DE1745508A1 - Process for the production of non-porous, rigid polyurethane masses - Google Patents

Description

The Upjohn Company

Kaiamazoo, me. _a V .S t «Am.

Process for the production of non-porous, start Pplyure th aninass en

The invention is concerned with the production of practical non-porous, rigid polyurethane wipes, which "stand out due to high notch

Characterized by toughness and general toughness.

The invention relates to a method for producing such Polyurethane races by reacting an aromatic polyisocyanate with a polyol, optionally in the presence of reinforcing material, the specialty of which is that it is used as a polyol component a mixture of a) at least one aliphatic Polyol with a functionality between about 5 and about 6 and a hydroxyl number between about 200 and about 750 and b) as much Phosphorus-containing polyol that the finished polyurethane uses contains about 2 to about 15 weight percent phosphorus.

The invention further includes the production of rigid polyurethane compositions, in which a reinforcing material is shown below marked type with a polyurethane marked above Is kind of glued. .

Non-porous polyurethanes by reacting a polyisocyanate with egg Producing polyol is known prior art, see example

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refer to the Saunders etc. handbook "Polyurethanes", Chemistry and Technology, Tell II (196 *), Interscience Publishers New York, Numerous different, commercially available polyisocyanates and polyols have already been used for this purpose, and, depending on the starting material, polyurethanes obtained with largely different properties.

One has also tried in many ways, rigid polyurethane masses with so high notch toughness so that it can be used, for example, as a material in construction and for the manufacture of people and loads car bodies, boat hulls and the like are suitable. The previous one Because of their insufficient strength, polyurethanes remained closed to a broad area of the market for rigid plastics, which was previously covered by insoesonderfc fiber-reinforced, thermosetting synthetic resins based on unsaturated polyester, phenol, epoxy, melamine and similar resin substances. "

Experience has shown that rigid polyurethane compositions can be produced with the aid of the invention, which are superior to the previously available rigid polyurethane compositions in terms of their physical properties, particularly in terms of notch toughness and hardness, and are of such a nature that they can be used in numerous structural applications not previously used by polyurethanes can use »

So if, within the meaning of the invention, polyisocyanates are identified below Types or their mixtures with a polyol mixture below of a defined type or several of them, you get polyurethanes that unexpectedly compared to polyurethanes from closely related reactant combinations by markedly superior properties, in particular excel in terms of structural strength. This property-

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differences are nooh more pronounced when one enters the reaction system Reinforcement materials such as glass fibers, synthetic fibers and the like Substances of the type identified below and documented by examples, brings in

The polyisocyanates used to carry out the invention are aromatic in nature, i.e. contain two or more isocyanate groups that are directly bonded to the same aromatic ring or to at least two different aromatic rings in the same molecule their commercially available 80/20 and 65/35 56 Oemisehe together with their dimer forms and their crude mixtures methylenebis (phenylisoeyanat) Tolidindilsocyanat (BEZW. 4.4 ^I -Diisoeyanato-3,3 -dimethyldiphenyl ^l), dianisidine diisocyanate (BEZW. 4, 4 ^f «J) iisocyanÄto-3,3 ^f -dimethoxydiphenyl), 4,4 ^I -diisocyanatodiphenyl, m-phenylene diisoeyanate, p-phenylene diisocyanate, -4,4 ', 4" -Triiso-

ylsocyanate
cyanato tripheny! methane, having terminal isocyanate groups, such as by trimerization of diisocyanates ^ as Tolylendiisocyapat _(obtained; moreover, the Polyisooyanat adducts that result from treating triplets, tetrols and higher Folyolen with excess polyisocyanates, such as the Trilsocyanat Adducts from the reaction of 1 mole of a triol, such as glycerol, trimethylolpropane, 1,2,6-hexanetrolene and the like, with 3 hol diisocyanates such as 4,4 ^t -ethylene bis {phenyl isocyanate), 2,4-tolylene diisocyanate, 2,6 -Tolylenedlisooyanate, or their

if necessary _w "^ _o " _v "- .- n ^ also in the Qßmit

mix -su * two or more can be used.

An aromatic * »is particularly suitable for carrying out the invention. Polyocyanate in the form of a polymethylene-polyphenylisocyanate-OemiejQhes

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which consists of about 35 to about 85 / 'of meth> ieriöis (phenyl isocyanate) and the rest of polymethylene polyphenyl isocyanate with a functionality greater than 2. Such polymethylene polypnenyl isocyanates are known and are generally formed by phosgenating polyphenyl polyamines containing methylene bridges, as obtained by reacting formaldehyde and hydrochloric acid with a primary aromatic amine, such as aniline, o-chloroaniline, o-toluene and the like, see, for example, the American patents 2,683,730, 2,950,263 and 3 012 üOÖ, the Canadian patent 700 026 and ^ the German Auslegeschrift 1 131877 · Preferred representatives of them are those whose methylenebis (phenyl isocyanate) content is either 50 wt .- ^ a total functionality of about 2.7 or 70 Ge, i, -% with a total functionality of about 2.2.

The aromatic polyisocyanates which can be used according to the invention also include those whose isocyanate is partially, in general to less than 33 wt .- #, is converted into the corresponding carbodiimide with terminal isocyanate groups, and obtained, for example if you either use the polyisocyanate with a carbodiimide formation catalyst, such as triethyl phosphate, heated or treated with a * carbodiimide, see British Patent 918 ^.

The "aliphatic polyol" portion of the invention The type of polyol used in the introduction consists of Bolchen polyols, the hydrocarbon residues of an aliphatic nature and do not have a remarkable aromatic content. To them belong with regard to the specified hydroxyl number limitation 1) Polyether polyols, e.g. the reaction products of ethylene oxide,

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Propylene oxide, butylene oxide, epichlorohydrin or other spoxides together with their skeleton with aliphatic polyols, such as glycerine, sorbitol, methylolpropane, 1,2,6-hexanetriol, pentaerythritol, sucrose or glycosides, such as methyl, ethyl, propyl, butyl or 2 -Ethylhexylarabinoside, -Xyloside, -Fructoside, -Glucoside, -Rhaninoside and the like together with their mixtures; the reaction products of ethylene oxide, propylene oxide or their mixtures with aliphatic polyols, such as tetramethylolcyclohexanol, trimethylolcyclohexanol and the like. 2) Polyester polyols, such as those obtained by reacting dibasic aliphatic carboxylic acids, such as adipic, amber, glutaric, pimeline | acid or its anhydrides and the like with excess aliphatic polyol, such as methylolethane, trimethylolpropane, mannitol, hexanetriol, glycerol, pentaerythritol and the like; henceforth polyesters as such by the polymerization of lactones, such as caprolactone with the suitable trifunctional £ trigger. ß. an aliphatic polyol of the type described above and the like, according to known processes, for example according to American patent 2,914,556.

One can also use mixtures of two or more polyols above marked type work, provided that the erfindungsgeraässen

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Limit values for overall functionality and hydroxyl number.

The phosphorus-containing polyols used to carry out the invention include those which, according to the Zerewltinoff test {J.Am.Chem.Soc. 49 (1927), 5I8I) at least two active hydrogen atoms in the molecule and in the rest have no active centers that react with isocyanate groups and commonly used to manufacture flame retardant polyurethanes will. Examples are alkylene oxide, e.g. ethylene oxide or

Poly-poly-pylene oxide adducts with phosphoric acid or phosphoric acids, e.g. acc

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U.S. Patents 2,372,244, 3,094,549 and 3,099,676; the polyalkylene phosphites, phosphates and phosphonates with terminal hydroxyl groups, e.g. according to American patents 3 009 939 * 3,094,549, 3,081,331, 3,092,651, 3,167,575, 3,184,497, and 3,225 Q10; Phosphites and phosphonates of monosaccharides and their oxyalkyl derivatives, according to American patent specification 3,219,658 or alkylene oxide adducts of monosaccharide phosphoroxy acid esters, as e.g. Belgian patent 661 824 are described, and furthermore the Phosphorus-containing polyols, which can be found, for example, in accordance with the American patent 2 931 7 ^ 6 obtained by chlorenedic acid (1,4,5,6,7,7-hexachloro- (2.2, l) -5-heptene-2,3-dicarboxylic acid) or related highly halogenated unsaturated acids or acid anhydrides in the presence of a Phosphorus compound such as phosphorus oxychloride, phosphorus pentachloride, hydroxymethylphosphonic acid. Phosphoric acid, phosphorus trichloride, benzenephosphonic acid, trismethylolphosphine oxide, bishydroxymethylphosphinic acid or the like esterified and the resulting compound optionally then copolymerized with an unsaturated monomer such as styrene.

The ratio of aliphatic to phosphorus-containing polyol is kept preferably between 10: 1 and 0.5: 1, of course the invention Requirement for at least 2 0ew, - # phosphorus content in the finished product Polyurethane has to pause. The latter is preferably set to about to about 13, and preferably about 5 to about 10 Qew .- $.

The polyurethane is formed from the components according to the invention by processes known per se, in which these components are either combined individually or, if desired, the polyols are combined beforehand.

can mix. The combining takes place at temperatures between approx

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10 and about 100 ° C and preferably between about 20 ° and about 50 °. Before doing this, the polyols are preferably made individually or preferably by vacuum evaporation to at least 0.05 and preferably below O ^ Pß wt .-? £ - anhydrous. -

Where necessary, a known type of catalyst is added to the reaction mixture, preferably an aliphatic or cycloaliphatic tertiary amine, such as trimethylamine, triethylamine, tri-isopropylamine, trihexylamine, triethylenediamine, N, N, N ^f , N ¹ -tetramethyl-1 ,> butanediamine, N, N-ί)! methyl anil in, N-methy! piperidine, M, N'-dimethyl- a piperazine, N-methylrtKDi'pholine, N-ethylniorpholine, '1,1,3, ^ - Tfcti'a ^ ethylguanidine, Ν, Ν-dimethylethanolamine, 2-methyl-4-ethylimida2ol or the like, too.

Instead of such a tertiary amine catalyst and together with it one can also use other known catalysts, as they are for example wisely described in the handbook by Saunders, I.e., Volume I, pages 228-2J2 are. In general, however, one chooses a catalyst which enables the polyol-polyisocyanate reaction slowed down so that the rieaktlonsgfemisch after for a while remains fl less capable of mixing together and a "life- ^ duration in the vessel "from about 2 seconds to about 5 minutes, so can be processed as long as between the initiation of the reaction and the start of gelation remain. Triethylaadn is preferably used for slow conversions or dimethylethanolamine and for comparatively fast running ones Conversions triethylenediamine,

Where appropriate, catalyst addition may have taken place simultaneously or subsequently for the polyol-polyisocyanate mixture it generally requires ^! no heat input due to the exothermic nature of the reaction

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Outside. After vigorous stirring, the reaction mixture is either pressed into a corresponding hollow mold or onto a profiled one Form surface sprayed on, with form size, shape and contour depend on the end use purpose of the rigid plastic. The mixture gels, solidifies and finally hardens in the contour of the Form from which it is finally removed as a solid.

It is preferred to bring aromatic polyisocyanate and polyol mixture in such proportions for the reaction that an isocyanate-hydroxyl-P-group ratio from a little over 1, i.e. from 1.05: 1 to about

1.1: 1 arises. You can also use a higher isocyanate content, for example

• work approximately in the extended range between approximately 1: 1 and / 3: 1,

However, this does not make work easier or product improvement

In the sense of a preferred embodiment of the invention, one sets the liquid starting mixture to a filler, which is generally used to improve the strength of the end product, but sometimes also as a neutral waste material to reduce product costs · without noticeable Reduce property impairment.

To Festigkeitsverb.esserung sieve are all _de: n isocyanate over neutral fillers that have been previously used for this purpose, eg FaserTiaterialien from strangverpressfcem or woven plastic material such as polyamide, polyester or the like, or glass or boron, carbon, graphite, beryllium or The same for such end products that are to be exposed to high temperatures. These fibers can either be added to the reaction mixture in short-cut or chopped form before the addition of the catalyst or, even better, prefabricated nonwovens or nonwovens tailored to the end product size and shape. Use felt or woven or knitted fabric. So you put that

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Reinforcing fiber material in a form, for example an edge density Injection molding double mold and presses the reaction mixture into it, where it wets, surrounds and envelops the fibers.

As a cheap reinforcing material for building panels, passenger and truck bodies and boat hulls, oil fibers pretreated with phenolic resin, such as those commercially available for insulation purposes, are particularly suitable. They can be easily cut beforehand. · Λ

As a neutral waste material, i.e. neither with the starting components len chemically reacts, their conversion is catalyzed and on top of that is acid, alkali, atmospheric and rot resistant, one uses preferably solids with grain sizes below about 100 and preferably below 50 / U, e.g. duct, furnace or other types of gas black, polystyrene, polyvinyl chloride, natural clays, including hard dry clay, Kaolin, china clay and the like, natural silica and such away. If necessary, these fillers are dried before addition to the reaction mixture. ™

The hardening of the rigid art produced in accordance with the invention takes place in mass In or on the mold itself for 1 to 20 minutes and, if necessary, after removal from it, continue to be by heating about 50 ° to about 150 °, with post-curing above 100 ° the additional Bring advantage that the end product compared to below lying temperatures cured improved thermal deformation resistance having.

The rigid polyurethane terraces produced according to the invention provide

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generally evenly deep dark brown to black colored solids, which are characterized by a very low value for Schruepmass in shape and high values for tear, pressure, bending and impact strength (according to the Izod impact pendulum test), Shore D hardness, thermal Deformation point, thermal deformation resistance and durability " against boiling water, polar and non-polar solvents, acids, alkalis and the like.

These properties make the products of the invention in particular Fiber reinforcement suitable for numerous purposes, including building board *! for supporting and partition walls, ceilings and floors outside and inside of buildings, machine housings and the like, including panels and forrate parts for passenger and truck bodies, Railway wagons, airplanes, surface and underwater vehicles, furniture and the like, as well as pipes, pipes, storage containers and so on. The polyurethane compositions produced according to the invention can also cut, punch, drill, thread and treat in leather, metal or woodworking manner so that you can get them for the manufacture of numerous mechanical components, such as chain or toothed guides, gear elements and the like that normally made of metal.

The following examples explain the invention on the basis of embodiments currently considered to be optimal, without restricting it thereto.
example 1

Polymethylene polyphenyl cyanate 13/5 g (1.0 equiv.) (As sold by the applicant under the trademarked trade name ^M PAPI ^M )

? raktiech anhydrous polyol 100 g (0.9 equiv.)

Type 0-2764 from Atlas Chemical Ind.

and probably a mixture of 109837/1559 a polyoxyalkylene ether and one
Poly (hydroxyalkyl) phosphate with the
Hydrosyl number 510 and 3.6 t Phosphoreehftlf) "- IP ^

Triethylamine- 0.5 g

were stirred together for 3 minutes at 20 °, and the resulting mixture was then immediately poured onto a sheet metal coated with polytetrafluoroethylene and cured for 5 minutes without external heat input. This gave a clear, dark brown, non-porous, rigid polyurethane composition which had high notch toughness, abrasion resistance and tear strength.
Example 2

Example 1 was repeated with the modification that the carrier sheet was covered with a 3 mm thick blank of phenolic resin-coated glass fiber Isollermatte before casting. The liquid reaction mass wetted the glass fibers smoothly and evenly and, after curing at room temperature (of about 25 °), produced a reinforced, rigid synthetic mass of excellent tensile strength and notch toughness. Example 3 -

Polyisocyanate ¹¹ PAPI ¹¹ according to Example 1 75 » ¹ 6 (0.55 Squiv.)

hexafunctional polyol 93r5 g (0.5 equiv.)

(Type Niax RO-350 from Union Carbide and probably a mixture of bis-diglycol phosphbenate and aromatic polyol with a hydroxyl number of 300 and 11 % phosphorus content)

Triethylamine 0.5 S

were processed according to the instructions of Beisniel 1 and provided one Polyurethane compound with the same properties as in this example.

If one "PAPI ^ -Polyisoeyanat according to example through eleventh equivalent amount of another polymethylene polyphenylisocyanats · replaced, as well as the Anmelderln under the registered trade name ⁿ Carwinate", type 390 P vertrieben'wird of equivalent weight 130,

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a non-porous, rigid polyurethane mass with comparable properties was also obtained.
Example 4

Polyisocyanate "PAPI" according to Example 1 11% 5 g (0.85 equiv.)

Polyol (type Pluracol 204-s from Wyandotte. 100 g (0.8 equiv.) Chemicals and probably a mixture of a phosphoric acid-alkylene oxide adduct and a hydroxyalkylated methyl sorbitol with a hydroxyl number of 450 and 5.6 % phosphorus content)

Triethylamine 0.5 g

were processed according to the procedure of Example 1 and provided one Polyurethane compound with the same properties as in this example. Example 5

Example h was repeated with the modification that the Pluracol 204-G polyol was replaced by the same amount of Pluracol 216-S from the same supplier, which is probably a mixture of a phosphoric acid-alkylene oxide adduct and a hydroxyalkylated sorbitol with the hydroxyl number 44o and 5.6 f phosphorus content, and the "PAPI" -

Polyisocyanate amount increased to 136 g (1 equiv.). Mati thus obtained a polyurethane composition with the same properties as in Example 1. Example 6

Polyisocyanate "PAPI" according to the example. 1 90 g (0, β7β equiv.) Polyol (type HLR-250 from Hooker Chemical llo g (0.64 equiv.)

and probably made of a polyester

Chlorendic acid and ph ^ sphorhaltige.n

Polyol with a hydroxyl number of 56 and 6 %

Phosphorus content)

Triethylamine 0.5 g

were processed according to the procedure of Example 1 and produced a polyurethane composition with the same properties as in this example. .

example 7th

Example 1 was repeated with the modification that instead of the

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"PAPI ^ -Polyisocyanats ^ an equivalent amount of methylenebis (phenylisocyanate) was used, as was also used by the applicant as "Carwlnate", Type 125 M, and supplied a polyurethane composition whose properties are comparable to those of the Example 1 product was.

Rigid polyurethane compositions with or without reinforcing additives can also be obtained in the manner described above if , instead of the polymethylene polyphenyl isocyanate, other aromatic polyisocyanates, such as crude or distilled 2,4- or 2,6-tolylene diisocyanate or o-tolidinediisocyanate, and instead of the polyol mixtures described, other combinations of aliphatic and phosphorus-containing polyols of a known type are used which meet the requirements according to the invention with regard to functionality, hydroxyl number, phosphorus content and the other specified properties.

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Claims (2)

Claims 1) Process for the production of non-porous, rigid polyurethane compositions high tensile strength and notch toughness by implementing a aromatic polyisocyanate with a polyol, optionally in the presence of reinforcement material, characterized in that, nan as Polyol component is a mixture of a) at least one aliphatic Polyol having a functionality between about 3 and about 6 and one Hydroxyl number between about 200 and about 750 and b). As much phosphorus Polyol uses that the finished polyurethane contains about 2 to about 15 aew .- $ phosphorus « 2) Method according to claim 1, characterized in that as Polyisocyanate component a polymethylene «polyphenyl isocyanate mixture used, which consists of about 35 to about 85 % of methylene bis (phenyl isocyanate) and the rest of polymethylene polyphenyl isocyanates with a functionality of more than 2. 109837/1559 BATH ORIGINAL