DE1444133A1 - Process for the production of inorganic or organic substances coated with polysiloxane-oxyalkylene block copolymers - Google Patents

Description

»Β. ΙΝβ. F.

PIPL..ING. Ö.

DK. B. T. PECHMANN

'PATBHTAJTWliTB

8 MUNICH O. SCHWEIQBRSTRASSX liuron S3 Oe Ol ΤΗ, ΙβΚΑΧΚΛΟΚΧΙΙΒ >

nonciutün κβηαηκ

description

to the patent application

HAA133

UKION CARBIDE CORPORATION Park Avenue, Hew York U. S.A..

"concerning

Process for the preparation of with polysiloxanes
Oxalkylene bloc copolymers coated inorganic
or organic substances "

The invention relates to coated organic and inorganic carrier substances, in particular organic textile material and inorganic oxides with a coating except for a siloxane-oxyalkylene bloc copolymer that is stable to hydrolysis and a method for their production.

909840/1639

It is known that organic textiles and inorganic-oxidisehe substances are opposed to hydrolyte Apply stable SilQxan-Oxyalkylene-BloekmischpQlymeriBate can to improve the physical properties of these substances. The hydrolysis stability this. Block copolymers are particularly important since the coating does not hydrolyze to any appreciable extent when the material so coated is moisture is exposed.

Inorganic, oxidic substances in various forms, e.g. powders, lasers and fabrics, are widely used used as stiffening or reinforcement for numerous elastomers and plastics. For the industry of particular interest is the use of a powdery, inorganic, oxidic material as a reinforcing material Filler for organic or polysiloxane elastomers (silicones) and the use of glass fibers or fiberglass fabrics to increase the strength of thermosetting plastics.

An important factor affecting the strength of the bond influenced between coated or uncoated inorganic oxides and the elastomer or plastic, is the extent to which the coated or uncoated inorganic oxide material Adsorbs water. This property of the coated or uncoated anortsanisohen Qxyde J.st von Be

909840/1639

interpretation, not only for the first formation of the connection, bonders also for the determination of the extent, in which the connection is caused by aging, heat or the influence of moisture gets weaker.

In many cases it is therefore desirable to reduce the tendency of the organic-oxidic substances to adsorb of 7 / water or to regulate dispersion in water. So it is common to use “a clay granulate as a carrier for insecticides To use substances, where the insecticidal "active ingredient to ^

adsorbed (or absorbed) in the clay granules is “coated this combination of insecticidal active ingredient and clay granules with a siloxane-oxyalkylene copolymer the invention, the speed at which the granules disintegrate and therefore the .Regulate the rate at which the insecticidal active ingredient is released in the event of exposure to the substance. A Another example are many fertilizers, which are mixtures with inorganic-oxidic substances. A with a mixed polymer, as it is for the invention ™

according to procedures is used, coated fertilizer granules offers the possibility of precise adjustment of the speed at which the fertilizer is spread solves.

One object of the invention is an inorganic oxide dis.es Material or a natural, semi-synthetic or synthetic organic textile material,

909840/1639

coated with a siloxane-oxyalkylene block copolymer which is stable to hydrolysis. Another object of the invention is a coated inorganic oxide material in which the tendency to adsorb water can be easily adjusted. A further aim of the invention is an organic textile material, cVu: - is better water-repellent and not over electrostatic charge: nei ^ t. Other objects of the invention are preparations and "/ learn to treat anorgani8cliTOxydiachen and organic fabrics with to hydrolysis stable siloxane Oxyallryl en-Βίο copolymer is at ₉ en

According to the invention, the inorganic oxide material which can be used includes; Fiberglass, quartz, Silicates, mica, sand, talc, biatome earth, clay, Asbestos, crystalline zeolites, iron oxides, zinc oxide, alumina, calcium oxide, barium oxide, ohromoxide, titanium dioxide and lime.

According to the invention, any natural, semi-synthetic or synthetic organic textile material can be covered. So can as natural and semi-synthetic textile materials are called: cotton, linen, eami, hemp, jute, wood fibers, paper, Leather, furs, feathers, cellulose ethers, cellulose esters - such as cellulose acetate and wood pulp -, regenerated

909840/1639

BATH ORIGINAL

Cellulose ~ rayon made by any process like according to Ä, era viscose or copper oxide ammonia process; natural silk, tussah silk and wool.

Suitable synthetic organic textiles can be made from single threads and endless fiber yarns, such as polyamides (NYLON), acrylates and vinyl and vinylidene fibers (ORION, AGEIIM, GRESIM, OTIDSIi,! DRALON, VEEEI, VINYON, TEFION), polyester fibers ( DAOBOH, TlSXEBNE) and polyethylene fibers. One can also treat% of öarngemisehen produced textiles, by spinning a combination of certain natural, semi-synthetic and synthetic parsers are from a whole number of above-mentioned textile and fiber materials, for example obion wool, NYION wool, obion-EAYON, BYNEI-VISGOSE , DAORON-BaumwoHe and DACRON-NYIiON.

According to the process according to the invention, the organic textile material can be mixed with the siloxane-oxyalkylene block polymers treat to water repellency of textiles to improve their softness, dirt repellency, crease resistance and dimensional accuracy as well to achieve a melting of the textile fiber.

The selection of the siloxane-oxyalkylene block copolymers used as treatment agents depends on the special au-improving properties of the textile

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materials. So you can, for example, to prevent electrostatic charging or to improve use any block polymer that can be used for dirt repellency purposes. Is first line to improve water repellency / are block copolymers with silicon-bonded hydrogen atoms, i.e., copolymers having units of the following formula 1-a, were used. Is the main objective of the coating a melting (lubrication) of the fibers becomes a Block copolymer without hydrogen atoms bonded to silicon is preferred.

That which can be used for the process according to the invention Textile material can be in the form of individual threads, rovings, yarns, mats or fabrics. The inorganic-oxydisohe Material can be in the form of powders,! Peilchen, roving, fibers, mats or ge * - weave apply. The principles of choosing a specific material and the shape of the material are well known.

909840/1639

The organosiloxane-oxyalkylene copolymers, the β loh for the preparations according to the invention belong to the class of block copolymers. Block thermoplastics consist of at least two sections or blocks, being at least one section or block of one type of repeating units or groups (e.g. siloxane groups, as in the case of the copolymers according to the invention) and at least one another section or block, on, another type of repeating units or groups (see e.g. -; xyalkylene groups, as in the case of the copolymers according to the invention). Block micropolymers can be linear, cyclic, branched or crosslinked.

The siloxane block in the copolymers for the Preparations according to the invention contain at least two siloxane groups of the formula

where J! a monovalent hydrocarbon residue, a halegön-substituted monovalent hydrocarbon radical or represents a divalent hydrocarbon radical and b is 1 or 2 or 3 · Preferably each contains Substituent E 1 to 20 carbon atoms. The groups E can be the same or different in each siloxane group or within the biloxane look. Auoh the values for b can be the same or different in the various siloxane groups in the siloxane look. The two-

909840/1639

Valuable hydrocarbon radicals E connect the siloxane block with the oxyalkylene block. Each Siloxanbloek contains at least one group of the formula (1) _? where at least one Best H is a divalent hydrocarbon radical. I) he polysiloxane block has a ratio of hydrocarbon groups to silicon atoms of Ί ti to

Examples of monovalent hydrocarbon radicals E in formula (i) are the alkenyl, cycloalkenyl, Alkyl, aryl, aralkyl, alkaryl and the oyoloalkyl radicals,

Examples of halogen-substituted monovalent hydrocarbons groups II in the formula (1) are the chloromethyl,! Erichloräthyl-, perfluoro vinyl, p-bromobenzyl, Iodophenyl, c * -chloro-ß-phenylethyl, p-chlorotolyl and Bromocyclohexyl radicals.

Examples of the divalent hydrocarbon group E in the formula (1) are the alkylene groups, the arylene groups and the alkarylene groups «is preferably the divalent hydrocarbon radical is an alkylene radical with 2 to 4 consecutive carbon atoms. Siloxane groups with divalent radicals as substituents can be illustrated, for example, by the formulas

-GH ₉ CH ₉ SiO ₁ c -CH ₉ CHCH ₉ SiO _{1 Λ} and -CH ₉ CH ₀ SiO-,

CC i, i>, <- c- I, U c. d _t {

CH ₅

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Η44Ί33

These divalent hydrocarbon radicals are attached to a silicon atom of the polysiloxane block via a silicon-carbon bond chained and to an oxygen atom of the .Oxyalkylene locks via a carbon-oxygen bond.

The siloxane block can contain siloxane groups, which are represented by the formula (1), wherein ent neither the same hydrocarbon radicals to the Silicon atoms or various hydrocarbon radicals are linked to the silicon atoms.

The siloxane block in the copolymers which are suitable for the preparations of the invention can be or contain more types of polysiloxane groups represented by the formula (I), provided that that at least one group has at least one divalent hydrocarbon substituent, for example, only ethylene-methylsiloxy groups can

be contained in the siloxane block or the siloxane block can contain more than one type of siloxane groups. Thus, the block can contain both ethylene-methylsiloxy groups and diphenylsiloxy groups, or it can contain the Block xthylenemethylsiloxy groups, diphenylsiloxy groups and contain diethylsiloxy groups.

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The Siloxanbloek, which is in the for the invention Containing mixed polymers suitable for preparations, trifunctional siloxane groups, bifunctional siloxane groups, monofunctional siloxane groups, or combinations of these siloxane groups with the same or different substituents. Because of the functionality of the siloxane groups the siloxane block can be mainly linear or cyclic or branched or it can be combinations of these Structures included.

The siloxane block which is contained in the mixed polymers suitable for the purposes of the invention, can organic terminal groups as well as monofunctional ones Contain siloxane terminal groups of the formula (1). For example, the siloxane block can be used as a terminal Group the hydroxyl group, aryloxy radicals, alkoxyreete and contain aoy / iloxy residues

The siloxane blocks in the copolymers which are useful in the preparations according to the invention prove to contain at least 2 siloxane groups of the formula (1). The siloxane blocks preferably contain a total of at least 5 siloxane groups represented by the formula (1) and the following formula (1-a). The part of the average Molecular weight of the mixed polymer, which can be traced back to siloxane blocks, can be up to au 50,000 or more.

809840/1830

ORIGINAL INSPECTED

H44133

flu {| Uo? afiWoolt know nefeen the groups of

(1) tin ο de ι · several silo groups of the formula

$ 41 · Same meaning as for ? f * §tl (i)! Wii% ft | · G © 4 · * is 1 or 2, f 1 or 2

1 «> $ w a« <§ *? 3

; p $ t OxyiliJtylfalilöoke in the copolymers,

di · filf the preparations according to the invention may WfjHlen USAGE-, each containing at least 2 oxy-

formula

(2)

WQ ^ el B ^{1 represents} an alkylene radical. The alkylene radical R * in formula (2) preferably contains 2 to 10 carbon atoms, in particular 2 or 3 carbon atoms. Dan copolymers Waaserlb'slichkeit is awarded when E contains ^one less than 3 carbon atoms. It is therefore important that at least one -CρΆ ^ Ο-ατην-ρβ is present in the copolymer if this is to be at least partially water-soluble. Examples of ^u xyalkylene groups represented by the formula (2) are the oxyethylene, oxy-1,2-propylene, oxy-1,3-propylene, oxy-2,2-dimethyl-1,3- propylene and oxy-1, 10-deoylene groups.

9098 ^ _{0/1639 ocrTPD}

ORIGINAL INSPECTED

The oxyalkylene blocks in the copolymers which are suitable for the preparations of the invention can contain one or more different types of oxyalkylene groups of the formula (2). For example, the oxyalkylene blocks can contain only oxyethylene groups or only oxypropylene groups or both oxyethylene and oxypropylene groups or other combinations of the various types of oxyalkylene groups of the formula (2).

The oxyalkylene blocks in the copolymers which are suitable for the preparations according to the invention, can have organic terminal groups. For example, the oxyalkylene blocks as terminal Groups the hydroxyl group, the jlryloxyrest, .. the llkoxyest and contain the alkenyloxy radical. Even a single one Group can be used as a terminal remainder for more than one Oxyalkylene blocks are used. For example, the glyceroxy group

ν HoCHG Hq

t ^C I t ^

0 0 0
»·» ■ -..-

serve as a terminal group for three oxyalkylene chains.

The oxyalkylene blocks in the copolymers which are suitable for the preparations according to the invention, each contain at least 2 oxyalkylene groups of the formula (2). Preferably each block contains at least

■ ""'"-■> ■■« ...': 9098 40/163 9

" ¹⁵ ■" HU133

, four such groups. The part of the total molecular weight of the mixed polymer which can be attributed to the oxyalkylene blocks can vary from 88 for (O ₂ H ^ O) ₂ to 50,000 or higher!

The block copolymers useful in the invention Suitable preparations can contain siloxane blocks and oxyalkylene blocks in various amounts. In order to achieve the desired properties, the copolymer should contain from 5 to 95 parts by weight of siloxane blocks and from 5 to 95 parts by weight of oxyalkylene blocks per 100 parts by weight Polymer included. The copolymers preferably contain 5 to 50 parts by weight of polysiloxane blocks and 50 up to 95 parts by weight of oxyalkylene blocks per 100 parts by weight of copolymer.

The block copolymers which are suitable for the preparations according to the invention can be more than contain one of the various blocks and the blocks can be arranged in various arrangements, so that linear, cyclic or branched structures result, the following classes of substances are examples for the siloxane-oxyalkylene block copolymers to be considered which are suitable for preparations according to the invention suitable:

0/1639

; : - - .; ■ -Λ. ■. ■■■■ -. '■: I

Copolymers containing at least one unit of the '"■ Λ Formula "" G- "'

li "'(U (J ¹¹ LU (I ¹ SiUx _. IP /

ν - * rl ΊμΓ> »'*

contain.

(B) copolymers containing at least one unit of the formula

_{30113 &} (4)

contain.

(C) copolymers containing at least one unit of the formula

G »'(OG ¹ O _n OG'

SiO _2-0 (5)

contain.

In the above formulas (3), (4) and (5), G means a monovalent hydrocarbon ^{radical or a halogen-substituted monovalent hydrocarbon radical, G 1} a divalent hydrocarbon radical, G "an ethylene radical with at least two carbon atoms, G ^flt a water atom or a monovalent hydrocarbon radical which does not contain any aliphatic unsaturated bonds, η an integer of at least 2 and c 0 or 1 or 2 in formulas (3) and (4) and 0 or 1 in formula (5). 3), (4) and (5) G can stand for the same or different radicals,

909840/1633

η preferably has a value from 2 "to 30 and G-" can mean the same or different groups ", that is to say the G group (OG- ¹ V) _n can be, for example, the groups: - (0C ₂ H ₄ ) _p - , - (0C ₂ H ₄ ) _p (O0 ₅ H ₆ ) _q -, - (OC ₃ H ₆ ) _p - or - (0O ₂ H.) (0OqH ₁ g) - means "where" at. Ρ and q. are integers with a value of at least 1.

The monovalent hydrocarbon radicals and halogen-substituted ones Monovalent hydrocarbon radicals G- in the formulas (3), (4) and (5) can be saturated or olefinic be unsaturated or they can belong to the unsaturated system of a benzene ring. Examples of monovalent Hydrocarbon radicals G- are the straight-chain aliphatic G-groups, the cycloaliphatic G-groups, the aryl groups, the aralkyl groups, the unsaturated ones straight-chain aliphatic groups and the unsaturated cycloaliphatic groups.

Examples of the halogen-substituted monovalent hydrocarbon radicals G are the chloromethyl, trichloroethyl, perfluorovinyl, p-bromobenzyl, iodophenyl, Ot- chloro-β-phenylethyl, p-chlorotolyl and bromocyclohexyl groups.

Preferably, the radicals G- and G- '/ "encompassed by the definition for R in the formulas (1) and (ia) _j7 contain 1 to 20 carbon atoms and the group G" / "encompassed by the definition for R' in the formula (2) J / 2 to 1D Koh-

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üuiii

carbon atoms. Yienn the remainder G- "· a monovalent Hydrocarbon radical without aliphatic ^ unsaturated Has bonds, it preferably contains 1 to 12 carbon atoms. /. ■

Examples of divalent hydrocarbon radicals. G ¹ in the formulas (3), (4) and (5) are the alkylene groups, the arylene groups and the alkarylene groups. In the formulas (5), (4) and (5) ″, G ¹ preferably denotes an alkylene radical having at least 2 carbon atoms.

Example for the alkylene groups G- "in the formulas ·" (5), (4) and (5) which contain at least 2 carbon atoms are the ethylene, 1,2-propylene, 1,3-propylene, 1,6-hexylene, 2-ethylhexylene-1,6 and 1,12-bodecylene radicals.

Examples for the G-ruppeh G · '"- in the formulas (3) ν' (4) and (5) are the saturated straight or branched chain ones aliphatic hydrocarbon groups, the saturated, cycloaliphatic hydrocarbon group pen, the aryl groups and the aralkyl groups. "

Compounds of the following formulas are typical examples of hydrolytically stable siloxane-oxyalkylene block mixed polymers which are suitable for the preparations according to the invention. In the formulas, χ means an integer. If the formula represents a unit of a "polymer", then it goes without saying that the polymer is saturated by terminal groups of the type described above. 9 0 9 8 ^ 0 / f 6 3 9 '^{;; {} '

CH ₃

CHo

ι ^D

CH ₃ (C ₃ Hg) ₃ (OC ₃ Hg) ₁₁ OCH ₂ CH ₂ -SiO

CH ₃

[CHo ^- SiO

-Sl-CH ₂ CH ₂ O (C ₃ HgO) _n (C ₃ H 6) CH ₃

12 ^CH 3

(C) (CHj) ₃ SiO

I J

SiO

cnr

CH ₂ -t

SiO

Si (CH ₃ ) ₃

CH ₂ CH ₂ O (C ₃ H ₆ O) ₁₁ (C ₃ Hg) CH ₃

(a) (CH ₃ ) ₃ sio

CH ₂ CH ₃ SiO

SiO

₆ Si (CH ₃ ).

CH ₂ CH ₂ OCc ₃ H ₆ O) ₁₄ (C ₂ H ^ O) ₁₈ (C ₃ Hg) CH ₃ CHsOCH ₂ CH ₂ OCH ₂ CH ₂ SiO

(f) Jc ₆ H ₅ OCH ₂ CH ₂ OCH ₂ CH ₂ SiO ₁ ^ J

(Gyclisclies Te1; ramer)

CH.

(CH ₃ J ₃ SiOSi-OSi (CH ₃ ) 3

CH ₂ CH ₂ O (C ₂ H ₄ O) ₄ CH ₃

909840/16

(H)

CH3 CH. CH-1 ^J 1 3 1 3

CH ₃ (CH ₃ H ₆ ) O (C ₂ HItO) ₇ (C ₃ H ₆ O) ₇ CH ₂ CHCH ₂ SiO (SIO) ₆

CH ₃ CH ₃

CH ₂ CH ₃

₃ (i) RcH ₃ J ₃ SiOJ ₂ Sl-CHgCHgO (C ₃ H ₆ O) ₁₄ (CH ₂ ) ₈ OCHgCHgSirÖSi (CH ₃ ) ₃ ""]

(J)

CH2CH0 CHgCHc

-Si-CHgCH ₂ O (CH ₂ CHgO) 19 (CHg J ₈ OCHgCHgSiO-

-ix

(lc)

• CHi

GH.

-SiCH ₂ CHgO (CHgCHgO) _χ9 (CHg) 3OCH ₂ CH ₂ -SiO-

0 '

Si (CH ₃ I ₃

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MU133

U)

GHgCH ₂

O (CgH ^ O) ₁₁ (C ₃ H ₆ ) CH ₃

t 3 Ne ₂ SlO

(m)

CHgCHgO (CH ₂ CHgO) ₁₇ CH ₃ .SlO- IcHgCHgOiCHgCH ₂ O) ₁₇ CH ₃ J

(n) (CH ₃ ) ₃ S1 Jo-έΐ ^) SlCH ₂ CH ₂ (OC ₂ H ₄ ) ₁ oOCH ₂

CHV »CH,

CHo

(CH ₃ ) ₃ S1 ί OSl J .OSl-CHgCHg-iOC ^ J ^ -OO ^^ H

('CH. \ CH- • A. -O-si Josic

(CH ₃ ) ₃ S1i O-Sl / OSlCH ₂ CH ₂ (OC ₂ H ^) ₁₀ O CH ₃ CH ₃

9098-0 / 1639

-JLO-

CHo CH ₃ CH ₃ (C3H6) 0 (C ₃ H6O) ₁₂ CH ₂ CHCH ₂ Si0

CH ₃ CH ₃

CH ₃ (C ₃ H ₆ ) O (C ₃ HeO) ₁₂ CH ₂ CHCH ₂ Si joSiiCHs) ^ ^

CH ₃

The siloxane-oxyalkylene block copolymers which are suitable for the preparations according to the invention, can be prepared by various processes known per se. For example, the for this Invention useful copolymers are prepared by a process, wherein one is a mixture of a Siloxane polymer containing a silicon-bonded halogen-substituted contains monovalent hydrocarbon radical and an alkali salt of an oxyalkylene polymer to a brings the temperature high enough to achieve a reaction of the siloxane polymer with the salt to form the interpolymer. This procedure is hereinafter referred to as the "metathesis procedure" denotes and includes a metathesis reaction represented by the following equation leaves"

• (6)

.2.

SILOXANJt- (OSiR X) ₁ . + (MO) _r -OXYALKYLENE ^ SILOXANJi- (OSiR ² O) _r -OXYALKYLENji + rMX

" ²¹ " HU133

2
In the equation, R means a divalent carbon

hydrogen residue, r is an integer with a value of at least 1, preferably from 1 to 4, X is a halogen atom, * M is an alkali metal, SIIOXAN is a siloxane block, OXYCLKYIEN an oxyalkylene block.

The copolymers suitable for the purposes of the invention can also be prepared by other processes are (referred to as "addition process") »where one is a mixture of a siloxane polymer, the one Hydrogen siloxy group (i.e. an HSiO group) Oxyalkylene polymer terminated with an alkenyloxy group and a platinum catalyst prepares the mixture brings to a sufficiently high temperature at which the siloxane polymer and the oxyalkylene polymer together react to form a mixed polymer. The last-mentioned addition reaction can be represented by the following equation

OTfAIErEBN- (OH ⁶ ) r + / ~ HSiO-_7 r SILOXAN>

OWALKYIEN- Z ~ ^OR5 SiO-J7 _r SILOXANE

In the equation, OXYALKYLENE, SILOXANE and r mean the above meanings for the formula (6), OR stands for an alkenyloxy radical and R ^ for an alkylene group with at least 2 consecutive carbon atoms. The addition method is applicable to the Production of such copolymers which contain a siloxane block attached to an oxyalkylene block

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is linked via an alkylene radical which has at least 2 '! has consecutive carbon atoms (e.g. an ethylene, 1,2-propylene or 1,2-butylene group).

When the polysiloxane-oxyalkylene block copolymer on Contains silicon-bonded hydrogen atoms, i.e. that it Contains units of the lormel (1-a), the addition method is used preferred. When one uses the metathesis procedure, many of the silicon-bonded hydrogen atoms become react with the alkali ions, which in the reaction Bgemisoh are present.

If the copolymer useful for the purposes of the invention contains olefinically unsaturated groups which are at Silicon atom are bonded (e.g. when R in the formulas (1) or (1-a) is an alkenyl or cyoloalkeny! Group) these copolymers are preferably added by adding the hydroxyalkylene polymer provided with a terminal alkenyloxy group to a monomeric, hydrolyzable silane with Silicon-bonded hydrogen, which is then a Mixed hydrolysis or mixed condensation with other hydrolyzable Silanes adjoins the hydrogen bonded to silicon and silicon-bonded unsaturated hydrocarbons. containing substance groups, using general

CH2-CHGH2 (QO ₂ H ₄ ) ßOGW usual procedures. This is how the reaction of / with CHaSiHGl ₉

in the presence of a Platinkatylysators with subsequent mixed hydrolysis of the product with OH ₂ -CHSi (OH ₃ ) Gl ₂ , OH and (CH ^) ₅ SiOl to a copolymer that is suitable for

909040/16 39

-23- H44133

gweo & s of the invention and units of the formulas

with end-handed »(öHj) contains ₅ Si0 groups.

Ö3P || atiteilox8ii-Oi: yalkylene blool copolymers, the substances for the preparations according to the invention have the following formulas;

9098 (0/1639

(ρ) (CH ₃ J ₃ Si

CH t

O 'Si ι

^CH 3-

CH ₃ O Si-OSi (CH ₃ ) 3

Molecular weight approx. 5600

(q) (CH ₃ J ₃ Si

Si

CH

3_

19th

O Si

OSi (CH ₃ J ₃

Molecular weight about 7000

0 Si CHq

ι J

Si
t

0 Si (GH ₃ ) ₃ (C ₃ H ₆ ) O (C ₂ H ₄ O) ₁₅ CH ₃

Molecular weight about 3100

9 0 9 8 /. 0 / T-6 3

The coated inorganic-oxide material according to the invention can be produced by dipping the oxide material into a polysiloxane-oxyalkylene block copolymer or a mixture of such copolymers, as they are useful for the process according to the invention, or by dipping the copolymer onto the surface of the oxide Material by brushing, spraying or other known means. The coated material can be used either alone or together with elastomers or plastics without further treatment. It is often desirable to heat the coated inorganic oxide material. This heating results in a coating that is more firmly bound to the oxidic material. The heating is to a temperature below the decomposition temperature of the oxide material and / or of the copolymer, preferably between ⁰ and 200 C, during take place for 5 minutes to 24 hours.

The textile material coated according to the invention can be prepared by conventional treatment methods of textile fibers, yarns or fabrics. very the coated textile material is expediently produced by dipping the material in a siloxane-oxyalkylene block copolymer, Remove the excess liquid by conventional padding and drying the cover at room temperature. That Copolymer can also be applied to the textile material

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by brushing, spraying, painting or similar means.

When manufacturing coated fabrics according to According to the invention by dipping, brushing, spraying or otherwise, a siloxane-oxyalkylene block copolymer is preferred in the form of a solution in an organic, volatile, liquid compound or to use an aqueous emulsion of the copolymer.

After the solution or emulsion of the copolymer has been applied to the material to be coated, the excess solvent and / or water is removed in a known manner, such as by drying in air or heating in a ventilated oven. In some cases, for example if a textile material with the aid of a Bloelamisslipolynierisats containing silicon-bonded fasserstoffatome, is to be made water-repellent, is.t it desirable to heat the coated parsers are heated to a temperature up to 200 ⁰ G, to harden the water-repellent coating .

Liquid organic substances are all volatile, liquid, organic compounds which dissolve the siloxane-oxyalkylene-TBio polymerizate or in which this can be dispersed . which does not affect the material to be coated ₉ usable _f

909840/1638

such as ether, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and other solvents such as carbon tetrachloride and carbon disulfide.

Are organic textile substances to be coated, for example, the siloxane-oxyalkylene block copolymer used according to the invention can contain Preparation in addition to an organic liquid

and / or water other substances as they like

commonly used for the treatment of organic Textiles are applied. For example, the preparation can contain emulsifiers to improve tolerance to improve the copolymer or the other substances with the organic liquid, or it hardeners may be included to improve the water-repellent properties.

As suitable emulsifiers for the preparations

for the treatment of the textiles according to the invention can '

the non-ionic, anionic or cationic emulsifiers are mentioned. Because of their compatibility, the non-ionic emulsifiers are generally preferred, for example alkyl ethers of polyalkylene glycols and esters of polyhydric alcohols or substances such as polyvinyl alcohol. Other suitable emulsifiers are, for example, triethanolamine, propanolamine, morpholine, oleic acid and stearic acid.

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The treatment preparations can also contain hardeners that improve the bond between Coating compound and textile base material are used. Such Hardener catalysts are particularly beneficial wherever a Blockmischpolyaierisat with bonded to silicon Hydrogen atoms to improve water repellency applied to textiles. Organic salts of lead, tin, zinc, copper, Zircon and titanium, as the organic part, acid groups of fatty acids are preferred in these salts.

■ According to a particularly preferred embodiment the invention is a Blockmisehpolymerisat with Silicon-bonded hydrogen atoms used that can form a stable dispersion in water, and gives the coated textiles good water repellency. In addition, these substances have the desirable property of being self-emulsifying in water are.

According to the invention both to improve the water repellency of the coated textiles such as are also substances used to form a stable emulsion without an emulsifier in water (self-emulsion) e.g. those whose siloxane block has a molecular weight between 1000 and 3500 and primary methyl hydrogen iloxy units. contains, and their oxyalkylene block has a molecular weight between 300 and 3000

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and contains xthyleneoxy primary units. Examples of such self-emulsifying block copolymers for improving the water repellency of organic textiles coated therewith are those which have been produced by converting an average of 1 to 5 hydrogen atoms bonded to silicon into a polysiloxane of the formula

(OH ₃ ) ₃ BiO [SiO] Si (OH ₃ ) ₃ ,

wherein χ is a value between 25 and 40, with the olefinically unsaturated group of the terminal alkyleneoxy group an oxyalkylene polymer of the formula

OH ₂ -OHCH ₂ O (O ₂ H ₄ O) ₇ OH ₃ , where y is a value between 5 and 15 '.

The tendency of an inorganic, oxidic filler to adsorb water can be adjusted by changing the structure of the siloxane-oxyalkylene-Slookmisohpolymerisats. Increasing weight quantities Siloxane blocks in the copolymer lead to a Coating that is more hydrophobic, while an increasing proportion of oxyalkylene blocks in the copolymer results in a coating that is relatively more hydrophilic. Increasing amounts of low

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molecular oxyalkylene units in the oxyalkylene blocks the coating is relatively more hydrophilic, while increasing amounts of higher molecular weight oxyalkylene units increase the hydrophobic nature of the coating. Oxyalkylene blocks with primary oxyethylene units are most hydrophilic. The tendency of the coated inorganic oxidic filler to adsorb water, can also be adjusted by changing the amount of coating mass applied, what expediently done by changing the concentration of the block copolymer in the solution, how it is used to treat the oxidic material. Sg it is possible to use a coated, inorganic, Cut out oxidic filler with an optimal water adsorption tendency for each special case.

Another advantage of the inorganic, oxidic substances coated according to the invention is that the Coating is stable to hydrolysis and therefore not attacked or attacked when stored in a humid atmosphere is destroyed or if they are processed with E la »toiler en or plastics under conditions where water is present. The siloxane-oxyalkylene block copolymers which can be used according to the invention hydrolyze not to any significant extent, even in contact with an acidic or basic aqueous medium.

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BÖrdroXyseetabilität the coating agent of the invention as NaOH suitable block copolymers _i:; , ^: is particularly advantageous when the inorganic

The oxide material is a fiberglass fabric. Coated glass fiber fabric having improved water-repellent yellowing and can be subjected without appreciable hydro- or destruction of the coating so a humid atmosphere relatively long time.

The siloxane-oxyalkylene block copolymers which can be used according to the invention and are stable to hydrolysis give the inorganic-oxide material

em antistatic properties, ie the merisat with a / inventively used siloxane Qxyalkylen-Blockmischpoly- coated inorganic oxide materials nei gen likely to derive a static electricity for charging.

The following examples illustrate the invention. Example I.

0 »3 g of finely divided silica was (oz. 4) in a vessel with a capacity of 113.4 g of and 50 cm of hexane was added. The silica dispersed in the hexane to form a slurry. Now 0.1 g of a siloxane-oxyalkylene block mixture was polymerizate with the formula

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(CH ₇ ), SiO SiO SiO / Si (CH,), 2 J \ I ha »f / 5 ^ ~>

, CH ₂ CH ₂ CH ₂ O (C ₂ H ₄ O) ₃ (C ₃ H ₆ O) ₂ ^ C ₄ H ₉

placed in the sludge, the vessel closed and shaken for about 1 minute, after which the contents were transferred to an evaporation dish. Most of the solvent was allowed to evaporate at the ratio within 10 to 15 minutes, then the filler was placed in an oven and held at 200 ^° C. for 45 minutes, then cooled and about 0.1 g filler was added to the vessel half-filled with tap water . Here the filler flocculated; the filler was kept flowable by vigorous stirring. Three days later the silica filler was still flowable and showed no settling. In contrast, untreated filler disperses instantly in water and settles to the bottom.

Example II

As in Example I, a 4% strength by weight solution of block copolymer was prepared in hexane. A sample of heat cleaned fiberglass fabric was immersed in this solution. The dry weight this fabric was 10 g, the wet weight 14 g, which means an uptake of $ 40 accordingly a coverage of the block copolymer on the fabric of $ 1.6 based on the weight of the fabric. This

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Tissue was hung and the solvent evaporated at room temperature. As a control, a second piece of glass fiber cloth was immersed in hexane. Both samples were air-dried for approximately 5 minutes and then cured at 200 ^° C. for 45 minutes. Haoh cooling was determined on two samples, the water repellency after the spray test (AATTC spray rating test).

template

treated with block copolymer Fiberglass fabric

Blind test Example III

The following preparations were made using a lock polymer of the average formula

Tabel Result Spray value perfect
water repellent 100 immediately wet 0

Si (CH ₅ ) ₅

CH ₂ CH ₂ CH ₂ O (C ₂ H ₄ O) ₇ CH ₅ prepared:

(a) 2 g copolymer, 96.7 g water, 1.3 g zinc octasol emulsion (hardener) with 3 wt .- # zinc,

(b) 1 g copolymer, 98.4 g water, 0.6 g zinc octasol emulsion with 3 wt .- ^ zinc,

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(°) 0 »5 g copolymer, 99.2 g water, 0.3 g zinc

octasol emulsion with 3 wt .- # zinc (d) 0.2 g copolymer, 99 _f 7 g water, 0.1 g zincootasol emulsion with 3 wt .- $ zinc.

A piece of HYLON fabric was immersed in each of the preparations (a) to (d) and ^{heated to 100 °} C. for 15 minutes. The antistatic properties of the samples were then determined by rubbing the samples on wool and then holding the samples in a petroleum jar over cigarette ash. They showed no noticeable ash uptake. In contrast to these excellent antistatic properties of the treated tissue took a tissue without treatment and one which at 10O ⁰ O 15 minutes long simply dried, after rubbing with wool all over the surface of cigarette ash on.

Example IV

It was a block copolymer of the average formula

(CH ₃ ) ₃ Si0 I SiO) I SiO J ₃₇ Si (CH ₃ )

and is hereinafter referred to as "Copolymer-I". 2 g Copolymer-I, 97 g water and 1 g zinc

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octasol emulsion as a hardener with 3 wt -. <fo zinc were (oz. 8) in a container with a capacity of 226, 8 g and shaken. A swatch of 20.32 20.32 cm (8 8 inch) cotton printing fabric was placed in the emulsion and shaken for 3 ° seconds. The fabric was then padded on a pad roller (padded), stretched on a rod and dried for 6 minutes at 160 ⁰ C. The cotton fabric treated in this way was tested according to the standard method (AATTC spray test) and gave a spray value of

The cotton fabric treated in this way could now stand at room temperature over the weekend and was then tested again according to the standard test. The fabric hardened in this way at room temperature for a weekend had a spray value of 100.

Example V

A mixture of 50 wt .- # Copolymer-I and 50 wt .-? 6 of a polymer of the formula

(CH,), SiO  I SiO) Si (CH,),

and this is referred to below as "Mixture II". Two treatment solutions were made, one with 2 grams of Copolymer-I, 96.6 grams of water

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and 1.4 g zinc octasol emulsion as hardener with 3 Gev /.- tf zinc and the other with 2 g mixture-II, 96.6 g water and also 1.4 g zinc octasol emulsion as hardener with 3 wt .- ^ Zinc. Two 8x8 inch cotton fabric swatches were immersed in each of the solutions and agitated for 3½ seconds. The treated tissue samples were then padded on a pad roll and dried for 5 minutes at 100 ⁰ G and then 5 minutes at 160 ⁰ C. According to the standard test (AATTC spray test), the l'asse. rejection of the treated cotton samples is determined, namely before '.', 'ashing, after washing once in a ::; usual author, -: table washing process with a commercially available cleaning agent and after 3 and 5 vials. The results are summarized in the following table:

Ehandlungs- prol c ! laughs C. after 1- ; tested 5- Löc-ung with treatment meli; som "Ά 1 • 80 ^ ash ⁸⁰ ₊ Copclymer-I -, 100 30th ⁸⁰ + ⁸⁰ , Copolymer-I 1 100 50- ⁸⁰ + - Lli.-churg-II 90 30- O ₊ LIi .; chung-11 80 ^ O

ns T) avenge

9 0 Vi. ' Γ. / r S j 9

BATH

Claims (9)

UU133 claims (American fit) 1. Inorganic-oxide or organic textile material, gekennzeichna t by a coating of a siloxane-oxyalkylene-BlockmLcclipolyiiieriyats, containing at least one oiloxan block with at least 2 siloxane units of the formula ^R b ^Si0 4-b ' wherein R is a monovalent, optionally halogen-substituted or a divalent hydrocarbon * denotes a group with 1 to 20 carbon atoms and b 1 or 2 or 3 and this siloxane block is at least contains a siloxane unit in which at least one substituent R is a divalent hydrocarbon group, and at least one oxyalkylene block with at least 2 oxyalkylene groups of the formula -R ¹ O-, in which H ^{1 is} an alkylene group with 2 to 10 carbon atoms, and the siloxane block with the oxyalkylene block is linked via the divalent hydrocarbon group. 2. Inorganic-oxide or organic textile material according to claim 1, characterized in that the üüc-xan block of the siloxane-oxyalkylene block copolymer additionally at least one siloxane unit of the formula ■■ ^ '■ • ■ ifir. , ^ 90 98 ^ 0/1639 133 ^R e ^SiO 4-ef contains, wherein E has the meaning of claim 1 and e O or 1 or 2, f 1 or 2 and (e + - f) 1 or 2 or 3 is. 3. Inorganic-oxide or organic !! textile material, marked .by a Coating made of a siloxane-oxyalkylene block copolymer, containing at least one unit of the formula ϊ — Λ * wherein G- is a monovalent, optionally halogen-substituted hydrocarbon group with 1 to 20 carbon atoms, G- 'is a divalent hydrocarbon group with 1 to 20 carbon atoms, G ^{! t is} an alkyl group with 2 to 10 carbon atoms, G- " ^{1 is} a molar atom or a monovalent hydrocarbon group without an aliphatic multiple bond with 1 to 12 carbon atoms and η is an integer γρη 2. to 30 and c is O or 1 or 2..; .. 4. Inorganisr.:h- oxidic or organic textile material, ge ke η η ζ eich η et ^: by a. : Coating with a siloxane-oxyalkylene block copolymer containing at least one unit of the sleeve ⁵ ·. · - "909840/1639 BATH ORIGINAL S is an, optionally halogen-substituted, monovalent quarry group with 1 to 20 Eoh— ijenstoffgEfcomen, G ^{1 is} a divalent hydrocarbon containing 1 to 20 carbon atoms, and G "is a Hicylengruppe with 2 to 10 carbon atoms and ri an integer from 2 to 30 land e is 0 or 1, or 2. 5- · Jaxargnniach-oxidic or organic Textile material, g e k e η η ζ e i c h η et through a coating of a siloxane-oxyalkylene block mixture polymer having at least one unit of the formula v; or at the 3- _one; : optionally, halogen-substituted, monovalent hydrogen group with 1 to 20 carbon atoms, G * a divalent hydrogen group with 1 to 20 carbon atoms, G "an alkyl group with 2 to 10 carbon atoms and G"'a hydrogen group; tom or a complete carbon dioxide group without aliphatic multiple bonds with 1 to 1-2 carbon atoms and η is an integer from Z to 30 and c is 0 or 1. 9 0 S i ;, 0/1 ς 3 -4Or- 6. Preparation according to claims 1 Ms 5, wherein the inorganic-oxidic material glass fibers or Quartz is * ^ 7. Glass fiber fabric or finely divided quartz, g e k e η η ζ e i c h η e t through a coating with a siloxane-oxyalkylene block mixed polymer of the average formula (CH,), SiO SiO) (SiO I Si (CH J, ^ ³ AI / 78 Λ [/ 5 ^ ^y V ^ CH ₃ / VcH ₂ CH ₂ CH ₂ O (C ₂ H ₄ O) ₃ (C ₅ H ₆ O) ₂ ^ ^ O ^ H ₉ 8. Nylon fabric, g e k e η η ζ e i e Ii η e t through, a coating of a siloxane-oxyalkylene-lock copolymer the average formula 9. Cotton fabrics, g e k e η η ζ calibrated η e t by coating with a siloxane-oxyalkylene block copolymer the average formula (GH, USiO 909840 / 1T39