction. However, higher flow rates, for example up to 50 m/sec., can be maintained in the constriction providing the disadvantage of the high pump pressure required for this purpose is accepted. Conversely, the pump pressure can of course advantageously be kept low at the preferred flow rate of 1 to 10 m/sec.
The constriction preferably has a constant diameter D over its entire length L. The length L is preferably at least twice the diameter D of the constriction. This configuration provides for particularly intensive mixing and adequately stabilizes the flow conditions.
In one particularly advantageous embodiment, the length L~ of the constriction of the axial stream to the point where it is combined with the lateral streams of the second component is between 0.5 and 2 times the diameter D of the constriction.
The measures described above ensure that mixing in the nozzle is optimal and that there is no caking of product.
A particularly high yield can be obtained with a ratio of the axial stream ~A to the lateral stream E.s corresponding to the following:
~A tSA ' VA ° V2A
_ ~ s 8s ° us ~ v2s where g is the density, V is the volume stream and v is the flow rate with A representing the axial stream and S representing the lateral stream, Mo3868 _g_ is from 0.01 to 1.0, and preferably from 0.02 to 0.5 and, most preferably, from 0.03 to 0.25.
The high yield obtainable in this way also guarantees a low energy input and short dwell zones.
In another particular embodiment, the flow cross-section is steadily enlarged or widened after the constriction. That is, the nozzle diameter steadily increases after the constriction such that the area of the flow cross-section is steadily enlarged. This rules out the possibility of swirling and backflow. It is obvious that the widening of the flow cross-section ends at a maximum which corresponds to the diameter of an adjoining pipe. Avoiding backflow offers a particular guarantee of a uniform reaction time, i.e. residence time of the prepolymer pending further processing.
In another variant of the process, the number i of bores for the lateral streams is between 2 < i < m and preferably between 4 < i < m, m being derived from the condition:
ac ~ D
> 1.1, preferably > 1.5 and, most preferably ? 2, m ~d with D being the diameter of the constriction and d the diameter of the bores.
This measure also has a favorable effect on mixing and hence on the reaction.
All the bores are preferably arranged in a common plane perpendicular to the constriction although other arrangements are also possible.
This ensures that the reaction can only start in this plane, i.e.
already reacting product no longer comes into contact with the second component.
Since the polyol/polyamine mixture generally represents the greater volume stream, it is generally passed through the constriction in Mo3868 -9a-accordance with the foregoing observations. In a preferred embodiment, component B), the isocyanate-reactive components are preferably delivered to the nozzle at a temperature of at least 100°C.
The mixing unit crucial to the invention is described in more detail with reference to the accompanying drawings with the reference numerals used in the drawings having the following meanings:
Mo3868 ~('J~~'~J~~~.
(I) nozzle to be used in accordance with the invention (2) feed pipe for the main stream (3) sudden constriction of the main stream (4) insert with built-in lateral bores causing the constriction (5) side bores (6) feed pipe for the sidestream (7) chamber surrounding the constriction {3) from which the bores (5) lead away . (S) steady widening at the nozzle exit (9) discharge pipe (i.e., dwell zone) D internal diameter of the constriction d diameter of the side bores L overall length of the constriction L1 distance from the beginning of the constriction to the plane of the side bores LZ distance from the plane of the side bores to the beginning of the steady widening.
The production of reaction mixtures using the mixing unit 2o according to the invention may be carried out, for example, according to the following description.
The main stream is delivered to a nozzle (I) through a feed pipe (2) which suddenly changes into a constriction (3) arranged in the nozzle (1). The constriction (3) is arranged in an insert (4). The constriction (3) has a constant diameter D over its entire length L. In the section L1 which corresponds, for example, to 1.5 times the diameter D of the constriction (3), bores (5), for example six in number, are regularly distributed over the circumference. Mutually opposite bores (5) are offset from one another by the diameter d so that the streams sprayed in pass by one another. The second component is delivered through a feed pipe (6) to a chamber (7) surrounding the constriction (3) from which the bores (5) lead off. The length L2 of the constriction (3) behind the bores (5) corresponds, for example, to the diameter Mo3868 ~~a~~?~.
D of the constriction (3). Behind the constriction (3), the nozzle (1) undergoes constant widening (8) at an angle a with the axis of, for example, 20°. The widening (8) is adjoined by a discharge pipe (9) of the same diameter as the feed pipe ~(2).
The discharge pipe serves as a dwell zone and may be adapted in length and diameter so that, under the selected reaction condi-tions, a complete reaction and possibly even a desired degree of branching is exactly achieved when the prepolymer is further reacted.
1o To avoid a relatively broad residence time spectrum in the case of relatively large diameters, fittings may be introduced to equalize differences in flow rate from the inside of the pipe to its periphery.
The reaction mixtures prepared using the mixing unit critical to the invention may be reacted with short-chain diols, diamines or hydroxyiamines to form thermoplastic polyurethanes or polyurethane ureas by known methods as described, for example, in German 0ffenlegungsschriften 2,302,564, 2,447,368, 2,549;372, 2,823,762, 2,842,806 and 3,224,324.
The invention is illustrated by the following Examples.
EXAMPLES
Exam~l a 1 100 parts by weight of a polyester of adipic acid and 1,4-butanediol (OH value 50, acid value 0.1), which had been activated with 10 ppm titanium tetrabutylate, were continuously mixed with 150 parts by weight liquid 4,4'-diisocyanatodiphenyl methane in a constant ratio in the special described nozzle (L = 10 mn, L1 = 6 mn, L2 = 4 mm, d = 0,7 rrm, D = 4 rrm, i = 6) to form a prepoly~r and reacted 3 0 in the following dwell zone by passing the polyester through the constriction and latzrally delivering t~'~e liquid 4,~+'-diisocyanatodiphenyl r,~ethane throrx3h the bores. A sample of the reaction product formed was taken and its residual isocyanate content was determined by potentiometric titration with dibutyl amine solution and alcoholic hydrochloric acid.
Mo3868 ~~~~~2~~
Residual NCO content ~ 18.91%, corresponding to a 96.8% conversion to the prepolymer; theoretical content for 100% conversion = 18.95fo.
Example 2 50 parts by weight of a polyester of adipic acid and .
1,4-butanediol (OH value 50, acid value 0.7), which had been activated with 10 ppm titanium tetrabutylate, and 50 parts by weight of a polycarbonate diol of Biphenyl carbonate and 1,6-hexanediol (molecular weight 2000) were continuously mixed with 49 parts by weight liquid 4,4'-diisocyanatodiphenyl methane in a constant ratio in the special described nozzle (L=lOmm, L1=6mm, L2=4mm, d=0,7mm, D=4mm, i=4) to form a prepolymer and reacted in the following dwell zone by passing the mixture of polyester and polycarbonate diol through the constriction and laterally delivering the liquid 4,4'-diisocyanatodiphenyl methane through the bores.
A sample of the reaction product formed was taken and its residual isocyanate content was determined by potentiometric titration with dibutyl amine solution and alcoholic hydrochloric acid.
Residual NCO content = 8.64%, corresponding to a 99.89 conversion to the prepolymer; theoretical content for 100fo conversion = 8.65%.
Exam~l a 3 50 parts by weight of a polytetramethyiene oxide ether (molecular weight 1000), and 50 parts by weight of a polytetramethylene oxide ether (molecular weight 2000 were continuously mixed with 96 parts by weight liquid 4,4'-diisocyanatodiphenyl methane in a constant ratio in the special described_nozzle (L=lOmm, L1=6mm, L2=4mm, d=0,7mm, D=4mm, i=4) to form a prepolymer and reacted in the following dwell zone by passing the polyether mixture through the constriction and laterally delivering the liquid 4,4'-diisocyanatodiphenyl methane through the bores. A sample of the reaction product formed was taken and its residual isocyanate content was determined by potentiometric titration with dibutyl amine solution and alcoholic hydrochloric acid.
Mo3868 residual NCO content = 13.72%, corresponding to a 98.7% conversion to the prepolymer; theoretical content for 100% conversion = 13.55%.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
i0 Mo3868
The present invention comprises combining the components (i.e., A) through D)) in a nozzle which has a constriction wherein a) either the isocyanate-containing components or the isocyanate-reactive components are passed axially through the constriction of the nozzle, thereby forming an axial stream, b) the other components are introduced laterally into the axial stream of components passing through the constriction via several bores distributed over the periphery of and in the walls of said constriction, thereby forming a lateral stream, and c) the resultant mixture comprising the axial stream and the lateral stream passes through a pipe in which the components react to form the prepolymer.
The pipe which provides a dwell zone for reacting the axial and lateral streams preferably has no inside mixing elements.
It has surprisingly been found that this process can be carried out with low pressure losses. In addition, despite short residence times, a high degree of conversion can be obtained through the extremely good mixing effect of the nozzle.
The nozzle used is also called an annular nozzle. The constriction of the first stream may take place suddenly or steadily. Since, in general, a pressure loss of only about 3 bar is necessary for obtaining optimal mixing in the annular nozzle, the pressures of the component streams may generally be kept low. Accordingly, the usual pumps may be used and any existing pipe systems may be retained. However, higher pressure losses Mo3868 -4a-may also be applied providing the disadvantage of higher component pressures is accepted.
Polyisocyanates A) suitable for use in the invention include any of the aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic diisocyanates known in the art.
Mo3868 ~~i~~~~1 Diisocyanates preferably used in accordance with the invention are aromatic diisocyanates such as naphthylene-1,5-diisocyanate; 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TOD D ;
1,4-diisocyanatobenzene and the correspondingly hydrogenated product; tolylene diisocyanates; and, most particularly, the diphenyl methane diisocyanates. It is particularly preferred to use 4,4'-diisocyanatodiphenyl metlhane or its isomer mixtures with up to 5 mol-% and preferably 1 to 4 moi-% 2,4'-di-isocyanatodiphenyl methane, generally accompanied by very small to quantities of the 2,2'-diisocyanatodiphenyl methane isomer.
The diisocyanates may be used with up to about 15 mol-(based on diisocyanate) of a polyisocyanate of higher functionality. However, the quantity in which the higher polyisocyanate is used must be limited to such an extent that a still meltable or thermoplastic polyurethane elastomer is obtained after the prepoiymers according to the invention have been subsequently processed to thermoplastic polymers. A
relatively large quantity of higher isocyanates generally has to be compensated by the use of on average less than difunctional hydroxyl or amino compounds or even mono-isocyanates, so that excessive chemical crosslinking of the product is avoided. Examples of isocyanates of relatively high functionality and monofunctional compounds C) can be found in the prior art cited above.
Monoamines, such as butyl or dibutyl amine, aniline, hydroxyl amine, stearyl amine, piperidine, and N-methyl stearyl amine; and monoalcohols, such as 1-butanol, 2-ethyl-1-hexanol, 1-dodecanol, isobutanol or tertiary butanol, cyclohexanol, ethylene glycol monomethyl ether, 1-octanol and stearyl alcohol 3o are examples of suitable monofunctional components.
When used, the monofunctional compounds are used in relatively small quantities, for example in quantities of O.D1 to 4% by weight, based on the weight of all the reactive components.
Mo3868 ~~i)~r'l Preferred hydroxy functional, relatively high molecular weight compounds 8) are polyester, polyester carbonate and polyether diols, for example polyester diols of linear or branched, aliphatic and/or cycloaliphatic diols and aliphatic dicarboxylic acids, more particularly adipic acid. However, they may also contain small quantities of aromatic dicarboxylic acids, more particularly phthalic acid and even terephthalic acid, and hydrogenation products thereof. Hydroxyl poly-carbonates and hydroxy polycaprolactones are also suitable.
to . Preferr~ are polyesters based on 1.4-butane diol and adipic acid having a molecular weight from 1500-50C0. Also preferred are hydroxyether diols based on ethylene oxide, propyl~nz oxide or mixed polyethers of propylene oxide and/or ethylene oxide and/or tetrahydrofuran, for exa<rple hydroxvether diols based on tetrahvdrofuran having molecular weights of from 1000 to 3000. Suitable polyols are described in details, for 15 example, in German Offenlegungsschriften 2,302,564, 2,402,840, 2,423,764, 2,549,372, 2,854,384, 2,920,501 and 3,405,531, U.S.
patents 3,963,679, 3,984,607, and 4,035,213, and German Auslegeschrift 2,457,387.
Relatively high molecular weight polyamine compounds B), 2o preferably containing primary aromatic amino groups, may also be used. Preferred representatives are obtained, for example, by (preferably basic) hydrolysis of the corresponding isocyanate prepolymers based on relatively high molecular weight poiyhydroxy compounds and excess aromatic diisocyanates.
25 Examples of these polyamines can be found in German Auslegeschriften 2,948,419, 3,039,600, and 3,112,118, and European patents 61,627, 71,132 and 97,869. The '419 reference also mentions other known processes for the production of aromatic amino compounds of relatively high molecular weight 30 (so-called aminopolyethers) which are suitable for use in the process according to the invention. Other production processes are described in French patent 1,415,317, and in German Auslegeschriften 1,694,152 and 1,155,907.
The usual auxiliaries D), such as catalysts, release 35 agents, antistatic agents, flameproofing agents and pigments Mo3868 ~~~~~~1 corresponding to the prior art (see, for example, German Auslegeschrift 2,854,409, German Offenlegungsschrift 2,920,501 and German patent 3,329,775), may of course be added before and/or during and/or after the polyurethane reaction.
Antioxidants and U~ absorbers (light stabilizers) may also be added in accordance with the prior art (see, a.g., German Auslegeschrift 3,405,531). Suitable catalysts include, for example, tertiary amines, organometallic compounds, more particularly organotin compounds, organolead compounds and organotitanium compounds, for example tin(II) acetate, tin(II) ethyl hexoate, dibutyl tin dilaurate or lead acetate. Preferred release agents are waxes and oils and, for example, long-chain compounds containing carboxyl, ester, amide, urethane or urea groups and silicones, for example of the type mentioned as ~5 release agents in German Offenlegungsschrift 2,204,470.
In the process according to the invention, the quantities of reaction components A) to D) for the polyurethane or polyurethane urea prepolymers are generally selected so that the NCO/OH or NCO/NHR ratio of isocyanate to OH compounds or amine compounds is between 11:1 and 1:1 and preferably between 6:1 and 3:1.
The components mentioned may be homogenized in the annular nozzle in pure form, in admixture with one another or in the form of partly reacted mixtures and subsequently reacted.
The larger volume stream is preferably guided through the constriction of the nozzle. Where substantially the same volume streams are used, each of the two components may form the middle stream or sidestream. Observing these measures ensures optimal mixing and, hence, a satisfactory reaction.
. The polyisocyanate-containing component stream is preferably passed through the side bores if the volume stream is smaller than the volume stream of the polyol or polyamine component.
If several prepolymer nozzles according to the invention are arranged in tandem to mix a prepolymer and optionally Mo3868 i -$-polyisocyanate-containing component with other components, such as a polyol or polyamine component or liquid additives, the polyisocyanate-containing component stream may also form the main stream.
In one preferred embodiment, a flow rate of 1 to 10 m/sec. is maintained in the constriction. However, higher flow rates, for example up to 50 m/sec., can be maintained in the constriction providing the disadvantage of the high pump pressure required for this purpose is accepted. Conversely, the pump pressure can of course advantageously be kept low at the preferred flow rate of 1 to 10 m/sec.
The constriction preferably has a constant diameter D over its entire length L. The length L is preferably at least twice the diameter D of the constriction. This configuration provides for particularly intensive mixing and adequately stabilizes the flow conditions.
In one particularly advantageous embodiment, the length L~ of the constriction of the axial stream to the point where it is combined with the lateral streams of the second component is between 0.5 and 2 times the diameter D of the constriction.
The measures described above ensure that mixing in the nozzle is optimal and that there is no caking of product.
A particularly high yield can be obtained with a ratio of the axial stream ~A to the lateral stream E.s corresponding to the following:
~A tSA ' VA ° V2A
_ ~ s 8s ° us ~ v2s where g is the density, V is the volume stream and v is the flow rate with A representing the axial stream and S representing the lateral stream, Mo3868 _g_ is from 0.01 to 1.0, and preferably from 0.02 to 0.5 and, most preferably, from 0.03 to 0.25.
The high yield obtainable in this way also guarantees a low energy input and short dwell zones.
In another particular embodiment, the flow cross-section is steadily enlarged or widened after the constriction. That is, the nozzle diameter steadily increases after the constriction such that the area of the flow cross-section is steadily enlarged. This rules out the possibility of swirling and backflow. It is obvious that the widening of the flow cross-section ends at a maximum which corresponds to the diameter of an adjoining pipe. Avoiding backflow offers a particular guarantee of a uniform reaction time, i.e. residence time of the prepolymer pending further processing.
In another variant of the process, the number i of bores for the lateral streams is between 2 < i < m and preferably between 4 < i < m, m being derived from the condition:
ac ~ D
> 1.1, preferably > 1.5 and, most preferably ? 2, m ~d with D being the diameter of the constriction and d the diameter of the bores.
This measure also has a favorable effect on mixing and hence on the reaction.
All the bores are preferably arranged in a common plane perpendicular to the constriction although other arrangements are also possible.
This ensures that the reaction can only start in this plane, i.e.
already reacting product no longer comes into contact with the second component.
Since the polyol/polyamine mixture generally represents the greater volume stream, it is generally passed through the constriction in Mo3868 -9a-accordance with the foregoing observations. In a preferred embodiment, component B), the isocyanate-reactive components are preferably delivered to the nozzle at a temperature of at least 100°C.
The mixing unit crucial to the invention is described in more detail with reference to the accompanying drawings with the reference numerals used in the drawings having the following meanings:
Mo3868 ~('J~~'~J~~~.
(I) nozzle to be used in accordance with the invention (2) feed pipe for the main stream (3) sudden constriction of the main stream (4) insert with built-in lateral bores causing the constriction (5) side bores (6) feed pipe for the sidestream (7) chamber surrounding the constriction {3) from which the bores (5) lead away . (S) steady widening at the nozzle exit (9) discharge pipe (i.e., dwell zone) D internal diameter of the constriction d diameter of the side bores L overall length of the constriction L1 distance from the beginning of the constriction to the plane of the side bores LZ distance from the plane of the side bores to the beginning of the steady widening.
The production of reaction mixtures using the mixing unit 2o according to the invention may be carried out, for example, according to the following description.
The main stream is delivered to a nozzle (I) through a feed pipe (2) which suddenly changes into a constriction (3) arranged in the nozzle (1). The constriction (3) is arranged in an insert (4). The constriction (3) has a constant diameter D over its entire length L. In the section L1 which corresponds, for example, to 1.5 times the diameter D of the constriction (3), bores (5), for example six in number, are regularly distributed over the circumference. Mutually opposite bores (5) are offset from one another by the diameter d so that the streams sprayed in pass by one another. The second component is delivered through a feed pipe (6) to a chamber (7) surrounding the constriction (3) from which the bores (5) lead off. The length L2 of the constriction (3) behind the bores (5) corresponds, for example, to the diameter Mo3868 ~~a~~?~.
D of the constriction (3). Behind the constriction (3), the nozzle (1) undergoes constant widening (8) at an angle a with the axis of, for example, 20°. The widening (8) is adjoined by a discharge pipe (9) of the same diameter as the feed pipe ~(2).
The discharge pipe serves as a dwell zone and may be adapted in length and diameter so that, under the selected reaction condi-tions, a complete reaction and possibly even a desired degree of branching is exactly achieved when the prepolymer is further reacted.
1o To avoid a relatively broad residence time spectrum in the case of relatively large diameters, fittings may be introduced to equalize differences in flow rate from the inside of the pipe to its periphery.
The reaction mixtures prepared using the mixing unit critical to the invention may be reacted with short-chain diols, diamines or hydroxyiamines to form thermoplastic polyurethanes or polyurethane ureas by known methods as described, for example, in German 0ffenlegungsschriften 2,302,564, 2,447,368, 2,549;372, 2,823,762, 2,842,806 and 3,224,324.
The invention is illustrated by the following Examples.
EXAMPLES
Exam~l a 1 100 parts by weight of a polyester of adipic acid and 1,4-butanediol (OH value 50, acid value 0.1), which had been activated with 10 ppm titanium tetrabutylate, were continuously mixed with 150 parts by weight liquid 4,4'-diisocyanatodiphenyl methane in a constant ratio in the special described nozzle (L = 10 mn, L1 = 6 mn, L2 = 4 mm, d = 0,7 rrm, D = 4 rrm, i = 6) to form a prepoly~r and reacted 3 0 in the following dwell zone by passing the polyester through the constriction and latzrally delivering t~'~e liquid 4,~+'-diisocyanatodiphenyl r,~ethane throrx3h the bores. A sample of the reaction product formed was taken and its residual isocyanate content was determined by potentiometric titration with dibutyl amine solution and alcoholic hydrochloric acid.
Mo3868 ~~~~~2~~
Residual NCO content ~ 18.91%, corresponding to a 96.8% conversion to the prepolymer; theoretical content for 100% conversion = 18.95fo.
Example 2 50 parts by weight of a polyester of adipic acid and .
1,4-butanediol (OH value 50, acid value 0.7), which had been activated with 10 ppm titanium tetrabutylate, and 50 parts by weight of a polycarbonate diol of Biphenyl carbonate and 1,6-hexanediol (molecular weight 2000) were continuously mixed with 49 parts by weight liquid 4,4'-diisocyanatodiphenyl methane in a constant ratio in the special described nozzle (L=lOmm, L1=6mm, L2=4mm, d=0,7mm, D=4mm, i=4) to form a prepolymer and reacted in the following dwell zone by passing the mixture of polyester and polycarbonate diol through the constriction and laterally delivering the liquid 4,4'-diisocyanatodiphenyl methane through the bores.
A sample of the reaction product formed was taken and its residual isocyanate content was determined by potentiometric titration with dibutyl amine solution and alcoholic hydrochloric acid.
Residual NCO content = 8.64%, corresponding to a 99.89 conversion to the prepolymer; theoretical content for 100fo conversion = 8.65%.
Exam~l a 3 50 parts by weight of a polytetramethyiene oxide ether (molecular weight 1000), and 50 parts by weight of a polytetramethylene oxide ether (molecular weight 2000 were continuously mixed with 96 parts by weight liquid 4,4'-diisocyanatodiphenyl methane in a constant ratio in the special described_nozzle (L=lOmm, L1=6mm, L2=4mm, d=0,7mm, D=4mm, i=4) to form a prepolymer and reacted in the following dwell zone by passing the polyether mixture through the constriction and laterally delivering the liquid 4,4'-diisocyanatodiphenyl methane through the bores. A sample of the reaction product formed was taken and its residual isocyanate content was determined by potentiometric titration with dibutyl amine solution and alcoholic hydrochloric acid.
Mo3868 residual NCO content = 13.72%, corresponding to a 98.7% conversion to the prepolymer; theoretical content for 100% conversion = 13.55%.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
i0 Mo3868
Claims (12)
1. In a process for the continuous production of polyurethane and polyurethane urea prepolymers by reaction of A) one or more organic polyisocyanates, with B) one or more isocyanate-reactive compounds having molecular weights of from 400 to 10,000 and being selected from the group consisting of polyhydroxy compounds, polyamine compounds, and mixtures thereof, C) optionally in the presence of one or more monofunctional compounds, and D) optionally in the presence of activators, stabilizers, lubricants and other additives, the improvement wherein the components are combined in a nozzle which has a constriction and wherein a) either the polyisocyanate components or the isocyanate-reactive components are passed axially through the constriction of the nozzle, thereby forming an axial stream, b) the other components are introduced laterally into the axial stream of components which are passing through the constriction, via several bores distributed over the periphery of and in the walls of said constriction, thereby forming a lateral stream, and c) the resultant mixture comprising the axial stream and the lateral stream passes through a pipe in which the components react to form the prepolymer.
2. The process of Claim 1, wherein whichever component has the larger volume is passed axially through the constriction, said components being selected from the group consisting of said polyisocyanate component and said isocyanate-reactive component.
3. The process of Claim 1, wherein a flow rate of 1 to 10 m/s is maintained in the constriction.
4. The process of Claim 1, wherein the constriction has a constant diameter over its length.
5. The process of Claim 4, wherein the length corresponds to at least twice the diameter of the constriction.
6. The process of Claim 1, wherein the length of the constriction of the axial stream to the point where it is combined with the lateral stream is between 0.5 and 2 times the diameter of the constriction.
7. The process of Claim 1, wherein the resultant mixture comprising the axial stream and the lateral stream is subjected to a constant constriction over a length at least corresponding to that section in which mixing is optimal and the resultant mixture is free of caking.
8. The process of Claim 1, wherein the ratio of the axial stream .epsilon.A to the lateral stream .epsilon.S corresponds to the formula:
where .delta. is the density, o V is the volume stream and v is the flow rate with A representing the axial stream and S
representing the lateral stream, and equals from 0.01:1 to 1.0:1.
where .delta. is the density, o V is the volume stream and v is the flow rate with A representing the axial stream and S
representing the lateral stream, and equals from 0.01:1 to 1.0:1.
9. The process of Claim 1, wherein the diameter of the nozzle widens steadily after the constriction.
10. The process of Claim 1, wherein the number i of bores for the lateral streams is between 2 < i < m, m being derived from the condition with D being the diameter of the constriction and d the diameter of the bores.
11. The process of Claim 1, wherein component B) is delivered to the nozzle at a temperature of at least 100°C.
12. The process of Claim 1, wherein C) said monofunctional compounds are selected from the group consisting of monisocyanates, monoalcohols, monoamines and mixtures thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4202972A DE4202972A1 (en) | 1992-02-03 | 1992-02-03 | METHOD FOR THE CONTINUOUS PRODUCTION OF POLYURETHANE AND POLYURETHANE UREA PRE-POLYMERS |
| DEP4202972.4 | 1992-02-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2088521A1 CA2088521A1 (en) | 1993-08-04 |
| CA2088521C true CA2088521C (en) | 2004-01-20 |
Family
ID=6450828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002088521A Expired - Fee Related CA2088521C (en) | 1992-02-03 | 1993-02-01 | Process for the continuous production of polyurethane and polyurethane urea prepolymers |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0554718B1 (en) |
| JP (1) | JP3169466B2 (en) |
| CA (1) | CA2088521C (en) |
| DE (2) | DE4202972A1 (en) |
| ES (1) | ES2083781T3 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4437586A1 (en) | 1994-10-20 | 1996-04-25 | Basf Schwarzheide Gmbh | Process for the preparation of thermoplastic polyurethanes |
| DE19520730A1 (en) * | 1995-06-07 | 1996-12-12 | Bayer Ag | Thermoplastic polyurethane urea elastomers |
| DE19520732A1 (en) | 1995-06-07 | 1996-12-12 | Bayer Ag | Thermoplastic polyurethane elastomers |
| US5700847A (en) * | 1995-12-04 | 1997-12-23 | Arco Chemical Technology, L.P. | Molded polyurethane foam with enhanced physical properties |
| US5668191A (en) * | 1995-12-21 | 1997-09-16 | Arco Chemical Technology, L.P. | One-shot cold molded flexible polyurethane foam from low primary hydroxyl polyols and process for the preparation thereof |
| DE19706030C2 (en) * | 1997-02-17 | 2000-07-06 | Bayer Ag | Method and device for producing filler-containing polyurethanes |
| DE19823393A1 (en) | 1998-05-26 | 1999-12-02 | Basf Ag | Prepolymers containing isocyanate groups and process for their preparation |
| US6051622A (en) * | 1998-09-17 | 2000-04-18 | Arco Chemical Technology, L.P. | Low resilience, low frequency molded polyurethane foam |
| DE102004027705B4 (en) * | 2004-06-07 | 2006-10-26 | Bayer Materialscience Ag | Process for the preparation of polyurethane and / or polyurethane urea prepolymers |
| CN101209405B (en) * | 2006-12-27 | 2013-08-28 | 宁波万华聚氨酯有限公司 | Hole jet type injecting reactor |
| DE102008003738A1 (en) * | 2008-01-10 | 2009-07-30 | Neopor System Gmbh | Method and associated apparatus for pressureless or near-pressureless introduction of foam in a pressurized stream of material |
| KR101529446B1 (en) * | 2011-10-24 | 2015-06-16 | 쇼와 덴코 가부시키가이샤 | Method for producing aliphatic polyester having increased molecular weight |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2854386A1 (en) * | 1978-12-16 | 1980-07-03 | Bayer Ag | METHOD FOR PRODUCING THERMOPLASTIC CHEMICAL MATERIALS |
| US4334783A (en) * | 1978-12-21 | 1982-06-15 | Showa Denko Kabushiki Kaisha | Mixing device |
| DE3744001C1 (en) * | 1987-12-24 | 1989-06-08 | Bayer Ag | Process for the continuous production of mono- or polyisocyanates |
-
1992
- 1992-02-03 DE DE4202972A patent/DE4202972A1/en not_active Withdrawn
-
1993
- 1993-01-21 ES ES93100874T patent/ES2083781T3/en not_active Expired - Lifetime
- 1993-01-21 DE DE59301754T patent/DE59301754D1/en not_active Expired - Fee Related
- 1993-01-21 EP EP93100874A patent/EP0554718B1/en not_active Expired - Lifetime
- 1993-02-01 JP JP03398593A patent/JP3169466B2/en not_active Expired - Fee Related
- 1993-02-01 CA CA002088521A patent/CA2088521C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05271372A (en) | 1993-10-19 |
| EP0554718B1 (en) | 1996-03-06 |
| ES2083781T3 (en) | 1996-04-16 |
| DE59301754D1 (en) | 1996-04-11 |
| EP0554718A3 (en) | 1993-09-29 |
| JP3169466B2 (en) | 2001-05-28 |
| EP0554718A2 (en) | 1993-08-11 |
| CA2088521A1 (en) | 1993-08-04 |
| DE4202972A1 (en) | 1993-08-05 |
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