RU2417237C2 - Oligo(alkynyl)alkoxysiloxanes for modifying fibre materials and synthesis method thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention discloses oligo(alkylene)alkoxysiloxanes of general formula

where R=CH₃; C₂H₅; C₃H₇; C₄H₉; x=1-4; m=5-15; and a method for their synthesis through hydrolytic condensation of alkynyl trialkoxy silane with given amount of water in a liquid alcohol-water medium while boiling.

EFFECT: disclosed compositions can be used to construct on the surface of fibre materials alkylene siloxane template polymer coatings of given composition, structures which can form nanosize template polymer coatings which bind all fibre materials into a single structure - layered composite material similar to phenol-impregnated modified wood or plywood.

6 cl, 1 tbl, 8 ex

Description

The invention relates to new chemical compounds, specifically to oligo (alkynyl) alkoxysiloxanes of the general formula

where R = CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ ;

x = 1-4; m = 5-15,

and the method for their preparation.

Oligo (alkynyl) alkoxysiloxanes are chemically active compounds. Alkoxy groups covalently bonded to silicon atoms are capable of undergoing condensation, alcoholysis, esterification, substitution by water, alcohols, carboxylic acids and halogens, and alkynyl radicals are capable of undergoing radical, ionic, and ion-coordination polymerizations by radicals, ions, and organometallic compounds (Ziegler-Natta catalysts).

They can be used to construct on the surface of fibrous materials alkynylsiloxane template (covalently linked to the surface of the fibrous material) polymer coatings of a given composition, structure and structure, which contain reactive alkynyl groups on the surface. Fibrous materials modified with such alkynylsiloxane polymer coatings acquire reactivity, i.e. the ability to polymerize under the action of radicals, ions, organometallic compounds and covalently bind together by a three-dimensional spatial network of propylene, butylene and hexylene groups forming a nanoscale template polypropylene, polybutylene, polyhexylene polymer coating (second generation coating) that covalently binds all fibers into a single structure - layered composite material similar to delta wood or plywood, where chemical is used as a binder cally active template alkinilsiloksanovoe coating and as a veneer - a fibrous material, or vice versa.

Such composite materials represent a conceptually new generation of high-strength non-woven textile materials, which can be manufactured using oligo (alkynyl) alkoxysiloxanes of the indicated general formula by the method of autogesion bonding of modified fibers. Modification of the fibers is carried out by impregnation with a 1% alcohol solution of oligo (alkynyl) alkoxysiloxane, drying at room temperature, in the presence of catalytic amounts (0.0006 to 0.12 wt.%) Of hydrogen peroxide, and calendering of the fibrous web is carried out at a temperature close to the fluidity temperature of the polymer fiber, a pressure of 20 · 10 ⁵ PA, a time of 0.02 s

These oligo (alkynyl) alkoxysiloxanes, their properties and the preparation method are not described in the literature.

Polyethoxysiloxanes are known (RF patent No. 2270892 dated 02.27.06. "A method for producing non-woven textile materials with increased strength, a stable aromatic odor and antimicrobial properties using polyethoxysilanes containing pharmacophore organoxysilane ligands") and oligoethoxy (iso-butoxy) siloxanes (patent RF №2182614 from 20.05.02 "nonwoven fabric"), which in the processing of fibrous materials can form on the surface thereof a coating of hydrated silica -. HO- (SiO _{2) x} -OH, gives the surface ti reactivity fibrous materials. Such polymer coatings increase the strength characteristics of non-woven textile materials obtained by auto-adhesion bonding of modified fibrous materials.

However, a significant drawback of the known oligoethoxysiloxanes and oligoethoxy (iso-butoxy) siloxanes is that the autogesion bonding of the fibers modified by them must be carried out at a temperature of at least 140 ° C.

The aim of this invention is the synthesis of chemically active, containing different functional groups (≡Si-OR, ≡Si (CH ₂ ) _x С≡СН), oligo (alkynyl) alkoxysiloxanes, which could be used as agents capable of chemically modifying the surface of fibrous materials active alkynylsiloxane template coatings (covalently bonded to the surface of the fiber) polymer coatings capable of forming nanosized template coatings (second generation coatings) covalently bonding all fibrous materials in a single design - a conceptually new generation of high-strength non-woven materials designed as delta wood or plywood, where the reactive template alkaline siloxane - polyalkylene polymer coating, or the second generation coating, and the veneer - fibrous material, or vice versa are used as a binder.

It should be noted that such non-woven textile materials can be manufactured by autogesion pressing in the presence of catalytic amounts of hydrogen peroxide at room temperature.

Reactive oligo (alkynyl) alkoxysiloxanes are obtained by hydrolytic condensation of alkynyl trialkoxysiloxane with a predetermined amount of water in a liquid alcohol-water medium during boiling.

As alkynyl trialkoxysilanes, it is advisable to use propargyl trimethoxysilane, butynyl trimethoxysilane, hexynyltrimethoxysiloxane, and methanol as the alcohol; propargyl triethoxysilane, butynyl triethoxysilane, hexynyl tripropoxysiloxane, and ethanol as the alcohol; propargyltripropoxysilane, butynyltripropoxysilane, hexynyltropropoxysiloxane, and propanol as the alcohol; propargyltributoxysilane, butynyltributoxysilane, hexynyltributoxysilane, and butanol as the alcohol.

It is advisable to carry out hydrolytic condensation in an alcohol-water medium with a given amount of water in excess of alcohol (Scheme 1, see the end of the description).

These oligo (alkynyl) alkoxysiloxanes are chemically active compounds and can be used to modify fibrous materials and construct on their surface alkynyl siloxane template polymer coatings of a given composition, structure and structure, which are capable of forming nanosized template polypropylene, polybutylene or polyhexylene coating (second generation coatings), covalently bonding all fibrous materials into a conceptually new generation of non-woven textile materials in.

For a better understanding of the present invention, the following examples of the preparation of oligo (alkynyl) alkoxysiloxanes are provided.

Example 1. Decapropargyldodecamethoxydecasiloxane (I). A mixture of 16 g (0.1 mol) of propargyltrimethoxysilane, 1.62 g (0.09 mol) of distilled water in 16 g of methanol was refluxed for 5 hours, then methanol was distilled off from the reaction mixture, and 11 was obtained in the residue. 52 g (97%) of compound (I), i.e. above 250 ° C at 760 mm Hg, n _d ²⁰ 1.4150; d ₄ ²⁰ 1.11 g / cm ³ .

Found,%: C 42.11; H, 5.21; Si 23.93.

C ₄₂ H ₆₆ Si ₁₀ O ₂ .

Calculated,%: C 42.46; H 5.60; Si 23.64.

Example 2. Pentapropargylheptaethoxypentasiloxane (II). Analogously to example 1, from 10 g (0.05 mol) of propargyltriethoxysilane, 0.73 g (0.04 mol) of distilled water in 12 g of ethanol, 7.0 g (98%) of compound (II) are obtained, i.e. above 250 ° C at 760 mmHg, n _d ²⁰ 1.4035; d ₄ ²⁰ 0.95 g / cm ³ .

Found,%: C 48.50; H 7.0; Si 20.1.

C ₂₉ H ₅₀ Si ₅ O ₁₁ .

Calculated,%: C 48.70; H 7.04; Si 19.63.

Example 3. Pentapropargylheptapropoxypentasiloxane (III). Analogously to example 1, from 12.2 g (0.05 mol) of propargyltripropoxysilane, 0.73 g (0.04 mol) of distilled water in 12 g of propanol, 7.7 g (95%) of compound (III) are obtained, i.e., bales. above 250 ° C at 760 mmHg, n _d ²⁰ 1.4140; d ₄ ²⁰ 0.99 g / cm ³ .

Found,%: C 53.0; H, 7.70; Si 17.85.

C ₃₆ H ₆₄ Si ₅ O ₁₁ .

Calculated,%: C 53.16; H 7.93; Si 17.26.

Example 4. Pentapropargylheptabutoxypentasiloxane (IV). Analogously to example 1, from 14.3 g (0.05 mol) of propargyltributoxysilane, 0.73 g (0.04 mol) of distilled water in 15 g of butanol, 8.64 g (95%) of compound (IV) are obtained, i.e. above 250 ° C at 760 mm Hg, n _d ²⁰ 1.4555; d ₄ ²⁰ 1.12 g / cm ³ .

Found,%: C 56.31; H 8.37; Si 15.87.

C ₄₃ H ₇₈ Si ₅ O ₁₁ .

Calculated,%: C 56.66; H, 8.62; Si 15.40.

Example 5. Decapropargyldodecaethoxydecasiloxane (V). Analogously to example 1, from 20.2 g (0.1 mol) of propargyltriethoxysilane, 1.62 g (0.09 mol) of distilled water in 21 g of ethanol, 13.3 g (98%) of compound (V) are obtained, i.e., bales. above 250 ° C at 760 mm Hg, n _d ²⁰ 1.4200; d ₄ ²⁰ 1.11 g / cm ³ .

Found,%: C 47.31; H 6.37; Si 21.12.

C ₅₄ H ₉₀ Si ₁₀ O ₂₁ .

Calculated,%: C 47.82; H, 6.68; Si 20.71.

Example 6. Pentabutinylheptabutoxypentasiloxane (VI). Analogously to example 1, from 15.0 g (0.05 mol) of butynyltributoxysilane, 0.73 g (0.04 mol) of distilled water in 16 g of butanol, 9.4 g (96%) of compound (VI) are obtained, i.e. above 250 ° C at 760 mm Hg, n _d ²⁰ 1.4515; d ₄ ²⁰ 1.12 g / cm ³ .

Found,%: C 58.32; H, 8.87; Si 14.93.

C ₄₈ H ₈₈ Si ₅ O ₁₁ .

Calculated,%: C 58.72; H 9.03; Si 14.30.

Example 7. Decagexynyldodecaethoxydecasiloxane (VII). Analogously to example 1, from 24.4 g (0.1 mol) of hexynyltriethoxysilane, 1.62 g (0.09 mol) of distilled water in 22 g of ethanol, 17.0 g (96%) of compound (VII) are obtained, i.e., bales. above 250 ° C at 760 mm Hg, n _d ²⁰ 1.4570; d ₄ ²⁰ 1.13 g / cm ³ .

Found,%: C 56.13; H, 8.11; Si 16.15.

C ₈₄ H ₁₅₀ Si ₁₀ O ₂₁ .

Calculated,%: C 56.77; H 8.50; Si, 15.80.

Example 8. Pentadecapropargylheptadecaethoxypentadecasiloxane (VIII). Analogously to example 1, from 30.3 g (0.15 mol) of propargyltriethoxysilane, 2.52 g (0.14 mol) of distilled water in 30 g of ethanol, 27.5 g (95%) of compound (VIII) are obtained, i.e. above 250 ° C at 760 mm Hg, n _d ²⁰ 1.4620; d ₄ ²⁰ 1.13 g / cm ³ .

Found,%: C 47.12; H 6.17; Si 21.78.

C ₇₉ H ₁₃₀ Si ₁₅ O ₃₁ .

Calculated,%: C 47.50; H 6.56; Si 21.09.

Compounds (I-VIII) are colorless transparent liquids that are readily soluble in aliphatic and aromatic hydrocarbons, ether, THF, dioxane, alcohols, acetone and insoluble in water. They have high chemical activity and can be used to modify fibrous materials. Modification of fibers, fabrics and textiles is carried out by impregnation with a 1% alcohol solution of oligo (alkynyl) alkoxysiloxane, drying at room temperature and heat treatment at 140 ° C for 20 minutes. The operation of impregnation, drying and heat treatment is repeated until a specified gain (0.05-10 wt.%) Of the alkynyl siloxane polymer coating is obtained on the fibrous material. In this treatment, alkoxyl groups (OCH ₃ , OC ₂ H ₅ , OS ₃ H ₇ , OS ₄ H ₉ ) bound to silicon atoms react with functional groups (OH, COOH, -C = O, -NH-C (O) - and others) of the polymer of the fibrous material and covalently bind to it, forming on the surface of the fibrous material an alkynylsiloxane template polymer coating. Such an alkynylsiloxane polymer coating is very firmly attached to the surface of the fibrous material, and it can only be removed by treatment with hydrofluoric acid or by prolonged boiling in a concentrated alkali solution.

A distinctive feature of alkynylsiloxane template polymer coatings is their chemical activity, i.e. the ability to polymerize under the action of radicals, ions, organometallic compounds (Ziegler-Natta catalysts) and lead to the formation of nanosized template polypropylene, polybutylene, polyhexylene coatings (second-generation coatings) bonding fibrous materials into a single structure - layered composite material, which is a conceptually new generation high strength non-woven textile materials.

Tests of textile materials manufactured by autogesion pressing of modified fibers from 0.05 to 10 wt.% Oligo (alkynyl) alkoxysiloxanes of the indicated general formula and a catalyst - hydrogen peroxide from 0.0006 to 0.12 wt.% Showed that they have high strength characteristics that are 13-20 times higher than those of native samples, stiffness decreases by 40-45%, and air permeability of nonwoven materials increases by 13-20%. Physico-mechanical properties of nonwoven thermally bonded materials are presented in the table.

Modification of the fibers is carried out by impregnation with a 1% alcohol solution of oligo (alkynyl) alkoxysiloxane, drying at room temperature, in the presence of catalytic amounts (0.0006 to 0.12 wt.%) Of hydrogen peroxide, and calendering of the fibrous web is carried out at a temperature close to the fluidity temperature of the polymer fiber, a pressure of 20 · 10 ⁵ PA, a time of 0.02 s

Scheme 1

where m = 10, x = 1, R = CH ₃ (I);

m = 5, x = 1, R = C ₂ H ₅ (II), C ₃ H ₇ (III), C ₄ H ₉ (IV);

m = 10, x = 1, R = C ₂ H ₅ (V);

m = 5, x = 2, R = C ₄ H ₉ (VI);

m = 10, x = 4, R = C ₂ H ₅ (VII);

m = 15, x = 1, R = C ₂ H ₅ (VIII).

Physico-mechanical properties of nonwoven thermally bonded materials obtained using decapropargyldodecaethoxydexylsiloxane (V) No. The content of the modifier, wt.% The content of catalyst, wt.% Press temperature, ° С Specific breaking load, N · m / g Elongation at break, ε _p ,% Stiffness, cH Breathability, dm ³ / (min · m ² ) one 0.05 0,0006 230 76.5 45 8.3 1070 2 0.25 0.003 230 73,2 thirty 6.2 1150 3 5 0.06 230 58.9 36 6.9 1090 four 10 0.12 230 57.3 42 7.6 1100 ^* the catalyst content in the nonwoven material is 0.12 wt.%.

Claims (6)

1. Oligo (alkynyl) alkoxysiloxanes of the general formula

where R is CH ₃ , C ₂ C ₅ , C ₃ H ₇ , C ₄ H ₉ ;
x = 1-4; m = 5-15. 2. The method of producing compounds according to claim 1, characterized in that the alkynyl trialkoxysilane is subjected to hydrolytic condensation with a given amount of water in a liquid alcohol-water medium during boiling. 3. The method of producing compounds according to claim 2, characterized in that proparnyltrimethoxysilane, butynyl-trimethoxysilane or hexynyltrimethoxysiloxane are used as alkynyltrialkoxysilane, and methanol is used as alcohol. 4. The method of producing compounds according to claim 2, characterized in that proparnyltriethoxysilane, butynyl-triethoxysilane or hexynyltriethoxysilane are used as alkynyl trialkoxysilane, and ethanol is used as alcohol. 5. The method of producing compounds according to claim 2, characterized in that propargyltropropoxysilane, butynyltropropoxysilane or hexynyltropropoxysilane are used as alkynyltrialkoxysilane, and propanol is used as alcohol. 6. The method of producing compounds according to claim 2, characterized in that propargyltributoxysilane, butynyl tributoxysilane or hexynyltriboxysilane are used as alkynyl trialkoxysilane, butanol is used as alcohol.