DE1495035A1 - Process for the preparation of polymer solutions and compositions containing them - Google Patents

Description

Jng. * »By Air Worth -l. ^ Ust 1963

A M ELIO T E X, ItJCi

Mt Fifth Avenue, New York 17, Ν, Υ ..

Process for the production of polymer solutions and compilations containing them.

Priority: U.S. Patent Application No. 216 73? from 1 h. August I962

The invention relates to a new process for the preparation of polymer solutions of polyurethanes and new obtained by the process /

According to the previous technology, polyas will be redeemed van polyurethanes with extended fats obtained by one of the following:

1 »: -ian läsr.t in the block a prepolymer with originated! ^ en 'Ir ^ ocyanat ^ ruppen react with a Kottenaandehnun ^ s! flittel, for example a GIy kol, a Di η mi η or another at least ^ two active hydrogen atom of a leading connection. The polymer obtained in this way is dissolved in a suitable solvent.

2. It is allowed a prepolymer having terminal Isocyanathrappfiii react: riit a Kettenaitödehnun ^ sifilttGl xn ^f iei-onwart a LCsurit-r.mittels.

The first process is restricted to chain-forming agents with moderate reactivity, such as polyof, terodor, polyether glycols and aromatic diamines. ioar.fi reaction is exothermic and cannot easily be r? ir: ci. re at, ie rondo η oyntemori to be controlled.

The sewing methods L5 Pu erforrlert usually heat Ui '' hei'tigos Hühren with Scherwirkunfi what is often an unf: r - // "ir-ir; causes chteri degradation, do ο polymer.

- ² - H95035

The second method is applicable to chain extenders with. faster responsiveness than the ^ ed that used the first method. Meanwhile is This method is not effective with chain extenders tint very quick reactivity, such as aliphatic « Diamines.

In such .Systemen with rapid reaction there i'nst invariably formation of gelled structures.

These can often dissolve again through vigorous, shearing stirring and heating. However this one calls The latter technique also causes partial degradation of the polymer, which makes the second method extremely useful severely limited.

It is known that mechanically superior properties can only be obtained with chain extenders which prevent the formation of short segments in the Induce polymer chains, which in turn have increased degrees of interactions with other similar and neighboring ones -Segruenteri of the polymer present. The one in the second Process used chain extenders with massively fast! Reactivities are generally diamines cyclic type or with steric hindrance, e.g. the pipernine and methanediamine. The cyclic or lateral groups with steric hindrance tend to the desired intermolecular attraction forces inside of the molecules of the polymer to decrease. The chain riaupdehnungerni such as ethylenediamine, tetramethylenediamine are propylenediamine, no important groups, rich for Rupture of intermolecular forces have and what as a result Polymers of urethanes with superior mechaja niche properties would, but cannot be used to give good quality polymer solutions by these two methods, because of them very increased reaction rate with the isocyanates, resulting in gelled structures with all of the above Disadvantages results.

L '' BAD ORlQiNAi.

9 0 mm / α

It was now found that the chain expansion ■. medium with very fast reactivity like ethylenediamine , can be used in the process according to the invention while avoiding these disadvantages. the have new polymers obtained according to the invention KXL an increased resistance to heat, to light and against chlorine and other improved properties compared to the products as they are when using the known Process of chain expansion can be obtained ..

The inventive method consists in a To prepare a polymer solution of polyurethanes in two stages:

1.) Reaction of a prepolymer with terminal isoeyanate groups with an approximately stoichiometric amount a chain extender with moderate reactivity w & e piperazine in the presence of a solvent, a viscous and still reactive interpolymer solution to get, and

2,) implementation of

a) all or part of the interim solution,

b) a prepolymer with terminal isocyanate groups and

c). an approximately stoichiometric amount (based on the final prepolymer) of a chain extender with very quick reactivity like ethylenediamine in Presence of an additional solvent to obtain a final polymer solution, which in a known manner can be spun wet or dry to obtain an elastomer which improved has mechanical properties and an improved resistance to heat, to light and to chlorine. The polymer solution obtained can also be used to make other shaped articles, e.g., films, that have these same improved properties.

1 1 0 8 9 _8AD

In a preferred embodiment of the invention, the prepolymer is added to the chain extender in solution in each of these stages. In this variant, in the first stage, a prepolymer with terminal isocyanate groups is brought into reaction in a slightly smaller amount than the stoichiometric amount in a solvent with a! Chain extender with moderately fast reactivity, e.g. such a diaraine as hydrazine, piperazine, diamine piperazine, methylimino-bis-propylamine, 1 _s ^l f-diamine-2-methylpiperazine or their mixtures or a glycol such as ethylene glycol or a mixture of glycols, which results in a viscous and still reactive polymer solution . This solution; or a part of it is then diluted with the addition of new amounts of the solvent, for example in a ratio of 1 part by weight of solution to 1 part by weight of solvent, and then a diamond is added to the diluted solution very quickly Add reactivity such as ethylenediamine, and finally further prepolymer is added in a slightly smaller amount than the stoichiometric amount, based on the second chain extension medium. The solution formed in this way contains a sequential polymer with increased molecular weight and terminal diamine residues. The solution has good rheological properties and is stable. Using about one mole of the first chain extender for every one mole of the second chain extender appears to be the best ratio in most cases.

According to a second embodiment of the invention, the first chain _{extender can be added to a solution (o of} a prepolymer with terminal isocyanate groups o and in this case "after dilution of the solution of the polymer, as above, new amounts of prepolymer are added to the diluted solution, and the second chain expansion agent with rapid reactivity is added to this mixture
The second variant is that the amount of each added nucleus ionic medium is slightly below the stoilometry, based on the respective polymer. ORIGINAL

H9S035

This second embodiment is generally there Polyraergebilden similar to those as they are obtained using the first variant, however with the difference that the molecules with isocyanate groups end instead of diamine residues,

As already mentioned, the preferred variant is the first case, which consists in adding the prepolymer to the fat-expanding agent in solution during each stage and keeping these chain-expanding agents in a slight excess with respect to the stoicometric amount of the respective prepolymers. When viewed in relation to the chain extenders, the new polymers resulting from the invention are mainly sequential copolymers with high molecular weights, which can be represented by the following general formula:

B ₁ B ₀ OH HO OH HO

r - I ² J, ι ·. · '■ ι *

_w (_C-NA _r NCQ)

0 R 'H 0 B ₁ O ₂

(-CNA ₂ -NCNB ₂ -N) _x -D

Larin is Q a divalent organic radical, selected from the following radicals

O ₁ G ₂

H-R.-H and

where h is a monovalent radical selected from ■ / our s to ff and the following radicals:

OH
·. I.

C - ^ - A ₁ -TCO

CNA ₀ - [TJO

BATH

OHH O
C-Ii-A ₁ -NCR ₁ ^ and

OHH O

In the general formula, A 1 and A ₂ , each have a molecular weight of at least 1000 and each consist of the remainder (after the removal of the terminal isocyanate groups) from the reaction of an excess of a diisocyanate with a compound selected from the class of polyester glycols, the polyethylene glycols and their mixtures. Α * and Ap can be the same and different and represent the radicals of the prepolymers used in the first and second stage of chain expansion. The radicals D can be the same or different,

⁵ R * and Rp are organic divalent different radicals, contain no more active hydrogen atom than the hydrogen of a hydroxyl radical, and they represent the residues of the diamines used in each case in the first and second stage of the chain expansion. R_ is an organic divalent radical without an active Hydrogen atom and it represents the remainder of the glycol used in the first stage. Ri is an organic monovalent radical and it is the bast of an organic compound which only contains a secondary or primary amino group and no more reactive hydrogen atoms than the hydrogen of a hydroxyl radical. B ₁ . and üni ^G i ^{uncl 1} ^ o

co represent hydrogen or monovalent organic equivalents

cd or various radicals that are not reactive

^ more capable hydrogen atoms than the hydrogen of a hydroxyl radical and also contain no groups -α which can react with active hydrogen. x, y and. oo ζ are generally positive integers; however, in a given polymer blend, x, y, or ζ can be cheesecloth in certain molecules. If y = ' ^Ί , 1εί w = 0 and since y is a positive integer, then w = 1.

As mentioned later, a secondary or primary amine is sometimes added with one or both of the chain extenders. As a result, certain molecules described under the above formula can with the. Remnants of such an amine end. Rj ₊ is the remainder of such a compound.

The preferred sequent! Erteη result from the application of the invention using a diamine in the first stage of chain expansion Mixed polymers are also represented by the above formula but in this case Q means the following radical

G ₁ Gp

and each of the radicals D, which are the same or different is selected from hydrogen and the monovalent radicals containing Rk.

As already mentioned, a chain extender with moderately fast reactivity (Di ami η or glycol) is used in the first stage of the invention using prepolymers are determined. An effective coast extender must react with the prepolymer in solution to form a viscous, homogeneous, and especially gel-free solution. For example, it has been found that the diamines, which have a higher reactivity than piperazine, are generally unsuitable. Hydpzine alone is an exception, since in this diamine the first amino group reacts very quickly, but the second anufcno group of this iolecule reacts much more slowly, so that the overall effect is that of a diamine with the same reactivity as that of piperazine. . ''.'_, .-

909808/1089

A great variety of diamines with rapid reactivity can be used in the second stage of chain expansion. According to a preferred Embodiment one uses aliphatic diaraine, because they have excellent mechanical properties finally lend produced end product.

A wide variety of prepolymers can be used according to the invention. The preferred ■ compounds which contain active hydrogen and for The preparation of the prepolymer are suitable include the polyalkylene ether glycols, the polyester glycols and their connections, pie are best for execution The glycols suitable for the invention have a molecular weight between 500 and 5000, preferably between 1000 and 3OOO, and are not very soluble in water. The best Results will be with glycols or glycol mixtures obtained with a melting point below 50 ° ..

Examples of useful polyether glycols according to the invention are polypropylene ether glycol, polytetramethylene ether glycol, Polypropylene ethylene ether glycol, polyhexamethylene ether glycol and the polymonomethylene ether glycol. That Polyethylene ether glycol is often mixed with other polyether or polyester glycols, but rarely alone used because of its relatively high solubility in water.

According to the invention useful polyester glycols are generally prepared by adding suitable Amounts of low molecular weight glycols with dicarboxylic acids ^ Diacid chlorides and diesters react leaves.

co examples of themselves for the method according to the invention

^ suitable glycols are ethylene, propylene, tetramethy1,

® neopentyl and ayijilylene glycol. For the formation of the pqlye

oqfS sterglykole useful dicarboxylic acids are succinic acid '

_ ^ 3 adipic acid, suberic acid, sebacic acid, azelaic acid

^ and terephthalic acid. Mixed polyester glycols

«?? using mixtures of glycols and / or

Low molecular weight dicarboxylic acids can

ι. w. π ι 4. +. BAD ORIGINAL L'leichJaiii; .has been used. ^p

U95035

The diisocyanate used to make each prepolymer can be aromatic, aliphatic, or cycloaliphatic. The aromatic diisocyanates, ie the diisocyanates in which the isocyanate groups are attached directly to the aromatic nuclei, are preferably used because their reaction rates are generally increased «

Among the diisocyanates that are suitable for the invention are, inter alia: tolylene-2, h diisocyanate, p-phenylene diisocyanate, methylenebis (H-pheny II socyanate), 1,6-hexame thy lendii socyanate, and the 1 , ^ - cyclohexylene diisocyanate. Mixtures of diisocyanates can also be used.

When forming a prepolymer for use in the process according to the invention, the exact proportion of diisocyanate used in the reaction, for example with the polyether or polyester glycol, should be selected according to the particular composition of the reactants used and the properties which one wishes to impart to the end products . In most cases there should be 1.5 to 2.5 isocyanate groups for each active hydrogen. The particular reaction conditions for the formation of the prepolymer also depend on these same factors. A preferred prepolymer may be prepared by mixing a rfols a Polyprofjrlen-A.ther-'jlykols from r4olekulargewicht 2000 of one mole of a poly glycol of molecular weight 2000 and ¹ I, 2 mol Me thy i-to-C ^ (3diplnpentyl?) - pheny II socyanate) under i-.irwarraen the mixture to 90 ° and hold at this

Temperature for 3 hours.
co

^ 'I ι general is a more convenient type of use

o> the method according to the invention is mixing ai

co part. Solvent with the "prepolymer before the

_ ^ let te nau'fj stretching. This has the effect of viscosity

° u'iK prepolymers to reduce unü cias frills uad

*O. Contract to redeem. In general, the con- Tt should

cen t ration in the solvent In the mixture of prepolymer and LÖBuhgsiöibtel before the chain extension 1 ^; Ö-2h

In the first stage of the invention, as Jsniiei already mentioned, the prepolymer having terminal isocyanate 'groups then slowly to the mass of the chain extension agent-containing solvent may be added, or, also, the chain extension agent may be a mass of the

the prepolymer-containing solvent can be added. However, the addition of the prepolymer to the. chain stretching agents dissolved in the solvent are preferred.

For the first stage of the invention suitable chain extension agents are hydrazine, the monosubstituted hydrazines, the symmetrical disubstituted hydrazines, piperazine, the substituted piperazines, ais the liaminopiperazine, the substituted di ami nopi per azine, the cycloaliphati see diamines, the methyl! mi no-bisaliphatic diamines, the diamines with steric hindrance and their mixtures. The piperazine and the 1, ^ f-diamino-2-methy 1-piperazine are the preferred compounds for the chain elongation in the first stage. Other diamines and glycols with moderately fast reactivity, such as ethylene glycol, can also be used, but the The use of diamines is preferred for this stage of the chain expansion because they result in a polymer with better properties, for example with regard to suitability for dyeing} on the one hand, the use of a glycol essentially anhydrous requires. Conditions.

A suitable solvent for the polyurethane, such as dimethylformamide, dimethylacetamide or dimethyl sulfoxide, can be used and the method of aettenausdehnant, is otherwise cfas usual.

After the first stage of chain expansion has

ο '■. the resulting intermediate polymer solution, which still

O _{3 is} reactive, preferably a viscosity of

* / ^ ° ^to 7 °° poisen and a solids content between ■ § 20 and 25 ^. The usual solvent of the polymer, such as

ο Ar dimethylformamide, dta dimethyl acetamide or dimethyl sulfoxide ^ ₃ ρ is then preferred in proportions of about 3 to about 6

-1 äf wise approximately k Gewientstellen solvent per part by weight of such a plift

In a preferred variant, das'Di ami η with very rapid reactivity is added to this dilute polymer solution and then additional amounts of prepolymer are added. The mixture obtained in this way reacts in the usual way and a viscosity of approximately ¹ K) O to 700 poises and a solids content preferably between 20-25 $ is obtained.

In this second stage of chain expansion, any diamine can react very quickly such as ethylenediamine, propylenediamine or another aliphatic diamine .be used. Ethylenediamine is preferred.

Regarding the total amount of chain extender η used, the first mean represents about 10 kO Mo, -% thereof and about 20 MoI ^ can be considered the best value. '

This polymer solution can then be spun wet or dry using conventional methods be improved to give an elastomeric thread Resistance to heat and a higher resistance to light and chlorine, it can also be used to make other shaped articles such as films, castings, and the like.

Various prepolymers with terminal isocyanate groups can be used in the two stages of chain expansion and a combination of chain expansion agents and also a combination of prepolymers can be used in one and / or the other; other of these stages to be needed.

It is not necessary for the additional solvent required in the second stage of chain extension to be added after the first stage. Ee can already be present in excess in the first stage. In this case, the total content of solids present after the first stage of chain expansion is "$ generally k ~ ¹ )% and the viscosity * + Ο-6θ poisen

.9.09008 / 1089- ^BAD

fr

A connection for the chain connection containing only one secondary or primary amino group can be used in a known manner in order to regulate the quality of the polymer solution. Such a compound can be added with the chain extender. This addition can take place in one and / or another stage of the chain expansion. However, it cannot be present in an amount exceeding δ- "JO Kol ~ $ of the total of the chain-extending agents used. In most cases the best concentration of such a compound should be below 5 mol% . Examples of useful compounds are dimethy I ami η, diethylamine, diethanoi- · ■ amine, N, N-dimethy1-1,3-propanediamine.

Dyes, pigments, antioxidants, stabilizers, and other additives can be used in the polymer of polyurethane can be incorporated by making them in any stage prior to the formation of the molded Adding items. They are preferably added to the solution of the polymer after the second stage of chain expansion to. If such compounds are to be added before the second stage, they must be im be substantially inert to the isocyanate and active hydrogen.

The following examples explain the invention even further, without any particular indication, they are all given Quantities expressed by weight or in percent by weight

example 1 A. prepolymer.

800 g poly (propylene adipate) glycol with terminal hydroxyl groups and a molecular weight of 2000 are mixed with * + 00 g polypropylene glycol of molecular weight 2000 and 305 g methylene n-bis (par aphenyl + isocyanate) . The mixture is then heated to 100 for 2 hours with constant stirring - a prepolymer to form with terminal isocyanate groups,

BAD ORIQfNAL

909808/1089

H95035

ά. First stage of the chain expansion.

The above-mentioned prepolymer is diluted with + 00 g of Diine thy I-formamide. A portion of this diluted prepolymer is then slowly stirred with a mixture of 1000 g of diethyl chloride, 0.2 g of piperazine and 0.0 ^l g Diethanoramine mixed to maintain a viscosity of approximately 600 poises.

C. Second stage of chain expansion.

HOÖ g of the polymer solution, the first stage described above, are mixed with 1350 g of Diine thy 1 for wanid, 6.5 g of ethylenediamine and 0.1 g of diethanolamine. Slowly with vigorous stirring, a portion of the diluted To this mixture is then ". Prepolymers from example to grhalten a viscosity of 800 poises added * + 0 g of a dispersion of titanium dioxide of 33 / έ in Dinethyl - /" ormamid are finally added ( 2.5 / ^; - 'J-η üesamtfeststoifen) and the s. Viscous polymer solution is v / κ in the V a κ u ffi e nt t.

D. Education, from threads.

The pigmented polymer solution obtained in the second stage under C. is filtered and at constant speed by means of a precision gear wheel through a spinneret with several holes of 0.12 mm Lurchinessei ·, immersed in an aqueous .Jpianbad with a ω Spun content of 2 ^% of dimethyl formamide. The semi-plastic filaments, formed when the polymer solution enters the bath, become grounded. united in a single multiple thread, which sförclm-bana and

to '. r. is led to a Upul device. Of the

co ftific continuous so formed ν ie 1-fold fade η ver

_ο colors:; i not noticeably ^ ise if he during

^ f-inor-hour 200 tel lon per million of active aqueous

- »■ ^f .i; loT · at '-Ο ausosot' /, t becomes, and has the following

Q ₀ [/ ry ^ ik-aische Eigeru: cJiaften: '/, ähigknit 0, M; _L / öen. ₉

l'ii, tnn _t G ¹ JQf ,, Reaktio! -irjvf> rtnögon at 200χ. Elongation 0.16 g / (iod., Toughness requirement of 10% after heating for 30 minutes aal '1 ^ 0 °.

Example 2:

A. Second Ke t th a usdehntingsstufe,

A portion of the diluted prepolymer, obtained according to 1 B., slowly becomes a vigorously stirred mixture of 300 g of a polymer solution originating from the first stage of 1 B., 1000 g of dimethylformamide. 0.3 g of diethanolamine and 7.0 g of 1,2-diamine propane were added. The addition is interrupted after a viscosity of 5ΟΟ-6ΟΟ poises has been reached, and 3> h g of a dispersion of 33% titanium dioxide in dimethylformamide is then added, which then represents a total of about 2.5% of solids,

B. Formation of threads.

The threads obtained, as described in 1 D. above, show only a slight discoloration after they have been exposed to an active aqueous chlorine of 200 parts per oil ion for one hour at 60 ° and are characterized by the following properties: Toughness 0, 28 g / d, elongation 700/5, reaction force at 200 / -. elongation 0.9 g / d, and change in the resistance by% after heating for 30 minutes on I5O ^0th.

Example 3

A. First stage of chain expansion.

200 g of a prepolymer, prepared as in 1 A. above, are thoroughly mixed with 6 ^ 0 g of dimethylformamide. Sian sets to this mixture, a solution of 10 g N, W ^{I-diamino-2-methylpiperazine} and 0.2 g of diethanolamine in 150 g dimethyl ®ã added <o formamide, until a viscosity of ^L h00 Poisen with vigorous stirring

co ^ is reached,

B. Second "stage of chain expansion"

2 ^ 3OO g of the polymer solution of the first stage of the chain

o tenansdehnung with 800 g of dimethylformamide and

cd 250 g of the same prepolymer used under 3 A.

mixed. To this mixture, add a solution of 7 g of ethylenediamine and 0.5 g of diethanolamine in? Nn <* iw »- ^ ·· ^ - · - · ■

until a viscosity of 600 Pöisen is reached, and then mixed with this viscous solution 35 S of a 33 $ -ϊSen. Dispersion of titanium dioxide in dimethyl formamide, making about $ 2.5 total solids.

C. Formation of threads,

The threads obtained according to 1. D. discolor look in quite a noticeable way when you look at them exposed to active chlorine as under 1 D. The mechanical properties are as follows; toughness 0.6 g / den., Elongation $ 550, reaction force at $ 200 Elongation 0.18 g / den., Loss of toughness 20 $ after Heat up to 150 * for 30 minutes

Examples

A prepolymer is prepared as under A of Example 1 with the modification that the molecular ^{ratio is 1} , the ratio between polyether glycol with molecular weight 2000 and polyester glycol with molecular weight 2000 is 2: 1 instead of 1.2.

A number of thread patterns are made using different diamines for the first stage the chain extension and of ethylenediamine for the second stage of the chain extension. The molecular proportions and the mode of operation are the same as those selected in example 1. Each sample contains approximately $ 2.5 wt. (See Table 1).

Example 11;

A portion of the same prepolymer also has one

Chain extension with a molecular mixture of 19; Xthylenediamine and diethanolamine in sufficient dimethyl- ' · Formed a $ 20 polymer solution

To obtain solids. σ>

The solution formed was extremely little

homogeneous and contained solid gel particles in a weak '> *.

viscous liquid phase »This suspension was on. q

© AD ORtÖfNÄL 90 ° warmed and. For 2 hours unloi · vigorous stirring ⁰ ^

üarauf- *. hold for a reasonably honio & e ne solution - ^ p

with a viscosity of 90 Pdisen. This solution was spun to obtain a thread pattern as in Example 1, which also contained about 2.5'Jo 'titanium dioxide by weight.

The properties of the threads obtained are shown in Table 1 below, in which mean / chain extender agents used in the first stage (the quoted ratios are molar), T = toughness expressed in g / den., A = elongation in % C = action, if 200 parts per million exposed to chlorine at 60 for 30 minutes, V = change in % of the toughness by heating to 150 ⁰ for 30 minutes.

E. Tabel 1 A. C. V example Piperazine T 650% slightly yellow -10 ■ h Methanediamine 0 * 51 720% no effect -20 5 / N, N ^I -diaminopiperazine 0.35 no effect 0 6th N, N »-Di anni> no-2-me thy 1-
piperazine 0.62 620 '^. eeh'r easy
yellow 0 7th ty1 methyliminobis
propylamine / NN ¹ -
diamino-2-methyl-
piperazine 0.55 68O ^ no effect + 5 8th 9/1 Ifethyliminobis-
propylaml n / N, N'-
diamino-2-methyl-
. piperazine 0.60 $ 700; slightly yellow - 5th 9 · h / \ N.N'-diaminopipera-
zin / methyliminobis-
propylamine o, 55 550% no effect + 10 10 Expansion of the chains o, 50 8oo # yellow - 60 11 0.25

σ co co ο oo

in a single stage
with ethylenediamine

The comparison of the properties of the samples die.ser Examples 1-10, produced according to the invention ' , Process with those of Example 11, the chain extension of which according to the second of the known and initially mentioned \ was obtained, shows'die Superiority of the properties of the polymeric products obtained using the invention. BADORi (SfNAl.

Example e 12-15

A series of thread patterns is made starting from various lorpolyoieren. The chain expansion agent of the first stage is in every pall methyl 1-iminobispropylaiain and the chain expansion agent of the second stage is ethylenediaini η. The operation and molar ratios are similar to that in that. Example 1 used _? and each sample contains approximately 2.5 wt. Titanium dioxide.

The properties of the threads are shown in the following table % , where: G = glycols used, M = molar excess in% of methylene bis (phenyl isocyanate), T, Ä, C and V have the same meaning as in Table 1, PM = molecular weight.

Table 2 example

2/1 poly (propylene adipate) -glycol PM 2000 / polypropylene ether glycol PM 2000 '

1/1 poly (propylene adipate) glycol PM 1000 / polypropylene ether glycol PM 1000

Poly (propylene adipate) glycol PM 2000

100

Poly (neopentyl adipate) glycol PM 2000 / polypropylene ether glycol PM 1000 '

T Ä

0, ^ 5 600 slightly yellow -10

0.52 MJO slightly yellow 0 0.63 580 no effect 0

550 no effect 0

9 09 8 0

Claims (10)

-is- 1435035 · Claims. 1. A process for the preparation of a polymer solution of polyurethane, characterized by the reaction of a torpolymer with terminal isocyanate groups with a chain extender of moderately fast reactivity from the group of diamines and glycols in the presence of a solvent _{t to} give a viscous and still reactive polymer intermediate solution, and by reacting this polymer intermediate solution with a prepolymer with terminal isocyanate groups and a diamine with very rapid reactivity in the presence of an additional amount of solvent. 2. The method according to claim 1, characterized in that the chain extender is a diamine from the Group hydrazine, monosubstituted hydrazines, symmetrical dl-substituted hydrazines, substituted or not substituted diaminopiperazines, cycloaliphatic diamines, methyllmino-bls-aliphatic amines and steric cycloaliphatic diamines and that the diamine is an aliphatic diamine, 3. The method according to claim 1, characterized in that the chain extension agent is piperazine and that the diamine is ethylene diamine. 4. A method according to _n claim 1., characterized in that the chain-extending agent of 1,4-diamino-2-methylplperazin and the diamine is ethylene diamine. 5. The method according to claim ¹ !, Characterized in that that about 4 moles of diamine to 1 mole of chain extender be used. 6. The method according to claim 1, characterized in that that the solids content of the intermediate polymer solution bia increases to about $ 20-25, and the additional The amount of solvent is approximately 3-6 5 parts, and preferably 4 parts by weight, per part of polymer intermediate solution. 909808/1089 7. Intermediate solution of polyurethane, prepared according to one of claims 1-6 8. High molecular weight polymer of polyurethane the formula B ₁ B ₂ OH HO OHHO 0 HH 0 B ₁ B ₀
Il I I * I ^Ί I ^ -GNA ₀ -NCNR ₀ -N) -D where mean * Q is an organic divalent radical selected from the following radicals
GG ₂ -N and NH ₁ -I the radicals D each a monovalent, equal or different radical selected from hydrogen and the following radicals If ■ CNA ₁ -NCO Ö H Il I
-N-Ao-NCO OH HQ . «■ ι ι π ■ CNA ₁ -NCR ₁₊
CNA ₂ -NCR ₁₊ A ₁ and A ₂ in the general formula are the same or different, ^ eaes has a molecular weight of approximately 1000 and each consists of the remainder, after removal of the terminal isocyanate groups, the reaction of an excess of a diisocyanate with a compound selected from polyester glycols , Polyether glycols and their mixtures,. 90 9 80 871089 .2O Βλ and Bp u.na G * and G ₂ are hydrogen atoms or organic monovalent, identical or different radicals, which contain no more active hydrogen atoms than the hydrogen of a hydroxyl radical, and are free of '_; Groups that can react with active water *, R. and Ro are organic divalent different radicals that do not have any more reactive hydrogen atoms than contain the hydrogen in the hydroxyl radical, R, is a divalent organic radical with no active one Hydrogen atom, Rk is an organic monovalent radical which is the Is residue of an organic "compound, κ the .only contains a secondary or primary amino group and which contains more unreactive hydrogen atoms than the hydrogen contains a hydroxyl radical, the x, y, i? are generally positive integers, / but can also be equal to O, and if y = O, then w = O, while if y is a positive integer then is -t w = 1. 9. Polymer according to claim 8, characterized in that in the general formula Q is the radical ? 1 h NR ₁ -N / and the radicals __ ·. ■ ■ D each is a / selected from hydrogen and monovalent R ^ enthalve? ScSldenIs are ^tendency radicals. ' 10. Threads obtained starting from a polymer according to Claim 8 or 9. 11. Polymer according to claim 9, characterized in that R the remainder of the piperazine after elimination of the two terminal active hydrogen atoms, Rp an iithyl radical, Βλ and Bp mean hydrogen. 12. Polymer according to claim 9, characterized in that Q & r radical of 1, ty-diamino-2-methyl-piperazine after 'Heaei-ti generation of the two terminal active hydrogen atoms, Rp' is an ethyl radical, B ₁ and B _{2 are} hydrogen . 9 0 9 8 0 8/1089 13. Polymer according spoke 12, characterized in that it is approximately, k mol Ä. thy! contains radical per mole of remainder of 1, ^I f-diamino-2-methylpiperazine. 1 ⁵ +. Threads obtained starting from a polymer according to any one of claims II-I3, ^BATH ORIGINAL 909 808/108 9