DE1942585A1 - Process for the production of polygamma methyl glutamate fibers - Google Patents

Description

Process for the hex position of poly-Y-methylglutamate fibers.

The invention "relates to a method of making fibers from poly-y-methylglutamate (hereinafter abbreviated to PMG) im Dry spinning process.

According to the invention, a spinning solution of the PMG is used, "consisting of a mixture of a chlorinated aliphatic Hydrocarbon, which is a good solvent for PMG, and another chlorinated aliphatic hydrocarbon, which is a non-solvent for PMG, and a higher boiling point than the good solver has.

009813/167

It is the object of the invention to provide FLJG fibers in the height-oriented Form and with excellent mechanical properties. '' "'' '

It is known in the production of PMG fiber η in the nose upper Dry spinning process a dope of PMG in chlorinated aliphatic hydrocarbons, such as luethylene dichloride, T | 2- ' Dichloroethane, trichloroethane, dichloroethylene ooer ethylenedi- '" Chloride, apply. These hydrocarbons are alone or in a mixture with diluents such as dioxane, icetone, Methanol or ethyl acetate, which are non-solvents for PMG, are - "" turns. It is also known to draw the fibers.

Tests have shown that homogeneous and transparent PMG fibers with good physical properties can be obtained by the known wet spinning process. The Tr oc ^ e nsi-inn process, on the other hand, only produced cloudy, devitrified, brittle and weak fibers as a result of poor spinnability and difficulties in regeneration. . _; "-.-

The object of the invention was to address the disadvantages of the known _:

Overcome dry spinning process. For examinations foe ^ \ With regard to the solvents that can be used, it has been found that chlorinated aliphatic hydrocarbons, previously known as good solvents for PMG were considered to be very different-

Have problem-solving abilities towards PMG and that you can ■ can be divided into three classes. One has good solution *

properties. The second has properties that vary between V

to a good | joser and a non-solver. and the third has the properties of a nonsolver. :, t ^ s

009813/1677

^:; .. ^; · ^ ..-- ^::: 1342585

The coagulation vexinogeneity of various chlorinated aliphatic Hydrocarbons versus a P ^ G solution is from the following Try to extract:

Everyone in the. Hydrocarbons listed in the first column of Table 1 were added dropwise at 20 ° C. with stirring to a polymer solution which consisted of 7 _t 2 g PLIG with a degree of polymerization of k 500 and 28.2 ecm 1,2-dichloroethane. The amount of hydrocarbon added in drops was measured, with which white turbidity and gelatinization are brought about. The results are shown in Table 1.

For comparison, these tests were carried out with acetone, methanol, and dioxane and ethyl acetate, which are known as non-solvents and diluents, respectively.

Table 1 Ethylene dichloride Kp. Coagulation 1,1-dichloroetha .. 41, o ° 0 o ° ecm 1,2-dicbloroethylene 57.3 21 chloroform 6o, o . ■ - ■ 2m 1,1, 'i-Irichlojrathan 61.2 OO Carbon tetracbloric 7 ^, 1 26th Trichlorethylene 76.7 25th 1,2-dichloropiopane 8b, 7 85 1,1,2-irichloethane 96, ^ 15th 1,3-dichloropropane 112.0 QO Tetrachlorethylene 120.4 16 Tetrachloroethane 121.1 acetone 146.3 Methanol 56.2 4 ./ '. Dioxane 64.5 2 Ethyl acetate 1 o1, ο 6th 77, o

009813/167 7

t A% X

As can be seen from table 1 he -χ-ν or, 1,1-Diohloräthanf 1 _s _3- ·: .- Mehlor ethylene, carbon of f tetjjaohlor id, 1,1,1-Ti lob los ~> ethane, - 1 , 2 ~ MeülQ3? Propane »1 ^ J-Sioblorpropan uttä Tatrachloräthyie η IkfatIoaer for PHG, T ₁ 2 ~ Dioblo3? Ä1; hari _v Mgthylendi- ■" -. Qlilojiä "» (^ lo ^ oüGEmj 1 ₅ 1 ^ S-feicliloxätbas and Tetjeaeblojcät-üaa slBd good Loser füj; PMG. fEsiQhloxätbyleii bat mittlarβ

ofßi oils - awisoben those of a good LÖseis and one egese The obasaktsiistiaobe Sigeusobaft the

as Nicötl @ s® £ MassifχϋθχΐθΏ KolilenTsasserstoffe iat.darin

zu.sefcenj that they gsgeaübes the Ijekaiintexi McbtlGsarn, like Aoetoii un4 Matbanol, an aehx low Eoagulatioasbsfäbigung which gives ana following ^ m hexvor ί.

A li & suEg vöii .PMG- iß 1, S-Bicblorätb an dur Gb © ine Düs θ is injected into a-letsaoblöraiibylen-Bad, is, desstabt as a result, ifli. Coagulation lediglioh a isser in ". GSI state Imoe Istkylaö © tat are also wia Äoetöü .. or Matbaaöl · ■ ■ lr PMG. '■■.' ■ - ■■ _-;:.:; -. '■ ■ -. ■■■ ': -' ■ "■■ ,. - .. ■ ·

It was "UM" found the following;

If "sine solution of PMG in 1 _i 2-MGblorätban is set to 'irerbCLtnismassig bohe temperatu £ _t ^ö such as 6o C, and then with gabraobt θ XBSX. Gems sen amount of a chlorinated älipbätisoben Koblenwasseistoüi'es, AEEI a Kicbtlöser · for PMG is and has a boiling point greater than 1 ₄ 2 - Dioblozätbaa "; The result is that a high-viscosity, homogeneous and stable polymer solution is obtained which is capable of being spinnable and filial and formed. This -tolymei solution "remains under pressure even after prolonged exposure.

■■. ■■ "■ .0-Ö9813 / 16.77 ■ ■ ■ - ■. '■'. -. ■" /

Even if tetrachlorethylene, which has relatively strong coagulation properties, is added to a solution of PMG in 1,2-dichloroethane and the mixing ratio of the ■ non-solvent to the good solvent 1,2-dichloroethane is 1 ι Λ (based on weight) "? , there is no white cloudiness or gelation in this polymer solution and this solution is ideally suited as a spinning solution for the dry spinning process.

Table 2 shows the properties of spinning solutions produced by Mixing different types of nonsolvents with one solution manufactured by PMG in 1,2-dichloroethane or methylene dichloride became.

009813/1677

attempt Mixed solvent _E wt -% Table 2 Wt% BaG * 15th PMG Viscose Spinning "He— 24 ETr. Solver (Jew. -% (PG) * activity of availability 26th solution (cm) 24 Nonsolver (poise) ■ '· • .3 1 7o 3o 15th 15ο 28 2 75 25th 145 25th 3 1,2-dichloro 75 25th 15ο 25th 4th ethane 6o Te trachl © räthyl®η 4o 15th 16ο 22nd 5 7o 1,2-dichloropropane 3o 1οο .12 ^k -. '■ " 6th 7o 1,3-dichloropropane 3o 15th 125 7th Methylene 7o Trichiorethane 3o 12ο ^Ί ^ "plsid 8th dichloride 7o Tetrachlorethylene 3o 15th 11ο 18th O ■ 9. 7o 1,2-dichloropropane 3o 15th 2,4oo 6? Ο 16 ο
c © 1o 1,2-dichloro 9o Carbon tetrachloride 1o 15ο '■, ..' iq. \ ■■ '■ QO 11th ethane 7o 1,1,1-trichiorethane 3o 2.5öO 71ο 12th Methylene 8o Dioxane 2o ' 13ο GO 13th dichiorid 1,2-dichloroethane 100 Ethyl acetate 0 2,4oo 14ο . ■ ■ Ό © ■ / ■■ ·. "-Jt 14th Methylene dichloride loo Dioxane 0 2,5oo . 11ο * PGs polymerization gas & d Ethyl acetate ¹ '- ■. . ' - ■ - *.,

The Wexi / θ for the degree of polymerisation are determined from the intrinsic molar viscosity of solutions in dichloroacetic acid. The viscosity of the solutions was measured with a botation viscometer at 25 ⁰ CJ. The values for spinnability are based on the distance in centimeters after which the polymer solution falls when a glass rod of 8 mm diameter with a round end is 5 mm deep into the solution is thawed and sucked up at a speed of 10 m / min.

Polymerrösungen were sprayed with a temperature of 5o ° C through a nozzle having o, 2 mm in a Öeffnungsweite Spianschacht containing the hot air from 9o ° G. The maximum draw and the p-structure content of the pre-drawn fiber is shown in Table J

-00081.3 / 1677

·· ■ $ ■

Φ Q CQ
■ »

■ St ..

P Φ

Cf Η ⁴ · Φ CO

ρ ο
ο «

■ a.

Mixed solvents

Loser

Weight ~

Qeww-% '. : HÄG ·: '■' BSI © / · ... ■ ¥ ißkosl- Yerstrelc- ß-,

.. ■■■ '■■■.' ■■■ Sew .- $ (PS) * did the Imag Form

/ ■ ^; '■.: ^■:' / λ '. . ^'■: I ■ ■ x. Solution ■■ masdmtaa (#)

'V' '' Sl

16 17

iinr.2
■■ <*>

Ν ·
ι **

αν

18 19

.6o

6 © '

ethyleii.

■ 35

2.4 © ©.

28ο

31ο. 29ο

6ο

.6ο ·. 6ο

sL% te.ylezk 35

2.5οο
2.5οο '

■ 25 © 24ο

2.25 *

.2; jib 1.95 '■■' ■■■ '/ 68

■ 2.15

2.11

68 ί65 *

21;

sum
comparison

27

28

6o

6o,

2.1oo

22o

240

Methylenedi chloricl

70 bioxane

7ο ethyl acetate

3ο 15 2j5oo

3ο 15 2.5οο

38o

1 »9ο

'. ".: ■■■ ' 1οο ethyläB, «Μ ·. . , '' '■' '■ ο' .. / ■ 25, ': :, 2.40.0 ■ : - ^: 1 »2ο ' . *. '' · ■ *. ■ 23 ■ ·. .... ■ ■. ■. ■ ■■ ■■
1 j 2 ~ Di chi OPr-
.. '■■ ■ ^ethane; '. . 1οο ■■ «ρ- '■. ''. ■, 15 ' ^: 2.5Ο0 45ο / ^: , ι , 25 1ο * :; Methylenes ■■■ '. ■ _;
aicjilorid fekan 7ο
■■■. '■ ^; , 8ο Bio3caii ^: .. ■; ■ '', "':' ■ ■ ·; , ■ '.' ·, 2ö ■,. ■; ■ 2,4οο
2.4 © ο ,1 ; ■ '. ■■■ 25th
26.-; ' 45Υ »
Ε7 CO NJ

1.76

t (tit

· ..- # -: '■'.: · 'Ο':? '- Ί942585

The values for the content of. ß-structure were calculated from "

-1 -1 the absorptions at 62o cm and 69 © cm for the stretched one Fiber on a -KBr plate · The calculation was carried out according to the BuJohl method with an infrared spectrophotometer.

The invention achieves the following advantages over the known methods *

The concentration of BIG in the spinning solution can be increased significantly. The spinning can easily be carried out with a strong increase in the ratio of winding or take-off speed to extrusion speed. Undrawn lasers can be obtained without adhering monofilaments and recrystallization. At a stretching of about 80 to 100 % , fibers of silky luster and high strength or tear length and elongation are obtained, which are suitable for textile purposes. The values for the wet strength are higher than those for the dry strength and a higher conversion from the α to the ß form is achieved during stretching.

Another advantage of the procedure is that throughout Solvent vapor in the spinning shaft the proportion of non-flammable solvent is greater and therefore no fire and There is a risk of explosion. So when spinning you have a high level of security because the heating temperature of the Air, the air flow and the concentration of solvent in the air can vary widely during this Factors in the known dry spinning processes are extraordinary. must be precisely regulated.

009813/1677

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942585

can

For the process, an HSG with an average degree of polymerisation used above 1500 is preferred a degree of polymerization above 2,000.

To produce the spinning solution, γ-methylglutamate-N-carboxyanhydride chlorinated aliphatic hydrocarbons that dissolve well in a PMG, such as methylene dichloride, chloroform, 1,2-dichiorethane, 1,1,2-triehlorethane and mixtures thereof are polymerized. Thereafter, according to the invention, the further chlorinated aliphatic hydrocarbon is added. This non-solvent for PMG, which must have a higher boiling point than the first-mentioned hydrocarbon, can z. B, 1,1-dichloroethane, 1,2-dichloroethane, carbon tetrachloride, 1,1,1-trichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, (Petrachlorethylene or a mixture of two or be several of these substances · You can also proceed in such a way that γ-methylglutamate-N-carboxyanhydride in the inventive Solvent mixture is polymerized.

According to the invention it is necessary that the boiling point of the non-dissolving hydrocarbon is higher than that of the dissolving hydrocarbon "

The mixing ratio of spruce solvent to solvent is generally in the range from about 1 s 9 to 1 1, based on weight. This mixing ratio can, however, be varied according to the type and combination of the two solvents. It is desirable to keep the proportion of nonsolvent as possible in such a range that the PMG solution does not gel and therefore it is advisable to use the intended amount

009813/1677

r i

add the remover to the previously warmed PMG solution.

The concentration of the FMG solution depends on the degree of polymerization of the PMG and the spinning conditions. In general, a concentration above 10% by weight is used. If desired, additives such as matting agents, coloring agents, antistatic agents, etc. can be added to the spinning solution.

The surprising effects occurring in the process of the invention are difficult to explain. There is "a close one Relationship between the precipitation mechanism of the PMG during the formation of the fibers and the physical properties of the formed fibers · If one uses a dope in which the solvent is a well-dissolving chlorinated aliphatic Hydrocarbon alone or a mixture with a strongly coagulating non-solvent such as methanol or acetone is When the solvent evaporates the concentration of the FMG in the spinning solution is very high · When a certain level is reached Concentration, the gelatinization or »precipitation of the FMG progresses rapidly. This becomes the process step of fiber formation discontinuous and a regeneration of homogeneous fibers cannot be brought about »As a result, whitish, cloudy, vitrified and brittle fibers are formed which are very heavy or not spinnable at all

If, on the other hand, one proceeds according to the invention, a relatively large proportion of nonsolvent is present in the spinning solution from the beginning, the coagulation ability of this nonsolvent being relatively low and the boiling point of this nonsolvent higher than that of the dissolver. As soon as the good loser is fully

009813/1677

constantly evaporated, the individual filaments are enclosed of the dissolver, which has a relatively low coagulation ability has «The spinning process according to the invention> runs essentially the same way in the dry spinning process like the wet spinning process and a completely new spinning technique was found

Exemplary embodiments follow the invention for further explanation ·.-'.-.

example 1

A solution of 3o ropes PMG with the green & moiaren Yiskositätszahl (^) of 2.4 (measured at 25 ^o ö ia dichloroacetic) "4-O parts of 1,2-Bichioräthan and 3o parts of 1,1,2,2-tetrachlorethylene would at 5 NC ° G and then filtered, deaerated · This spinning solution was atirch ■ a nozzle with 24 holes of 12 mm in diameter o _t in d @ a Spisnschacht injected. Hot air of 1o $ * C flows through & © n spinning chute at a speed of 2 © oa / ain.

The fibers were drawn 1.9 times «their properties are shown in Table 4. The fibers were silky Appearance with an elegant sheen

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Table 4

Trial denier dry-barrel ratio dry-no. strength strength of wet elongation

too dry-

_ _____ "___ fes tigke it

29 1.9 d 2.7 β / α 5.1 d / g 115% 23%

Test of wet stretching, knot ß-form strength

29 25 % 2.2 g / d 72 %

Example 2

Different spinning solutions were prepared by changing the combination of solvents and the concentration of HaG and, as in Example 1, processed. The results of experiments 3o to 37 are shown in Tables 5 and 6.

00981371677

Tabel

S pinnι ο sung

Solvent mixture

Attempt Kr.

Solver

% By weight non-toxic

% By weight PMG FMG Viscous! - Weight% (PG) * did dei?

Solution ** __ (poise)

1,2-dichloroethane

5o Sun 85

Tetrachloroethane

Methylene chloride

6o 1,2-dichloropropane

6o carbon tetrachloride

* PG ϊ degree of polarization **: viscosity measured at 5o ° C 5o
2o
15th

4o

35
35

55

2,3oo

35 chloroform 6o 1,1,1-trichloroethane 4o 55 36 1,2-dichloroethane 6o Tetrachlorethylene 4o 2o 37 5o Tetrachlorethylene
1,2-dichloropropane 25th
25th 35

26o 27o

38o 28o

19o

25o

OD CXJ

Tabel

Spinning conditions speed Withholding Temp, im Ehys »Properties of the drawn fiber strength wet strain wetFoa (%) attempt Extrusion take-off (m / min.) ratio Spinning denier dry , Cs / a) dry C%) 78 No. speed ^% 23o shaft
CC) (d) (g / d) 2.9 26th 74 (m / min.) 2oo 1.15 11o 2.8 2.5 24 23 76 3o 2oo 185 1, o5 1o5 2.2 2.3 2.7 21 21 69 31 19o 2o5 1, o3 1oo 2.5 2.5 2.6 2o 24 32 18o 2oo 1, o8 1o5 2.7 2.5 3.2 22nd 26th "* .65 33 19o 2oo 1, o5 1o5 3.0 3, o 2.5 25th 22: 34 19o 1, o5 1oo 2.7 .2.4 2o 35 19o 2.9

36 19o 194 1, o2 Ho 1.5 2.3 2.4 22nd 23 .: 37 2oo 23o 1.15 Ho 2.6 2.9 3.2 26th 28 * ' ... 63 I * *
• ·

Elongation: 1.8 times

Spinneret: 24 holes, / 6 ο, 12 mm

Deduction ratio: take-off speed / extrusion speed

• CD

cn

OO

cn

Claims (4)

Claims · β 1. Process for the production of poly-γ-methylglutamate fibers, characterized in that a spinning solution of the poly-γ-methylglutamate is made containing a chlorinated aliphatic hydrocarbon, which is a good solvent for poly-γ-methylglutamate and another chlorinated aliphatic hydrocarbon that is a non-solvent for poly-γ-methylglutamate and has a higher boiling point than the good dissolver, and that this spinning solution is sprayed into heated air to form fibers will. 2. The method according to claim 1, characterized in that in the solvent mixture as a good solvent methylene dichloride, Chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane or a Mixture of two or more of these substances is used. 3. The method according to claim 1 or 2, characterized in that in the solvent mixture as a nonsolvent 1,1-dichloroethane, 1,2-dichloroethylene, carbon tetrachloride, 1,1,1-trichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, tetrachlorethylene or a mixture of two or more of these substances is used. 4. The method according to claim 1 to 3 »characterized in that that the mixing ratio of non-solvent to good solvent in the range from about 1: 9 to 1: 1 (based on weight) lies. Ö 0 9 8 1 3/1 6 7 7