RU2387677C1 - Oligo(alkylene)alkoxy siloxanes for modifying fibre materials and synthesis method thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: oligo(alkylene)alkoxy siloxanes of general formula

are proposed, where R=CH₃; C₂H₅; C₃H₇; C₄H₉; x=0,1; m=5-15, as well as a method for their synthesis through hydrolytic condensation of alkylene trialkoxy silane with given amount of water in a liquid alcohol-water medium while boiling.

EFFECT: design of a method for obtaining chemically active compounds which contain different functional groups, which can be modify the surface of fibre materials with chemically active alkylene siloxane template polymer coatings.

3 cl, 1 tbl, 8 ex

Description

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

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

x is 0.1; m = 5-15,

and the method for their preparation.

Oligo (alkylene) alkoxysiloxanes are chemically active compounds. Alkoxy groups covalently bonded to silicon atoms are capable of entering into the reactions of condensation, alcoholysis, esterification, substitution under the action of water, alcohols, carboxylic acids and halogens, and alkenyl radicals are capable of entering into the reactions of radical, ionic and ion-coordination polymerization under the influence of radicals, ions and organometallic compounds (Ziegler-Natta catalysts).

They can be used to construct on the surface of fibrous materials alkylene siloxane template (covalently linked to the surface of the fibrous material) polymer coatings of a given composition, structure and structure, which contain reactive alkenyl groups on the surface. Fibrous materials modified with such alkylene siloxane 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 ethylene or propylene groups forming a nanoscale template polyethylene or polypropylene polymer coating (second generation coating), which covalently binds all fibers into a single structure - a layered composite material similar to delta wood or plywood, where a chemically active template al is used as a binder ilensiloksanovoe 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 (alkylene) 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 (alkylene) alkoxysiloxane, drying at room temperature in the presence of catalytic amounts (from 0.0006 to 0.12% by weight) 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 (alkylene) alkoxysiloxanes, their properties and the production method are not described in the literature.

Polyethoxysiloxanes are known (RF Patent No. 2270892 of 02.27.06 “Method for the production of nonwoven textile materials with increased strength, a stable aromatic odor and antimicrobial properties using polyethoxysilanes containing pharmacophore organoxysilyl ligands”) and oligoethoxy (isobutoxy) siloxanes21 (RF Patent No. 21 dated 05.20.02 “Non-woven textile material”), which, when processing fibrous materials, are capable of forming hydrated silicon oxide coatings on their surface

- HO- (SiO ₂ ) _x -OH, giving the surface of fibrous materials chemical activity. 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 (isobutoxy) siloxanes is that the self-adhesive 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 CH = CH ₂ , x = 0.1), oligo (alkylene) alkoxysiloxanes, which could be used as agents capable of modifying the surface of fibrous materials with chemically active alkylene siloxane template coatings (covalently bonded to the surface of the fiber) polymer coatings capable of forming nanoscale template coatings (second generation coatings) covalently linking all fibrous materials All in a single structure - a conceptually new generation of high-strength non-woven materials designed as delta wood or plywood, where the reactive template alkylene siloxane polymer coating or the second generation is used as a binder, and the fibrous material is used as veneer, or vice versa.

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

It is advisable to use vinyltrimethoxysilane and allyl trimethoxysilane as alkylenetrialkoxysilanes, and methanol as an alcohol; vinyltriethoxysilane, allyltriethoxysilane, and ethanol as the alcohol; vinyltripropoxysilane, allyltripropoxysilane, and propanol as the alcohol; vinyltributoxysilane, allyltributoxysilane, butanol as 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).

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

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

Example 1. Decavinyl dodecamethoxydecasiloxane (I). A mixture of 13.8 g (0.1 mol) of vinyltrimethoxysilane, 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 the residue 7.04 g (97%) of compound (I) were obtained, b.p. above 250 ° C at 760 mm Hg, n _d ²⁰ 1.4180; d ₄ ²⁰ 1,1180 g / cm ³ .

Found,%: C 5.25; H, 9.00; Si 38.35.

C ₃₂ H ₆₆ Si ₁₀ O _21.

Calculated,%: C 5.32; H, 9.21; Si 38.90.

Example 2. Pentavinylheptaethoxypentasiloxane (II). Analogously to example 1, from 9.5 g (0.05 mol) of vinyltriethoxysilane, 0.73 g (0.04 mol) of distilled water in 12 g of ethanol, 6.42 g (98%) of compound (II) are obtained, b.p. above 250 ° C at 760 mm Hg,

n _d ²⁰ 1.4050; d ₄ ²⁰ 0.9543 g / cm ³ .

Found,%: C 43.92; H 7.38; Si 21.53.

C ₂₄ H ₅₀ Si ₅ O _11.

Calculated,%: C 44.0; H, 7.69; Si 21.43.

Example 3. Pentavinylheptapropoxypentasiloxane (III). Analogously to example 1, from 11.65 g (0.05 mol) of vinyltripropoxysilane, 0.73 g (0.04 mol) of distilled water in 12 g of propanol, 7.15 g (95%) of compound (III) are obtained, b.p. above 250 ° C at 760 mm Hg, n _d ²⁰ 1.4160; d ₄ ²⁰ 0.9938 g / cm ³ .

Found,%: C 49.23; H 8.36; Si 18.37.

C ₃₁ H ₆₄ Si ₅ O ₁₁ ..

Calculated,%: C 49.42; H 8.56; Si 18.64.

Example 4. Pentavinylheptabutoxypentasiloxane (IV). Analogously to example 1, from 13.72 g (0.05 mol) of vinyltributoxysilane, 0.73 g (0.04 mol) of distilled water in 15 g of butanol, 8.10 g (95%) of compound (IV) are obtained, b.p. above 250 ° C at 760 mm Hg, n _d ²⁰ 1.4585; d ₄ ²⁰ 1.1265 g / cm ³ .

Found,%: C 53.45; H, 9.12; Si 16.15.

C ₃₈ H ₇₈ Si ₅ O ₁₁ .

Calculated,%: C 53.60; H, 9.23; Si 16.49.

Example 5. Decavinyl dodecaethoxydecasiloxane (V). Analogously to example 1, from 19.5 g (0.1 mol) of vinyltriethoxysilane, 1.62 g (0.09 mol) of distilled water in 21 g of ethanol, 12.11 g (98%) of compound (V) are obtained, b.p. above 250 ° C at 760 mm Hg,

n _d ²⁰ 1.4225; d ₄ ²⁰ 1,1150 g / cm ³ .

Found,%: C 42.80; H, 7.40; Si 23.0.

C ₄₄ H ₉₀ Si ₁₀ O _21.

Calculated,%: C 42.75; H 7.33; Si 22.73.

Example 6. Pentaallylheptabutoxypentasiloxane (VI). Analogously to example 1, from 14.45 g (0.05 mol) of allyltributoxysilane, 0.73 g (0.04 mol) of distilled water in 16 g of butanol, 8.84 g (96%) of compound (VI) are obtained, b.p. above 250 ° C at 760 mm Hg, n _d ²⁰ 1.45385; d ₄ ²⁰ 1.1235 g / cm ³ .

Found,%: C 55.95; H 9.78; Si 15.35.

C ₄₃ H ₈₈ Si ₅ O ₁₁ .

Calculated,%: C 56.03; H, 9.623; Si 15.24.

Example 7. Decaallyldodecaethoxydecasiloxane (VII). Analogously to example 1, from 20.43 g (0.1 mol) of allyltriethoxysilane, 1.62 g (0.09 mol) of distilled water in 22 g of ethanol, 13.22 g (96%) of compound (VII) are obtained, b.p. above 250 ° C at 760 mm Hg, n _d ²⁰ 1.4590; d ₄ ²⁰ 1.1320 g / cm ³ .

Found,%: C 47.0; H 8.0; Si 20.5.

C ₅₄ H ₁₁₀ Si ₁₀ O ₂₁ .

Calculated,%: C 47.12; H, 8.05; Si 20.40.

Example 8. Pentadecavinylheptadecaethoxypentadecasiloxane (VIII). Analogously to example 1, from 28.54 g (0.15 mol) of vinyltriethoxysilane, 2.52 g (0.14 mol) of distilled water in 30 g of ethanol, 15.9 g (95%) of compound (VIII) are obtained, b.p. above 250 ° C at 760 mmHg, n _d ²⁰ 1.4650; d ₄ ²⁰ 1.1329 g / cm ³ .

Found,%: C 45.67; H 7.71; Si 16.38.

C ₆₄ H ₁₃₀ Si ₁₅ O ₃₁

Calculated,%: C 45.84; H 7.81; Si 16.45.

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 (alkylene) 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 predetermined weight gain (0.05-10% by weight) of alkylene siloxane polymer coating is obtained on the fibrous material. With 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 alkylene siloxane template polymer coating (Scheme 2). Such an alkylene siloxane polymer coating is very firmly attached to the surface of the fibrous material and can only be removed by treatment with hydrofluoric acid or by prolonged boiling in a concentrated alkali solution.

A distinctive feature of alkylene siloxane 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 nanoscale template polyethylene or polypropylene coatings (second-generation coatings) that bind fibrous materials into a single structure - layered composite material, which is a conceptually new generation of high-strength non-woven textile materials.

Tests of textile materials manufactured by autogesion pressing of modified fibers from 0.05 to 10% (mass.) Oligo (alkylene) alkoxysiloxanes of the specified general formula and catalyst from 0.0006 to 0.12% (mass.) Showed that they have high strength characteristics, 12–20 times higher than similar characteristics of native samples, stiffness is reduced by 30–40%, and air permeability of nonwoven materials is increased by 15–18%. 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 (alkylene) alkoxysiloxane, drying at room temperature, in the presence of catalytic amounts (from 0.0006 to 0.12% by weight) of hydrogen peroxide, and calendering of the fibrous web is carried out at a temperature close to the temperature of fluidity of the polymer fiber, a pressure of 20 · 10 ⁵ PA, time 0.02 s.

Scheme 1.

mCH ₂ = CH (CH ₂ ) _x Si (OR) + (mI) H ₂ O

where m = 10, x = 0, R = CH _3> (I);

m = 5, x = 0, R = C ₂ H ₅ (II), C ₃ H ₇ (III), C ₄ H ₉ (IV);

m = 10, x = 0, R = C ₂ H ₅ (V);

m = 5, x = 1, R = C ₄ H ₉ (VI);

m = 10, x = 1, R = C ₂ H ₅ (VII);

m = 15, x = 0, R = C ₂ H ₅ (VIII).

Table Physico-mechanical properties of nonwoven thermally bonded materials obtained using decavinyl dodecaethoxydexylsiloxane (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, εр,% Rigidity, cN Breathability, dm ³ / (min · m ² ) one 0.05 0,0006 230 56.7 32 7.5 1090 2 0.25 0.003 230 60.0 24 5.7 1100 3 5 0.06 230 54.3 29th 5,4 1070 four 10 0.12 230 52.3 31 6.0 1050 * the content of the catalyst in the nonwoven material 0.12% (mass)

Claims (3)

1. Oligo (alkylene) alkoxysiloxanes of the General formula

where R = CH ₃ ; C ₂ H ₅ ; C ₃ H ₇ ; C ₄ H ₉ ;
x is 0.1; m = 5-15. 2. The method of producing compounds according to claim 1, characterized in that the alkylene 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 if vinyltrimethoxysilane or allyltrimethoxysilane is used as an alkylenetrialkoxysilane, then methanol is used as an alcohol; if vinyltriethoxysilane or allyltriethoxysilane is used, then ethanol is used as the alcohol; if vinyltripropoxysilane or allyltripropoxysilane, then propanol; if vinyltributoxysilane or allyltributoxysilane, then butanol.