CS224611B2 - Method for producing silyled polyethers - Google Patents

Description

The present invention relates to silylated polyethers and, more particularly, to a process for preparing silylated polyethers. The present invention also relates to textile materials coated with silylated polyethers and to a method of coating such textile materials.

Hitherto, textile materials have been treated with compositions comprising an hydroxyl-terminated organopolysiloxane, a crosslinking agent, and a catalyst to impart a soft, silky, durable feel to these materials. (See Burrill U.S. Patent No. 3,376,459 and Richardson U.S. Patent No. 3,770,489). Although treatment with these organopolysiloxanes is very effective for the desired purpose, the treated materials acquire certain undesirable properties. For example, organopolysiloxane-treated textile materials tend to become easier to spot. In addition, organopolysiloxanes tend to impart hydrophobic properties to the treated textile materials, which reduces the pleasant properties of the material. Furthermore, organopolysiloxanes are generally applied to textile materials in the form of emulsions and these emulsions tend to separate during application, causing uneven coating. If these coated textile materials are subjected to further processing such as dyeing or printing, the uneven dispersion of the organopolysiloxanes on the surface of the textile materials adversely affects the print quality and coloring of the materials. Another disadvantage of the organopolysiloxanes is that they generally require more than one component and once the components are mixed, the resulting mixture has limited stability.

Silicone-containing materials which impart dirt-repellent or dirt-releasing properties to textile materials are described by Pittman in US Patent Nos. 3,716,517 and 3,716,518. These silicone-containing materials are prepared by copolymerizing at least one monomer capable of producing oleophobic properties with at least one monomer capable of cause hydrophilic properties. As the oleophobic monomer, a silane containing a terminal perfluoroalkyl group having 3 to 18 perfluorinated carbon atoms is used. The hydrophilic monomer used is a silane which contains two or more alkylene oxide groups in which the alkylene groups contain from 2 to 6 carbon atoms. These hydrophilic monomers are prepared by converting a mono-etherified polyalkyleneoxyglycol into the corresponding allyl ether by reaction with an alkyl bromide in the presence of a base, and then reacting the intermediate obtained with a strong hydrogen-containing catalyst in the presence of a platinum catalyst. and then a hydrogen-containing silane and a platinum catalyst are added to the resulting intermediate.

In the preparation of the hydrophilic monomers described above, one of the essential components is the unsaturated polyethers which are not readily available commercially. These terminally unsaturated polyethers can be prepared by reacting monoetherified polyalkyleneoxyglycols with allyl chloride. Further, the silicone compounds described by Pittman et al. Contain an ester group, while the silylated polyethers of the invention contain diester bonds.

Therefore, one of the advantages of the present invention is that the silylated polyethers of the invention use materials that are more readily available than polyoxyalkylene glycols and haloalkylsilanes. Another advantage of the silylated polyethers of the invention is that the silylated polyethers crosslink to form hydrophilic coatings on the treated textile materials. Hydrophilic properties improve the comfort of textile materials by absorbing body sweat. Further, the silylated polyethers of the invention impart softness to the treated textile materials, which removes the hard feel delivered to the textile materials by treatment with aminoplasts. It has also been found that the silylated polyethers of the invention are equal to aminoplasts and can, in certain applications, replace aminoplast resins.

It is an object of the present invention to provide a process for preparing silylated polyethers. According to the present invention, silylated polyethers are prepared which can be applied to textiles, materials and give them a soft silky touch and dirt build-up resistance. The silylated polyethers of the invention applied to textile materials impart hydrophilic properties to them. The silylated polyethers of the invention are water soluble and do not degrade before or / and during application to textile materials. A one-component, water-soluble, stable silicone containing fabric treatment agent is prepared from the silylated polyethers of the invention.

The object of the present invention is a process for the preparation of silylated polyethers of the general formula ^H 2 ^(OC n ^H 2n> x ^R S <j ^{HR k} c

CH ₂ (OC _n ^H _2n ) _x Й A _d wherein at least one R is a radical of formula

0 №! II

-OC-R-C-O wherein the residue is bonded to the polyether by an ester bond and the remaining R groups are selected from the group consisting of oxycarbon residues containing up to 16 carbon atoms, hydroxyl, or a radical of formula

0

II and II

-OC-R -C-O-H

22461 1 wherein ^R1 is a divalent hydrocarbon radical selected from the group obssbující - _{(CH2) y} -, -CH = CHnebo cyclic moiety selected from záhrmjící CGH ^, _'Q CGH CGH qa C ₁₀ H _6, A is a radical selected silicon obMhujjcí group záurující cationic or anionic radicals of the formula iP-score ²⁾ ^

wherein R, which may be identical or different, are monovalent hydrocarbon radicals having 1 to 18 carbon ^uh> I ^k u, ^{R 3} is a divalent hydrocarbon unnecessarily ^{to 1} and ^{y ≥ 18} atom uih.íku, ^£ is a number. from 0 to 4, b, £ and <1 are numbers from 0 to 1 and the sum of £, c and £ must be at least 1, and if b, c or · £ are 0 then R must be a hydro1 or o2 hydrocarbon residue or the remainder of the formula

O is a number from 0 to 2, j is 2, 3 or 4, p is a number of at least 1 and up to 600, and p is a number from 0 to 8, characterized in that ox is ^^ and ^^ ^ ene glycol of the general formula p ^{(0C _H2n> OG} _x ^p ' «ЛА ^OG' and WaAt" where G is hydrogen or alkyl having 1 to 18 carbon atoms, at least one subssituent be G.musí hydrogen, R is 0 to 4, n is 2, 3 or 4, and R is from 1 to 600, reacted with a compound selected from the group consisting of dicarboxylic acid and ... its cyclic intydride at a temperature of from 80 to 185 ° C and then reacting the resulting product at 50-185 ° C with a haloalkylalkoxysil of general formula.

? ·

XR ³ Si (OR ²⁾ ₃ _ _e wherein R ^2, R ³ and ^£ MMJ výěe Uve ^d Eny meaning and X is ^at allo ^g EUA.

These silylated polyethers may be applied to textile malteiály so that they form a coating ďofiluí UP ^and *

The oxalkylene glycols and copolymers thereof used to prepare the compositions of the present invention are known compounds. . .

In general, these polymers are prepared or various alcohols are used as initiators by copolymerization of the propylene oxide / propylene oxide. Examples of alcohols are glycerol, methanol, ethylene glycol, ethanol, tert-butanol and the like. Suitable examples of cyclic anhydrides which may be used in the preparation of the compositions of the invention are succinic acid anthyrides, glutaconic acid anhydride, maaic acid anhydride, 1,2- cyclohexanedicarboxylic acid, 1-cyclohexene-4-dicarboxylic acid anhydride, 3-cyclohexene, 2-dicarboxylic anhydride, 4-cyclohexene-1,2-dicarboaxylic acid amide, 1,8-naphthenic acid anhydride and phthalic anhydride.

If dicarboxylic acids are used, they are preferably used. esterification catalysts such as titanates, alkali metal hydroxides and mineral acids.

Suitable examples of useful dicarboxylic acids having up to 10 carbon atoms are shearanic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.

Halogenoalkanes which may be used in the preparation of the silyonic polyethers represented by the formula

1 ²

XR ³ Si (ОН ²⁾ ₃ _ ^п wherein R ² and R ³ and £ mm meaning indicated above and X is a halogen atom such as chlorine, bromine or iodine.

Preferred are examples of the halo-2-carboxylic acids used, chloropropyldiminoxysilane, chloropropyl propylene dimethyl oxysilane, chloropropyldimethyl ether: xyssian, bromobutylethyldimethyl oxysilane and the like.

In the above reactions, the ratio of the cyclic anthyride or dicarboxylic acid to the hydroxyl groups attached to the polyether may be expanded to a wide extent. For example, the admixture ratio of cyclic anthyrides or dicarboxylic acid. to the hydroxyl group, it may be polyvalent from 0.17: 1 to 1.25: 1, with the preferred ratio of cyclic anhydride or dicarboxylic acid to hydroxyl groups being from 0.33: 1 to 1.1: 1, with at least one hydroxyl group on mdetol is reacted with a cyclic anhydride or dicarboxylic acid.

In the subsequent silylation of the polyethers, the molar ratio of the carboxylic acid moiety resulting from the reaction of the cyclic anhydride with the above compound to the haloeenalkylated silane moieties may range from 0.17: 1 to 1.25: 1.

Suitable examples of silicon moieties represented by A are:

CH-I ³ ch. | · ^{3 (СНз)} 2 -C ₃ H ₆ Si (OCH ₃ ) ₃ , -C ₄ H ₈ Si (OC ₂ H ₅ ) ₃ , -C 4 Si (OCH ₃ ) ₂ , -СзНб31ос ₂ н &, “ ^C 3 ^H 6 ^S1 ° 1,5 ' ^"C 18 ^H 3 ^{6S l} = ^{1, 5> 'C} 10 ^H 20 ^S ^ ^OC 2 ^H 5 R 2

The unsatisfied bonds of the silicon atoms in the above formulas are satisfied by the silicon-oxygen-silicon bonds.

Suitable examples of the oxyhydrocarbyl radicals represented by the C1-C18 radical are methoxy, ethoxy, ethoxy, butoxy, octyloxy, dodecyloxy, and octadecyloxy. Examples of suitable divalent hydrocarbon residues represented by the symbol ^r1 with 1 to ¹⁰ . at ^ (m ^ ^s alkyl. щсПу are! ^, ethyl. ^, • trimethyl ^, ^ ^^ Amet n, ^p nl ^ ^'y ^ am ^ ⁿ Y5 224,611 polyoxypropylene, hexamethylene, octamethylene and decamethylene. Examples of the divalent aryl radicals R ¹ is phenylene, naphthenylene and cyclohexenylene.

Suitable examples of monovalent hydrocarbon radicals R are alkyl radicals, e.g. methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl and octadecyl, aryl radicals, e.g. phenyl, alkylaryl radicals, e.g. tolyl, xylyl and ethylphenyl, cycloalkyl radicals, e.g. cyclobutyl, cyclohexyl, cyclodecyl, arylalkyl radicals, for example benzyl, 2-phenylethyl, 2-phenylpropyl.

Suitable examples of divalent hydrocarbon radicals R ³ are ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, dodecamethylene, hexadecamethylene and octadecamethylene.

The silylated polyethers of the invention can be applied to textile materials in admixture with other substances which have hitherto been used to impart certain properties to the textile material. Other substances that may be used in admixture with silylated polyethers are lubricants, agents that impart abrasion resistance to treated fibers, substances that improve the odor of the treated substances, antistatic lubricants, fiber softeners, 2 extinguishing agents, spotting agents and agents used for non-crease adjustments. Examples of agents used for creasing are aminoplast resins such as urea and formaldehyde resins, melamine and formaldehyde resins and dimethyloldihydroxyethylene urea, which may contain magnesium chloride, zinc nitrate as catalysts. Other non-creasing agents are phenol-formaldehyde and hydroxyethyl methacrylic resins.

Ř

The silylated polyethers of the invention may be applied in concentrated form or in aqueous solution or as aqueous dispersions or dissolved in organic solvents such as di-n-butyl ether, aromatic hydrocarbons and / or chlorinated hydrocarbons.

These silylated polyethers exhibit a number of excellent properties. Thus, they can be prepared as being water-soluble. They can also be prepared to be water-insoluble but readily emulsifiable or dispersible in water without the aid of emulsifying or dispersing agents.

The amount of silylated polyethers dissolved or dispersed in water may vary within wide limits. In general, the amount of silylated polyethers present in the aqueous solution or dispersed in water may range from about 0.25 to 99%, preferably from 1 to 60%, and most preferably from about 2 to 50%, by weight of the silylated polyethers and solvent.

The silylated polyethers of the invention and optionally other substances can be applied to all textile materials, preferably organic textile materials, to which the organopolysiloxanes have so far been applied or may have been applied. Examples of such textile materials are wool, cotton, rayon, natural silk, hemp, polypropylene, polyethylene, polyester, polyurethane, polyamide, cellulose acetate, polyacrylonitrile fiber, and blends of these fibers. The textile materials may be staple or monofilament.

The silylated polyethers of the invention and other materials may optionally be applied to textile materials in a manner commonly known as spraying, dipping, coating, sanding. by calendaring or sliding the fibers over the substrate _f which is saturated with the silylated polyethers of the invention and optionally other materials.

Generally, the solids delivered to the fabrics are in the range of from 0.025 to 20%, and preferably from about 0.05 to 10% by weight of the original textile material.

After treatment of the textile material, it is dried at an elevated temperature, for example from about 50 to 200 ° C for a short time, for example for 3 to 15 minutes.

The fabric to be treated should contain from about 0.025 to about 10, based on the dry weight of the composition of the invention used for treatment.

The silicone-treated teatile materials of the present invention exhibit all of the properties of prior art treated textile fabrics, such as soft touch and, moreover, have a hydrophilic property and have a hydrophilic property. against spotting.

Certain features of the present invention are further elucidated in the following examples, in which all parts are shown. unless otherwise stated, the parts are thrust.

He did

(a) A mixture containing about 106.1 parts of succinic anhydride and 2,000 parts ^of ethylene ethylene oxide for pentanolic copolymers. 6360 and the ratio hmoonostním oxy · "e ^ o ^ к methylacetylene; ^] ^] ro ^p; ^; i.enu 7: 3 zanMvá ^18h Odin re ^ NADO rises to ¹⁷⁵ ° C. MMN ⁿ KLY prodnkt is another yellow ch ^ v ^ benzotriazoles ^0.004 m ² / s at ²⁵ ° C and containing KYSE ≤ n ≤ 56 oilirkoiotlro ^TU per gram (theory 0.5).

b) About 258.6 parts of the above finished product were mixed with 29.8 parts of chlorotriptyltriorthoxysilate, 15.2 parts of amine treeta and 100 parts of toluene, and the mixture was heated to boiling for 9 hours. The white solid by-product was filtered off. This product was Мгп ^ ГЮоуйо as tri e tyliminhy ^ οοΠΙοι '! d.

^You café. l ^p from ^d. and ^e is ^p odpetfí. and obtained with a high viscosity of ^0.03 m ² / s at ²⁵ ° C. Part of the resulting pr ^ uktu dissolved in a ^DE in the PM ^ ^ i ^p s ¹⁷² ° C. ^{This results in a} rotating rubber film of the product.

Example 2

(a) A mixture containing about 106.1 parts of succinic acid a. 2,000 parts of ethylene-ethylene-rtyl-pentyl-tertiary copolymer of 6,360 and a molar ratio of: ethylene to oxypropylene of 7: 3, 0.1 parts of sulfuric acid and 500 parts of xylene are boiled and boiling water is collected in the DeraoStar. extension. The xylene is removed under vacuum (1 mmHg) at a temperature of up to ca. 150 [deg.] C. The resulting carboxyl-functional polymer is a yellow capsule having an acid content of about 0.59 milligrams per gram (theory 0.5).

About 258.6 parts of the product added in paragraph (a) above were mixed with 29.8 parts of chloropropyl propyl trititoyl, 15.2 parts of treedyamine and 100 parts of toluene, and heated at reflux for 9 hours. The liquid product containing a white solid precipitate was filtered. The white solid precipitate was idrntifUOovέoa as trrthytehedrtchhoride _β

Volatile subjects. The product was removed in vacuo (1 mm Hg) to give a product similar to the dyed polymer formed in Example 1.

Example 3

The procedure of Example 1 was repeated but 155 parts ftatJnnhydridu aOlydrir was replaced by succinic acid portion of the resulting product was dissolved in water and the water is evaporated in Maintaining Method Statement ^p ^ s ¹ 7 ² ° C. ZIS ^Ka ^ obivý medic ^ th film.

22461 1

The procedure of Example 1 was repeated, but 105 parts of maleic anhydride were replaced with succinic anhydride. Part of the resulting ^P ro ^d uktu was dissolved in in ^DE-A in ^d was evaporated, and the ^p ^ i ECI during heat-T. E 172 ° C. ZIS Å ^{to d} robivý gummy film.

Example 4

Comparative Example V,

About 258.6 parts of a polyoxyethylene-propylene pentanol copolymer of a molar eccentric monomer of 6,360 and a 7: 3 molar ratio of oxyethylene to oxypropylene were mixed with 29.8 parts of chloropropyl propyl chloride at 1 ° C for 1 hour. with water and then the water is ⁱ i ^p and the ECI ^{p p} s ¹⁷² ° C. ZIS ^Ka ka ^p alný _Шо? ^kt projecting into the cavity is not screened.

EXAMPLE 5 A textile fabric which is dense and cotton (65/35) is about three. The crosslinked polyethers of the present invention are fabricated by adding the fabric to aqueous solutions containing 0.7% by weight of the various compositions prepared in the Examples and 1.7% by weight of dimethyldihydropylethylene, wherein the percentage of the surfactant is based on the total weight of the solution. The fabric is then dried for two minutes at 170 ° C in an air circulation oven. Hyddooflní charakter ;! fabrics were determined by the procedure described in the AATCC test method 39-1977 entitled Wetealilitd: Svaluativi of. Each fabric is then washed and stelovili again. Table I shows the results of these tests.

Comparative Example Vg

Extensive textile fabric! The cotton / cotton blend (65/35) was treated with an aqueous solution containing 1.7 percent of diethyloldhyloxyoxyamide as described in Example 5. The treated fabric had a hard, firm feel. The test results are shown in the following table:

Table 1

Wetting time (s)

Example # Original 1. washing 2. washing 3. washing 4. washing 5. washing 1 5 6 8 8 1 0 11 2 4 7 8 8 11 1 2 3 7 8 1 1 1 2 12 13 4 13 8 9 1 2 13 comparative Example V ₂ 1 0 1 1 - - -

Example 6

The procedure of Example 5 was repeated except that the dacron fabric was treated with an aqueous solution at a rate of 5% by weight, based on the aqueous solution, of the compositions described in the Examples. In the aqueous solution, diethyl dihydropylethylamine was omitted. Nast ^d dwelling table summarizes the results of these tests:

Example # Original wetting time Wetting time after the first wash 0 1 0 min 1 0 min 1 3 p 20 p 2 4 p 22 p 3 5 sec 30 p 4 4 в 25 p

The above table shows that each composition according to the invention imparts heterogeneous properties to the treated fabric and, after one wash, the fabric has a soft silky touch.

Example 7

The fabrics, including cotton, wool, nylon and rayon, are treated with the blend of Example 1, following the procedure described in Example 5. The treated fabrics exhibit hydrophilic properties and have a soft, silky feel.

Claims (2)

A process for the preparation of silylated polyethers of general formula a wherein at least the ^d en Subbu ^with ituent ^{R eh} unnecessarily ^{to the} general formula wherein the radical is attached to a polyether ester linkage and zbývvaící R groups are selected from the group of radicals oχyulhLlVlΓíklvých obsaauUících to 18 carbon atoms, hydroxyl or a radical of the formula 0 0 H i n -OC * R-COH, wherein ^R1 is ^d ^ vojvazn ^{characterized} uftLov flasher residue ^Yb in early obsstoUící group - ^CH = ^CH or a cyclic radical selected from the group ^C 6 ^{H 4} zaurnUící ^»C 6 ^H 8> ^C 6 ^H 10 ^{C 8} 1 ° ^H 6 ^»A residue of ^ f ^ a ^ UUI ^ (^: s selected from the group silicon zaurnUíeí cationic or anionic radicals of the formula I ² As H ² R _{3 e} 9 224611 о wherein R, which may be the same or different, is a monovalent hydrocarbon radical of 1 to 16 carbon atoms, R 1 is a divalent hydrocarbon radical of 1 to 16 carbon atoms, d is a number from 0 to 4, b, d and d are numbers from 0 to 1 and the sum of b, c and d must be at least 1 and if b, p or d are 0, then R must be a hydroxy or oxycarbon radical or a radical of formula O 0 β í I ' -O-C-R -C-OH e is a number from 0 to 2, n is 2, 3 or 4, x is a number of at least 1 and up to 600, and χ is a number from 0 to 8, characterized in that the oxyalkylene glycol of the formula OG OG G is hydrogen or alkyl of 1 to 18 carbon atoms, with at least one substituent G being a hydrogen atom,? Is a number from 0 to 4,? Is 2, 3 or 4 and i is a number from 1 to 600; with a compound selected from the group consisting of dicarboxylic acid and its cyclic anhydride at a temperature of from 80 to 185 ° C, then reacting the resulting product at a temperature of 50 to 185 ° C with a haloalkylalkoxysilane of the formula ^R e If XR ³ (OR ²⁾ ₃ _ _e wherein R ^2, IP and e are as defined above а X is halogen 2. A process according to claim 1, wherein the haloalkylalkoxysilane is chlorpropyltrimethoxysilane.