DE1277481B - Process for surface treatment of organic polymers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Int. Cl .:

C09d

GERMAN

PATENT OFFICE

EDITORIAL

German class: 10 p.m. - 3

Number: 1277481

File number: P 12 77 481.1-43 (D 48449)

Filing date: October 18, 1965

Opening day: September 12, 1968

The invention relates to a new process for treating the surfaces of solid organic materials Polymers which have been produced by vinyl polymerization.

The treatment according to the invention can reduce the surface properties of the polymers mentioned be changed, d. That is, the production of polymer surfaces is made possible which Oil-repellent, hydrophobic, hydrophilic, and receptive to printing inks and dyes as required and have either high or low slip resistance.

In the case of polyethylene, this means z. B. that therefrom solvent-resistant containers with oil-repellent Surface can be produced. Polyethylene with an amino-functional, hydrophilic one The surface is receptive to permanent printing and dyeing. Finally, the finishes can of polyethylene films are modified so that they are compared to other treated polyethylene films have a high coefficient of friction, making larger amounts of film easier to handle are.

The inventive method for the surface treatment of produced by vinyl polymerization, solid organic polymers is characterized in that a coating agent made of organosilicon compounds, which are free from aliphatic multiple bonds and at least one group of the formula

HSR'Si =

contain, in which R 'denotes a divalent hydrocarbon radical without aliphatic multiple bonds, applied to the surface of the solid, organic polymer and with it through the action of energy is irreversibly connected.

Any solid "vinyl polymers" are suitable for the process according to the invention, including any any organic polymer is to be understood that by polymerization of compounds that aliphatic, unsaturated C - C bonds, such as the vinyl group, are obtained. Examples these are polyethylene, polypropylene, poly (acrylonitrile butadiene styrene), polystyrene, polymethyl methacrylate, Poly (acrylonitrile styrene), polyisobutene, polyvinyl chloride, polyvinyl acetate, poly (vinyl chloride-vinylidene chloride) and organic rubbers such as natural rubber, ethylene propylene cyclohexadiene terpolymer, Styrene butadiene rubber and butadiene acrylonitrile rubber.

Process for the surface treatment of organic polymers

Applicant:

Dow Corning Corporation, Midland, Mich.

(V. St. A.)

Representative:

Dr. B. Passport, lawyer,

8000 Munich 22, Von-der-Tann-Str. 14th

Named as inventor:

William G. Gowdy, Freeland, Mich .; Joseph W. KeU, Midland, Mich. (V. St. A.)

Claimed priority:

V. St. v. America October 21, 1964

(405570),

dated May 3, 1965 (452921) -

Examples of divalent hydrocarbon radicals R 'are methylene, dimethylene, trimethylene, isobutylene, Hexamethylene, octadecamethylene and cyclohexylene radicals as well as radicals of the following formulas:

CH ₃
- CH-

CH ₃
CH2CHCH2

-CH,

- CH ₇ CHCH, -

CH

CH ₂ CH, -

isobutylene, trimethylene and dimethylene radicals are particularly preferred.

«09 600/572

The type of organosilicon compound used is not relevant in the process of the invention decisive, there only has to be at least one group of the formula HSR'Si = present per molecule. the The nature of the surface produced on the vinyl polymer changes depending on the type of used organosilicon compound, which can be, for example, a hydrolyzable organosilane.

In this embodiment of the process according to the invention, the surface of the solid vinyl polymer is applied in the first stage of the process, a film of silanes a) of the formula

(HSR '~) ASiX ₄ - _m - _n

and / or their partial hydrolyzates, where R is monovalent, optionally halogenated hydrocarbon radicals, without aliphatic multiple bonds, X is hydrolyzable groups without aliphatic multiple bonds or hydroxyl groups, R 'has the meaning given, m 1, 2 or 3, π 0.1 or 2 and the sum of m + η is 1,2 or 3.

Examples of hydrocarbon radicals R are methyl, ethyl, isobutyl, cyclohexyl, octyl, octadecyl, Phenyl, diphenyl or tolyl radicals; Examples of hydrogen halide radicals R are 3,3,3-trifluoropropyl, 4-chlorooctyl, bromocyclohexyl, dichlorophenyl and Bromophenyl residues. If several radicals R and R 'are present, these can be identical or different be.

The radicals X can be known, hydrolyzable groups, e.g. B. alkoxy radicals, such as methoxy, Ethoxy, isopropoxy, hexoxy and 2-ethylhexoxy radicals; Halogen atoms such as chlorine or bromine atoms; Acyloxy groups such as formate, acetate or butyrate radicals; isocyanate groups substituted with hydrocarbon radicals, how

Si

/ CH ₃

ONC

OCCH ₃

HSCH (CH ₂ ) ₁₀ SiNCO

C ₃ H ₇

CH,

and

HSCH ₂ CHCH ₂ - Si (OCH ₃ ) ₂

C ₄ H ₉

The compound of the formula

HSCH ₂ CHCH ₂ Si (OCH ₃ ) ₃

CH,

CH,

C ₂ H ₃ '

CNO

is preferred. Silanes without a hydrolyzable group, e.g. B.

HSCH ₂ CHCH ₂ Si (CH ₃ ) ₃

CH,

CNO-

45

C ₄ H ₉

CNO-

QH ₁

17th

or the isocyanate group. Lower alkoxy groups are preferred as X radicals.

Examples of suitable silanes for the process according to the invention are those of the formulas

HSCH ₂ Si (OC ₂ Hs) ₂
CH ₃

CH ₂ CH ₂ CF ₃ HS (CH ₂ ) ₃ SiCl

are also useful in the process of the invention; this creates hydrophobic surfaces.
The action of energy mentioned in the second stage of the method according to the invention can be carried out in many ways. The type of energy exposure is not critical, but some types of energy application will produce better results. For example, the vinyl polymer surface can be heated in the absence of air, whereby the necessary energy is supplied so that the organosilicon compound bonds permanently to the organic polymer.

Another preferred type of energy application is that the solid with the organosilicon compound coated organic polymer is exposed to ultraviolet radiation. For every Combination of organic polymer, organosilicon compound, there is a specific UV dosage, with which the best results for the desired purpose are achieved. However, there is no known one theoretical calculation possibility for the optimal dosage, but in the following examples

some advantageous dosages are given. The effective dosages are generally between 5 and 40 minutes, if the organic polymer 15.24 cm from a standard UV lamp. The energy can also be applied by γ-radiation take place or through peroxide catalysts in connection with heat.

When the energy is applied to the silicone-coated organic surface, it is likely that the mercaptan groups from the molecules of the organosilicon compound with the organic polymer in the following way with the formation of a chemical bond between polysiloxane and organic Polymer react:

= SiR'SH + = C = C =

s SiR'SH + -CH-C- = SiR'S-C-CH =

= SiR'SC - C - + H ₂

After this reaction, the organosilicon compound is believed to be with the organic surface chemically bonded so that it cannot be removed by solvent washing. This solvent washout can be used as a test to determine if the Organopolysiloxane is actually associated with the organic polymer.

Optionally, the treatment of vinyl polymer surfaces with the above described hydrolyzable silanes (a) including the action of energy on the surface of the Vinyl polymer, whereby (a) is irreversibly bonded to the vinyl polymer, on the same surface of the vinyl polymer is a film of compounds (b) of the formula

20 preferably from 1 to 75 mole percent of (a) and 25 to 99 mole percent of (b) are used.
When using compounds of the formula

(C _x F _{2 x + 1} CH ₂ CH ₂ ) _m SiX4_ _m _ "

and their partial hydrolyzates, in which χ preferably has values from 4 to 14, in that described above They will contain oil-repellent vinyl polymer surfaces.

When using compounds of the formula

35

• R.

and / or their partial hydrolysates or of the formula X ₄ _ _m _ "Si (R" NHQ) _m
R _n

and their partial hydrolyzates, preferably the compound of the formula

(CH ₃ O) SiCH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂

or their partial hydrolyzates or silicic acid and / or their partial condensates are applied, in which R, X, m and η have the meaning given, R "an alkylene radical with not more than 4 carbon atoms, Q a hydrogen atom or the group of the formula - R" Means NH ₂ and χ is a positive integer. R ″ can be any alkylene group, for example the methylene, dimethylene, trimethylene or the group of the formula

- CH ₂ CHCH ₂ -

These compounds (b) listed above presumably react with the hydrolyzable groups of under (a) defined mercaptosilanes or their partial hydrolysates and are thereby with the surface of the vinyl polymer connected. If appropriate, the compounds (a) and (b) can also be used simultaneously are added to the vinyl polymer, hydrophilic vinyl polymer surfaces were obtained. Water-soluble dyes, printing inks and pastes, e.g. B. pigment-containing polyamide resins can can be permanently applied to a surface treated in this way, making the dyeing more thermoplastic Fibers and the printing of thermoplastic films becomes possible.

By drying silica and its partial condensates finally on the polymer, what essentially leads to a silicon dioxide surface that is bound to the vinyl polymer, the coefficient of friction of the vinyl polymer is increased, which is particularly advantageous when Sliding is undesirable.

Further useful additives for mercaptosilane-treated vinyl polymer surfaces are polyglycols with terminal functional groups which react with the hydrolyzable groups on the vinyl polymer surface. In this way, hydrophilic or slightly hydrophobic surfaces can be produced.
To accelerate the reaction of the substances listed above with the mercaptosilane-treated surface, catalysts can optionally also be used, e.g. B. KOH, FeCl ₃ , tin octoate, trihexylamine and others for hydrolysis and con-

densation of silanes with hydrolyzable groups known catalysts.

Another embodiment of the process according to the invention consists in that as organosilicon compounds liquid organopolysiloxanes with a viscosity of at least 45 cSi / 25 ° C are used are essentially composed of units (c) of the formula

R _n Si0 ₄ _ _n

and units (d) of the formula

(HSR'-) _m R _t SiO ₄ _ _m _ _k

CH ₃

OSiR'SH

CH ₃

10

15th

20th

are constructed, in which R and R 'have the meaning given, m is 0, 1 or 2 and has an average value of 1.8 to 2.2, ml, 2 or 3 and an average value of 1.0 to 3.0 has, k is 0, 1 or 2 and has an average value from 0 to 2, the sum of m + k is not greater than 3, and where per molecule an average of at least two units (d) and at least five times as many units (c) as Units (d) are present.

Due to the connection of the organopolysiloxanes with the vinyl polymer surfaces, on these formed a permanent lubricant.

"Permanently" is to be understood as meaning that the siloxane coating does not come from the organic polymer a siloxane solvent can be washed off without simultaneous removal of the external Surface of the organic polymer.

The liquid organopolysiloxane generally has a viscosity of at least 45 cSt / 25 ° C necessary so that this does not penetrate into the organic polymer and thereby the polymer surface leaves, but with some organic polymers organopolysiloxanes can also be used lower viscosity can be used. The upper viscosity limit of the organopolysiloxane is not decisive, but it must be able to be distributed well on the organic polymer. Preferably however, the organopolysiloxane used should have a viscosity below 5000 cSt / 25 ° C.

In this embodiment of the process according to the invention, organic polymers are used as organic polymers Rubbers preferred.

The organopolysiloxanes are linear dimethylpolysiloxanes with terminal units of the formula The expression "apply to the surface" states that the organopolysiloxane applied in this way is present on the surface in perceptible amounts should be, d. H. as a polysiloxane film, with the siloxane component on the vinyl polymer surface can be applied in a direct or indirect manner.

When applying the organopolysiloxanes in pure undiluted form to the organic polymer Difficulties arise easily with the siloxane concentration; these are therefore preferably in Form of solutions and emulsions used.

The mercaptosilanes and mercaptosiloxanes used in the process of the present invention are generally known and can be prepared in various ways. Terminal polysiloxanes Mercapto groups can be obtained by equilibrating cyclic polysiloxanes with the desired Containing radicals R with a mercaptodisiloxane of the formula

(HSRO ₃ -, SiOSi (R-SH) ₃ _ _k

wherein R, R 'and k have the meaning given, are obtained in the presence of an acidic clay catalyst. The mercaptodisiloxanes can be obtained by hydrolysis of the corresponding mercaptosilanes which have a Si-bonded hydrolyzable group, e.g. B. a chlorine atom, are prepared.

Another method for preparing mercapto terminated polysiloxanes is in that polysiloxanes with terminal hydroxyl groups and the desired radicals R with Compounds of the formula

CH, OSiR'SH

55

60

preferred whose viscosities are in the range from 100 to 1000 cSt / 25 ° C.

(CH ₃ O) ₂ SiCH ₂ CH ₂ CH ₂ Cl

NaSH .

wherein R and R 'have the meaning given, are reacted in the presence of tin octoate, methanol is produced as a by-product. Furthermore, can be used for the production of the invention Mercaptosiloxanes Silanes that contain only R groups and hydrolyzable groups with - R'SH groups containing silanes mixed hydrolysed or cyclic siloxanes containing only R groups are equilibrated with polysiloxanes containing —RSH groups.

Mercaptosilanes, which either directly in the process according to the invention or for the preparation of the Mercaptosiloxanes which can be used according to the invention can be used in the following manner produced: If there are 1 or 3 carbon atoms between a mercapto group and Si atom, the corresponding Chloralkyl compounds with a terminal chlorine atom reacted with NaSH according to the following Scheme:

(CH ₃ O) ₂ SiCH ₂ CH ₂ CH ₂ SH

CH ₃ CH ₃

If there are 2, 4 or more C atoms between the mercapto groups and the Si atom, the corresponding Olefin compounds with a terminal double bond reacted with thioacetic acid after following scheme:

CH ₃

CH ₃ OSiCH = CH ₂
CH ₃

O
CH.CSH

CH,

CH ₃ OSiCH ₂ CH ₂ SCCH ₃
CH ₃

CH ₃

CH ₃ OH

CH ₃ OSiCH ₂ CH ₂ SH + CH ₃ OCCH ₃

CH,

However, the mercaptosilanes can also be prepared by any other known method will.

A preferred method of applying energy to mercaptosiloxane-treated polymers is in that the organic polymer, preferably rubber, in a mold to the vulcanization temperature is heated using the mercaptopolysiloxane as a liquid mold release agent. on in this way vulcanized molded bodies with stable surface slip resistance are obtained, what is based on the fact that at least part of the siloxane is bound to the organic polymer has been.

example 1

A rubber molding compound was produced from the following components:

Parts by weight

Styrene-butadiene rubber prepolymer 23.8

Polybutadiene rubber prepolymer ... 16.2

Surface active silica 20.2

Zinc oxide 1.7

Coumarone-indene resin 3,4

Sulfur 0.8

Stearic acid 0.34

55

In the following experiment, a polysiloxane of the formula

The slip resistance of the rubber samples was tested by the so-called "Crock test" in which a 1.27 cm ball bearing is rubbed back and forth for 15.24 cm about 60 times per minute and the weight of the ball bearing on the rubber is 6.8 kg. The time to failure is the time until the onset of cracks and abrasion phenomena on the rubber.

a) The rubber ^{molding compound listed above was vulcanized for 45 minutes at 160 °} C. and a pressure of 351.5 kg / cm ² and then coated with isopropyl alcohol. After 5 minutes of the Crock test, the rubber showed severe abrasion.

b) The rubber molding compound listed above was vulcanized as under a) and then the polysiloxane applied. The treated rubber withstood the Crock test for 4 hours without abrasion. On the other hand, it was treated the same Rubber cleaned with isopropyl alcohol and subjected to the Crock test was up after 5 minutes strong abrasion to be noted.

c) The rubber molding compound listed above was vulcanized as under a), but the polysiloxane was used as a mold release agent. The vulcanized rubber was made with isopropyl alcohol cleaned and tested on the Crock test device. After 4 hours it was more moderate Determine abrasion on the rubber.

d) The above-mentioned rubber molding compound was vulcanized for 1 hour at 175 ° C. and a pressure of 351.5 kg / cm ² using the polysiloxane as the mold release agent. "The vulcanized rubber was cleaned with isopropyl alcohol and tested on the Crock test device. After 4 hours, no abrasion was found on the rubber.

e) The rubbers produced according to a) and c) were tested for their physical properties tested with the following results:

rubber Shore hardness tensile strenght
at the breaking point
in kg / cm ² Elongation in% a)
c) 80
85 186.3
202.5 530
700

Example 2

SiO

CH,

CH,

SiCH ₂ SH

Standard rubber molding compounds were produced from the ingredients given in Table I. Each molding composition was vulcanized 45 minutes at 160 ° C and a pressure of 351.5 kg / cm ^2, wherein each at a sample a dimethylpolysiloxane having terminal Mercaptomethylgruppen, a viscosity of 400 cSi / 25 ^o C and about 150 dimethylsiloxane units was used as a mold release agent .

with a viscosity of about 50 to 60cSt / 25'C The rubber samples were then used with Iso. 'propyl alcohol washed.

809 600/572

CH ₁

HSCH ₃ SiO

CH,

~ TA CH ₁

The slip resistance and strength properties of each compiled:

Table I.

Sample are in the following table I,

treatment Shore hardness tensile strenght
in kg / cm ² Elongation in ° / Crock test Rubber composition no 81 144.8 510 Time until
fail Natural rubber Siloxane release agent 85 141.3 500 30 seconds Natural rubber 4 hours no 91 229.2 510 30 minutes Ethylene propylene cyclohexadiene Siloxane release agent 90 223.6 500 30 seconds Ethylene propylene cyclohexadiene no 87 176.8 520 > 24 hours Styrene butadiene rubber 1 minute mixed with polybutadiene Siloxane release agent 88 179.3 510 Styrene butadiene rubber 12 hours mixed with polybutadiene no 97 249.6 285 Butadiene acrylonitrile (high nitrile 2 minutes proportion of) Siloxane release agent 97 242.6 290 Butadiene acrylonitrile (high nitrile 8 hours proportion of) " no 83 271.4 400 Butadiene acrylonitrile (lower
Nitriiantein Siloxane release agent 85 258.7 410 1 minute J. NILX1 let Il LOIl ^
Butadiene acrylonitrile (lower > 24 hours Nitrile content) no 88 130.1 650 Butyl rubber Siloxane release agent 87 126.6 675 20 seconds Butyl rubber no 84 204.6 500 40 minutes Styrene butadiene rubber Siloxane release agent 85 210.9 535 45 seconds Styrene butadiene rubber 35 minutes

Example 3

Standard rubber molding compositions were produced from the ingredients given in Table II and vulcanized as in Example 2, the specified polysiloxanes being used as mold release agents

35 were turned. Before the samples were tested on the Crock test device, they were tested as in Example 1 described, washed in isopropyl alcohol. The results are shown in Table II below compiled:

Tabel ] Organopolysiloxane CH ₃ 'CH ₃ SiO
I. CH ₃ Crock test
Time until
fail Rubber composition [I. HSiO SiO I ₃ yrs
V25 ° C SiH
I. CH ₃
100 c CH ₃ j
S1 / 25 ^O ( γν I.
ι CH ₃
: ·) 4 hours a) styrene butadiene rubber mixed with
Polybutadiene CH ₃ / CH ₃ Ϊ SiO CH ₃ HSCH ₂ SiO , CH ₃ ,
3t / 25 ° C SiCH ₂ SH
I. b) styrene butadiene rubber mixed with
Polybutadiene CH ₃
52 cS ~ 2o CH ₃ 12 hours CH ₃ CH ₃ c) styrene butadiene rubber mixed with
Polybutadiene HSCH ₂ SiO SiCH ₂ SH CH ₃
400 c -150 ( 12 hours : h ₃

*) This is a comparison experiment. This and the following show the superiority of mercaptosiloxanes over siloxanes with functional SiH group.

13th

continuation

Rubber composition Organopolysiloxane 2 'CH ₃ ' -150 Siloxane from a) Crock test
Time until
fail d) ethylene propylene cyclohexadiene terpoly
merisat Siloxane from a) SiO Siloxane from b) 1 hour e) ethylene propylene cyclohexadiene terpoly
merisat Siloxane from c) \ CH ₃ / > 24 hours f) styrene butadiene rubber Siloxane from a) Siloxane from c) 1 minute g) styrene butadiene rubber Siloxane from b) 1 hour h) styrene butadiene rubber Siloxane from c) 1 hour i) styrene butadiene rubber 3 hours j) butadiene acrylonitrile rubber (lower
Nitrile content) ( CH ₃ CH ₃ ^ 3 hours k) butadiene acrylonitrile rubber (lower
Nitrile content) HSCH ₂ CHCH ₂ SiO _1/2 > 24 hours 1) Butadiene acrylonitrile rubber (lower
Nitrile content) I CH ₃ j
400cSt / 25 ° C > 24 hours

. · Λ λ ' ^un S ^m ^ exposed to a standard UV lamp. the

Example 4 irradiated products were made in isopropyl alcohol

The following vulcanized rubber samples were washed and tested using the Crock test from Example 1

were tested with a thin layer of Mercapto-35. The results are shown in Table III below siloxanes coated and put together with an ultraviolet ray:

Table III

Rubber composition

Organopolysiloxanes

Irradiation

Crock test

Time until

fail

a) natural rubber

b) natural rubber

c) natural rubber

d) natural rubber

no

CH,

CH, \ / CH, \

HSCH ₂ CHCH ₂ SiO ₁₇₂

CH ₃

440cSi / 25 ^o C

/ 2

SiO

I ₃

Siloxane from b)

CH ₃
HSCH ₂ SiOi _{/ 2}

CH

3/2

CH ₃ SiO

I

51 cSt / 25 ° C

I3 In

no

5 minutes of UV exposure at 15.2 cm
Distance from UV source

15.2 cm UV exposure
Distance from UV source

15.2 cm UV exposure
Distance from UV source

20 seconds

15 minutes

4 hours

4 hours

continuation

Rubber composition Organopolysiloxanes Irradiation no Crock test
Time until
fail e) styrene butadiene rubber no 15 minutes UV exposure
radiation with 15.2 cm
Distance from UV source 45 seconds f) styrene butadiene rubber Siloxane from b) 30 minutes of UV exposure
radiation with 15.2 cm
Distance from UV source 5 minutes g) styrene butadiene rubber Siloxane from b) no 30 minutes h) ethylene propylene cyclo-
hexadiene terpolymer no 15 minutes UV exposure
radiation with 15.2 cm
Distance from UV source 30 seconds i) ethylene propylene cyclo-
hexadiene terpolymer Siloxane from b) 30 minutes of UV exposure
radiation with 15.2 cm
Distance from UV source 10 mins j) ethylene propylene cyclo-
hexadiene terpolymer Siloxane from b) 30 minutes of UV exposure
radiation with 15.2 cm
Distance from UV source > 16 hours k) ethylene propylene cyclo-
hexadiene terpolymer Siloxane from d) no 1 hour 1) styrene butadiene rubber
with polybutadiene no 15 minutes UV exposure
radiation with 7.6 cm
Distance from UV source 1 minute m) styrene butadiene rubber
with polybutadiene Siloxane from b) 30 minutes of UV exposure
radiation with 7.6 cm
Distance from UV source 5 minutes n) styrene butadiene rubber
with polybutadiene Siloxane from b) 30 minutes of UV exposure
radiation with 15.2 cm
Distance from UV source 1 minute *) o) styrene butadiene rubber
with polybutadiene Siloxane from b) 1 hour UV irradiation
lung with 15.2 cm from
stood by UV source 30 minutes p) styrene butadiene rubber
with polybutadiene Siloxane from b) no 2 minutes*) q) butyl rubber no 30 minutes of UV exposure
radiation with 15.2 cm
Distance from UV source 20 seconds r) butyl rubber Siloxane from d) 1 minute **)

*) This indicates that there was a UV overdose here.

**) The tensile force required to remove a transparent adhesive tape from the q) rubber was 750 g. The required pulling force to separate this tape from the r) rubber was approximately half: 400 g. That clearly shows the presence of one Surface lubricant.

Example 5

Steel plates made with the silane of the formula (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂

were primed with polyethylene or acrylonitrile butadiene styrene films that were 0.0076 to 0.0127 cm thick.

The thermoplastic sides of these panels were then coated with films of the following mercaptosiloxanes coated and irradiated with UV light. They were then wiped with isopropyl alcohol and 65 tested to break on the Crock test device of Example 1.

The results are summarized in the following Table IV:

Tabel IV Organopolysiloxanes -2 CH ₃ π 440cSt / 25 ° C Irradiation no Crock test
Time until
fail Organic polymer no SiO Siloxane from c) no 1 minute a) polyethylene Dimethylpolysiloxane
350cSi / 25 ^o C CH ₃ Siloxane from c) 5 minutes b) polyethylene CH ₃ CH ₃ no no HSCH ₂ CHCH ₂ Si0 _1/2 Siloxane from c) 5 minutes c) polyethylene CH ₃ 5 minutes of UV irradiation
lung with 15.2 cm from
stood by UV source 15 minutes UV exposure
radiation with 15.2 cm
Distance from UV source 10 mins d) polyethylene no 35 minutes e) polyethylene 15 minutes UV exposure
radiation with 15.2 cm
Distance from UV source 5 minutes f) acrylonitrile butadiene
Styrene 22 minutes g) acrylonitrile butadiene
Styrene

B e i s ρ i e 1 6

Natural rubber was made with a liquid polysiloxane coated, which consists essentially of 40 mol 35 solution of the silane of the formula percent units of the formula

air dried and exposed to a UV lamp at a distance of 3 inches for 10 minutes.
Then a 10 weight percent lo-

55 mole percent units of the formula 'CH ₃

SiO

40

45

and 5 mole percent units of the formula [(HSQH ^ SiO, /,]

existed, with an average of two mercaptosiloxy groups per molecule, 1 hour exposed to y radiation of 2 megarads. The rubber treated in this way had a surface with permanent gliding ability.

Example 7

A 1 percent by weight solution of a partial hydrolyzate of the silane of the formula

HSCH ₂ CH ₂ Si (OCH ₃ J ₂

CH ₃

in toluene was applied to 210 denier 35 count polypropylene yarn. Then this turned on

60

65 (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂

applied to the yarn in isopropanol and dried the yarn at 127 ° C. for 5 minutes.

The yarn was then dyed with a 1% solution of a water-soluble dye and dyed for 5 minutes dried at 127 ° C.

The yarn was then commercialized in an automatic washing machine for one turn Washed detergent and hot water. No color fading of the yarn was observed.

The experiment was repeated, but without the treatment with the mercaptosilane hydrolyzate, i. H., the yarn was treated with the aminosilane only.

The dye could be removed from this second sample by hand washing with warm soapy water will.

Example 8

a) A thin film of the silane of the formula
HSCH ₂ CHCH ₂ Si (OCH ₃ ) ₃

CH ₃

was applied to a polyethylene sheet, which was then 10 minutes of a UV lamp at a distance 7.6 cm was exposed.

A thin film of 3,3,3-trifluoropropyltrimethoxysilane was then applied to the treated polyethylene surface applied and left to stand for a few minutes. Subsequently, the surface was treated with acetone

809 600/572

washed to remove non-adherent silane, and then dried.

The contact angle of a drop of mineral oil on the treated polyethylene surface was 20 °. This indicates mediocre oil repellency.

The contact angle of a drop of mineral oil on an untreated polyethylene surface was determined found at 0 °, corresponding to no oil repellency.

The contact angle of a liquid drop on the surface is the angle between the surface and the side of the drop where it touches the surface. It serves as a measure of tolerance the materials from which the drop and the surface are made.

b) The experiment described under a) was repeated; instead of the 3,3,3-trifluoropropyltrimethoxysilane however, became the silane of the formula

C ₇ F ₁₅ CH ₂ CH ₂ SiCl ₃

'20

used. The contact angle of a drop of mineral oil on polyethylene treated in this way was 45 °, which indicated a strong oil repellency.

c) A polyethylene container was treated according to b) and found to be suitable for storage of oils was suitable for long periods of time.

Example 9 A thin film of the formula silane

HSCH ₂ CHCH ₂ Si (OCHs) ₃ ^

CH ₃

35

was applied to a polyethylene sheet, which was then 10 minutes of a UV lamp at a distance 7.6 cm was exposed. Treated films made of mercaptosilane-grafted polyethylene were produced. Then a thin film of the silane became the formula

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂

applied to the treated polyethylene sheets and dried.

A polyamide coating resin, which is used as a printing paste, was then applied. the Adhesion of the resin to the coated polyethylene film was excellent and the bond broke not apart even when turning sharply. • The experiment was carried out without mercaptosilane treatment, but with aminosilane treatment, repeated.

The adhesion of the polyamide coating resin to the polyethylene was poor.

Example 10

The top film was then peeled off across the bottom film, requiring a force of 120 g was to move the slides. It follows that the treated surfaces have an initial Had a coefficient of friction of 0.96. Untreated polyethylene films subjected to the same test began to move at a pulling force of 65 g, from which it can be seen that you initial coefficient of friction was 0.52.

The treated polyethylene films from Example 9 showed a coefficient of friction of 0.36 below same test conditions.

Example 11

The mercaptosilane-treated polyethylene from Example 9 was mixed with an ethylene-propylene-polyglycol copolymer treated by reacting with the epoxysilane of the formula

O
CH ₂ CHCH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

was end-blocked, the terminal hydroxyl group of the polyglycol with the silane epoxy group reacts by grafting the molecules.

This treated polyethylene was dried for 10 minutes and the excess unbound material washed out with isopropanol.

The dried polyethylene was tested for water compatibility. The contact angle of a The water droplet on the treated polyethylene surface was 0 °, which indicated that the surface was hydrophilic.

Untreated polyethylene had a contact angle of 45 ° with water.

Example 12

A butadiene acrylonitrile rubber ring was made with the silane of the formula

/ HSCH ₂ CHCH ₂ \ Si

ON = C

^ CH ₃

/ 2

/ 2

Two polyethylene films which had been treated with mercaptosilane according to Example 9 were coated with an aqueous dispersion of colloidal silicon coating agent: cium dioxide (a partial silica condensate) and then dried. They were then washed with water to remove excess silica and dried again. ⁶ 5

The films were then placed on top of one another with the treated sides touching and a 125 g weight placed on top.

coated and dried in the presence of UV radiation. Subsequently, the same ring was used one of the following compounds coated with gentle heating. The result was each an oil-repellent rubber ring that is resistant to swelling in organic solvents.

C ₉ F ₁₉ CH ₂ CH ₂ SiCl ₂ CH ₃

Partial hydrolyzate of (C ₄ F ₉ CH ₂ CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₂

/ C ₂ H ₅

(CF ₃ CH ₂ CH ₂ ) ₃ SiONC

Partial hydrolyzate of C ₇ F ₁₅ CH ₂ CH ₂ Si (OCH ₃ );

■ 3) 2

IO

3. The method according to claim 1 and 2, characterized in that the organosilicon compounds in addition to silanes (a) and / or their partial hydrolyzates, compounds (b) of the formula

(C ₁ F _{2x + 1} CH ₂ CH ₂ LSiX ₄ ^ _n

and / or their partial hydrolysates or of the formula X ₄ ^ _n Si (R-NHQ) _n ,

Claims (1)

Patent claims: 1. Process for the surface treatment of solid, vinyl polymerised, organic polymers, characterized in that a coating agent consists of Organosilicon compounds that are free from aliphatic multiple bonds and at least a group of the formula HSR'Si = contain, wherein R 'is a divalent hydrocarbon radical Without aliphatic multiple bonds means applied to the surface of the solid organic polymers and with this is irreversibly connected by the action of energy. 2. The method according to claim 1, characterized in that the organosilicon compounds Silanes (a) of the formula (HSR ' 35 and / or their partial hydrolysates are used, in which R monovalent, optionally halogenated hydrocarbon radicals without aliphatic multiple bonds, X denotes hydrolyzable groups without aliphatic multiple bonds or hydroxyl groups, R 'has the meaning given, m 1, 2 or 3, π O, 1 or 2 and the sum of m + η is 1, 2 or 3. and / or their partial hydrolysates or silicic acid and / or their partial condensates are also used, in which R, X, m and η have the meaning given, R "is an alkylene radical with not more than 4 carbon atoms, Q is a hydrogen atom or the group of the formula - R "means NH ₂ and χ is a positive integer. 4. procedural part according to claim 1, characterized in that that as organosilicon compounds liquid organopolysiloxanes with a viscosity of at least 45 cSt / 25 ° C, consisting essentially of units (c) of the formula R "SiO ₄ _" and units (d) of the formula where R and R 'have the meaning given, η is O, 1 or 2 and has an average value of 1.8 to 2.2, m is 1, 2 or 3 and an average value of 1.0 to 3.0, k is 0, 1 or 2 and has an average value of 0 to 2, the sum of m + k is not greater than 3, and wherein per molecule an average of at least two units (d) and at least five times as many units (c) how units (d) are present. 809600/572 9.61 O Bimdesdruckerei Berlin