AU628378B2

AU628378B2 - Polysulphide sealing compositions

Info

Publication number: AU628378B2
Application number: AU41064/89A
Authority: AU
Inventors: Karoly Discho
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1988-09-08
Filing date: 1989-09-06
Publication date: 1992-09-17
Anticipated expiration: 2009-09-06
Also published as: ATA209689A; GB8919954D0; JPH02127492A; HK129095A; GB2224033A; CH678429A5; FR2636068A1; BE1003366A3; FR2636068B1; GB2224033B; ES2018914A6; IT1232222B; AU4106489A; IT8948342A0

Description

I I628378 COMMONWEUALTH OF AUSTRALIA PATENTS ACT 1952 fOW EIESECCATION NAME ADDRESS OF APPLICANT: Sandoz Ltd.

Lichtstrasse CH-4002 Basle 0:00 Switzerland :00: 0: NAME(S) OF INVENTOR(S): Karoly DISCHO SADDRESS FOR SERVICE: DAVIES COLLISON Patent Attorneys I Little Collins Street, Melbourne, 3000.

COMPLETE SPECIFICATION FOR THE INVENTION ENTITLED: "Polysuiphide Sealing Compositions".

The following statement is a full description of this invention, including the best method of performing it known to me/us:la- Case 154-0140 POLYSULPHIDE SEALING COMPOSITIONS The invention relates to novel compositions containing a polysulphide suitable for use as a sealing compound, which compositions have improved storage stability and which can be used as crosslinkable sealing compounds in the building industry.

Liquid polysulphides (thioplasts) and comparable polymers have been known for a long time as raw materials for the so-called "elastic" sealing compounds. They crosslink by reaction with oxidation agents, causing the terminal mercaptan groups to be converted into disulphide bridges of the elastic polysulphide molecule. Crosslinking can also take place by means of auto-oxidation for example with the oxygen found in air. This however impairs the storage stability of the sealing compounds, since an ever-increasing elastic layer forms on the surface of the compound, which finally renders the product useless. It is also known that this cross-linking can be controlled by using retarding agents such as stearic acid, which imparts to the sealing compounds a certain, but still insufficient storage stability.

To alleviate this problem, there is provided a composition suitable for use in sealing comprising i) a polymeric compound which is a bi- and/or trifunctional polymeric compound having sulphide groups, and is selected from polyether compounds A), hydrocarbon polymer compounds A 2 I polysulphide polythiol polymer compounds A 3 Spolyalkylene sulphide polymer compounds A 4 and LY"UP-; ;lr I-1 -2- Case 154-0140 polyurethane compounds As), and mixtures of such compounds, (hereinafter defined as component and ii) a hydroxy aromatic carboxylic acid (hereinafter defined as component ii).

Preferably component i) is present in an amount of 3 to 99.9 parts more preferably 15 to 50 parts, most preferably 30 to 40 parts (based on 100 parts by weight of composition).

These polymeric compounds have a molecular weight greater than 1000 and are defined in Ullmanns Encyklopddie der Technischen Chemie, 4th edition, volume 14 (1977) the contents of which are incorporated by reference.

The polymeric compounds of component i) which are commercially available are for example "Thiokol" LP (trade mark) (Thiokol Chem.

o: Corp., Trenton/N.J., USA) and Thioplast G (VEB-Chemiewerk, Greiz-Dblau) products.

It would appear that the aromatic hydroxy carboxylic acid act as a retarding agent for antioxidative crosslinking and thereby provides satisfactory storage stability for component without adversely affecting the time for crosslinking after addition of the oxidation agents.

Preferably component ii) is a hydroxy benzoic acid.

Component ii) is preferably present in an amount of 0.1 to 10 parts, more preferably 0.5 to 5 parts based on 100 parts of component i).

Preferably, component ii) may additionally include an aromatic carboxylic acid, more preferably benzoic acid. In such a case the amount of aromatic carboxylic acid present is preferably 0.1 to 9.9 3 Case 154-0140 parts, more preferably 0.5 to 5 parts based on 100 parts of component i) preferably in a ratio of 2:1 to 1:2 of the hydroxy aromatic carboxylic acid to aromatic carboxylic acid. Preferably the ratio of hydroxy aromatic carboxylic acid to aromatic carboxylic acid is about 1:1.

Compositions according to the invention may also contain one or more of the further components (herein defined as component iii) selected from the following: softeners (such as chloroparaffin and benzylbutyl phthalate), active and inactive fillers (carbon black, pyrogenic silicic acids and calcium carbonate), pigments (titanium dioxide and lampblack) and other known additives as defined in Ullmann's Encyklopgdie der Technischen Chemie, 4th edition, volume 14 (1977), page 261 to 265, the contents of which are incorporated herein by reference.

Preferably in a composition according to the invention, there is 45 to 70% of component iii).

Compositions according to the invention are normally free of any solvent, such as water and/or organic solvents.

During the production of the compositions according to the invention, component ii) (optionally with a softener in the form of a solution), is added to the liquid polymer prior to adding any other products of component iii), and the remaining components are mixed with the "stabilised" polymer in the conventional order at an elevated temperature, preferably at temperatures of 50-600C.

In a preferred embodiment, hydroxybenzoic acid is mixed with a softener, e.g. benzylbutyl phthalate, to form a solution containing preferably 1-10% hydroxybenzoic acid. The solution is incorporated with the liquid polymer before the solid components.

The compositions according to the invention may be used as one component in two pack sealing compositions, adhesive components, coating masses, fillers and joint sealing compounds in the building 4 Case 154-0140 industry. For this purpose, shortly before use, they are mixed in known manner with hardening agents, i.e. so-called 2K-oxidation agents, such as lead dioxide or manganese dioxide pastes, and crosslinking occurs within 2 to 3 days. Prior to adding these hardening agents, however, the compositions according to the invention can remain stable in storage for as long as several months at room temperature. This can be tested by artificially exposing the composition to a temperature of 70 0 C and observing how long it takes for an undesirable skin formation to occur (which is induced after a few days). This has a correlation with the storing stability observed in practice.

Further according to the invention there is provided a two pack sealing composition comprising a composition according to the invention described above and a hardening agent (hereinafter defined as the hardener).

Preferred hardening agents used with the compositions of the invention are selected from lead dioxide paste, a manganese dioxide paste, zinc oxide and inorganic or organic peroxides.

These hardeners can also be used in the form of hardener compositions comprising the hardener and one or more compounds selected from 4, fillers, softeners, other polymers such as epoxy resins and catalysts to speed up hardening. Such a preferred composition comprises i) zinc oxide, lead dioxide or manganese dioxide; ii) optionally an amino containing compound and iii) a disulphide (e.g tetramethylthiuram disulphide) (as catalysts).

A preferred hardener composition comprises (based on 100 parts of hardener composition) i) 2 to 50 parts of zinc oxide, lead dioxide or manganese dioxide; ii) 10 to 60 parts of softeners and fillers benzylbutyl 5 Case 154-0140 phthalate, chloro paraffin and silicic acid) and iii) 1 to 10 parts of a disulphide (e.g tetramethylthiuram disulphide).

Preferably 5 to 20 parts (more preferably 6 to 10 parts) of a hardener or hardener compositions defined above are mixed in use with 100 parts of a composition according to the invention.

Based on 100 parts of component i) 1 to 60 parts of zinc oxide, 4 to 9 parts of lead dioxide or 7 to 11 parts of manganese dioxide should be added in order to crosslinking to ocur within 2-3 days.

0 *go o S S S

S.

00 S r ;j -I -6- Case 154-0140 The invention will now be illustrated by the following Examples in which all parts are by weight.

EXAMPLES 1 TO Preparation of the composition is effected by mixing the components in the order given in a vacuum mixer. The 2-hydroxybenzoic acid is used as a solution in benzylbutyl phthalate only in Examples 5 to Care must be taken that the mixing temperature as far as possible does not exceed 60 0 C. The compositions can be seen in Tables 1 and 2 below.

S

a 0* S. S a.

0 55 0 SS S

S

S Tab e 1 I I I I I Examples 1 2 3 4 Polysulphide("Thiokol R" LP 32) 44 44 44 Polyetherpolyol with terminal mercapto groups (viscosity ca. 60,000 mPa.sec., SH content ca. 44 2-hydroxybenzoic acid 0.05 0.2 1.0 0.05 calcium carbonate 24 24 24 24 titanium dioxide 20 20 20 flowers of sulphur 0.05 0.05 0.05 0.05 chloroparaffin 11.90 11.75 10.95 11.90 100 100 100 100 I I I I -7 Table 2 lExamples I5 6 7 18 I9 IPolysuiphide II I I("Thiokol R11LP32) 130 30 130 1- 31 120 IThiokolIt LP3 I 31 I LP2 I jPolyether polyol I 2-hydroxybenzoic acid 0.3 I 0.2 I 1.0 1 0.05 I 0.2 I0.2 ben.-ylbutyl phthalate I 14 I 14 I14 I14 I 15 I14 Ibenzyl alcohol J j I 2 j jbenzoic acid 1 0.251 I I I liron oxide black 16 1 I- -I calcium carbonate 1 45.451 22 1 22 1 22 1 46.8 1 23 1 titanium dioxide I 20 1 20 1 20 1 1 20 1 Ilamp black I 1 1 1 1 1 1 2 1 pyrogenic silicic acid 1 1 1i 1 1 1i 1 flowers of sulphur J I 0.05 j 0.05 I 0.05 1 1 0.751 Ichioroparaffin I 11.75 I10.95 I11.90 I 1 11.751 100.0 100.0 100.0 100.0 100.0 100.0 4- 4 0

SW

~4.

4 *0 S 0 .4.

0* 4 4 b 94 4 9 too 1) is the same polyether polyol as in Table 1.

If in Examples 1-4, 1 part of lamp black is additionally added, grey coloured sealing compositions can be obtained (Examples 6-8) and if as in examples 5 and 9 titanium dioxide is missing, black sealing compositions are obtained.

In Examples 5 to 10, by adding benzylbutyl phthalate, the sealing composition becomes more supple, and by adding 1 part of pyrogenic silicic acid, somewhat lower tensile stress values are obtained, while the other properties remain unchanged (see Examples 6-8 and 8 Case 154-0140 Application Example A 100 parts of the composition of Example 7 is mixed with 6 parts of a hardener composition comprising 49.0% manganese dioxide 2.4% tetramethylthiuramdisulphide and 48.6% benzylbutylphthalate This produces a grey coloured sealant having good resistance to continuous stress which solidifies at 35 0 C within 3 hours and has a time for crosslinking of 1 day.

O**

Application Example B 100 parts of the composition of Example 9 is mixed with 8 parts of a hardener composition comprising lead dioxide 3% tetramethylthiuramdisulphide and 57% benzylbutylphthalate A black coloured mass having an elongation at break point after crosslinking of 200%.

Application Example C 100 parts of the composition of Example 10 is mixed with 14 parts of a hardener composition comprising 38% zinc oxide 2% N,N-diphenylguanidine 6% tetramethylthiuram disulphide 2% pyrogenic silicic acid and 52% chloroparaffin A white sealing mass results with good stability which takes 3 days to crosslink fully.

Claims

1. A composition suitable for use in sealing comprising i) a polymeric compound which is a bi- and/or trifunctional polymeric compound having sulphide groups, and is selected from polyether compounds A 1 hydrocarbon polymer compounds A 2 polysulphide polythiol polymer compounds A 3 polyalkylene sulphide polymer compounds A 4 and polyurethane compounds A 5 and mixtures of such compounds, (hereinafter defined as component and ii) a hydroxy aromatic carboxylic acid (hereinafter defined as component ii).

2. A composition according to Claim 1 in which component i) is a polysulphide.

3. A composition according to Claim 2 in which the polysulphide is a liquid polysulphide.

4. A composition according to any one of the preceding claims in which component i) is present in an amount of 3 to 99.9 parts (based on 100 parts of composition). A composition according to any one of the preceding claims in which component ii) is a hydroxy benzoic acid.

6. A composition according to any one of the preceding claims in which component ii) is 2-hydroxy benzoic acid.

7. A composition according to any one of the preceding claims in _I 10 Case 154-0140 which component ii) is present in an amount of 0.1 to 10 parts based on 100 parts by weight of component i).

8. A composition according to Claim 7 in which component ii) is present in an amount of 0.5 to 5 parts based on 100 parts by weight of component i).

9. A composition according to any one of the preceding claims in which component ii) may additionally include an aromatic carboxylic acid. A composition according to Claim 9 in which the aroamtic carboxylic acid is benzoic acid.

11. A composition according to Claim 9 or 10 in which the amount of aromatic carboxylic acid present is 0.1 to 9.9 parts based on 100 parts by weight of component i).

12. A composition according to Claim 11 in which the amount of 000.. aromatic carboxylic acid present is 0.5 to 5 parts based on 100 parts of component i).

13. A composition according to Claims 10 to 12 in which the hydroxy aromatic carboxylic acid and aromatic carboxylic acid are present in a weight ratio of 2:1 to 1:2 of the hydroxy aromatic carboxylic acid to aromatic carboxylic acid.

14. A composition according to Claim 13 in which the weight ratio of hydroxy aromatic carboxylic acid to aromatic carboxylic acid is •about 1:1. A composition according to any one of the preceding claims containing one or more of the further components (herein defined as component iii) selected from the following: softeners, Zc re6 active and inactive fillers, and 11 Case 154-0140 pigments.

16. A composition according to Claim 15 in which the proportion of component iii) present is 45 to 70% by weight.

17. A polysulphide containing composition substantially as herein defined with reference to any one of Examples 1 to

18. A two pack sealing composition comprising a composition according to any one of the preceding claims and a hardening agent.

19. A two pack sealing composition according to Claim 18 in which the hardening agent is selected from lead dioxide paste, a manganese dioxide paste, zinc oxide and organic peroxides (hereinafter defined as the hardener). A two pack sealing composition according to Claims 18 and 19 in :which the amount of hardener is 5 to 20 parts used with 100 parts of a composition according to any one of Claims 1 to 17.

21. A two pack sealing composition according to any one of Claims 18 to 20 in which the amount of hardener used is 6 to 10 parts per 100 parts of composition.

22. A two pack sealing composition according to any one of Claims 18 to 21 in which the hardener is used in the form of a hardener composition comprising the hardener and one or more compounds selected from fillers, softeners and catalysts to speed up C C hardening.

23. A two pack sealing composition according to Claim 22 in which the hardener composition comprises i) zinc oxide, lead dioxide or manganese dioxide; ii) optionally an amino containing compound (as catalyst); and iii) a disulphide. i iA 12 Case 154-0140

24. A two pack sealing composition according to Claim 23 in which the hardener composition comprises (based on 100 parts of hardener composition) i) 2 to 50 parts of zinc oxide, lead dioxide or manganese dioxide; ii) 10 to 60 parts of softeners and solvents; and iii) 1 to 10 parts of a disulphide A two pack sealing composition substantially as herein described with reference to any one of Application Examples A to C. Dated this 10th day of July 1992 SANDOZ LTD. by its patent attorneys Davies Collison Cave *o *o r I o