DE1259500B - Use of a polymer mixture based on polypropylene for the production of threads and fibers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

DOIf

German: 29 b-3/65

Number: 1 259 500

File number: E 20120IV c / 29 b

Filing date: November 2, 1960

Opening day: January 25, 1968

The invention relates to the use of a polymer mixture consisting of polypropylene and 1 to 25 percent by weight of certain copolymers for the production of threads and fibers.

Crystalline polypropylene is known to be chemically very inert and hydrophobic. It can therefore also not with the usual dyeing processes, and not even with dyes soluble in hydrocarbons and permanent dyeing of disperse dyes. Another disadvantage known so far Threads and fibers made of polypropylene consists in their inadequate stability against light and Weather conditions.

The object of the invention was to modify polypropylene in such a way that the modified Polypropylene can easily be spun threads with a variety of disperse dyes and so-called pre-metallized dyes can be colored.

It has been found that threads and fibers of the desired properties can be produced, if you use a polymer mixture of polypropylene and 1 to 25 percent by weight for their preparation a copolymer with a certain minimum proportion of acrylic acid or methacrylic acid ester units used.

The invention thus relates to the use of a polymer mixture consisting of Polypropylene and 1 to 25 percent by weight of a copolymer, which is at least 25 mol percent from units of the general formula

CH ₂ C—

C OR ₁

; l

where R is a hydrogen atom or a methyl group and R _{1 is} an alkyl, alkoxyalkyl, cycloalkyl, aralkyl or aryl group with up to 12 carbon atoms, and the rest of the radicals of an unsaturated polymerizable monomer with one or more carbon-carbon - Double bonds are used to make threads and fibers.

Polymer mixtures are preferably used in which the copolymer is at least

Use of a polymer mixture
Polypropylene base for making threads
and fibers

Applicant:

Eastman Kodak Company, Rochester, N.Y.

(V. St. A.)

Representative:

Dr.-Ing. W. Wolff and H. Bartels, patent attorneys, 8000 Munich 22, Thierschstr. 8th

Named as inventor:

Harry Wesley Coover Jr.,

Frederick Blount Joyner, Kingsport, Tenn.

(V. St. A.)

Claimed priority:

V. St. v. America February 4, 1960 (6598) - -

Mol percent consists of units of the structural formula given.
It is also preferred to use mixtures which contain 5 to 15 percent by weight of the copolymer.

Surprisingly, it has been shown that the shades produced by means of a certain dye on threads made of pure polypropylene on the one hand and on threads made of those used according to the invention Mixtures obtained on the other hand, are completely different from one another. It has also been shown that the threads and fibers which can be produced from the polymer mixtures used according to the invention They are 3 to 4 times more resistant to oxidative degradation than threads and fibers made of one unmodified polypropylene.

The increased resistance of the threads and fibers from mixtures used according to the invention ultraviolet light and against weather conditions as well as oxidation compared to unmodified Polypropylene threads and fibers have not yet been fully clarified. Presumably work the modifying copolymers as a kind of absorbent for chemically effective. Radiant energy and thus prevent the polypropylene from decomposing by a radical mechanism.

709 720/475

3 4

The mixtures of crystalline polypropylene and

threads and fibers which can be produced according to the invention can be one or more of the copolymers

can, moreover, be prepared in various ways with any desired for polyolefins, namely

conventional, known stabilizers further compared to mechanical mixing of the polymer

thermal degradation and weathering components or common failures from solutions

influences are stabilized. When using such. The mechanical mixing can, for. B. by means of

like stabilizers, it has proven to be useful rollers at elevated temperatures or by means of

moderately proven, the stabilizers are added to the mixtures of an extruder,

to be added to threads before spinning. The copolymers can have molecular weights

From the polymer numbers used according to the invention of 1000 and above,

Threads and fibers can be mixed. A polypropylene is preferably used

the equally favorable, high strength properties with a density of over 0.900 and a basic

and low elongation values and other favorable viscosity, measured in tetralin at 145 ° C, of 0.9

Have properties such as from unmodified to 1.2. The density value refers to the

Threads and fibers made from polypropylene. 15 on a sample determined value, the sample

This result is therefore over-tempered in order to achieve maximum crystallinity surprising, because the invention was for modification. For this purpose, the sample was placed in a tube Polypropylene not used polymers and under high vacuum or in a nitrogen generally in a satisfactory manner for modifying the atmosphere to just below the softening of Filaments and fibers made of polyolefins used 20 points heated, after which they were slowly cooled, can be. If one spins, for example, Ge The basic viscosity results from the equation: mix from one of the polymers described

and a high-density polyethylene, it turns out that [N] ==,

that the two components are not comparable with one another C

are bearable. A mixture of polyethylene and 35

one of the mixed poly used according to the invention in which means:

merisate »supplies, for example, in melt spinning _{N the ratio of the} viscosity of an approx

Threads that consist of individual segments are 0.25 percent by weight solution of the

If such a thread is drawn, strong fibrous polymerizate in tetralin increases the viscosity of the

do gymnastics, d. that is, it becomes practically worthless pro-30 tetralins alone and products received.

As monomers with one or more carbons, the concentration of the polymer in grams

fabric-carbon double bonds for production per 100 cm ^ solution, the copolymers used according to the invention

all monomers come into question, which are with 35

Acrylic and methacrylic acid esters of the specified is a polypropylene with an intrinsic viscosity

Allow the structure to copolymerize. Suitable of higher than 1.2 used, so it usually is

Thus, the most varied of unsaturated poly- required, the resulting mixtures thermally

merizable monomers with one or more, a lower viscosity to degrade to optimal

preferably terminal carbon-carbon 40 melt-spinning and filament properties.

Double bonds. Suitable monomers are: The temperatures required for such a degradation

for example vinyl esters, vinyl amides, vinyl nitriles, temperatures are usually above 300 ⁰ C, so that

Vinyl ketones, vinyl halides and vinyl ethers, <x, ß- occasionally depolymerizations of the mixed polymer

unsaturated acids or their esters, olefins, sate can take place. Polypropylene with basic viscosity

Diolefins and the like may be mentioned, for example, acrylic properties below 0.9 can also be used.

nitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl det are, but do not lead to threads

chloride, vinylidene chloride, methyl vinyl ketone, vinyl optimal physical properties,

acetate, fumaric acid, maleic acid and itaconic acid- The mixtures used according to the invention can-

ester, 2-chloroethyl vinyl ether, methylenemalononitrile, NEN by conventional spinning processes, for example

Acrylic acid, N-vinylsuccinimide, N-vinylphthalimide, 50 using the melt spinning process, dry spinning

N-vinylpyrrolidone, butadiene, isoprene and vinylidene or wet spinning processes are spun,

cyanide. Depending on the shape of the nozzles, threads with different

Although the mixed different cross-sections used according to the invention, e.g. B. shamrock-shaped

polymers are preferably produced with at least 50 molar or Y-shaped cross-sections,

percent from acrylic acid ester or methacrylic acid 55

There are ester units of the structure given, Example 1, however, are also advantageous results

obtained such copolymers, which only to There were several mixtures of crystalline

about 40, 30 or even 25 mole percent of acrylic-polypropylene with an intrinsic viscosity of 1.0 and

acid ester or methacrylic acid ester units of 60 with a density of 0.912 as well as a mixed polymer

specified structure exist. Mol percentages of sat from methyl methacrylate and ethyl fumarate in the

However, at least 50% is beneficial because the ratio 98: 2 is made by having particles of the two

because if the copolymers contain polymers, they would be mechanically mixed with one another.

Less than 50% of these units denote larger amounts by having the mixture melted and out of the

of the mixed polymer, based on the weight of 65 melt, was pressed out in the form of a rod,

the polypropylene mixture, which has to be shredded again. The received

Sen, in order to mix the desired properties thereof, have been added by the melt spinning process

to lend. Threads, consisting of 34 single threads, spun, ■■

From the threads obtained knitted hoses were knitted, which z. B. with 4 - (4'-Hydroxy, ethylanilino) -5 - nitro -1,8 - dihydroxyanthraquinone and a neutral coloring, pre-metallized dye by boiling in for 1 hour dye aqueous dye liquors in deep colors. Even deeper shades were obtained when using a Carrier, e.g. B. benzyl n-butyrate obtained.

All samples showed excellent fastness properties to ultraviolet light 20 hour exposure in a fadeometer.

Example 2

Mixtures of crystalline polypropylene and a copolymer of methyl methacrylate were used and vinyl acetate in a ratio of 80:20 and prepared by the melt spinning process Threads spun from 34 individual threads. The spun threads had the following properties:

Ratio of polypropylene to copolymer in ° / o

Viscosity of the threads

Total titer den

Strength, g per den

Strain, %

Young's modulus, g per den

Characteristic values
92: 8 I 87: 13 I 75: 25

1.03
211

7.25
20th
68

1.03
208

8.25
22nd
80

248

4.76 29

45

merisate of ethyl acrylate and vinylidene chloride in a ratio of 95: 5 instead of the methyl methacrylate-vinyl acetate copolymer used. Solid threads with excellent dye affinity were obtained.

Equally favorable results were obtained if instead of the above-mentioned copolymer a Copolymer of methyl acrylate and vinyl chloride in a ratio of 94: 6 was used.

Example 6

Knitted tubes from the threads could easily be made with 4- (4 '- / 3-Hydroxyäthylanilino) -5-nitro-1,8-dihydroxyanthraquinone as well as with other disperse dyes and dye pre-metallized dyes. Deep colors with good light and gas fastness properties are obtained.

Example 3

The procedure described in Example 2 was repeated, but this time a copolymer was used from methyl methacrylate and styrene in a ratio of 50:50 instead of the methyl methacrylate-vinyl acetate copolymer used. The filaments obtained had strengths of 4.5 to 7.0 g per denier and were easy to mix with disperse dyes and premetallized dyes dye in deep shades.

Example 4

The procedure described in Example 2 was repeated, but this time a copolymer was used of ethyl acrylate and acrylonitrile in a ratio of 90:10 instead of the methyl methacrylate-vinyl acetate copolymer used. Filaments with tenacity of 7.25, 5.85 and 4.53 g per denier were obtained. All threads fell into dye deep shades with excellent lightfastness properties.

Example 5

The procedure described in Example 2 was repeated, but this time a mixed polymer was used: a mixture of 9 parts of crystalline polypropylene (basic viscosity = 1.05; density = 0.914) and 1 part of a mixed polymer of ethyl acrylate and 2-chloroethyl vinyl ether in a ratio of 95: 5 prepared by evaporating a solution of the copolymer in toluene in the presence of particles of the polypropylene in a conical mixer in vacuo. The solvent-free mixture was then melt extruded into a rod about 3.2 mm in diameter, after which the rod was cut into particles about 3.2 mm in length. The particles were then spun at a spinning temperature of 230 ⁰ C by the melt spinning method to threads of 34 individual filaments. For spinning the unmodified polypropylene, a melt spinning temperature of 280 ° C. was required to achieve optimal spinning results. The threads were knitted into knitted tubes with which dyeing tests were carried out. The threads had excellent dye affinity, particularly for disperse dyes and premetallized dyes. Deep shades were obtained, for example, with a neutral coloring, pre-metallized dye, as well as the following dyes: 4-anilino-3-nitrobenzenesulfonamide, 4 - (4 '- methyl - 2' - nitro - benzene) 3-methyl-5-pyrazoline, 4 - [4 '- (Benzolazo) -benzolazole] -phenol, l'-amino-4-hydroxy-2-phenoxy-anthraquinone, 4- (4'-nitro-benzolazo) -N-ethyl-N - /? - hydroxyethylaniline , 1-methyl-amino ^ -ß-methylethylaminoanthraquinone and 4- (4 '- /? - hydroxyethylanilino) -5-nitro-1,8-dihydroxyanthraquinone.

Correspondingly favorable results have been obtained when instead of the above-mentioned copolymer one composed of methyl acrylate and vinyl chloride in a ratio of 94: 6 or a copolymer composed of trimethylcyclohexyl acrylate and bis- (norcamphanylme-

ethyl) fumarate in a ratio of 50:50 or a copolymer from methyl methacrylate and ethyl maleate in a ratio of 98: 2 was used.

The threads and fibers which can be produced from the polymer mixtures used according to the invention can be processed in the same way as conventional threads and fibers made of polypropylene. For example they can be used for the production of wool-like blankets, for the production of covers for Car seats and used to make ship ropes.

Claims (1)

Claim: Use of a polymer mixture consisting of polypropylene and 1 to 25 percent by weight a copolymer which is at least 25 mol percent of units of general formula -CH, - C- C OR ₁ Il ο where R is a hydrogen atom or a methyl group and R _{1 is} an alkyl, alkoxyalkyl, cycloalkyl, aralkyl or aryl group with up to 12 carbon atoms, and the rest of the radicals of an unsaturated polymerizable monomer with one or more carbon-carbon Double bonds are used to make threads and fibers. 709 720/475 1.68 © Bundesdruckerei Berlin