DE1273743B - Acrylonitrile polymer fibers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

DOIf

German class: 29 b -3/65

Number: 1273 743

File number: P 12 73 743.8-43 (P 25587)

Filing date: August 26, 1960

Opening day: July 25, 1968

The invention relates to acrylonitrile polymer fibers having a very permanent gloss and a method to manufacture the same.

Acrylonitrile polymer fibers with uniform Initial gloss shows the tendency, during normal textile processing theirs To lose shine. For example, the initially shiny fibers usually become a bit dull, when exposed to heat and moisture, such as washing, Steam pressing, bleaching and dyeing. This loss of gloss turns out to be dull in the case of undyed goods and noticeable as dulling and lightening in the case of colored material. This is special troublesome when irregularities occur in a single textile product as a result of local fluctuations in the treatment conditions.

While special treatments can be used to reduce this difficulty, they are Treatments have not proven entirely satisfactory. Procedures in which to improve the durability of the gloss of the fiber all traces of that used in fiber production Solvent are removed, are too expensive for the technical implementation. The same applies to dyeing processes in which the matted fibers are dyed with a large amount of dye.

From US Pat. No. 2,888,434 it is known that fibers made from copolymers of acrylonitrile and vinylphosphonic acid bis (2-chloroethyl) ester are manufactured, a © lower tendency to accumulate electrostatic charges, a better dyeability with disperse dyes !! and have a lower flammability than fibers made from other copolymers of acrylonitrile.

According to the invention, however, is primarily a high durability of the gloss Fibers achieved.

The fibers according to the invention made of acrylonitrile polymers with a content of bound acrylonitrile of at least 70 ^fl / o and a further content of a haloalkyl ester of an oxygen acid of phosphorus are characterized in that in the state of physical distribution they are a neutral or acidic haloalkyl ester of phosphoric acid of the general formula

R ₁

Acrylonitrile polymer fibers

R ₂

Applicant:

E. I. du Pont de Nemours and Company,

Wilmington, Del. (V. St. A.)

Representative:

Dr.-Ing. W. Abitz and Dr. D. Morf,

Patent attorneys,

8000 Munich 27, Pienzenauer Str. 28

Named as inventor:
Ansom Mack Hayes,
Wilmington, Del. (V. St. A.)

Claimed priority:

V. St. ν. America dated August 27, 1959 (836 339)

in the Ri and R2 haloalkoxy radicals with 1 to 5 carbon atoms in the alkyl chain and 1 to

4 halogen substituents in the chain mean, R) represents a haloalkoxy group of the same kind or a hydroxyl group and the total number of Halogen atoms in the phosphoric acid ester is at least 3, in amounts of 3 to 20 percent by weight, based on the polymer.

The polymerized acrylonitrile content of the fibers is preferably at least 85%.
Amounts of phosphoric acid haloalkyl ester of

5 to 15 weight percent is particularly preferred as it gives the best results. Amounts, which exceed 20 percent by weight should be avoided as they are easy to deteriorate other properties of the fibers, such as tensile strength, modulus and wet strength.

The fibers according to the invention therefore differ fundamentally from the fibers according to FIG U.S. Patent 2,888,434 in that it does not use the organic phosphorus compound as a chemical Part of the polymer chain of the copolymer of which they are made, but in the physical Contain mixture with the acrylonitrile polymer. The added phosphorus compound has furthermore does not have any unsaturated bonds and is therefore not polymerizable.

The fibers with a very permanent gloss are produced according to the invention by a spun a homogeneous solution, which contains about 5 to 35

IM MlIiV

weight percent of the polymer with a content of bound acrylonitrile of at least 70 percent by weight and, in addition to the solvent, about 3 to 20 percent by weight of phosphoric acid haloalkyl ester, based on the polymer.

The phosphoric ester can be added before, simultaneously with or after the addition of the solvent take place. The phosphoric acid ester can also be freshly spun, solvent-laden Feed fibers before or during the drawing and extraction by treating the fibers in a bath containing the phosphoric acid haloalkyl ester contains. The spinning solution or the treatment solution containing the phosphoric acid ester can be used as a stabilizing agent for the phosphoric acid ester, for example, add a compound that reacts with hydrogen halide, z. B. a base, a reactive unsaturated compound or an epoxy compound.

In carrying out the invention, one can use conventional means, e.g. B. according to the USA patents 2,628,223, 2,748,106, or 2,777,832, an acrylonitrile polymer. Then one will homogeneous solution prepared in an inert solvent containing about 5 to 35 percent by weight polymer contains. You can use the known organic and inorganic solvents that are inert to the polymer. The choice of solvent depends on whether the wet or dry spinning technique is used Applies. In the dry spinning process, organic solvents such as dimethylformamide, dimethylacetamide, dimethylmethoxyacetamide, N-formylmorpholine, N-formylhexamethyleneimine, cyclic butadiene sulfone, cyclic tetramethylene sulfone, p-phenylenedianiine, Use m- and p-nitrophenols. Inorganic solvents are suitable for the wet spinning process, such as metal halides and thiocyanates, and those described in U.S. Patents 2,648,646 bis 2,648,649 described salts and mixed salts.

The phosphoric acid haloalkyl esters are in the concentrations used according to the invention generally completely miscible with the polymer and provide clear, homogeneous fibers unimpaired physical properties. Phosphoric acid haloalkyl esters, which are in water only weak, d. H. up to about 0.5%, are soluble, however, give the fibers permanent durability of shine.

The phosphoric acid haloalkyl esters which can be used according to the invention, those mentioned in the examples below include phosphoric acid tris- (2,3 - dibromopropyl) - ester, phosphoric acid - tris- (2,3 dichloroethyl) ester, phosphoric acid tris (chloroethyl) ester and phosphoric acid tris (dibromoethyl) ester. However, other phosphoric acid haloalkyl esters can also be used use in equal amounts, e.g. B. chlorine, fluorine and bromine substituted methyl, Ethyl, propyl, butyl, isobutyl or tert. Butyl ester, including those that have different alkyl groups in the same molecule. Typical Examples are phosphoric acid tris-chloroethyl ester, phosphoric acid tris-bromoethyl ester, phosphoric acid monochloroethyl - monopropyl ester and phosphoric acid mono-2,3-bromopropyl ester. The phosphoric acid bromoalkyl esters are preferred over the corresponding fluorine or chlorine compounds, because they provide better gloss stabilization and greater compatibility with polyacrylonitrile demonstrate.

The acrylonitrile polymers of which the fibers are made can, in addition to acrylonitrile, one or more contain several other ethylene unsaturated monomers in the molecule. Examples of such monomers are referenced in U.S. Patents 2,436,926, 2,485,241 and 2,837,501. The polymers should preferably have an average molecular weight of 40,000 to 150,000.

One of the main advantages of the invention is that it is made from the additive-containing polymers spun fibers have a uniform initial luster, which is practical during processing remains unchanged. Another advantage is that the fibers have the good physical properties typical of acrylonitrile polymers. this is particularly surprising because the addition of substances that are not copolymerizable monomers generally leads to a deterioration in properties. Besides, these are Polymer solutions can be spinned better, which means working with a lower percentage Solvents in the solution than in the previously known spinning solutions and enables spinning relieved by coarse denier threads. All of these advantages come with spinning threads from copolymers of acrylonitrile and bis (2-chloroethyl) vinylphosphonate according to U.S. Patent 2,888,434.

The gloss of the fibers in the examples is determined by the following method: Man winds a series of strands of thread on a rectangular frame. To remove surface effects the frame is then immersed in a liquid that has a similar index of refraction as the fibers. Then it will go through light falling on the frame determines the fibers. A suitable liquid for fibers made from acrylonitrile polymers is anisole.

The degree of gloss of different fiber samples can be calculated using the following formula:

Gloss (%) = 100 [Number ( ₉ 00 (A) yy ^

where L = width of the thread strand in the light beam in centimeters, t = number of thread strands.

The optical density is equal to log - ^ -, where / 0 = light intensity without yarn, / = light intensity in the presence of the yarn (determined with the electrophotometer using a blue filter with a peak transmission at 4200A). Fibers with a gloss above 90% are not considered to be considerably matted, while values of 60 and less mean considerable matting.

The degree of matting can be determined in the case of colored goods by looking at the degree of efficiency a given amount of dye is observed for coloration. With non-matted Fibers will get deeper and more vivid tones. Changes in fiber density are

also a sign of changes in the gloss. In general, there is a strong gloss hand in hand with a high density.

In the following examples, parts and percentages relate to weight.

example 1

10 parts of a polymer of 94.6% acrylonitrile, 6% methyl acrylate and 0.4% sodium styrenesulfonate, which is produced by emulsion polymerization with a persulfate-bisulfite redox catalyst, are mixed with 20 parts of dimethylformamide ^{under nitrogen at 50 ° C. with constant stirring} mixed to a homogeneous solution, to which a phosphoric acid haloalkyl ester is then added. The type and amount of the phosphoric acid ester are given in the following table. The mixture is then ^{spun at 100 °} C. at a speed of 274 m / min through a spinneret with 0.15 mm holes down into a tube 5.5 in length and 20.3 cm in diameter, the same from Nitrogen with 250 ⁰ C is flowing through. The still solvent-wet fiber emerging from the tube is passed through a hot water bath, where it is washed and stretched threefold. The washed fiber is for 9 minutes

ίο, 125 ⁰ C dried. A shiny, solid fiber with a residual solvent content of 2 to 3% is obtained. To test the resistance of the knot under the action of heat and moisture, the fibers made with the various phosphoric acid haloalkyl esters are immersed in a boiling 0.1% aqueous detergent solution for 10 minutes, then rinsed with pure water and dried at room temperature.

' Phosphoric acid haloalkyl esters

1. None

2. Phosphoric acid tris (2,3-dibromopropyl) ester

3. Phosphoric acid tris (2,3 "dichloroethyl) ester.

4. Phosphoric acid tris (chloroethyl) ester

5. Phosphoric acid tris (dibromoethyl) ester

·) T / E = tear strength (j / efaty / Dehming (%).

The values in the table show that the addition of phosphoric acid haloalkyl esters to the spinning solution leads to fibers with a permanent gloss without the physical properties being impaired.

Gloss value after §0 additive before the cooking 91 % 93 89 91 93 10 91 90 15th 93 15th 91 10

Change in density
while cooking

Example 2

40

A polyacrylonitrile fiber is produced according to Example 1 with the exception that the phosphoric acid haloalkyl ester is not added to the spinning solution. The exiting from the tube, still solvent wet fibers are passed through a bath of 8O ⁰ C, the 20% Phosphorsäuretris- (2,3-dibromopropyl) ester, 10% tert. Contains butanol as a wetting agent and water, and stretched to four times its original length. 15% of the phosphoric acid haloalkyl ester is absorbed. The treated fibers are tested according to the method of Example 1 for the durability of their gloss. A gloss value of 90 before boiling and 85 after boiling is obtained.

The durability of the gloss is given to these fibers by removing the still solvent-laden Yarn drawn in a bath which contains the phosphoric acid haloalkyl ester.

0.015 '

0.003

0.005

0.002

0.003

Physical Properties

TVE *)

1.6 / 60
1.5 / 60
1.4 / 65
1.4 / 60
1.5 / 65

Claims (1)

Claim: Fibers composed of at least 70 °, acrylonitrile units containing polymer, characterized in that they a neutral or acidic halogen;) Iky! ester of phosphoric acid of the general formula P = O in the Ri and Ra haloalkoxyresia with 1 to 5 carbon atoms in the alkyl cell and 1 to 4 halogen substituents in the cell. R3 is a haloalkoxy radical of the same Λ11 or represents a hydroxyl group and the total number of halogen atoms in the phosphoric acid ester is at least 3, in amounts of 3 to 20 percent by weight - based on .ml il; i, Polymers - included. Documents considered
U.S. Patent No. 2m 434.