DE1263291B - Cross-linking of high molecular weight substances - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN mj9w> PATENT OFFICE C08j

EDITORIAL

Int. CL:

German class: 39 b

Number: File number: Registration date: Display day:

H 42168IV c / 39 b March 30, 1961 March 14, 1968

The cross-linking of high-molecular substances of natural or synthetic origin through short-term Heating them in the presence of a small amount of a crosslinking agent is one Problem of great technical importance in the finishing of different types of fabrics, when printing the same with pigments, when manufacturing non-woven fabrics, coverings, Adhesives for a wide range of materials and for printing on paper.

A number of compounds containing two or more alkyleneimide groups are useful as crosslinking agents known for high molecular weight substances, but they tend to decompose easily, especially from moisture and carbon dioxide. If they are kept in isolation, they are certainly not all unstable; however, when mixed with a high molecular weight substance, they behave as unstable substances, which are practically useless for an application on an industrial scale.

The subject of the invention is a process for crosslinking high molecular weight organic substances, characterized in that poly (N, N-ethylene amidophosphates) or their thio derivatives of the general Formula crosslinking of high molecular weight substances

Applicant:

Hodogaya Kagaku Kogyo Kabushiki Kaisha,

Tokyo

Representative:

Dipl.-Ing. Dr.Ing. R. Poschenrieder,

Patent attorney,

8000 Munich 8, Lucile-Grahn-Str. 38

Named as inventor:

Hisayuki Sato, Tokyo;

Homei Ito,

Hiroshi Imagome, Yokohama (Japan)

Claimed priority:
Japan March 31, 1960

HCn

Il Il

: - ρ - ο - α - ο - ρ - ν;

/ CH

R '

to solutions of high molecular weight substances mixed their aqueous dispersions or applying to solid high molecular weight substances, dries the materials and 3 to 30 minutes at 100 to 200 ⁰ C brings wherein A is a divalent radical of aliphatic, cycloaliphatic, heteroaliphatic or heterocyclic series, Xi and X2 represent oxygen or sulfur atoms, R and R 'represent hydrogen atoms or a monovalent hydrocarbon radical and Yi and Y2 denote an alkoxy, or thioalkoxy, amido or alkylenamido radical, corresponding to the formulas

- OR ", —SR", —N:

and

-N

/ CHR ₁

CHR,

corresponds, where R ", Ri and R2 stand for a hydrogen atom or a monovalent hydrocarbon radical. Compounds corresponding to the general formula are e.g. B.

N S S N

ch

P - O - CH ₂ CH ₂ - O - P

CH ₂

CH ₂

CH ₂

809 518/707

CH ₃ CH _2x /
In ) N H ₅ C ₂ O ^ / / _χ / N O / O - CH ₂ ( -CH; CH ₂ - O : η ₂ - 0 - O Ν ' CH ₃ / CH ₂ OC ₂ H ₅ OC ₂ H ₅ CH _2x CH ₂ / CH _2x N ) ν \ \ ΙΙ II / / CH ₂ S Ν (I
II / ^X CH ₂ / CH ₂ CH _2x US I. Ρ - P. -P O Ν ( / CH ₂
S ν; CH ₂ / CH ₂ / Mil CH ₂ / ; ν s /
N M.
Ni ^ CH ₂ ' M / CH ₂
ν (I Il / \ γ · ττ
II / CH ₂ Il / Xr ¹ W
II / CH ₂ ρ
/ / N S ^X CH ₂ -P -P CH _2x CH, \ CH _2x ρ - ⁷ MII -CH -CH ₂ CH ₂ - O / CH ₂ / CH ₂
O Ν ( M. M / CH ₂ CH ₂ / C. 1 ) Ρ - 2CH ₂ - -CH ₂ CH ₂ ^ CH ₂ II / ^X CH ₂ N (I I.
CH ₃ - \
:H/ CH ₂ / CH ₃ -P XCH ₂ CHv CH _2x ο- - Q- M / CH ₂ / CH ₂ CH _2x ) NS
Mil 'I X CH ₂ / N (I
^X CH ₂ S Ν ( CH ₂ / ρ - CH ₂ / / CH ₂ II / ^X CH ₂ CH _2x O - CH ₂ CH ₂ - -CH; CH ₂ - O -CH; , CH ₂ S Ν ( P. II / ^X CH ₂ M / CH ₂ ) N 0 CH ₂ / - Q- -P ν (I CJHL ₂ N ^X CH ₂ Ρ - I. CH ₂ ' S. ο- / CH ₂ -CH; .CH ₂ CH ₂ N -HC 1/ ^X CH ₂ - 0- CH ₂ ' ο- S. -CH ₂ CH ₂ > N 0 - 0- Ρ - ο- - · CH ₂ CH ₂ - - 0- CH ₂ ν O \
/ CH- CH ₂ / -0 -

As high molecular substances, the properties of the above mentioned crosslinking process can be improved, the following may be mentioned: linear high molecular Substances of natural origin, such as B. starch, alginic acid, gelatin and cellulose fibers, Cellulose derivatives, such as. B. etherified or esterified cellulose, also high molecular weight substances that by

Polycondensation or polyaddition arise, such as. B. saturated or unsaturated polyesters, alkyd resins, Polyamides and polyurethanes, polyvinyl compounds, such as. B. polyacrylic acid, polyacrylates, Polymethacrylic acid, polymethacrylates, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride and its Copolymers, natural rubber, synthetic rubbers, such as. B. butadiene-styrene mixed

polymers, butadiene - acrylonitrile copolymers, polyisoprene and other high molecular weight substances of linear structure.

Among the substances listed here are linear high molecular substances that active hydrogen atoms, ζ. B. in the form of —NHa—, = NH, - COOH, --OH and - SH groups are easily crosslinked by ethylene amido groups.

The effect of entering of the present invention in the application of the crosslinking process, is eye-catching, that the high molecular weight substances, which contain the mentioned types of substituents, when heated to a temperature above about 13O ⁰ C in the presence of an amount of 1 to 15% of the crosslinking agent harden within a few minutes, giving them considerable resistance to various types of solvents. The crosslinking process also proves to be effective when applied to linear high molecular weight substances which do not contain any of the reactive groups mentioned.

When mixing the crosslinking agents with linear high molecular substances, all the kneading methods which are carried out in combination with a heat treatment, e.g. B. processing on heated rollers, technically not because of the sensitivity of the crosslinking agents to reactivity useful. A suitable procedure for preparing the mixtures is to use the crosslinking agent to add solutions of the high molecular weight substances or aqueous dispersions of these substances, so that homogeneous mixtures arise; and this way of working is indeed the appropriate method to achieve the technical success of the present invention.

The physical and mechanical properties, such as B. the hardness, flexibility, elasticity and the feel of the cured products can be achieved by adding, depending on the desired end use Plasticizers, epoxy resins, unsaturated polyester and alkyd resins and / or precondensation products of thermosetting resins such as etherified methylol urea or etherified Methylolmelamine compounds, to form a solution of the composition of matter according to the present invention Invention to be discontinued.

The crosslinking method of the invention can be applied to a variety of materials Find; This makes it possible to fix pigments, pastes (emulsions of the type oil-in-water) on the fabric by padding or to apply printing, the pastes pigments, thickeners, high molecular weight substances of natural or synthetic origin, organic solvents or diluents and the crosslinking agents and then dried and then hardened in the heat. The fabrics treated in this way show not only one special high resistance to irradiation but they also prove to be excellent in their Wet friction resistance, e.g. B. when creasing when washing by hand.

Tissues of natural or synthetic origin are soaked with aqueous dispersions or solutions and "hardening" according to the invention are permanently stabilized and retained in their structure effective anti-crease equipment. It also increases the introduction of nitrogen atoms by the treatment mentioned, the affinity of the fabric treated in this way for direct dyes and for basic dyes. * Most of the known alkyleneimino derivatives can be a viscose base solution are not added without the latter thereby forfeiting its spinnability, namely because of the extraordinarily high reactivity that these show in viscose at room temperature, whereby the viscose gels easily. Different from these known crosslinking agents, the crosslinking agents of the invention are Room temperature completely stable, even in viscose, and they can therefore be used for the production of Viscose with improved properties are used. Viscose solutions to which the crosslinking agents of the present invention have been added can be spun in the usual way; the so woven and the thermal treatment subjected viscose rayon shows itself to be remarkably improved in quality.

The method of the invention can also be used for fixing colored or undyed fiber stacks, the so-called flakes, are used. So it has so far not been possible to to get a product that is resistant to hand washing if you use a Rubber film coated or printed with a known paste, this then in an electrostatic Field sprinkled with flakes, dried, removed the excess flakes and heated the whole thing, to fix a certain amount of the flakes on the foil. However, the same procedure is used below Use of a paste carried out, which one in place of the known crosslinking agent, the crosslinking agent added to the invention, the flakes once fixed do not fall off the film, even if it is rubbed when it is wet. Herein lies a remarkable advantage that the Application of the crosslinking agents of the present invention. So through the Application of the crosslinking agents of the present invention does not apply the flakes alone to flat surfaces, but can also be fixed on curved surfaces, regardless of the degree of Bulge and curvature. To the objects or substrates on which the flakes according to Invention can be fixed, include all possible types, including fabrics, rubbers, non-woven fabrics, leather, paper, cleaning cloths, wood, veneer panels, clay surfaces, synthetic resins, Concrete, slate, all kinds of toys, ceramic goods, metals and the like.

Nowadays the so-called non-woven fabrics are made by joining disorderly Fibers made with adhesives are widely used for wadding garments. So far, these non-woven fabrics have been manufactured in such a way that the Fabric web either with aqueous dispersions or with emulsions of natural or synthetic Rubber soaked, the additives of vulcanizing agents, vulcanization accelerators and aging retarders contained, and then dried in the heat. The non-woven fabrics made in this way are elastic and can hardly be crumpled or creased, but do not pose any satisfactory problems.

due to their poor resistance to aging and their inadequate properties Resistance to solvents such as those used in dry cleaning, especially against chlorinated hydrocarbons such as trichlorethylene. Few of them suffice in each With regard to the requirements for elasticity, flexibility, resistance to aging and resilience against organic solvents. In practicing the present invention, however, one can Process the fabric in such a way that it is not only in terms of its elasticity, flexibility and resistance to aging largely improved, but also remarkably resistant to organic Solvents that are commonly used in dry cleaning.

As fibers that can be processed into the fabric web, you can, for. B. the most diverse fibers of animal origin, such as alpaca wool, rabbit hair, camel hair, cashmere wool, wool, Mohair, llama hair and silk, as well as vegetable fibers such as cotton, kapok, linen, hemp, synthetic fibers such as B. viscose rayon, cellulose acetate, vinylidene chloride-vinyl chloride mixed polymer fibers, Polyamide fibers, polyester fibers, polyacrylonitrile fibers, and mineral fibers such as glass wool and asbestos fibers.

In the following examples, the parts and percentages mean parts by weight and percentages by weight, respectively.

There is now a printing paste using this latex according to the following approach manufactured:

example 1

The following emulsion is made with the help of a high-performance homogenizer:

50 parts of ethylene glycol bis (thionophosphoric acid di-N, N-ethylene amido ester) according to formula I, 2 parts of polyoxyethylene alkyl ether (nonionic surface-active agent), 948 parts of water.

35

40.

This emulsion is applied to a bleached viscose rayon fabric by padding. The fabric is dried and ^{cured at 150 °} C. for 3 minutes. The fabric treated in this way had been considerably improved in its structural stability, in its grip and in its crease resistance. A viscose artificial silk fabric treated in this way can be dyed bright red with brilliant scarlet 3R, while the viscose artificial silk that has not been treated in the manner described has only a lower affinity.

Example 2

55

A mixed polymer latex containing 40% solids is made as follows:

40 parts of a monomer mixture consisting of 78 parts of butyl acrylate, 20 parts of acrylonitrile and 2 parts of acrylamide is made with 1 part of a 14% aqueous solution of sodium oxoctadecanesulfonate, 0.5 parts of potassium persulfate and 58.5 parts of water mixed and polymerized in an autoclave, until the reaction of the monomer mixture has ended, with a mixed polymer latex ' is obtained which contains the polymer in an amount of 40%.

300 parts of the latex described above, 200 parts of a 5% aqueous solution of

Methyl cellulose,
100 parts of a 20% aqueous paste of a

Copper phthalocyanine pigments, 20 parts of diethylene glycol bis (phosphoric acid di-N, N-ethylene amido ester) according to formula IV, 70 parts of water,
10 parts of a 50% strength aqueous solution of

Ammonium nitrate,

300 parts of naphtha (mineral spirit) (boiling range 150 to 21O ⁰ C).

These ingredients are homogenized with the help of a high-performance mixer until the heavy fuel is completely emulsified and the printing paste is thus ready for use.

This printing paste is then printed on cloth of cotton, viscose and rayon, dried and subjected to a 5 minute heat treatment at 13O ⁰ C. The prints finished in this way are not only excellent in terms of their lightfastness and their fastness to washing, but they also show no tendency to peel off, even when washing is carried out by hand, a treatment of which substances are made by the usual pigment printing process have been printed, do not withstand to a technically satisfactory extent.

Example 3

100 parts of the latex described in Example 2, 5 parts of ethylene glycol bis (thiophosphoric acid di-N, N-ethylene amido ester) according to formula I,

100 parts of water

are homogenized to a milky dispersion in a high-performance mixer. This aqueous dispersion is sprayed onto the surface of a fabric web made of disordered polyester fibers, so that the fibers are connected to one another, but the fabric web surface remains porous as it was. The web is then immersed in this aqueous dispersion and soaked with it, then squeezed between rollers so that it is well impregnated with the dispersion serving as binder, the excess binder being removed by the squeezing, is then dried and for 5 minutes exposed to a heat of 150 ^° C., so that the fibers in the fabric web are definitely brought into mutual contact or mutual superposition.

The non-woven fabrics obtained in this way have excellent flexibility, Elasticity, resistance to aging and an excellent grip and change these properties not if they are treated with solvents such as those used in dry cleaning come, such as B. trichlorethylene. Not, woven cloths made with the help of said aqueous ones Dispersion produced differ from those produced by means of known binders were produced, largely by the fact that

R. > HC ^ Xi Ο — A — O X ₂ R. Il T τ - ρ - - Ρ --Ν ( HC _x I. / CH V Yi Y ₂ I. ^ CH R '

the former do not yellow even after prolonged exposure to sunlight.

Claims (1)

Claim: Process for crosslinking high molecular weight organic substances, characterized that one poly (N, N-ethylene amidophosphates) or their thio derivatives of the general formula IO dries and brings 3 to 30 minutes to 100 to 200 ⁰ C, where A denotes a divalent radical of the aliphatic, cycloaliphatic, heteroaliphatic or heterocyclic series, Xi and X represent ₂ oxygen or sulfur atoms, R and R 'represent hydrogen atoms or a monovalent one Hydrocarbon radical and Yi and Y2 denote an alkoxy, thioalkoxy, amido or alkylenamido radical corresponding to the formulas OR ", SR ", —N: - Ν; , CHR ₁
^ CHR, to form solutions of the high molecular weight substances or their aqueous dispersions or mixes up applies solid high molecular weight substances, which corresponds to substances, where R ", Ri and R2 for a hydrogen atom or a monovalent hydrocarbon radical.