DE1570896A1 - Process for the production of linear polymers - Google Patents

Description

DR. E. WIEGAND DIPL-ING. W. NIEMANN DR. M. KÖHLER DIPUlNG. C. GERNHARDT

TELEPHONE, 555476 8000 MÖNCHEN 15, TELEGRAMS. PATENT WALNUT LITRASSE 1β

July 21, 1969 W, 11 926/64 13 / Ko / Loe P 15 70 896.0

Monsanto Company
St * Louis * Missouri (VS-fc.A.)

Method of making linear Polymers

The invention relates to the production of linear, segmented or parcellular polymers which are suitable for the formation of elastic threads. In particular, the invention relates to elastic threads "which are formed from polymers having alternating" soft "and" hard "segments in their internal structure, the" hard "segments being derived from 1 _# 3-benzene-bis (methylamine).

Polymers of this general type have recently become a widespread application in the production of elastin see fibers or threads found. polymers »

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welohθ structurally duroh the presence of a low-ohmic or "soft" polymeric portion or Segments which are identified by a urethane bond with a high melting or "hard" section or segment result in an elastic one Behavior in the case of fibers made from these polymeric materials

Obgleloh elastic fibers or threads, which are divided into sections or from the previously known parcellular polymers of the type indicated above are obtained, many excellent properties have and have many qualities that speak for them, there has been a continuing technical need or a continuing need to improve certain important properties which are still deficient. Such an inadequacy or deficiency is insufficient elastic recovery, when the fibers or threads undergo deformation (stress) duroh a stretched state over long periods of time be subjected. Other disadvantages result from the unusual sensitivity to degradation and degradation * coloration when exposed to active chlorine, which is used in most technical lead-based melters, or

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to the oxides of nitrogen and other combustion gases, which occur with gas dryers

Therefore, it is an object of the invention to provide of synthetic, elastic fibers or threads with a satisfactory dimensional recovery, after being in a stretched state for long Periods of time had been held

Another purpose of the invention is to provide of elastic fibers or threads made of segmented or linear polymers subdivided into sections with improved resistance to degradation by chlorine containing bleach

Yet another purpose of the invention is to provide of elastic fibers or filaments, which on exposure to the oxides of nitrogen and other exhaust gases themselves do not discolor and do not suffer degradation

Other purposes of the invention are from the following Description visible

The purposes of the invention are achieved through the creation or manufacture of an elastic fiber or thread from a section divided into sections or parzellarisohen polymer achieved, which from

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a plurality of intralinear structural units of the general formula

HO OH HOH HOH

IM Hl f! Tt tfft

- {fi-lJ-C-O-E-O-C-lHj

consists, in which ζ and y integers above Hull, B a long-chain, linear, polymeric best with eioh repeating ester or ether bonds and one Represent Phenylenreet or alkylenediphenyl radical

As indicated above, the polymers which form the elastic fibers or threads according to the invention are composed of "white sections ¹ * and" hard

"Assembled in an alternating arrangement in the polymer chain. The" sections soft portion "consists of the Best upon removal of the terminal OH groups by a endigenden with hydroxyl polyesters or polyethers having a melting point below about 6O ⁰ C and a molecular weight in Bereioh of about 600 to $ 000th this section or this segment is through a urethane to a second or "hard segment" attached, which at least one eioh repeating unit of a Harnstoffpolymerisats having a melting point above about 200 ⁰ C at a molecular weight of above about 10000 showing · the newly -

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like use of l, 3-Benzörbis- (methylamine) as a reactant for the formation of the second or "hard section" is essentially the improvement of the Properties of the elastic fibers or threads formed from the polymers according to the invention brought about

These polymeric materials can be prepared in accordance with known, generally practiced procedures for the production of polymers, the parcellular or In particular, a hydroxyl-terminated polyester is first used or polyether reacted with the aromatic diisooyanate to form the "prepolymer" or "soft portion" terminated with isocyanate Diisooyanate is used in a molar excess over the polyhydrooxyl compound used, i.e. in a molar ratio of 2.5 * 1 to 1.5 * 1 »with a ratio of 2: 1 Preference is given to this isooyanate-terminated or "capped" polymer Intermediate is then formed with the novel, chain-extending compound, 1,5-benzene bis (methylamine) that part of the resulting polymer reacted which has urea bonds and that represents "hard segment" or the "hard portion".

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The reactions used to form these polymers are carried out at moderate or medium temperatures. The reaction of the diisocyanate with the polyhydroxy I compound can be carried out by mixing the anhydrous or dry reagents at steam bath temperatures. However, when using known catalysts, for example tin (II) octoate with a polyester as a reactant, this ^{"capping" reaction 11} can be carried out at room temperature , 3-Benzene bis (methylamine) is generally carried out at temperatures close to room temperature and does not require a catalyst.

In the reaction of the end with isocyanate groups

Pre-polymer with 1,3-benzene bis (methylamine) can be different Polymerization processes are used, for example block, interfacial or solution polymerization procedures However, the preferred method is solution polymerization. The solvent used for this is relatively inert towards the reactants. Suitable solvents include, for example, Ν, Ν-dimethylfirmamide, Ν, Ν-dimethylacetamide, tetrahydrofuran and dimethyl sulfoxide, dimethyl formamide and Dimethylacetamide in particular

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preferred as these are solvents for spinning suitable solutions of fibers or threads immediately or made directly to graze.

As indicated above ₉ , the "soft portions" of the elastomer are derived from a polymerizate having terminal hydroxyl groups, which is derived from the formula below

HO-E-OH

can be shown in which E is a long-chain polymeric radical means in which v / iederhölende. Ester or ether bonds are present, i.e. a polyester or polyether radical. The main features are that the polyester or polyether is bifunctional, has a melting point below about 60 C and a molecular weight in the range of about 600 to 5000 possesses, with 750 to 3500 being preferred

The linear ones used in practicing the method according to the invention Polyesters of low molecular weight can by reaction γόη acids, esters or acid halides with a molar excess of glycols can be produced

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Suitable glycols are the polymethylene glycols, e.g., ethylene, propylene, butylene, becamethylene, substituted Polymethylene glycols, for example 2,2-dimethyl-1,3-propanediol and the cycloaliphatic glycols, for example cyclohexanediol. These glycols can with the appropriate molar amount or in the appropriate molar ratio with aliphatic, oycloaliphatic or aromatic acids or their ester-forming derivatives for the production of polymers are reacted with low molecular weight and terminal or terminating hydroxyl groups. Suitable acids for the preparation of the polyesters are succinic acid, adipic acid, suberic acid, and sebacic acid Isophthalic acid. The alkyl and halogen substituted derivatives of these acids can also be used reach.

For use in practicing the process. according to the invention also those endigende on Hydoxyl polyesters are considered, which are obtained by reaction of a lactone having at least 6 carbon atoms in the inputs with a AlkylengJLykol v / ground · Suitable laotane ^ caprolactone, c (zeta) -önantholacton, ^ -Caprylolaoton and their methylfe-substituted derivatives. Examples of applicable glycols are

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JLttaylene glycol, propylene glycol, b & tylene glycol.

The formation sur d @ r ^B w calibrate Abschnitt® "Sea Elaste =" mers used polyester do not need to homopoly = marls ate limited * to seirip as copolymers is the same way. "Usable s ± _o nä Satsäofelieh werä®n mixed polymer = © * often preferred _? ä & they a gestagene gaBg to the necessary crystallization in the la ab = ".schnitte- subdivided or segmeatiert ^ a,! EnöpoXymeri" = sat aigeseao ϊώ 5® ^ ® ^ffi ^ aIl is in polyester so it. "below 60 ⁰ G

tsieteigan

Alternatively kö-ane-n gu ö @ n © star di @ .hydrosylb @ end @ ten

as stated above ₉ o Btlspiel® for applicable © _ΰ biftacktion you poly = »(alkylenö2syä)« glycols _p like poly «(äthylea«

(oota3aethylexi »oxide)« »glycol ₉

and poly (d @ oamethylenosyd) glycol

can the Polyäthsr a mixed polymer consist®

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Original

Diisocyanates the aromatic diisocyanate of phenylene, Bipbenylen- and Alkylendiphenylarten may be used on · Suitable diisocyanates sL nd as m-phenylene, p-phenylene diisocyanate, toluene diisocyanate, 4 '4 ^I -Biphenylendiisocyanat, 4, .4 ^I -Diphenyldime- · thylmethandiisooyanat , ρ, ρ'-Ieopropylidenediphenyl diisocyanate and ρ, ρ'-methylenediphenyl diisocyanate. The preferred diisocyanate is p ^ p'-ethylene diphenyl diisocyanate.

By the reaction between the polyhydroxy compound and the Diisooyanat the urethane bond between the "soft" and "hard" sections or segments of the elastomeric polymers formed according to the invention · As indicated above, the "hard ¹ · section by reacting the isocyanate-PoIyhydroxyverbindung is with The preferred length of the "hard section" depends on the melting point of the section and, to some extent, on the lecular weight of the "soft section" The "hard section" can be regulated by adding additional amounts of diisocyanate together with 1,3-benzene bis (methylamine) in the chain-extending reaction However

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⁸ ^ D ORIGINAL

40 square meters _o '** $ Bobo fur

a ₀ "it is © about 60 to 9!

in area

tis ^ C §s

eggs

la the

1 _; Θ free

4ο®- © der äaräber aiafw @ Is © Q

.äas Mol ^ kulargswleät should

w®lcls © m O ^ the yislcosity

the viscosity eiten wä "b © I represents the same temperature" and the coase feratioa Ia |

In 100 ml Xsösuag

si ISsmag

BATH ORIGINAL

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The polymers prepared according to the invention can be carried out using dry or wet spinning procedures Threads produced. When using one of these working methods, the usual conditions apply with the modification that the spinning speeds are usually lower than those normally used for Spinning other textile threads are applied. Wet spinning becomes H, H-dimethylformamide and If, N-dimethylacetamide preferred as solvents and these solutions are usually extruded into a hot water bath or sprayed out

Usually there is no stretching or drawing operation needed to develop satisfactory elastic properties in the threads according to the invention. However the overall properties of the threads are often improved by a stretching work step which is increased Orientation and Xrystallinity brings about in the final structure.

The invention is explained in more detail below with the aid of examples. The physical properties reported were on the Instron Paser- Padenpriifvorrichtung or (Instron fiber testing device) measured · "Pestigkeit" is a measure of the tensile strength of parsers are Päden or, expressed in g per the (g / den) .- "elongation ¹ * is the percentage

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tual © Y @ 2? läs, gerumg der Pases' odes · des Fadens-am. Break = .. point «. ⁰⁹ 25sijausgs © 2 ^s ljol-aag ⁱ¹⁸ od © ^ ^ elastic recovery ™ lot the percentage Hückketa gu the Aafaags length I & ner = Üal "b © lae? Minute aaejadem äe% ZMg or the tension

eiues i ^ ob © fs'elgelasseQ © d © 3? abegetenvioxäea is _D - on % Q% b @ l the Ausaaß i? oa 1005 ^ 3® ^ isat

© iner Miaut ©

Example 1 '■.

500 g of Cö _D 33 mol) © Ιώθβ aus'.Adipic acid and a ¹ mixture of clay 8 mol Äthylöuglykol and 2 mol l _ö .2 "= PropyleQ" =. liorgestalltaö polyester - (molecular weight 1514p

74 _S 3) vnirden ^{: dissolved} in 220 ml simetaylformamide ο 172 g CO2 688 mol) p _s p ⁹ -Mö-bhylaiiaiphenyläiisocjana "(; were 'given and .the temperature, the solution set to 23 · * · 24 ° Ό' 6. 5.BiI a l -. ^ Gen solution toa

optoate in the heptane was added and the reaction I lay under nitrogen for 2 hours

temperature TOU 25 ° 'G stirred. The ergefeeade isocyanate-modified polyester represents the 'HTorpolymerisat',

4 "75 S l">". Benzolbis- * (methylaiain) were then dissolved in 450 ml of dimethylformamide; the additions of 100 g of the

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The "prepolymer solution" obtained above for the diamond solution resulted in a polymer solution with a Brookfield viscosity of 15,000 contipoice. The solution containing the polymer was then naßgooponnon in a Limethylformaiaid-water bath at 4O ⁰ C, whereby elastic fibers or threads cit the following tone 1 strength 0.703 g / den, elongation 86.35 / ^ »were obtained,

BaispLei 2

274 g a 65 ~> li, en "öcarr ^ of ^ olytttr y 'sines iloiekiilar aov.I h: ·· -:} of 2 * 500 v, iru · -. · :; ir. IOO nil .Di-: a-3 ti · / lj? oi. ^l fjauj, ii;, - ol -..-,,.: ^, «, ρ * -! =, · I,!, - / J. ^ jU ^ hoaj 1-J lioo cyaiiat becameü vigoj., I,, utui aie T e up tu u tu,. · U ■. / 23 '"' ^ eitr; yi * o _{ ; öLi ;, lia itoak; · .. ion.Vi.isoimüfi vu; o «fit r OUcknfcof during 45 lüitir.tcii £ Ϊ -'Uh et and da j bi ^ .i rr. ⁱ ; obeude "Vorpol / morlsab" was be 'making the ^ following

5.4 g of 1,5-benzene bis (methylamine) were in 400 ml M.methylformamide dissolved · The addition of 145 g of the above "prepolymer solution" described resulted in a © Solution containing polymer with a Brookfield

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TisJfeosity of 12 QOO Centipoise «Mes ©

where © lastlachβ fibers or threads with

ti. strength © 5 ^ 4 g / äeng

weight 2850rHyäroxyl & a & l 39s? 4) in 375 "®1 Mmetäylfosmamid g @ 15st _o ■ 100 g (D ₀

the femperatiär. to 23 ^ct 24 ^Θ 0 © iageregelt «, 3 ®3. © Ines

ZiBn (lI) «- ootoat la Heptaa warden as Catalyst discontinued 'Di® Beaktioa was' during a half an hour with stirring under nitrogen "at 23 ° - 24 ° C let progress »

That indicated in the above. Orphan obtained? Orpolymerisat was treated with l _t ~ 3 Ben2ol "bis- (methylamine) in the following ^V,! Else extended" 4 "05 g ij ^ -BenzolMs- (methylamine)? / Orden in 420 ml of dimethylformamide» dissolved Then 141 g the above-Vorpolymerisatlösung the DiaminlSeung sngegeben _s whereby a polymer-containing solution was obtained having a viscosity of 20, 000 Öentipoise. This solution mirde

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BATH ORIGINAL

in a dimethylformamide and water in the ratio of . 25 * 75 containing bath wet-spun, with an elastic thread or fiber material with the following ■ Properties obtained were firmness 0.771 g / den; Stretch 656ft stretch recovery 88.6%

Example 4

310 g of a polyester with a molecular weight of about 2000 (Hydroxylzabl 54.6), which was derived from a mixture of 80 parts by weight of caprolactone and 20 parts by weight of methylcaprolactone, were dissolved in 150 ml of dimethylformamide. 82 g of p, p'-methylenediphenyl diisocyanate were added and the temperature was adjusted to 25 ° 0. 5 ml of a 1J & Lgen solution of stannous octoate in heptane were added and the reaction mixture was stirred for 1 hour under nitrogen. This prepolymer solution was used to prepare the following polymer solution. 5 »4 g of 3-benzene bis (methylamine) were dissolved in J> 60 ml of dimethylformamide. Then 122.5 g of the prepolymer solution were added to the diamine solution, a polymer-containing solution having a viscosity of 10,500 centipoise being obtained . This polymer solution was in a dimethyl

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8A OHlGtNAL

formamide-water bath at 4O ⁰ C wet spun, said fibers or filaments having the following properties were obtained »strength 0.64 g / d; Elongation $ 698; Stretch recovery 92

As indicated above, according to the ~ The elastic fibers or filaments made of the invention provide exceptional dimensional recovery after being maintained in the stretched state for extended periods of time. These Property is an end use in apparel applications particularly advantageous, for example in medical Surgical stockings, with the wearer's body holding the garment in a stretched position lasts for long periods of time during use.

The superior ability of the fiber * or thread material according to the invention for elastic recovery after a Stretching for long periods of time was achieved by a Comparison with an elastic thread or fiber material shown, which from polymers replacing the 1,3-benzene bis (methylamine) according to the invention by known amine chain extenders, for example ethylenediamine, ootamethylenediamine or 1,4-benzene bis (methylamine) was produced. That is, those used in the comparison

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elastic pads were derived from polymers or prepared according to the procedure described in Example 1 with that given above Modification regarding the substitution of 1,3-benzene bis (methylamine) have been made

The test method used to determine this property was as follows Testing yarn samples were clamped onto a support frame or frame with one end of the yarn clipped or clamped to a movable rod was. The samples were then run simultaneously at a rate of $ 500 per minute to four times their length original length stretched. The test samples were then left in the stretched state for a period of 24 hours and then released or relaxed by adding they were cut off at the lower bracket. After a relaxation period of 10 minutes, the lengths were of the samples measured. This test is known as the "deformation encoder" deformation test ("set" test) and the test results are referred to as "deformation" ("set"). That is, the "deformation" ("set") is the percentage deviation from the original length after the stretching or stretching period and the relaxation period from the stretched state

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Percentages that represent more satisfactory results

The bottom results listed in the table below were obtained when testing fibers or threads which were obtained from the polymers corresponding to the polymer described in Example 1 with the only modification that the "hard abscisine%" lsa ^{w was used} by means of chain extension Eeaktionstdlnehmer received was varied · The with "A" designated test sample ordered from filaments or threads, which had been produced exactly according to the procedure described in Example 1 ·

Versuohs- used elongation deformation test medium . ■ __ worth

F.
A. 1,3-benzene bis (methylamine) 37 B. l, 4 ~ benzene bis (methylamine) 60 C. Ethylenediamine 60 D. Ootamethylenediamine

SLe conferred remarkable superiority over the known diamonds by 1,3-benzene bis (methylamine) is from the test results listed above clearly visible · The surprising award of 1.3- » Benzene bis (methylamine) in this ability or property is particularly also through a comparison with the

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isomeric 1,4-Benzolbis »- (methylamine) displayed, which despite its close chemical relationship actually does not provide any particularly good property in" deformation "or" deformation ^{11 "}

The superior resistance of the elastic filaments or threads according to the invention to discoloration by Chlorine bleach was presented by a preliminary comparison with fibers or threads made of a polymer, since it differs from the polymers according to the invention differ only in that the known chain extender, Hydrazine, instead of!, ^ - Benzolbis-Cmethylamine) according to of the invention was used. A similar comparison was made in terms of resilience Discoloration from combustion gases, i.e. atmospheric Carbon oxides, executed

To determine the effect of chlorine bleach on the discoloration, a test method was used in which the test samples made of the elastic fiber or fiber material were treated for 20 hours at a temperature of 49 ⁰ C in a solution with 1 1 of available or obtainable chlorine from sodium hypochlorite. The discoloration was then assessed using control samples and an Ifcrasell color chart as reference points

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(■ guides) 'assessed visually for relative accuracy.

The standard AATCC method 23-1957, which is given under the title "The Colorfastness of Textiles to Atmospheric Oxides of Eitrogen", was used to determine the part stability with respect to exhaust gases. In this test method, Paser or thread test samples are placed on hooks and then ^{rotated in an oven at about 60 0} C (14O ⁰ I ¹ ), which contained exhaust gases from the combustion of natural gas. (Natural gas), until a standard control sample of colored Acetate fabric exhibited a labeled change in saturation. As with the chlorine bleach test, discoloration was determined visually using control samples and Uunseil color cards with numerical ratings.

The test results obtained are summarized in the table below. The ^{test sample labeled "E n} consists of fibers or threads which were produced in accordance with the procedure described in Example. The test sample" G "was obtained from a polymer which was prepared in a corresponding manner with the modification that hydrazine was used as the chain extender in the formation of the polymeric "hard portion ¹ *" instead of 1,5-benzene bis (methylaiaine) .

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BATH

Test used extension exhaust gas chlorine sample mean test bleach value mean S 1,3-benzene bis (iaetbylamine) light yellow 2 ⁺ G hydrazine dark yellow 4 ⁺

+1 »excellent

5 «not, acceptable or unusable

As can be clearly seen, the elastic fibers and threads according to the invention show their greatest usefulness in the manufacture of fabrics and garments in which an elastic quality is required. They can be used for these end uses as uncovered or uncovered threads, or they can be covered or covered, such as rubber in such areas of application They can also be colored by common dyes and have good resistance to white (perspiration) or fats (lubricating greases) and many other common chemicals .

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Claims (1)

1. Process - for the manufacture of linear sow with iaer essentially linear ^ In divided! Structural "part © in." saw! from inträlinsar © »StsnÄturelnhelten d © £» general HO
ι η ... (R-N-C-O-E " W B HO H D 53 Q HIGH Ο 91 0 -CH, consists, in which χ and y gasis® numbers above MuIl ₀ E a long-chain linear polymeric radical with a content of repeating bonds from ester and ether groups and R an aromatic RsSt ₉ consisting of a phenylene, biphenylene "or Alkylendiphenylrest ₉ · len _t depicting characterized as & a compound of general structure OHi - C = N-R-N-C-O-E-O-C-N-R-NsC H 0 t η 0 H ti f with the compound of the structural formula below H ₂ N-CH ₂ - reacting, wherein der.Rest E has a structure such that a hydroxyl-endigendes polymer HO-E-OH a melting point below about 60 ⁰ C and a molecular weight in the range of about 600 has up SOOO, wherein the structure • · NOH '"■' HOH lilt A IHI . (RNCN-CH ₂ - / X-CH ₂ -NCN) - represents a repeating unit of a linear urea polymer with a melting point above 200 ^° C. with a molecular weight of about 10,000 and about 60 to 91% by weight of the polymer of the structure divided into sections HO OH IM If t (R-N-C-O-E-O-C-N) - matters 2 · The method according to claim 1, characterized in that a compound of the general structure 0 HO OH 0 ti ι η nt ti CsN-R-N-C-O-E-O-C-N-R-NsC is used, in which E is a linear polyester residue with a molecular weight between about 750 and 3500 'or means a linear polyether radical with a molecular weight between 750 and 3500. 909885/1625 BATH 3, method according to claim % or 2, characterized »that one is a compound of the general structure OHO OHO M I It Wl- '11 C = N-R-N-C-O-E-O-C-N-R-N = C used, in which the remainder R after removal of the Isocyanate groups from the H, H'-diphenylmethane diisocyanate represents remaining aromatic radical. 9098 86/1625 BATH ORIGINAL