JPH02127492A - Controlled curing of polymers - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to compositions suitable for sealing containing aromatic hydroxycarboxylic acids and based on polymeric compounds having at least one sulfide group. Such compounds have improved stability on storage. They are used in the construction industry as adhesive components, coating materials, fillers and joint sealing compounds.
s).

The present invention provides a sealing compound (sealing compound).
Novel compositions containing polysulfides suitable for use as compound compounds. The composition has improved storage stability and can be used in the building industry as a crosslinkable sealing compound.

Liquid polysulfides (thioplasts) and similar polymers have long been known as raw materials for so-called [elasLiC] sealing compounds. They are crosslinked by reaction of the terminal mercaptan groups with an oxidizing agent resulting in the conversion of the elastic polysulfide molecules into disulfide bridges.

Crosslinking can also occur by autoxidation (eg by oxygen in the air). However, this reduces the storage stability of the sealing compound. This is because an ever-increasing elastic layer forms on the surface of the compound, which ultimately renders the product unusable.

This crosslinking is caused by a retarding agent.
It is also known that this can be controlled by using ts), for example stearic acid.

This imparts a certain, but still insufficient, storage stability to the sealing compound.

In order to more or less solve this problem, we now provide: 1) a polymeric compound (defined below as component i) containing at least one sulfide group (preferably a polysulfide, more preferably a liquid polysulfide); ii) a hydroxyaromatic carboxylic acid (defined below as component i) A composition suitable for use in a sealing is provided.

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

Preferred polymeric compounds which can be used as component i) are di- and/or trifunctional polymeric compounds having sulfide groups, in particular polyether compounds AI), hydrocarbon polymer compounds A,), polysulfide polythiol polymers Compound A3) Polyalkylene sulfide polymer Compound A4) Polyurethane compound As) or a mixture of these compounds.

These polymer compounds have a molecular weight of 1000 or more and are commonly used in Ullmann's Encyclopedia.
y k I op M d i e de r
Technischen Chemie) 4
Edition, Volume 14 (1977). Incorporate the contents as a reference.

Commercially available polymeric compounds of component i) include, for example, the product thiokol LP (Thio'col Chem, Co.
rp, ), New Chassis-H Trenton, USA) and Thiogelasto (Thio
plast) G (VEB-Chemiewerk, Ge1
z-D5+au)).

Aromatic hydroxyl carboxylic acids are oxidative crosslinking retarders (
acting as retarding agents);
After addition of the oxidizing agent, it appears to give a satisfactory storage stability for component i) without adversely affecting the time for crosslinking.

Preferably component (1) is hydroxybenzoic acid, most preferably 2-hydroxybenzoic acid.

Component i) preferably contains 0.1 to 10 parts, more preferably 0.5 to 5 parts based on 100 parts of component 1).
present in an amount of

Preferably, component M) may additionally contain an aromatic carboxylic acid, more preferably benzoic acid. In such cases, the amount of aromatic carboxylic acid present is preferably such that the ratio of hydroxy aromatic carboxylic acid to aromatic carboxylic acid is 2:
Preferably the amount is from 0.1 to 10 parts, more preferably from 0.5 to 5 parts, based on 100 parts of component 1), in a ratio of 1 to 1;2. Preferably the ratio of hydroxy aromatic carboxylic acids to aromatic carboxylic acids is about 1
It is 2l.

The compositions of the present invention may also contain one or more additional components (herein defined as component i) selected from:

Softeners (e.g. chloroparaffins and benzylbutyl heptalate); Active and inert fillers (carbon black, pyrogenic silicic acid and calcium carbonate); Pigments (titanium dioxide and lamp black); Ullmann's Encyclopedia.
Ullmanns
Encyclopedia der Techni
schen Chemie) 4th edition, Volume 14 (19
77) and other additives described on pages 261-265. Its contents are included here as a reference.

Preferably 45 to 70% of component ii) is present in the composition of the invention.

The compositions of the invention typically do not require any solvents, such as water and/or organic solvents.

During the manufacture of the compositions of the invention, component ii) (optionally with a softener in the form of a solution) is added to the liquid polymer prior to the addition of any other component ii) product, and the remaining The ingredients are mixed in the usual order with the "stabilized" polymer at elevated temperature, preferably at a temperature of 50-60°C.

In a preferred embodiment, hydroxybenzoic acid is mixed with a softening agent, such as benzylbutyl heptatarate, to produce a solution preferably containing 1-10% hydroxybenzoic acid. The solution is mixed into the liquid polymer before the solid components.

The composition of the invention is useful in the building industry for two-back sealing.
Components in the pack sealing composition, adhesive components, coating materials, fillers and joint sealing compounds
It can be used as For this purpose, shortly before use, they are treated in a known manner with a hardening agent, viz.
The so-called 2 is mixed with a monoxide agent, such as carbon dioxide carrier or manganese dioxide paste. Crosslinking then occurs within 2-3 days. However, even before adding these curing agents, the compositions of the present invention can be stable in storage for several months at room temperature. This can be tested by artificially exposing the composition to a temperature of 70°C and observing how long it takes for the formation of an undesirable film to occur (it does occur after a few days). This has a correlation with the storage stability actually observed.

Moreover, in accordance with the present invention, a two pack se
aling) composition is given. Preferred curing agents for use with the compositions of the present invention are selected from 2M (tJ9 paste, manganese dioxide paste 1-1 zinc oxide and inorganic or organic peroxides).

These curing agents may also be used in the form of curing agent compositions consisting of a curing agent and one or more compounds selected from fillers, softeners, other polymers, such as epoxy resins, and catalysts to accelerate curing. It is also possible. Such preferred compositions include i) zinc oxide, lead dioxide or manganese dioxide; b) optionally an amine-containing compound i
i) (as catalyst) consisting of a disulfide (eg tetramethylthiuram disulfide).

Preferred hardener compositions include (based on 100 parts hardener composition): i) 2 to 50 parts of zinc oxide, lead dioxide or manganese dioxide; 1i) 10 to 60 parts of softeners and fillers, e.g.
1 to 10 parts of a disulfide (eg, tetramethylthiuram disulfide).

Preferably, 5 to 20 parts (more preferably 6 to 10 parts) of the curing side or curing agent composition described above are mixed with 100 parts of the composition of the invention.

In order for crosslinking to take place within 2 to 3 days, based on 100 parts of component i), from 1 to 60 parts of zinc oxide, from 4 to 9 parts of carbon dioxide, or from 7 to 11 parts of manganese dioxide are added. Should.

The invention will now be illustrated by the following examples. All parts in the examples are by weight.

Examples 1 to IO The preparation of the composition is carried out by mixing the components in the order given in a vacuum mixer. Example 5 to IO
2 as a solution in benzylbutyl phthalate only in
-Hydroxybenzoic acid is used. Care should be taken that the mixing temperature does not exceed 60°C as much as possible. The composition can be seen in Tables 1 and 2 below.

If 1 part lamp black is additionally added in Examples 1-4, a gray sealing composition is obtained (Examples 6-8) and if as in Examples 5 and 9 If the titanium dioxide is absent, a black encapsulant composition is obtained.

In Examples 5 to IO, the addition of benzylbutyl phthalate made the sealing composition more flexible, and the addition of one part pyrogenic silicic acid gave a somewhat lower value of tensile strength. while other properties remain unchanged (see Examples 6-8 and IO).

Application example A 100 parts of the composition of Example 7 and 49.0% manganese dioxide 2.4% tetramethylthiuram disulfide and 48.6% benzylbutyl phthalate and 6 parts of a curing agent composition consisting of:

This solidifies at 35°C within 3 hours and
A gray sealant is produced with good resistance to continuous stress, with a crosslinking time of days.

Application example B 100 parts of the composition of Example 9 and 40% lead dioxide 3% tetramethylthiuram disulfide and 57% benzylbutyl heptatalate and 8 parts of a curing agent composition consisting of:

Black material with elongation at break after 200% crosslinking.

Application Example C 100 parts of the composition of Example 10 and 38% zinc oxide 2% N,N-diphenylguanidine, 6% tetramethylthiuram disulfide, 2% pyrogenic silicic acid, and 52% chloroparaffin and 14 parts of a curing agent composition consisting of:

A white material that takes 3 days to fully crosslink resulting in good stability.

The main aspects and configurations of the present invention are as follows.

1, i) a polymeric compound containing at least one sulfide group (hereinafter defined as component i); and Li) a hydroxyaromatic carboxylic acid (hereinafter defined as component i). Composition suitable for use in sealing.

2. The composition according to item 1 above, wherein component i) is a polysulfide.

3. The composition according to item 2 above, wherein the polysulfide is a liquid polysulfide.

4. A composition according to any preceding clause, wherein component i) is present in an amount of 3 to 99.9 parts (based on 100 parts of the composition).

5. The polymer compound that can be used as component i) is a di- and/or tri-functional polymer compound having a sulfide group, and polyether compound A), hydrocarbon polymer compound A, polysulfide polythiol The composition according to items 1 to 4 above, which is selected from: polymer compound A3) polyalkylene sulfide polymer compound A4) polyurethane compound i) and mixtures of these compounds. 6
, wherein component ii) is hydroxybenzoic acid.

7. The composition according to any of the above items, wherein component 11) is 2-hydroxybenzoic acid.

8. Ingredient ii) is 0.0 parts based on 100 parts of component 1).
A composition according to any of the preceding clauses, present in an amount of 1 to 10 parts.

9. Ingredient Li) is 0.0 parts based on 100 parts of component 1).
A composition according to paragraph 8 above, present in an amount of 5 to 5 parts.

Composition according to any of the above items, in which the IO1 component (i) may additionally contain an aromatic carboxylic acid.

11. The above 1st θ where the aromatic carboxylic acid is benzoic acid
Composition as described in section.

12. Component 1) The composition according to items 1O to 11 above, wherein the amount of aromatic carboxylic acid present is from 0.1 to 10 parts based on 100 parts.

13. Component 1) The composition according to item 12 above, wherein the amount of aromatic carboxylic acid present is from 0.5 to 5 parts based on 100 parts.

14. Hydroxyaromatic carboxylic acid to aromatic carboxylic acid, the first as described above, wherein hydroxyaromatic carboxylic acid and aromatic carboxylic acid are present in a ratio of 2:1 to 1:2.
The composition according to items 1 to 13.

15. The composition of item 14 above, wherein the hydroxy aromatic carboxylic acid to aromatic carboxylic acid is in a ratio of about 1:1.

16. The composition according to any of the preceding clauses, containing l or more additional components (herein defined as component i) selected from active and inert fillers, and pigments.

17. A composition according to paragraph 16 above, wherein the amount of component i) present is from 45 to 70%.

18. A composition containing a polysulfide substantially as herein described in connection with any of Examples 1-10.

19. A two pack seal consisting of the composition and curing agent described in any of the above sections.
ng) Composition.

20. Two-pack sealing according to paragraph 19 above, wherein the hardening agent is selected from carbon dioxide paste, manganese dioxide paste, zinc oxide and inorganic or organic peroxides.
pack sea I ing) composition.

21 The above first item, wherein the composition according to any one of the above items 1 to 18 is 100 parts and the amount of the curing agent used is 5 to 20 parts.
Two pac sealing described in items 9 to 20
k sealing) composition 022, the amount of curing agent used is from 6 to 10 parts.
sealing) composition.

23. Any of the above items 19 to 22, wherein the curing agent is used in the form of a curing agent composition consisting of a curing agent and one or more compounds selected from fillers, softeners, and catalysts that accelerate curing. Two pack sealing (two
pack sealing) composition.

24. The hardening agent composition is i) zinc oxide, lead dioxide or manganese dioxide; ij)
optionally an amino-containing compound (as a catalyst), and i) a two-pack encapsulation according to item 23 above, which may also be a disulfide.
pack sea I ing), l formation. 25. The curing agent composition is (based on 100 parts of curing agent composition), 1
00 parts i) 2 to 50 parts of zinc oxide, carbon dioxide or manganese dioxide: 1i) 10 to 60 parts of softeners and fillers, and 1i
i) the above 24th compound consisting of I to 10 parts of disulfide;
Two pack sealing (two pack se
aling) composition. 26. A tack sealing composition substantially as herein described in connection with any of Applications A-C.

Claims (1)

[Claims] 1. i) a polymer compound containing at least one sulfide group (hereinafter defined as component i); and ii) a hydroxy aromatic carboxylic acid (hereinafter defined as component ii); ) A composition suitable for sealing use. 2. Two pack sealing comprising the composition according to claim 1 and a curing agent.
)Composition.