SU1429937A3 - Adhesive compound - Google Patents

Abstract

An adhesive having an improved shelf life contains the following constituents: from 2.5 to 100 parts by weight of at least one isocyanatosilane of the formula <IMAGE> in which R<1> is a monovalent, aliphatic, cycloaliphatic or aromatic radical having 1 to 20 carbon atoms, R<2> is a monovalent, aliphatic, cycloaliphatic or aromatic radical having 1 to 8 carbon atoms, a is zero or 1, and Z is a divalent organic radical which is bonded to the silicon atom via a carbon-silicon bond, and from 5 to 200 parts by weight of an aromatic nitroso compound. The adhesive may additionally contain film-forming additives and inert fillers.

Description

"

ISO

QD WITH

00

 cm

1 14

The invention relates to iso-silicate adhesives, and can be used to attach rubber to steel and fiberglass in the manufacture of products for various industrial areas.

The purpose of the invention is to increase the strength of the adhesive joint between rubber, steel or fiberglass under conditions of exposure to boiling water or sodium chloride solution.

The adhesive composition is applied to the surface of the substrate (steel, stack) in the usual way by dipping, spraying an, smearing it with a brush. After connecting the surfaces of the rubber and the substrate, heating is performed.

; The strength properties of adhesion I compounds are tested according to ASTM,: standard D-429, method B is 45 ° at an angle as follows, Obra-Itsi are incised and bent towards the substrate in boiling water for I 2 h, shred from the substrate at an angle j45 ° at 20-24 ° (RT), after an incision and exposure to a 5% solution of sodium chloride (spray)

Table 1 May contents, h, in composition

Isocyan Tyn

polymethylene polyphenylene isocyanate component

(PIC)

Dinitroso - benzene

Isocyanato-propyltristoxysilane

Soot

Film-forming agent - chlorosulphonated polyethylene

for 48 hours at 38 ° C, the method of rubber separation from the substrate is tested. The results of the peel tests are expressed in percent of the gap that occurred in the rubber (R),

The isocyanatesilanes used are obtained by pyrolysis of the corresponding carbamates, and isocyanatesilane adducts are obtained by adding a solution of organosilane to the solution of the polyisocyanate at 10-100 ° C under stirring conditions in the presence of dilaurate dibutyl tin.

The adhesive composition of the invention should be diluted with an aromatic or aliphatic hydrocarbon. The degree of dilution has no determining s | acheni because

this does not prevent the formation of a corresponding thickness of the weave in the process of application,

In the implementation of the invention, the adhesive composition may contain carbon black and a film-forming additive (chlorosulfurised polyethylene, butadiene-acrylonitrile rubber, natural rubber, etc.).

Example 1, Preparing the following

the compositions shown in table 1.

15 30

thirty

30 30

15 15 l 40 40 40

35

35 35

The composition is prepared by mixing in the usual manner.

Samples of adhesive joints between rubber and steel are heated at for 15 minutes and tested in boiling water. Results of rupture testing;

(control) (control)

OK (after 1 / 4-1 h)

26R

59R

64R

Example 2. In the reactor, equipped with a mixing device and a thermostat, load 133 mas. PIZ of the function (yo NCO) 2.7, 533 ma.ch. trichlorethylene and 0.1 ml of dibutyl dilaurate. Stir in a stream of nitrogen, add 60 wt.h. hydroxyproshtrimethoxysilane and 140 May, h. trichlorostilen.

The mixture is shaken for 5 minutes, and then to 20-24 C. A PIC adduct is obtained with hydroxypropyltrimethoxysilane of functionality (NCO) 1.8 of the following structure: O

-Ш - С - О - (СН), - 81 (ОН,) з

-CH-C-W- (CH2) s3110SNz) s The ratio of molar equivalent

The ratio of the molar equivalent of free isocyanate to the adduct is 2.8: 1,

The resulting adhesive composition 35 of the free PIC and the adduct in the reaction

put by dipping on the cloth with a mixture of 8.1: 1,

fiberglass and dried over the resulting adhesive composition

 6 h. Then it is attached to polychloro with the addition of trichlorethylene and benroprene rubber. Ash is applied to the surface of the steel and

 The sample is tested after thermally 40j fiberglass cloth and is combined

works at 165.5 C for 20 minutes at a discharge at 20-24 C. At the same time, the following results were obtained:

(

ten

29937

PRI me R 3. Prepare the composition, as in example 2, but to the mixture 350 wt.h. PICs add 1486 mash, trichlorethylene and 193 mash. With stirring. methylaminopropionmethoxysilane at 772 May, h, benzene to achieve a technological viscosity of a mixture containing free PIC and PIC adduct with methylaminopropyltrimethoxy silane functionality (NCO) 1.7 of the following structure: O

AND

, 5 - Н-С-К-1СН2) (ОСНз} з

SNS

The ratio of molar equivalent of free isocyanate and adduct is 2.2: 1.

Example4. Prepare the composition, as in example 2, but i000ma.h. PIC and 100 masoch. trichlorethylene was added 179 mas per hour, y-aminopropyl trimethoxyelyan in 1611 mac. ABOUT

-CH-C-W- (CH2) s3110SNz) s The ratio of molar equivalent

20

25

thirty

with diurethane ajm aizi aJM nitrile elastomer

The sample is subjected to heat treatment at 152 s for 30 min and tested for rubbing at 20-24 C in

The results are shown in table 2.

Table 2

54.3

100R

Fiberglass

 The control sample was prepared using a 10% solution of PIC in trichlorotiline as an adhesion coMPoposition.

I Example. Prepare the composition as in example 2, but by 170 May, h. y-aminrpropyltriethoxy- | ssh1ana in 1611 may. benzene added - JOT with stirring 400 May, h about ShZ And PIC adduct with | f-aminopropyl tri-1 etokeieilane functionality (NCO)

1.7 building structure: About

- KH-0-lH-lCH2b Si (OC 2 H 5) s The ratio of the molar equivalent of free SCH and adduct in the reaction mixture is 2,

PRI me R 6. Prepare the composition, as in example 2, but to 170 ma.ch. Y-aminopropyl trimethoxyeyelane at 716 May, h, benzene is added with stirring, 750 mash. trichlorethylene. Thus, a reactionary free PIC and adduct are obtained in a molar ratio of 6.6: 1,

The resulting adhesive composition is nano-t on urethane rubber and bonded with. by steel.

For control, a 25% solution of PIC in trichlorethylene is taken as the adhesive composition.

Samples are tested at 20-24 and, as well as when 1- VII are exposed to salt,

The results are given

in tabl, 3.

53.4

49,8

54.3

15.4

. 100R 100R 100R

5 OR

T a b l and c a 3

Troll

Troll

Troll)

110.3 122.5 94.3

67.0 78.0 63.0 84.4

100R

100R

50R

Gap at 100 C,%

100R 100R 10 OR 100R

Spray - Exposure, salt, gap after - 72 hours, more than 168 hours, separation,

90R

75R

60R

bOR

I-, -,

Take a position like

170 May, h

p 7. Prepare com- in production 2, but

- lmgg gm - g1piptr methox; h

silane at 716 mph. trichlorethylene is added with stirring to

760 ma.ch. PIC and 750 ma.ch. trichlorethylene. The composition is then diluted with 200 mash. trichlorethylene stirred for 5 min and cooled to 20-24 C.

Laughs of JIHU and adduct at a ratio of 6.6: 1 (reaction time)

Adhesive composition specified by the top of the etapi. The resulting samples are consumed on a substratum (natural - tested at rysh, at 20-2A s, as well as rubber, soft rubber based on 30 on the effect of boiling water (and), natural rubber, rubber based on 1 Triple butyl rubber) and combined with nps in Table 5.

Table3

A reaction mixture is obtained, including a free-form PIC and an adduct (the ratio of the molar equivalent of 6.6: 1), with the ratio of components shown in Table 4.

TableA

100

100

100

100

Butyl rubber based rubber

100 100 00

thirty

30 30

35

35

Breaking OR by hand

48.0 100R

47.6 40.8

100R 90R

Example 9. A composition is prepared as in Example 2, but to 750 mas. PIC at 3000 mph., Trichloro ethylene, under stirring, 170 m.h. H-aminopropyl-trimethoxysilane and 716 May, h. trichlorethylene.

A reaction mixture of free PIC and adduct and y-aminopropylmethoxysilane functionality (NCO) 1: 7 is obtained. The equivalent molar ratio of PIC and a syrup is 6.6: 1 (reaction mixture).

Based on the reaction composition, an adhesive composition is made up, the compositions of which are listed in Table 8.

T blitz

1 U29937

Continuation of table.8

Content, ma.-h ,, in

Koshoztsy 5 - .. R.-,

C-1 C-2 C-3 C-4 B

. |., ....: g

Chlorosulfonated polyethylene - 35

Chloroacrylonitrile-dichloro-butadiene copolymer — Trichloroethyl 400 400 Xylene 260 260

35

400

472

Said adhesive composition was held at 20-24 ° for a long period and measured in terms of (Brookfield viscometer, spindle 2 at 30 rpm)

The viscosity values obtained are listed in Table 9.

Components

100 100 100 100 100 30 30 30 30 30

- 35 - -. - - - 35 - - - - 35 - - - - - 35

330 220 220 168 337

400 715 715 777 598

12

Table9

PRI me R 10. Prepare the composition, as in example 2, but to 170 mach. -aninopropyltrimethoxy

20 silane 385 wt.h. xylene and 358 parts by weight; trichlorostille; with stirring, 750 parts by weight, PIC, 1500 parts by weight. xylene and 1500 wt.h. trichlorostilen. A reaction mixture consisting of PIC and PIC adduct with X -amino g propylmethoxysilane is obtained with a molar ratio of free PIC and adduct of 6.6: 1.

Based on the reaction mixture, an adhesive composition is obtained, the compositions of which are listed in Table 10. I Table 10

Content, parts by weight, in the composition

D-1 I D-2 1 D-3 I D-4 G D-5

For sample preparation, this composition is applied to the surface of steel, combined with rubber based on natural rubber, and tested at 20–24 ° C.

The results are shown in the table 15.

Table 15

2.89 2.89.

97R 100R

Claims (3)

1. An adhesive composition comprising an isocyanate component and a nitroso compound, characterized in that, in order to increase the strength of the adhesive bond between rubber and steel or glass fabric under conditions of boiling water or sodium chloride solution, it contains as an isocyanate component polymethylene polyphenylene diisocyanate, and as a nitroso compound T a b l and c a 14  NIN is .robenzene, and additionally contains isocyanato. Propyl triethoxysilane of the formula OCN-tCH2) 3-Sl (OC2H5) g or a mixture of polymethylene polyphenylene diisocyanate with an adduct of polymethylene polyphenylene diisocyanate with subroxypropyltrimethoxy- or ethoxysilane, or with J-aminopropyltrimethoxy- or methoxysilane NH C-A- (CH2) 3SUOE) 3 35 A -0-, -snz, -SgNz, t n 40 45 50 55 when the molar ratio of the components of the mixture is 2.2-8.1: 1, respectively, phi, the following ratio of the components of the composition, May, h: Polymethyl NPolyphenylene diisocyanate2, 5-50.0 Dinitrosobenzene 5,0-200,0 From Oscianato about Piltriztoksnilan 15.0 or A mixture of polymethylene polyphenylene diisocyanate with adduct at molar ratio 2.2-8.1: 1 47.5-100.0 2. The composition according to claim 1, of which is that it additionally contains 35 May, h film-forming agent, 3. Composition according to claims, 1, o tl and h ayu with the fact that it additionally contains 40 wt, h, soot-V