DE2159173A1 - Thermoplastic and elastic polyurethane products - Google Patents

Description

Thermoplastic and elastic polyurethane products

The invention relates to novel polyurethanes, in particular on elastic polyurethane products, which are referred to below as polyurethane elastomers. The polyurethane elastomers are preferably thermoplastic. The invention also relates to the various Types of application of the products individually or as a mixture. The invention also includes a new manufacturing process for polyurethane products which are particularly suitable for the production of the aforementioned polyurethane elastomers.

Generally speaking, the manufacture of polyurethane products is based for condensation between hydroxyl groups and isocyanate groups according to the following equation:

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-N = C = O + -OH

The resulting urethane group thus forms a link between the one originally attached to the isocyanate group or radicals bound to the hydroxyl group. The isocyanate group can be replaced by an isothiocyanate group. Because of However, in the following, simplification and abbreviation is only for isocyanate groups and compounds with such groups Molecule the talk. If polyfunctional hydroxyl and isocyanate compounds are used, the condensation can take place Of course, it continues to progress and then leads to the formation of polyurethane molecules that have more than one urethane group and possibly even a greater number of such groups, including those of the original compounds radicals originating from the urethane groups mentioned are interconnected.

The elastomers produced according to the invention essentially consist of linear polyurethane molecules as they are obtained when starting from diols and diisocyanates: As is known to the person skilled in the art, such molecules can dereit crosslinked be that molecules of a diisocyanate O = C = N-R ^ = N = C = O (where R. is a divalent hydrocarbon radical, the may contain substituents with atoms of elements other than carbon and hydrogen) with hydrogen atoms from urethane groups from other polymer chains react so that bridges of the general formula:

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, ο

Il

-N-C- first chain

O = C
I. Networking NH
ι about diiso- E. cyanate molar NH cool ι

-N-G- second chain

form. However, one wants the elastomers defined above produce, so one must generally ensure that a network is not at all or at least not to a large extent Scope takes place. On the other hand, however, education so-called "areas" are favorable, which is still to be dealt with.

The production of linear polyurethane molecules from low molecular weight Diols and diisocyanates can be done in a single stage. If in this one-step technique Mixtures of diols and / or mixtures of diisocyanates are used, the result is generally one irregular or even completely arbitrary (statistical) distribution of the corresponding radicals in the long-chain Molecules. In addition, networking and even branching can hardly be avoided, especially if like this usually the case, substantial amounts of catalysts must be used.

With the help of a prepolymerization technique in which the Polymerization is carried out in several stages, on the other hand, a regular structure can be achieved. Is working one in only two stages, then in the first stage a

2 0 9-8 2 5 / .10-9 4

Proportionally low molecular weight prepolymer produced, while the prepolymer condenses in the second stage is with a so-called chain extender, which then leads to the formation of the desired high molecular weight polymer. At work

menr as

In two stages, the chain extension can be used to form a further, larger prepolymer.

In addition to the possibility of building regular polymer ♦. molecules, the multi-stage process still offers the advantage that no catalysts have to be used and that moreover, the reaction is easier to control. This is advantageous in all cases where the properties of the Product may only fluctuate within narrow limits.

It should be noted that, if necessary or desired, a crosslinking of the long-chain linear molecules, in which diol and diisocyanate radicals are linked by urethane groups, can be effected later. To this Purpose one leads a treatment with a so-called hardening or Crosslinking agent through. As a rule, the temperature must especially when the prepolymerization technique is used would be higher than the manufacturing temperature in order to effect the crosslinking of the linear molecules. Suitable Curing agents are especially the low molecular weight diisocyanates. However, as far as the invention relates to manufacturing methods relates, it concerns only a process using the prepolymerization technique and no subsequent hardening is performed.

Among the thermoplastic and elastic polyurethane products to which the invention relates are those of of particular importance, which consist of linear polymers of the following general formula, contain such polymers or are based on them:

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O = C = N = R.

H
¹ T

-COR ₂

- Q ₂ -

It

Here, Q ₁ stands for a group of the general formula:

f I -OCNR.

it I

or

Ή Η

.0-CNR. ¹ -NCOR ₀ ¹¹¹ Ii I it * -

) _ CNR. ¹¹ ■ ι <

and Qo for. a urethane group

-O-C-N-π O

or a group

the formula:

H
-OCN-RV

II ■

H -C-N-

Il

and

η stands for an integer, preferably from 5 to 60, in particular from 10 to 30;

R ₁ and R, - represent radicals derived from low molecular weight diisocyanates, which can be the same or different,

R ₂ and R ₂ represent radicals derived from high molecular weight diols

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represent kale, which can be the same or different; and R ₂ represents a radical derived from a low molecular weight diol.

The molecular weight of the high molecular weight diols from which R ₂ and R ₂ are derived is preferably in the range from 150 to 4-500, in particular from 500 to 2,500. The molecular weight of the low molecular weight diols from which R ₂ ab- ^r can be derived , is preferably in the range from 60 to 250 and in particular from 60 to 150, molecular weights of 60 to 100 being particularly preferred. The molecular weight of the low molecular weight diisocyanates is preferably in the range from 100 to 500, in particular from 150 to 300.

Suitable low molecular weight diols include the alkylene glycols as well as their low molecular weight polymers and / or copolymers. Examples of such diols include: ethylene glycol, 1,2-propylene glycol and its 1,3-isomer, usually as trimethylene glycol as well as the various diols derived from η-butane and isobutane, in particular 1,4-butanediol, which is also known as tetramethylene glycol.

All diisocyanate-substituted aliphatic, cycloaliphatic ^, aromatic or mixed hydrocarbons. In addition to the two isocyanate groups, other substituents can also be present which of course must not interfere with the reaction leading to the formation of polyurethane. Particularly suitable Diisocyanates include methylenediphenyl diisocyanate (with the isocyanate groups in the para position) and toluidine diisocyanate of the following formula:

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OGN / \ / \ _ NCO

Toluene diisocyanate, usually present as a mixture of 2,4- and 2,6-isomers, and naphthalene diisocyanate, usually only or at least predominantly the 1,5-isomer.

Among the high molecular weight diols, the polymers or copolymers of low molecular weight diols are preferred, in particular those of low molecular weight diols which have been referred to above as being preferred with regard to their use for providing the radical ^ . In other words, these high molecular weight diols are linear polyethers with two hydroxyl groups at the chain end or derivatives of such linear polyethers which carry methyl or ethyl groups as substituents on all or some of the radicals they consist of. The presence of such substituents at the end of the chain can result in one or both of the hydroxyl groups not being of a primary but of a secondary nature. The arrangement of the substituents in the polymer molecule can be isotactic or syndiotactic, so that the polymers in question can easily be made to crystallize. However, non-crystalline atactic polymers with a more or less random and non-stereospecific distribution of the substituents can generally be produced more easily and therefore more cheaply.

Preferred among the polyethers mentioned are the poly-1,2-propanediols and the poly-1,4-butanediols, i.e. the homopolymers of 1,2-propanediol or of 1,4-butanediol. The last--

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ren have straight chains without methyl or ethyl substituents and primary hydroxyl groups at the chain end. The poly-1,2-propanediols, on the other hand, have methyl substituents. Are they generated in a way that can be called normal if one considers molecular weights in the above according to the invention Wants to maintain range, the distribution of the methyl groups is atactic and the hydroxyl groups at the end of the chain are predominantly or practically all of a secondary ^ nature. This normal manufacturing process that is so economical is that it can be applied on an industrial scale, consists in the polymerization of propylene oxide, '' where a small amount of propylene glycol is necessary, to get the chain formation going according to the following. Equation:

HOC _x H ^ -OH + H _x CC CH ₀ > HOO _x IL-OO _x IL-OH

^ b ^ H ^

Further propylene oxide can then be added, so that polyether chains of the following general formula are formed:

OC ₅ H ₆ -J- OH

where η is an integer. It has been found, however, that polyether chains are also in general the general formula:

2 0 9 b / ·· ■ '*, ·.

H ₅ C-CH = CH

(i.e. the so-called "allyl form" / or "piopenyl form"). To explain this effect one can assume that the "chains in question are not from a propylene glycol molecule start, but from an ion formed by propylene oxide, which is subjected to a desmotropic rearrangement is:

H ₂ C

H ₂ C = C-CO "^ HH ₂

HxC-C = CO "

HH ₂

The original ion is formed from propylene oxide in such a way that that a proton is split off, which is then transferred to a proton present in the reaction medium Hydroxyl ion occurs. The ions with olefinic double bonds can together with one or more Molecules of propylene oxide form larger ions and finally take up a proton again or they take first the proton and then react with the propylene oxide.

Generally speaking, the process according to the invention consists in that one consists of relatively high molecular weight diols

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produces polyurethane products together with low molecular weight diols. According to a preferred embodiment, it comprises the process the production of prepolymers by condensation of high molecular weight diols with low molecular weight diisocyanates in a molar ratio of about 1: 2. The prepolymers produced in this way have the general formula:

f ■? *

if one starts from a diol with the formula HORoOH and a diisocyanate with the formula O = C = NR _-1 -N = C = O. The high molecular weight diols and low molecular weight diisocyanates which have already been described above as being particularly suitable are preferred.

In general, the condensation reaction becomes the most convenient carried out at a temperature which is above the melting point of the low molecular weight diisocyanate. However, for the purpose of better control of the process and in view of economy, the temperatures should cannot be increased too far above the melting point. In general there is no need to have temperatures of more than 50 or even more than 20 ° C above the melting point apply. Temperatures less than 10 ° or even less than 5 ° above the melting point have generally been found also proven to be useful. The reaction is * ■ preferably in the absence of solvents and diluents carried out. Preferably they are even carried out under essentially anhydrous conditions, i.e. that Water is excluded from the reaction mixture to such an extent that the reaction occurs essentially between the hydroxyl groups and the isocyanate (or isothiocyanate groups runs. In general, in such cases, the water

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215S173

- ΛΛ - '

content of the reaction up to about 0.1% by weight of the reaction mixture be. If the reaction mixture contains a larger proportion of water, e.g. up to about 0.5% by weight, in this way a "water-branched" prepolymer is obtained. The reaction will take place practically in a dry atmosphere inert gas, e.g. nitrogen or carbon dioxide, and optionally carried out under reduced pressure.

You can use a catalyst, but it has has generally proven to be more expedient to work without a catalyst, otherwise the reaction leads to the formation of less regular molecular structures tends, what then the favorable properties of the prepolymers produced polyurethane products impaired. It is known that for condensation between hydroxyl groups and Isocyanate groups, which lead to the formation of urethane groups, tertiary amines, e.g. triethylenediamine and dirnethylaminoethanol, can be used as catalysts. In general, compounds of the transition metals, in particular tin compounds, e.g. dibutyltin dilaurate, are used as cocatalysts and stannous octoate are used.

It should be noted that polymers of the general formula given above, in which the symbols follow Have meaning:,

I _ _E II

HHJ ₇₁ - H '

Q ₁ = -0-CNR ₁ -NCOR ₂ - ^ - OCNR ₁ -

and

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HH. H

it I ti ^ - ti OOO

by condensation of the prepolymer with a low molecular weight diol HOB, OH as a so-called chain extender, can be produced. Low molecular weight diols with primary hydroxyl groups, which are more reactive, are preferred are called secondary or tertiary hydroxyl groups. 1,4-Butanediol, which is particularly preferred, is without major Cost is available. This is true to an even greater extent for ethylene glycol, but this has the disadvantage that it is overly hygroscopic. 1,4-butanediol can be dry slightly by heating under reduced pressure, and it is desirable to do so before starting the condensation reaction. Preferably the chain extender is used used in an amount slightly below the equimolar ratio, i.e. in an amount from 80 to 95 mol%, so that the molecular weight of the Product can control. Theoretically were when applying infinite chains arise from equimolar fractions. In addition, as can be seen from the general formula, it is desirable that there are isocyanate groups and no hydroxyl groups at both ends of the chains.

Instead of 'low molecular weight diols, other low molecular weight bifunctional compounds with active Hydrogen atoms can be used as chain extenders. Such compounds include diamines with primary or secondary Amino groups, dicarboxylic acids, hydroxyamines and oxy and amino acids. The following connections, for example, can be used: Ethylenediamine, trimethylenediamine, tetraraethylenediamine, m-phenylenediamine, naphthylaminedieiiiin, toluene-2,4-diamine,

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Aminobenzylaniline, aminodiphenylamine, 2-aminoethyl alcohol, 2-amino-1-naphthol, m-aminophenyl, glycolic acid, α-hydroxypropionic acid, Aminoacetic acid and aminobenzoic acids If a solid difunctional compound is used, then is this is preferably one with a relatively low melting point, which should be, for example, below 150 0, since then the mixing process is facilitated. The use of all these connections is generally covered by the scope of the invention, although, of course, only the use of diols leads to polymers which of the above correspond to the given general formula.

Used instead of low molecular weight diols high molecular weight diols for the preparation of the polymers according to the invention from the prepolymers mentioned above, this gives products according to the above general formula, in which the symbols have the following meanings:

R ₁ >> ■ = R ₁ = R ₁ - - -; R ₂ = R ₂

Q = -OCNR.- I it ■

H 0

Q ₀ = -OCN · ^d II

H 0

₂ is the remainder of the high molecular weight diol used to make the prepolymer, while

the rest of the used as an Eetten extender

II is high molecular weight diol. R ₀ can in principle

I.
be identical to R ₀ , but this is preferred

• wise not the case. 209 82 5/1094

Chain extension with a low molecular weight or high molecular weight diols Generally speaking suitably set in motion by moderate heating, for example at 25 "to 100 ⁰ O, preferably 30 to 75> and in particular 40 to 60 ° C, with a temperature of around 50 ° C is particularly preferable. Since the reaction is exothermic, is carried out as soon as a temperature increase comes the reaction. preferably, the leaves ..Temperatur not higher than "maximum rise 150 ⁰ G, with temperatures between 50 and 100 C and in particular between 60 and 85 ° C are preferred. A temperature in the region of 75 ° C is very useful. The gelling process is generally complete within 5 to 120 minutes, preferably between 5 and 60 and in particular within 10 to 30 minutes. Usually gelation takes about 15 minutes.

From the above in the preparation of prepolymers from high molecular weight diols and low molecular weight diisocyanates For reasons outlined above, it is preferred to use neither catalysts nor solvents, although they do is also possible within the method according to the invention.

The 'process is of particular importance for the manufacture of polyurethane elastomers whose properties are within the following ranges:

Tensile strength in kg / cm 100 to 1,000, preferably

300 to 600

Elongation at break in % 300 to 1,000, preferably

500 to 800

Module 100% in kg / cm ² Module 300% in kg / cm ² Shore A hardness

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25th
30th until
until 50 preferably 15th
50 until
until 400,
200 preferably 25th
40 until
until 90
70 preferably

Angular tensile strength in kg / cm 20 "to 100, preferably

40 to 80 ..-

Of course, the optimal values depend on up to one to a certain extent on the starting material concerned. In general, the polyurethane elastomers according to the invention can be used for a wide variety of purposes. .., for which rubber and rubber-like substances have proven suitable. Please refer to the * " References to literature on rubber and rubber-like substances. An example is the use of the invention Polyurethane elastomers mentioned for the production of shoe soles. A blowing agent and a foam stabilizer can also be used in the final stage of the manufacturing process work in so that you get a foam.

It is known that block copolymers can be obtained which contain certain * regions ("domains") which are formed from groups derived from diisocyanate molecules are. It is not chemical forces that hold such groups together. Reference is made to this based on a work by J.A. Koutsky et al. in J. Polymer Science, Section B, Polymer Letters, Vol. 8, pp. 353-359 (1970). The areas or domains just mentioned are responsible for the desired degree of rigidity, while those parts of the molecular chains that adhere to these areas are crucial for the desired degree of flexibility and stretchability. Since the binding forces in the areas, in contrast to the bridges formed by the crosslinking agents, are of a non-chemical nature, the structure of the block copolymers * can be modified by heating to be broken up. This means that the products are thermoplastic, which turns out to be beneficial for recycling and reusing the polyurethane products Objects that are not fit for use, e.g. by

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■ ·. 2153173

- 16 wear, have lost, has proven.

However, there is a certain regularity in the molecular chain structure Condition for the formation of block copolymers with the domains mentioned above on a larger scale. However, a complete absence of networks and branches is not necessarily required either, as will be demonstrated in the results given in the examples. The scope of the invention should therefore not be restricted by the exclusion of all products with little crosslinking and / or branching and all forms of processes which lead to the formation of such products.

According to a preferred embodiment of the invention A diisocyanate prepolymer is condensed in the process of the type mentioned above with a diol prepolymer (produced by condensation of a similar one Diisocyanate prepolymer with a low molecular weight diol in a molar ratio of about 1: 2). The diisocyanate prepolymer can be represented by the formula:

TT TI

O = C = NR. ^ NCOR ^ -OCN- R " ¹ ^ = C = O

¹ It ^ - Il I

0 0

and the diol prepolymer by the formula: III ^H TT ^H TT ^H TT ^H TTT

-OCNR. -NCOR ₀ -0-CNR ^ Ve-CO-Ro -OH

- 11 II <- Il \ - u C.

0 0 0 0

It is easy to see that condensation of the two compounds must lead to a chain, which is preferred

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that represented by the above general formula Has structure.

Good results have been obtained with, for example

Products of this general formula where E. as well as

R. for the group:

that is to say for the radical from methylenediphenyl diisocyanate, while R ₉ and R _{0 represent} the radicals from one

II are poly-1,2-propanediol, where the R ₀ corresponding poly-1,2-propanediol is either identical to that represented by R ₀ or has a molecular weight below it.

* TTT

divorces; and while R _{2 represents} the radical -CH ₂ -CH ₂ -OH ₂ -CH ₀ -

which is derived from 1,4-butanediol. Of course, polymers in which R ₀ and R _{0 are} identical can in principle also be obtained by condensation of the diisocyanate prepolymer with a low molecular weight diol —OH, for example 1,4-butanediol, in slightly less than that

equimolar amount. The preparation of the diol prepolymer from the diisocyanate prepolymer can be avoided in this way. However, the diol prepolymer is very useful as an intermediate when R ₀ and R _{0 are} not identical. In addition, the condensation of a diisocyanate prepolymer with a diol prepolymer always offers certain advantages, which will be explained in more detail below.

The molecular weight of the formula represented by the above

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given long chain molecules is in the range of

20,000 to 200,000, preferably from JO,000 to 100,000.

Because terminal hydroxyl groups tend to affect strength exerting an adverse effect on the product, it is desirable to prevent the formation of polymer chains with terminal Favor isocyanate groups. Therefore, in the final condensation reaction, a slightly molar one An excess of diisocyanate is generally expedient. If you use approximately equimolar proportions of the two reactants, there is too great a chance that long-chain Forming too large molecules with terminal hydroxyl groups. This is always true, no matter what Type is the end stage of the condensation reaction, and also the preferred embodiment of the process according to the invention, where the final polymer is obtained by condensation of a high molecular weight diol and a high molecular weight diisocyanate, both of which have been obtained by previous condensation reactions are no exception here.

The use of poly-1,2-propanediol in the usual way produced by condensation of propylene oxide under the influence of a basic catalyst, as high molecular weight Diol, as described above, is not only dated attractive from an economic point of view, but has also produced very good results. The one at room temperature liquid poly-1,2-propanediols can does not add much to the intermolecular forces, however this is not an objection when in sufficient concentration Areas are present which are formed by residues derived from low molecular weight diisocyanates.

In contrast, the presence of a proportion of polyether molecules with terminal unsaturation has a disruptive effect. Such polyether molecules that are only attached to one

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Side have a hydroxyl group can of course only react with isocyanates on this side. In the case of the block copolymers obtained at the end, the structure of which contains the areas mentioned, there is a risk of that the unsaturated side of the polyester chain forms a loose chain end and thus a break in the molecular one Arrangement caused. Therefore, if you have poly-1,2-propanediols with terminal unsaturation in the area of 3 to 15 M ° l-% used, it is mostly the physical properties of the elastomers obtained as end products are quite poor. It is known, however, that this level of unsaturation in the commercial poly-1,2-propanediols is normal. The amount of unsaturation can be determined based on the iodine number. In general, the molecular tends to be Unsaturation in commercial poly-1,2-propanediols also to increase with increasing molecular weight. '

Surprisingly, it has now been found that the introduction of a hydroxyl group is not necessary and that one very usable products are obtained if the unsaturation is suppressed or at least significantly reduced by adding hydrogen chloride to the olefinic double bonds.

The amount of hydrogen chloride, which is to be distinguished from the poly-1,2-propanediols each incorporated _f, can be calculated from the course of unsaturation. However, more than the stoichiometric amount may be required if the commercial poly-1,2-propanedi oil in question contains one or more impurities which are capable of binding hydrogen chloride.

The above-described polymerization of propylene oxide is

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generally carried out under the influence of a basic compound, in particular in the presence of an alkali hydroxide, such as sodium or, preferably, potassium hydroxide. Subsequent to the polymerization, the basic compound, preferably with a strong mineral acid, becomes one Salt neutralizes. As far as lower polymers are concerned these salts can be easily washed out, but this becomes more and more difficult with increasing molecular weight. Contain the commercial products with a higher degree of polymerization therefore often all or part of the neutralization formed salts. The commercial products available under the name "PPG" on which the examples are based lying attempts seem to have been used in general To contain slightly basic potassium phosphates as impurities. Although only small amounts of such phosphates be considered, their presence may make it necessary to add more hydrogen chloride than the Theoretically necessary stoichiometric quantities for the complete elimination of the unsaturation.

On the other hand, it is not beneficial to use the hydrogen chloride to be used in greater excess over those quantities which are necessary to remove the unsaturation and to cause a neutralization of basic impurities, otherwise the average molecular weight of the polymer the tendency shows to largely decay, probably due to hydrolysis of the ether bridges.

In the treatment of poly-1,2-propanediols with the addition of hydrogen chloride to the double bonds of the hydrogen chloride in the form of gas applied v / ground, but _(also solutions of hydrogen chloride in organic or inorganic solvents thereof, of which aqueous solutions are particularly preferred. Preferably one uses · usually concentrated aqueous solutions, for example a

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Have an HCl concentration of 30 to 37% by weight. The treatment preferably comprises moderate heating to, for example, 50 to 100 ° and is carried out under an inert gas, nitrogen being preferred for reasons of economy. You can work under reduced pressure, but atmospheric pressure or even excess pressure of, for example, up to 10 at.abs. preferable. Generally speaking, the most suitable temperatures are in the * range from 65 to 95 ° G, preferably 75 to 85 G, with a temperature around 80 ° C. generally being regarded as the most suitable. After the treatment, which lasts 0.1 to 10 hours, preferably 0.5 to 2 hours and in particular about one hour, the 1,2-propanediols are preferably dried by heating under reduced pressure. The temperatures are expediently the same as during the treatment. At a drying ^{temperature of approximately 80 °} C., for example, a pressure of approximately 1 mmHg has proven to be particularly suitable. Drying can take 1 to 10, preferably 2 to 5 hours, drying times of about 3 hours generally being the most practical.

It has also been found that in other cases the treatment of the poly-1,2-propanediols with hydrogen chloride can be omitted and these are used immediately and without prior hydrogen chloride treatment to form polyurethanes can. Although this type of poly-1,2-propanediol is about 3 mol% Has unsaturation, the hydrogen chloride treatment is not necessary and excellent products are obtained Properties. Without giving a theoretical explanation of this favorable effect here, it was possible to -. but find that the type of poly-1,2-propanediols used was absolutely neutral, so that, based on the instantaneous knowledge, one can say that the main The effect of an acid treatment is that when one of

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runs out of an alkaline poly-1,2-propanediol, the reaction medium is made acidic, resulting in the formation stimulates urethane groups and suppresses side reactions. If, on the other hand, the poly-1,2-propanediol is absolutely neutral was, the use of hydrogen chloride was unnecessary, as shown in Example 10. For use with the preferred embodiment of the described above Process according to the invention must be prepared from high molecular weight diisocyanates high molecular weight diols, where one then finally by condensation of these high molecular weight diols with high molecular weight diisocyanates final polymers obtained. The production of these end polymers from diisocyanate prepolymers by Condensation with an almost equimolar amount of a low molecular weight diol as a chain extender has been detailed already described above. If the low molecular weight diol is used in a molar ratio of approximately 2: 1 with regard to the diisocyanate prepolymer and otherwise keeps the conditions essentially the same as for a chain extension, which leads to the formation of the final polymer, the desired diol prepolymers are obtained. Preferred 1,4-butanediol is also used here as a low-molecular diol, which has previously been subjected to a dry treatment. This fact is due to the same reasons as them shown above in connection with the chain extension that leads to the formation of a final polymer became. When the diisocyanate prepolymer is reacted with 1,4-butanediol, a Diol prepolymer with reactive primary hydroxyl groups. The final condensation can therefore be expected to proceed more smoothly than when used to make the final polymer the diisocyanate prepolymer is reacted with a conventional poly-1,2-propanediol, the secondary hydroxyl groups having. The conversion of poly-1,4-butanediol, which has primary hydroxyl groups, with diisocyanate

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polymerizaten to the final polymer takes place in to a more satisfactory extent and at a higher speed. If appropriate, diol prepolymers can of course be used can also be prepared from biisocyanate prepolymers obtained by reacting Poly-1,4-butanediol or any other polyether diol with primary hydroxyl groups with a low-molecular diisocyanate When poly-1,2-propanediol initially in a Diisocyanate prepolymer and then this in turn Diol prepolymer is to be converted, it is not just a matter of terminal secondary hydroxyl groups to be replaced by terminal primary hydroxyl groups, but it is also important that the structure of the The polymer obtained in the end is most advantageous in terms of the desired properties.

Among the polymers of the above general formula in which R- and Rp are identical, those have proven particularly useful in which R ₀ (= R ₀ = Rp) is derived from a poly-1,2-propanediol whose molecular weight is in the range from 600 to 2,000, in particular from 750 to 1,500. Particularly preferred among these molecular weights 1000-1400, and primarily those, from 1 100 to 1 200. ■ _K

If the substituents Ro and Rp are different, so the former is preferably derived from a poly-1,2-propanediol with a molecular weight of 500 to 1,000, preferably from 600 to 800, while the latter is preferably derived from a poly-1,2-propanediol, its molecular weight is between 1,000 and 2,000, and is preferably 1,400 to 1,600.

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In the case of the molecular weights given above, the distances between the "regions" or "domains" are such that that are desirable for thermoplastic elastomers Properties are guaranteed.

In the manufacture of the final polymers, either from a prepolymer and a low molecular weight chain extender or from two prepolymers, must be the respondents and who may be existing additives are always intimately mixed, for which purpose in generally a roller device is particularly effective. In many cases, however, mixing in a rubble, Pouring or spraying device more useful. This is particularly the case when the device is used for application. of the mixture on a surface or for introduction into a Form, with the implementation predominantly after the application or introduction and usually only to a lesser extent in one previous stage takes place.

If you use such rubble, pouring or spraying devices, so one must, if the viscosities of the two reactants are too different, with certain difficulties take into account the dosage and proper mixing. In addition, the volume ratio at Mix too much from 1: 1 if the molecular weights of the reactants differ greatly. But now have at the preferred embodiment of the invention Process the two reactants roughly the same Molecular weight and therefore differ only little in their viscosity, so that they are in a volume ratio react of almost 1: 1, and the mentioned difficulties avoided to a completely satisfactory extent will.

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The preferred reaction conditions in the described preferred embodiment of the "method are essentially the same as in chain lengthening reactions of a different kind, e.g. those in which a low molecular weight Diol is used as a chain extender when the reactions mentioned to produce the final polymer can be applied.

In all cases, regardless of the mixing technique used, a foaming agent, i.e. a gas or a gas-forming Substance are added to the reaction mixture and also a foam stabilizer, i.e. a. Surface-active material Properties, usually a silicone. It is known that such additives can be selected appropriately achieve that the end product is in a state built up from microcells, either with, as desired open or closed cells.

It goes without saying, however, that the invention is in no way restricted to the production of foams. In general the polyurethane elastomers produced according to the invention can be further processed in the same way as other elastomers including the usual rubber fabric e. It goes without saying that the material in the foamed or non-foamed state can be of the most varied Additives can be added together or individually, including processing aids, light stabilizers and anti-oxidants and also optionally Fillers and / or dyes of all kinds.

The dry thermoplastics obtainable according to the invention Elastomers can be used in the same way as the usual rubber materials are processed. Extender oils can be used as well as other rubber-like substances are incorporated. For this

0 9 8 2 5/1094

Can use the usual processing equipment including mixer mills, Banbur ^ y mixers, extruders and Calenders can be used. The deformation can, for example take place by compression or injection molding.

The elastomers can be used in adhesives, especially in solvent-based ones can be used. The adhesives can be pressure sensitive or contact adhesives *.

be.

ι ·

The solutions of the elastomers can be used for coating purposes, either with the aid of rollers or applied by spraying.

The elastomers can also be used to modify thermoplastics including polyethylene and polypropylene or used by bitumen.

The elastomers are also suitable as packaging materials, e.g. for medical equipment and for food. They can be made into foils that can be used to make a wide variety of items. Foils can also be used as bases for other materials, e.g. can be used as a support layer for felt carpet tiles.

The elastomers can generally be used for all purposes in the usual rubber or rubber sector, where there are economic advantages based on easier processability without vulcanization, arrives. A wide variety of polyurethane elastomers can be used Articles of daily use are produced, e.g. mats, such as those used as a support for turntable turntables serve and bath mats, soaps for toy cars, baby cups, Erasers, dust covers, aerators for liquid

209825/1094

1159173

taps, drip vessels, wheels for household or Hospital purposes, ski goggles, safety masks, electrical " see plugs, padding for vacuum vessels, clothes hangers, flexible magnets, acid lines for batteries, covers for car steering wheels and wig stands. Of course this list is by no means exhaustive.

The use of the polyurethane elastomers is of particular importance in the manufacture of footwear. This can be made from elastomers, but also from others Fabrics, e.g. canvas covered with elastomers, Shoes and boots are made. In addition, you can The elastomers serve as the material from which the footwear, e.g. soles, heels or pads for paragraphs.

The polyurethane elastomers according to the invention are extremely resistant to petroleum and mineral oil, and they their high wear resistance makes the Use in pumps, e.g. circulation pumps.

The invention is illustrated by the following examples explained. ,

example 1

HCl treatment of commercially available poly-1,2-propanediols

Commercially available poly-1,2-propanediol products with an average molecular weight of 750 or 1,500 or 2 000 made in the usual way by condensation of propylene oxide under the influence of a basic catalyst were treated with hydrogen chloride subject. Because of the way they are made, these polymers are atactic and have essentially only secondary ones

209825/1094

Hydroxyl groups. In each of the tests, a sample of the poly-1,2-propanediol in question was one mole under a nitrogen pressure of about 1.5 at. Abs. Stirred for about one hour at 80 G with 35% aqueous hydrochloric acid. After the treatment, the samples were dried at a pressure of 1 mmHg and a temperature of 80 ^° C. for 3 hours. The results are shown in Table I * ":

TABLE I ■. "

sample
No. medium treat-
Molecular amount
weight in g untreated
delt Iodine number Uncomfortable
heitgrac ml HCl
aq
_i attached. chlorine
salary
in % 1 750 750 1.10 3.25 untreated 2 750 untreated
delt
1,500 0.11. 0.3 3.25 0.20 3
4th 1,500
1 500 _f . 1,500 1.02
0.87 6.0
5.0 untreated
1.0 Nile
0.03 5 1 500 ' 1,500 0.72 4.2 2.0 0.06 6th 1,500 1,500 0.11 0.6 6.0 0.18 7th 1,200 untreated
delt 0.09 0.5 12.0 0.21 8th 2,000 1.70 13.4 untreated -

2,000

2,000

0.17

1.3 13,

0.28

After all of the samples were treated with the aqueous hydrochloric acid in an amount sufficient to remove the unsaturation to cancel completely (samples No. 2, 6 and 9), the chlorine content in the end was slightly higher than on the basis of the original Unsaturation was theoretically to be expected; (Theory for sample 2 0.15% by weight, for sample 6 0.14% by weight and for sample 9 0.2J% by weight J. The additional chlorine content is

209825/109 4

apparently due to the fact that some hydrogen chloride acid was bound by potassium phosphate, which is in 'the relevant commercial poly-1,2-propanediol as Contamination was present.

It should be noted that the treatment did not lead to a significant change of the molecular weight, except for sample 7 ₅ where the amount of aqueous hydrochloric acid used and the theoretical exceeded by twice. The decrease in molecular weight from 1,500 to 1,200 is probably due to the hydrolysis of the ether bridges.

Example 2

Production of prepolymers by condensing poly-1,2-propanediols with low-molecular diisocyanates in a molar ratio of about 1: 2

The terminal hydroxyl groups of poly-1,2-propanediols v / earth replaced by groups of the general formula:

O = C = N-IL-N-C-O-

I t!

H 0

by condensation of the poly-1,2-propanediols concerned with a low molecular weight diisocyanate of the general formula:

O = C = NE ₁ -N = C = O.

a) Poly-1,2-propanediol with a molecular weight of 1,500 1, ^ - diisocyanatonaphthalene

The poly-1,2-propanediol samples 3 to 6 from Table I in

Example 1, all with a molecular weight of

1,500, but treated with various amounts of aqueous salt

2Ü9825 / 1094

acidic, namely with 0, 1.0, 2.0 and 6.0 per mole (1,500 g) of polymer were condensed with 1.5 diisocyanatonaphthalene in the form of a commercial product with a molecular weight of 210. Due to the fact that the hydroxyl groups of the poly-1,2-propanediol product are secondary, the reaction proceeds rather slowly and there is therefore a risk that the diisocyanate will homopolymerize because it is "particularly susceptible to a reaction of this type, all the more so than the temperature above the melting point (128.5 ° C) of the diisocyanate must be kept, which is quite high. The undesirable homopolymerization reaction of the diisocyanate could largely be suppressed by the fact that the reaction medium was slightly acidic immediately before the reagents were introduced by adding 35% by weight aqueous Hydrochloric acid was added in an amount of 0.4 ml per mole of the saturated poly-1,2-propanediol In all cases the molar ratio of poly-1,2-propanediol to diisocyanate was 1: 2. The Re The action was started each time at 130 ° C. and continued at temperatures of 130 to 140 ° C., so that “for example, it was over in about half an hour. The yield corresponded to theory, ie one mole of prepolymer was formed per mole of 1,2-propanediol fed in.

The molecular weight of the resulting prepolymers was about 2 050, which is higher than. the sum of the molecular weights of the components. This can be attributed to some elongation of the chains through which polymer molecules move with higher molecular weight formed.

b) poly-1,2-propanediols of molecular weight 750 and 1,500 with methylenediphenyl diisocyanate

The poly-1,2-propanediol samples 2 and 6 from Table I, Example 1, with molecular weights of 750 and 1,500, both of which

209825/109 4

had been pretreated with dilute hydrochloric acid in order to bring about practically complete saturation, were condensed with commercially available methylenedipheriyl diisocyanate. In the case of the commercial product in question, no acidification whatsoever was necessary. Its melting point is 39.4 G and the reaction temperature was 80 ° C. in all cases and the reaction time was 4 hours. The further reaction conditions ₍ and the results are shown in Table II.

TABEL

II

Poly-1,2-propanediol molar ratio yield molecular

• = 5 — τ- nis Diiso- an Vor large-

lioxeioi- _t light

a £ s Tab I. from lab.l

2 2 6

_{cyanate too}

stwicht weight;

750

r "

750 1,500

1.95: 1 2.2: 1

1.95: 1

Pre-examination

polymer weight of the number (mol%, result calculative Vornet on polymers "PPG")

91.7
91.8
88.0

1,350

1 340

2 250

1 2 3

The three prepolymer samples from Table II were all highly transparent. The molecular weights were something here too higher than expected from the molecular weights of the ingredients, probably due to some Chain extension that led to the formation of polymer molecules with higher molecular weights.

The Vorp ο lym test ITr; 2 contained, calculated on the prepolymer itself, about 10 mol% free methylenediphenyl

209825/1094

diisocyanate, which corresponds approximately to the amount of diisocyanate that is theoretically required for the implementation of the Hydroxyl groups necessary amount of diisocyanate was added.

Tests were also carried out with a commercially available one Lower purity methylenediphenyl diisocyanate that was liquid and had an average molecular weight of 280, while the solid product used above is 250. It turned out to be in this case necessary to use a tertiary amine in an amount of 0.4-5 g per mole of poly-1,2-propanediol as a catalyst. If no amine was added, the formation of a precipitate was evident from the isocyanate came to watch. The amine used was a commercially available one Triethylenediamine. Otherwise, the conditions and results essentially corresponded to those given in Table II for prepolymer samples # 1 and # 3.

Example 3

Production of elastomers from diisocyanate prepolymer by condensation with a low molecular weight diol in approximately equimolar proportions

From prepolymers obtained by condensation of a commercially available Medium molecular weight poly-1,2-propanediol 1,500 with 1,5-diisocyanatonaphthalene or from commercial poly-1,2-propanediol of molecular weight 750 by condensation with methyleaidiphenyl diisocyanate were obtained according to Example 2, elastomers were produced. The prepolymers in question were condensed with a low molecular weight diol, namely 1,4-butanediol, in approximately equimolar proportions. The 1,4-

209825 / 109A

Butanediol was made by heating for two hours each time .Dried to 70 under 1 mmHg pressure. In all attempts was the molar ratio of 1,4-butanediol to that in question Prepolymer approximately 0.95 to 1.00. After an initial 50 C, the temperature then rose to 75 ° C · Die Gelation was completed in about 15 minutes. For post-curing, the temperature was raised for a further 24 hours Held at 100 ° C. . ** '

The properties of the elastomers obtained go out Table III.

TABLE III:

2 09825/1094

Molecular
weight of the
Polypropane
. diols
[ HOl loading
hand-
ment according to
Example 1.
(ml HCl _aq
per MoI) TABEL III ro ro
ο ο
VJI VJI
ο ο properties train
firm
speed
in ρ
kg / cm fracture
deh
tion
in of the elastomer Angle-
Train-
consolidate
speed
(ASTM _v
D 624)
in kg /
cm N3 Prepoly -
mer, received
from diol
sample no ..,
v.Table: 1,500
1,500 unconcerned
acts
1.0 Use
detes
Isocya
nat, s.
Example 2,
Part ... Prepoly-
test kular- ■
Mr ... from selected
Table IC of the previous
ι, poly
mers 2 050 150
220 370
500 Shore
A-här-
, te 27
30th cn
CD to 5
ο
co
oo 4 1,500 2.0 a)
a> 2 050 225 460 83 °
83 ° 31.5 1,500 6.0 a). 1,350 275 565 84 ° 37.5 750 3.25 a) - 1 340 400 350 84 ° 75 ι 750 3.25 b) 1 on elastomers with (375) 300
(350) 82 ° VM
45 ^
(35). 2
V. (Excess) 2 Octyl phthalate i 73 °
(68 °) *) Numbers in brackets relate i as a plasticizer • module
100 %
in
kg / cm ^£ VJI VJI
-vJ VJi 56 59 50

The beneficial effect of unsaturation removal by HCl treatment is clear from Table III.

It can also be clearly seen that the presence of free diisocyanate is undesirable because it reduces the elasticity and increases the stiffness of the elastomers. This is probably due to the fact that part of the Λ , 4-butanediol is consumed by reacting with the excess diisocyanate. This then leads to irregularities in the structure of the polymer chains.

Example 4

Production of elastomers from a diisocyanate prepolymer using diols of increasing molecular weight.

The experiments from Example 3 were repeated, including prepolymer no. 1 from Table II (obtained from HCl-treated poly-1,2-propanediöl with a molecular weight of 750 Methylenediphenyldiisqcyanat) was used while, however the 1,4-butanediol as a chain extender was replaced by a number of other diols of increasing molecular weight. The reaction conditions including the molar ratio of the diol for the prepolymer corresponded to those in Example 3. The properties are shown in Table IV of the resulting elastomers. For comparison, the values from Table III, which relate to the use of 1,4-Butanediol-750, included in Table IV. In the second place, the results can be seen from Table IV, which were obtained in an experiment in which a mixture of 1,4-butanediol and a condensation product of glycerol and 3 moles of propylene oxide in a molar ratio of 97j5: 2.5 was used; the condensate is a commercial product and contains primary hydroxyl groups. His presence

209825 / 109Λ

leads to a proportion of branched-chain molecules "educates.

TABEL IV deh module Elastomers Tensile strength _ ■ 40 - Properties of the tion in
% 100% Shore Α angle * speed
(ASTM D 624) Diol tensile strength fracture in ο
kg / cm hardness in kg / cm 26th speed in 350 75 kg / cm 350 50 80 24 350 . 45 82 ° 60 21st 1,4-butanediol 400 45 84 ° 1,4-butanediol *) 350 325 80 ° 1,6-hexanediol 400 43 Di-1,2-ethane 375 65 ° diol 300 28 Tri-1,2-ethane 400 60 °. diol '400 550 22nd Tetra-1,2-ethane 15th 60 ° diol 230 Poly-1,4-butane _nn
diol, 2000 mole ^IUU w.

mixed with condensation product from glycerin and 3 moles Propylene oxide.

From Table IV it can be seen that those with lower Elastomers made from diols had a high degree of hardness and that these elastomers were tough and fairly were brittle. With increasing molecular weight of the diol and thus with decreasing hardness, the appearance became greater rubber-like and the elasticity increased. At a molecular weight of the poly-1,4-butanediol / became softer

from 2000 209825 / .109A

Get rubber. It is shown accordingly that by corresponding Selection of the diol, the product properties can be adapted to the intended application.

It can also be seen from Table IV that a relatively small The proportion of branched-chain molecules can be tolerated as it does not seriously impair the Properties of the elastomer leads.

Example 5

Further chain extension of diisocyanate prepolymers with a low molecular weight diol in a molar ratio of 1: 2 in the formation of diol prepolymers

The diisocyanate prepolymers of samples 1 and 3 Table II, obtained according to Example 2b (from poly-1,2-propanediol with samples 2 and 6 from Table I and the diisocyanate according to Example 2b) were reacted with 1,4-butanediol in a molar ratio of 1: 2. The 1,4-butanediol was before

dried by heating in vacuo (1 mmHg) at 70 ° C for two hours.

The condensation of the diisocyanate prepolymer with sample 3 from Table I (obtained from polypropanediol 1,500) with 3,4-butanediol was modified by changing the molar ratio of Prepolymer to 1,4-butanediol was increased from 1: 2 to 1: 3.

In all three experiments, the initial reaction temperature was 50 ° C and was then increased to 75 ° O. The molecular weights of the resulting diol prepolymers are shown in Table V.

. 209825/1094

T Diisocy- ABELL E. V Diiso- MoIe- 1 poly Diol prepoly Molecu HCl Use cyanate ku- 3 mers before- mer, received largew. Treatment detes Prepoly 1 ar 3 1,530 poly- from Diolprob " of the poly lung Iso- merpro- ge w. 2 430 mer- No. ... of apropane according to cyanate, be no ... of 2 430 sample Table I. cLiols Example 1 see example . the end result- No... Part 2... Table II deep end Diol Pre 2 1 6th 750 3.25 b) 2 6th 1,500 6.0 b) 3 1,500 6.0 b)

That given in Table V for Diol prepolymer sample # 3 Molecular weight refers to the prepolymer itself. The average molecular weight was lower due to the presence of excess 1,4-butanediol. These excess amount was practically not converted. As a result, there was diol prepolymer obtained as the end product 1j4-butanediol dissolved, the proportions of 1,4-butanediol and diol prepolymer were essentially equimolar.

Example 6

Elastomers made from a diisocyanate prepolymer and a Diol prepolymer

In each case, elastomers were produced by condensation of a diisocyanate prepolymer with sample no. 1 or no. 3 from Table II with one of the diol prepolymers of Table V. In each case, 0.95 moles of the diol prepolymer was

209825/1094

tes combined with 1 mole of the diisocyanate prepolymer. Prior to mixing the former was at about 10O ⁰ G and the latter has been heated to about 70 ° C. No catalyst was used. The two prepolymers were mixed intensively by stirring. The reaction mixture completely gelled within about 15 minutes. Post-curing

was carried out at 100 ^{° C. for 24 hours.}

The properties of the elastomers obtained go out Table VI.

TABLE VI

Diisocyanate Diol Molecu Properties of the train fracture module Elastomers Win- prepolymer largew. firm deh 300% kel- Per- molecular prepolymer speed in tion in ρ Shore Train- be largew. Per kg / cm ² in % kg / cm A-här- firm No... be te speed in Ta No... in bark in Ta kg / cm II bark (ASTM V D624) 1,530 400 350 50 75 2 430 50 1,000 15th 15th 1 1 350 2 430 150 900 30th 82 25th 3 2 250 1 2 430 300 850 30th 30th 40 1 1 350 2 40 1 1 350 2 55 3

It can be seen from Table VI that properties are obtained which are particularly preferred for most of the usual practical purposes if radicals alternate, each of which is derived from poly-1,2-propanediol with a molecular weight of 750 or a molecular weight of 500. 209825/1094

The presence of free 1,4-butanediol results in a Modification of the properties, which may not necessarily be desirable, depending on the application in practice is provided. The effect can be attributed to the condensation of the diisocyanate prepolymer with free 1,4-butanediol will.

Example 7

The last of the four thermoplastic polyurethane elastomers listed in Table VI was rolled at 160 ° C for 10 minutes. The product resulting from this treatment web was pressurized deformed (for 3 minutes at 15O ° C., Only on contact pressure, then 10 minutes at .150 ⁰ C under high pressure, then cooling to room temperature over 15 minutes under high pressure). A uniform sheet 2 mm thick was obtained. The tensile strength and the elongation at break were still the same as indicated in Table VI, ie they were 300 kg / cm ^{2 and / or 300 kg / cm 2,} respectively. 850 % .-

In this V / else could be apart from plates or panels various molded articles produced including, for example shoe soles, so-called. Mechanical goods such as z * B. ". Automobile industry used vd.rd and trays, such as ice cube carrier.

Example 8

The elastomer used in Example 7 was applied to a roll device processed at 160 ° C, using various stabilizers and processing aids (e.g. a commercially available available poly-1,4-propanediol with an average molecular weight from about 400 in amounts from 0 to 250% by weight, calculated on the elastomer) and fillers (e.g. so-called brighteners, i.e. Calcium carbonate in amounts from 0 to 2200 wt .- / ij, calculated

209 82 5/109 4 _B AD

on the elastomer) were added. In addition, pigments were added in order to obtain colored, e.g. green, yellow, red and blue products. The properties of a typical product with 10% by weight of polypropanediol-4-00 and 100% by weight of brightener, both calculated on the elastomer, were: tensile strength 120 kg / cm ² and elongation at break 500 %.

Example 9

The masses prepared according to Example 8 could by means of the compression set described in Example 7 are formed. They could also be used to create objects, such as pipes, drilling and profiles at temperatures deformed between 160 and 170 ° by extrusion.

All kinds of objects including those in example 7, i.e., shoe soles, mechanical goods and trays,. E.g. ice cube carriers could be made from the same masses

are made by injection molding at temperatures between 160 and 200 ° C. . .

B ice pie 1 IQ.

a) Preparation of a prepolymer by condensation of Poly-1,2-propanediol (molecular weight 1,300) with methylene

diphenyl diisocyanate

In the preparation of prepolymer carrying terminal isocyanate groups, 1 mole of poly-1,2-propanediol (molar weight 1,300, molecular unsaturation 3.25%, absolutely neutral) was reacted with 2 moles of methylenediphenyl diisocyanate; the reaction was carried out under nitrogen and continued at 80 ⁰ G 3 to 4 hours. A highly viscous prepolymer was obtained. . The poly-1,2-propanediol had not been subjected to any pretreatment with hydrochloric acid.

209825/1094

b) Production of a prepolymer with terminal Isocyanate groups

The prepolymer prepared as above was reacted at 60 to 90 C with 1,4-butanediol (molar ratio of prepolymer to 1,4-butanediol the same. 1: 2). The reaction mixture was under Stirred nitrogen for one hour and overfold to one temperature held at about 75 ° C. A highly viscous prepolymer with terminal hydroxyl groups was obtained.

c) Manufacture of elastomer

For the preparation of an elastomer, one mole of the prepolymer having terminal isocyanate groups was intimately stirred for 15 minutes with 0.95 and 0.97 mole of the prepolymer having terminal hydroxyl groups, wherein the temperature was 110 ⁰ C, and no catalyst was used. The reaction mixture was then completely gelled in an oven at 100 ° C. within 2 hours and post-cured at 5 ° C. for one week.

d) Properties of the elastomer

With a rotating knife strips were cut from the elastomer obtained in this way, which strips are used for the production of Experimental samples were used. -

Properties of the elastomers

Tensile strength in kg / cm module 300 % in kg / cm ² elongation at break in %

PATENT CLAIMS: 209825/10 9 4

NCO / OH = 100/95 NCO / OH = 100/97 340 245 31 31 980 730

Claims (1)

2T59173 PATENT CLAIMS 1) Thermoplastic and elastic polyurethane products according to the general formula: O = C = N-R "- - H H NC-0-R ₂ ^I -Q ₁ -NGOR ₂ ¹¹ -Q Jl 0 -Q ,, - N = C = O, ¹ wherein Q _{1 is} a group of the general formula: ^H I .LO-GNR.- Λ ^Λ 0 or a group of the formula: -0-CNR ^ -NCOI
ff ^Ί if
OO H ϊ-N-R. η ο H and Q ₂ for a urethane group -OCN- or one Group of the formula: H _τ I ^Η ] ΓΤΤ OCNR. ^{x LJ} - ^X- OCN Il ■ f { ² ff O O O 209 82 5 / 109.4. , stand; - ■ '-.- ·: η is an integer, preferably from 5 to 60, in particular of 10 is Ms 30; R ^ and R * of low-molecular Diisocyanate-derived radicals represent the same or can be different; R ₂ and R ₂ radicals derived from high molecular weight diols represented, which can be the same or different; R _{2 is derived} from a low molecular weight diol Radically represents. 2) polyurethane products according to claim 1, characterized in that the molecular weight of the high molecular weight diols, of which R ₂ and. R ₂ originate from 150 to 4,500 _t, in particular 500 to 2,500. 3) Polyurethane products according to claim 1 or 2, characterized in that the molecular weight of the low molecular weight diols from which R ₂ ** originates from 60 to 250, in particular 60 to 150 and preferably 60 to 100. 4) polyurethane products according to claim 2, characterized in that the high molecular weight diol from which R ₂ and R ₂ originate is a poly-1,2-propanediol. 5) polyurethane products according to claim 3 »characterized in that the low molecular weight diol, TTT from which R ₂ ^x is derived is 1,4-butanediol or 1,6-hexanediol. 6) Pölyurethanprodukte according to claim 1 to 5, characterized geke · η η ζ η et verifiable that R ₁ ¹ and R ¹ * represents radicals derived from 1,5-diisocyanatonaphthalene or Methylendiphenyliisocyanat. 2: 0 ■ a b 2 b I 'G y U Process for the production of the thermoplastic and elastic polyurethane products according to Claims 1 to 6, characterized in that characterized in that a diisocyanate prepolymer of the formula HH O = G = NR. ^I ^ NC-0-R _o ^I -0-CNR. ^I -N = C = 0, ¹ Ii ■ ■■ Il ^Ί . 0 0 where R. for one of a low molecular weight diisocyanate radical derived and Rp for one of a high molecular weight Radical derived from diol, reacted with a diol prepolymer the formula: TTT TT TT TT TTT R ₉ - ¹ - -0-CNR ₁ -NCOR ₉ ¹ -OCNR _i ¹ - ^L -NCOR ₉ ¹¹¹ -OH ² ft ¹ Il ² Il ¹ II ^Z 0 0 0 0 - where R ^ for one of a low molecular weight diisocyanate II
derived radical, R _P for a, from a high molecular weight TTT Diol derived radical and R ₉ for a from a low- radical derived from molecular diol, where both R ₁ and R ₁ as well as R ₂ ¹ and R ₂ ¹¹ can have the same or different meanings and the molar ratio of the reactants is approximately 1: 1. 8) Method according to claim 7 »characterized in that R ₂ ¹ and R ₂ ¹¹ both stand for radicals of a poly-1,2-propanediol with a molecular weight of 600 to 2,000. 9) 'A method according to claim 7 or 8, characterized in that R ₁ ¹ and R ₁ ¹¹ are both radicals derived from methylene diphenyl diisocyanate. 5/1094 21-597 10) The method of claim 7 or 8, characterized in that R ₁ ¹ and R ₁ ¹¹ are both radicals derived from 1,5-diisocyanato naphthalene. 11) Method according to claim 7 Ms 10, characterized in that Rp is one of 1,4-butanediol; 1,6-hexanediol; Di-1,2-ethandiol; Tri-1,2-ethanediol or Tetra-1,2-ethanediol-derived radical represents. 12) Method according to claim 7 Ms 11, characterized in that the molar ratio of the diisocyanate prepolymer to the diol prepolymer is between 0.90: 1 and 0.99: 1. 13) Method according to claim 7 to 12, characterized in that the reaction temperature between 25 and 100 °, preferably between 30 and 75 ° C lies. 8647 209825/1094