DE2036250A1 - In stock, hardenable polythiol polymer compound - Google Patents

Description

The invention relates to storage-stable, curable, liquid polythiol polymer sealing and coating compounds or adhesive compounds with a latent hardening agent incorporated therein for the polymer and mechanically destructible capsules which contain an activator for the hardening agent, such as water, for example. The hardening of the mass is initiated at the time of application by subjecting the mass to mechanical forces, for example by passing it through a gear pump.

The invention relates to single-component systems lageritab11 «, curable, liquid polythiol polymer sealing compound

109800/2002

sen or adhesive masses with a latent embedded therein Hardening agent and an encapsulated activator for the hardening agent and a method for hardening such compositions.

Liquid polythiol polymers, as described, for example, in U.S. Patents 2,233,390, 2,436,137, 3,243,411, 2,466,963 and 1,789,958, have a wide range of possible uses with regard to the properties of the cured polymers. These polymers have been found to be excellent for use in caulking, caulking, adhesives, etc. Because of the nature of the curing agents for such polymers, it has long been impossible to make polythiol polymer compositions; to be processed into products that can be traded, that can be stored and that represent one-component systems. It was therefore necessary to mix the mass immediately before use or to pack the components in two parts, one of which contained the polythiol polymer and the other the hardening agent. A series of moisture-activated polythiol polymer compositions w , which are present as one-component systems, was then developed, for example by US Patents 3,225,017, 3..3 * 9. 0 * 7 ,. 3 402 151 and 3 * 02 155 is shown. These compositions harden to form elastomeric solids when exposed to a moisture-containing environment. The amount of time required for curing will vary depending on the amount of moisture available and the particular curing mechanism. From a practical standpoint, diet can sometimes be a disadvantage, especially on assembly lines in the automotive industry or in the manufacture of prefabricated elements where rapid curing occurs

109809AiO02

desirable, if not necessary at all. One way of hardening to accelerate polythiol polymer masses activated by water, is that, water with the help of a brush or a spray nozzle to be applied to the surface of the mass. However, this is time consuming and not always practical in industrial applications. This principle was also applied to the hardening of to accelerate polythiol masses activated by bases, as in British Patent 901,600.

Accordingly, the main aim of the present invention is to Storage-stable sealing compounds or adhesive compounds based on liquid polythiol polymers in the form of one-component systems that can be activated upon application to give rapid curing at ambient temperatures.

A second object of the invention is to provide a method for activating the above-described masses by simple mechanical means To obtain funds.

The above objectives can be achieved by first using a shelf-stable, forms curable sealant or adhesive compound by a polythiol polymer, one or more latent curing agents for the polymer and one in mechanically destructible, impenetrable capsules made of a material that is in the components the mass is essentially insoluble and does not react with these components, encapsulated activator for the curing agent mixed together and then, if desired, the mass mechanical forces, whereby the activator capsules are broken and a hardening is initiated when the mass is applied to a substrate.

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• κ ■. ■■; ■ ■ ;;. . ■■ - .; ■ .:

There are three essential components of the compositions according to the present invention, namely a liquid polythiol polymer, i.e. a polythiol polymer which is pourable at 25 ° C or a blocked polymer which behaves like a polythiol polymer when cured, a latent or dormant curing agent for the polymer, i.e. a curing agent that the polymer only in Presence of an activator hardens, as well as an encapsulated one Activator for the hardener. For technical reasons, "it may be desirable to use a mixture of curing agents or a mixture of activators. In addition, the compositions contain the various additives commonly found in Sealing compounds, caulking compounds or adhesive compounds are used, such as fillers, pigments, solvents, plasticizers, thixotropic agents and the like Specific examples of these components are shown below.

Polythiol polymers

Examples of the types of liquid polythiol polymers used for ^ Use in the masses according to the present invention suitable net are listed below. It can be seen that the essential point is that the polymers contain -SH groups or groups that behave like -SH groups during curing, such as blocked -SSH groups. That The hydrocarbon backbone can be saturated or unsaturated be aliphatic or aromatic backbone and it can be interrupted by other groups, such as by Xther, thioether, siloxyl, urethane or polysulfide groups.

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a) Liquid polyalkylene polysulfide polymers with -SH end groups, made in accordance with U.S. Patent 2,466,963 and molecular weights on the order of 500 to 25,000 own and viscous liquids with viscosities are in the range of 300 to 100,000 cP at 25 ° C. The industrial important liquid polymers of this type are special in the article by Fettes and Jorczak in "Industrial and Engineering Chemistry ", Volume 42, Page 2217 of 1950 and Volume 43, page 324 of 1951. They become general made from bis-ß-chloroethyl formal and settle in essentially composed of repeating groups fSCHpCH ^ QCHpOCHpCHpS} and have free mercapto end groups, through which they form a solid elastomer

·. mers can be hardened. In the manufacture of this

Volume ',, - mercial polymer is a small / trichloropropane mixed in a conventional manner with the bis-.beta.-chloräthylformal to provide a slightly cross-linked structure during curing. Particularly industrially valuable polymers are, for example, those with preferably repeating groups, such as (ethyleneoxy) methane, bis (butyientoxy) * ethane, Bie «(ethylene oxy and BiB (butylene) oxy groups and an average molecular weight of about 2,000 to 10,000, preferably between 3,5OO and 8,000.

b) Liquid Polyeulfidpolyjnere with -SSH endblocked large Schwefeiatorazahl in the Polysulfldgruppen as writing in US Patent 3,331,818 are besahrieben or Pölyeul ^ ,, _f · fidpolymer in blocked form, wherein the end groups -SSH _t "

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are blocked with aldehydes or ketones, as in the USA _o . Patent specification 3 422 077 is described,

c) Liquid polyethers with -SH end groups, such as polypropylene glycol with -SH end groups described in the United States patents

3,258,495, 3,361,723 and 3,431,239.

d) -SH-terminated hydrocarbon polymers such as -SH-terminated polybutadiene described in U.S. Patent 3,234,188 and in Chemical and Engineering News, April 4, 1966, p. 37, copolymers of butadiene and -SH-terminated acrylonitrile, as well as the alkane polyethiol, aralkane polythiol, and arene polythiol polymers described in the United States patents 2,230,390, -2,436,137 and 3,243,411.

e) Liquid polyurethanes with-SH end groups, such as those in the USA patents 3,440,273 and 3,446,780.

f) Liquid poly (alkylene sulfide) polymers with.-SH end groups, as described in U.S. Patents 3,056,841 and 3,070,5 & 0 are described

\ g) liquid geminal dithioether polythiol polyraers, as described in

U.S. Patent 3,413,265 * h) Liquid hydrocarbon polysulphide polymers with -SH end groups, as described in U.S. Patent 3,423,374 are, .

Hardening agents

A wide variety of organic and inorganic curing agents are known for liquid polythiol polymers. A comprehensive list of these is given in aaylord "High Polymers", Volume XIII,

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"Polyethers", Part IH _9, page 165, Interscience Publishers, New York (3L962) and in the United States patent documents 3,225,017 and 3,402,155 listed. A recently found enrichment of this Li3 te is calcium orthoplumbate, the use of which as a hardening agent is described in US patent application Ser. 770 of October 25, 1968. As described therein, calcium orthoplumbate is a latent or dormant water activatable curing agent and is normally used in an amount of from about 12 to about 50 1/8 weight of the liquid polythiol polymer. Roughly speaking, it takes about 1/2 mole of water to activate 1 mole of calcium orthoplumbate.

The preferred curing agents for use in the present Invention are those that are latent or dormant, but upon activation give a rapid cure of the polymer. This category includes, for example, calcium orthoplumbate, calcium peroxide, barium peroxide, lithium peroxide, zinc peroxide and Manganese dioxide. The latter two require hardening agents a basic activator, while the first four are basic themselves and only require water as an activator. If wanted, can be used to further accelerate the hardening process Base can be added. Of course, the characteristics of the pre- "' underlying invention can also be applied to slower curing systems, such as those produced by iodine donors are activated as described in U.S. Patent 2,727,883, or the water activated chromate and Bichromate adhesion systems disclosed in U.S. Patent 2,787,6O8 are described. Suitable curing systems for each special

109809/2002.

Polymers are known to the person skilled in the art, and the selection of suitable ones Curing agent is used depending on the rate of cure desired and in the final composition. desirable properties definitely ο

Encapsulated Activators - '^;..; -

As indicated above, the most common substances for activating the curing of liquid polythiol polymer compositions are water and bases. The latter are, for example, organic amines ₉ such as diethylenetriamine ₉ ethylenediamine _s n-butylamine, triethanolamine, _v triethylenetetramine, dibutylamine ₉ tri- (dimethylaminomethyl) phenol and piperidine or basic inorganic compounds such as ammonia or alkali or alkaline earth oxides _s hydroxides or - salts of weak acids. In the present invention, it is preferred that the activator be a liquid or in solution, although slower acting solid activators can also be used if desired.

The encapsulating material for Aktivatorkapseln should be a length of material in respect of all components that are used in the curable Polythiolpolymermasse is relatively inert and impenetrable. It should have a fairly high melting point, preferably greater than 77 ° C (170 ° F), so that it can withstand elevated temperatures that might arise during storage. Suitable substances are, for example, gelatin, gelatin / gum arabic, Methyl-cellulose ₉ starch, Polyuredthane and waxes. The main requirements are that the material be mechanically breakable or destructible by any of the methods described below and that it can

109809/2002

over the activator and the other constituents of the mass formerly is essentially inert. The breakable ship of the cape * its depends largely on the size of the capsules and the Thickness of the capsule walls and is also in units of the groove load measured. '' With a certain capsule size, the payload (the amount of encapsulated material) is greater, the thinner * the shell is. In the present invention, the following capsule properties are suitable, as can by known: encapsulation methods, ie · for example in "Chemical Engineering" »4 * bessembeü * 1967 * page

177, Pig »7 are. 5,000 < JL · www '■ * Capsule properties 95 Preferred area 65 .-> ■■■ ^: Size (/ U) - 5th 100 - 1
i
2 Wide range 1,000 Payload {%) 50 - 50 - Fragility ^ t
(Pound / capsule) 0.5 - 25 - 0.1

Weight loss (based on the weight of the active

vatore), open to the

Atmosphere ^ Ll, ₍ : ■■. I

Jf / day at 24 ° C 0.01 - 0.15 0.05 '* 0.1

Ϊ / day at 5 * »° C 1.5 - 6.5 2 * 4

This size range is recommended for use in applications where fine dispersion of the activator is required. However, it has a stronger mechanical force to rupture the capsules are applied, such as by using color-mill, a Rotorflügel- / _b \ radmischers or a gear pump "

* 'This area can be used »where fine dispersions

•: are not required. The capsules are easier to break

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bar and can be broken by hand failure if necessary become, although_ of course others with greater Power working devices can be used -as for example a gear pump or a rotor-impeller mixer, especially for use on an industrial scale.

The breakability of the capsules depends on the brittleness of the Shell material and is also a puncture of both size as well as the payload, since larger sizes and payloads «a. Fragility only becomes apparent under the action of greater forces » Although capsules with a low force breakability are desired from the point of view of application, care must be taken be that the capsules do not break prematurely when they are mixed with the masses. The capsules can be mixed in by hand. In industrial applications, mixers such as a Meyers mixer, a Hobart mixer, and a Marco Rotofeed mixer suitable »A Pyles pump can be used to transfer the capsule-containing sealing compound without that premature breakage of the capsules occurs. As expected would be, the more stable the mass during storage, the less them during the storage of the capsules or during the Transfer handled by lines or pipes or mechanically is claimed.

Methods of activation

Small amounts of the polythiol compositions of the present invention can by grinding using a mortar and a Plunger or by mixing in a small container using a propeller mixer. For areas of application where a thin coating is used to bond two substrates together, it is sufficient to apply

109809/2002

strate a simple pressure and shear force to the To activate hardening of the mass. For large volume industrial sealant applications, however, is the easiest way activating the one that mass through the gear pump or through a Pyles rotor impeller mixing head, which the provide necessary shear forces to the capsules immediately to break in a continuous process prior to use. In general, therefore, the masses according to the vo & legends Invention can be activated by any mechanical means providing sufficient pressure and / or sufficient Provide gravity to break the activator capsules and so to release the activator and to mix with the mass and initiate hardening through the latent hardening agent already present therein.

The following examples serve to further illustrate the invention.

Examples 1 to 5

As shown in Table I, Examples 1-5 illustrate the variety of curable polythiol polymer compositions which can be used in the process of the present invention. The constituents of each mass, with the exception of the water capsules, were ground together on a paint mill. "Am the following day the water capsules were mixed in by hand. Samples of the final compositions were tested for stability investigated, i.e. with regard to non-hardening during storage at room temperature and at 50 ° C. Samples were also examined with regard to hardenability by breaking the activator capsules.

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tested by placing about 100 g of the corn in a container with a double propeller mixer with 100 revolutions per minute 3 blended up to 5 minutes. The chemical nature of the used liquid polythiol polymers were as follows;

Polymer % SH Molecule argeic. ■ basic structure

A 1.38 4780 polyether with aromatic groups B 2.3 2OOO-3OOO polypropylene glycol with urethane groups C 2.2 3000 butadiene / acrylonitrile 75/25 _v

D HQOO ( ₂ iJ ₂₂₁ J

P with 2 % crosslinking

E 4000 similar to D ₉ but with only 0 _s 5 % crosslinking

The amounts of the ingredients in the above compilation are given in parts by weight. The water capsules used in Examples 1, 2, h and 5 were encapsulated with a wax with a melting range of 82 to 84 ° C. The size range of the capsules was 2000-336O, µ with a payload of 60.6 %. The weight loss ranged between 0.12 and 0.09 % at 24 ° C, 50 % relative humidity for a period of time

P ■ '■ ■

19 days.

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Table I.
■, - ''examples; ,

JL -L ₁ J. JL »J £,

Polymer ABODE

100 100 100 200 100

Zinc peroxide '· 2'. . - - ^: - -

Calcium orthoplumbate, -> - - 40 -,

Calcium peroxide. ■ 6 · ^J - - * - 8

Manganese dioxide - '5 5' - ·· ■ · "" "·

Titanium dioxide,. 50 - '-

Calcium oxide. * - - - 10 '- - 5

Calcium carbonate "· 20 - 50. - _s Chlorinated biphenyl,

Plasticizer - -. - - - 40 Poly- Λ-methy lstyrene,

Plasticizer "40 40 40 -— '-—

Soot, Sterling R —- ■ - - -— 20. "

Carbon black, Sterling MT - 50 - - 50

Carbon black, SRP - 60

Ethylenediamine, % on 5A-

Molecular sieves 5 - - - - - - '

Potassium tert-butyl alcohol - 1 ',,, 0.2

Triethanolamine * - - '- - -. o, 5.

Toluene - - .— - · 3.5 '

Water capsules 7> 5 5 12 5,

Stability at room temperature. ^l

(TaKe). . - .—. .— .—. > 84 ·. -

Stability at 50 ° C (days) <6> 48 > 25> 6> 14

: at Ml

Curing time after mechanical Activation (hours) ^ 24 immediately Λ immediately 1

remotely. ■, telbar,

*) also contained 0.5 parts. - "-;. '

each one surface i ;

active agent and one.:

UV stabilizer. ' Examples 6 to 20

The examples listed in Table II illustrate the invention continue and show variables such as the size of the cap, Weiohmaoh ·! ·,,

\ Solvents and other additives * »':,',.

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Table II

'"". ·' Examples

• ■■ <v "- ■■ ... ■ · ■ ■ ** - '· ■ ■ · ^; ■. ·

, _ 6 ν 7 L. JL 1P_ 1L · - IL- 13_ ii-'15_ M- iL. IL. ISL 19L

Polymer E * 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100

Soot, Sterling MT vi ^ i 60 60 60 50 50 60 60 60 * 50 50 50 40 50 40 50

Carbon black, sterling R 5 25 25 5 5 * 5 20 20 20 20 20 20 20

Carbon black, Pelletex SRP No. 3 5 5 τ -..— ² · - ■ - - '■ ---' - - · - -

Chlorinated paraffin wax. ■

hydrogen, plasticizer -— - —- -— -— -: "'" -. "-—-, --- —- - 40 -—

Chlorinated biphenyl, plasticizer 40 - ~ - - - - -? - -> - .40 40 40—- JtO

Butyl benzyl phthalate ... _: / ^y 40 40 40 40 40 40 40 40 40 ~ - · «- ■ ■

Calcium peroxide 12 12. 12 8 8 12 12 12 10 10 8 8 8 8 8

Calcium oxide. ' - —- - 5 5 —- · .— - 5 * 5 5 5 5 5 5

Thickener 3 3 3 .-- · - 3 3 3—- -— --- ■, --- - -—-

Toluene · ^s 5 - - - - - - - - ■ - - 3.5 3.5 - ■■ 3.5 _f

gj ^ je-Tris-idimethyiaminOmethyl) - ^

phenpl. , - ■ '; - ".. ■ ^ 3 2 - = -— 2 ¹ - ^k - 3 - ——— - —- - - · i

^ A molecular sieves' 3 3 3— - ■ - 3 3 3. - ■ —- -—.--- ■ .—. -

Triethanolamine ", _; - - - · ~ - ' ---- - - -; -..--- -— -—, -— - 0.5 0.5 <s>

Triäthylent et ramin: -— - ■ - - ■ -— —- 'r— - * - —- —-- -— 0.5 - P *

. ■■■■ ι * '. ·' '',. · ■ "■ '■' ■ ';. ·". ■ ■■■. ■ ■ ■. '·' Is * -

Continuation from Table II Examples

OO O CO

Water capsules

Packing stability at: 21 ° C Hl © C 49 ° C 5 ¹ » ⁰ C

70 ° C

Cure time (hours) at room temperature

6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 7.5 7.5 7.5 10.1 10.1 9.1 9.1 5.3 5 7.6 5 7.7 5 4, 9 4.9

IW> ew ^ ßW > 2W> 2W> lMo> lMo > 2W> 3W> 3W> 2W> 2W> lMo > 1W> lMo 3T 1-2W 2W> 2W> 2W 1-2W 1-2W—-> 3W > 3W> 2W> 2W ylMo > iW> lMo 3T 5-7T 1-2W> 2W> 2W 1-2W 3-7T 2-4W -—- —— - - —— -.— ——

: ■ -, ^ -. 3-7T 3 ^ 7T> 3T 1-3T 1-3T LV- 16- 7- 7- Ί4-. 3-7T VlMo

V3W 2lT 12T 12T 3OT

-, -.— _r ^ --— 1-3T 1-3T -> - ' 3-7T 3-7T 1-4T 1-4T 2T 3R l- ^ T

0.5 NB NB 15 15 3.5 NB

ÜN ON 1-3T 1-3T NB NB 15

LV = slightly viscous; V = viscous; Overnight = overnight; NB = not determined; W = weeks; T «days; Mon = months

Ca) CT) Κϊ

The properties of those used in Examples 6-20 Capsules are listed in Table III.

Table III 9undlO Examples 14-19 \ 840-1410 11-13 2000-3360 20th $ -8 49.5 840-1410 57.8 800 Size,, u 119Q-168O 172-178 55.7 178-185 60 Payload, % 68 125 > l60 Melting point, ⁰ C 130 > 2W
> 2W
> 2W
5-7T
2T 1 * 04 > 2W
> 2W -
> 3W '
3-7T fragility
Pound / capsule > 2W ■ not
checked Packing stability
lity at: 21 ° C
41 ° C
49 ° C
54 ° C
70 ° c > 2W
1-2W
5-7T 2-4W
1-3T.

W s weeks; T = days

The capsules used in Examples 14-19 were with coated hydrophobic starch.

Examples 21 to 26

Various encapsulated activators were hand mixed with 100 grams of Polymer E and 5 grams of MnO ₂ (inactive form) using 1.25 grams of each activator as shown in the table below. The hardening was activated by vennahlening with a mortar and pestle. The stability of the same uncured mixtures also containing 50 g of Sterling MT carbon black was observed.

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Tabel Activator IV Stability at
55 ° C, days example NaOH Capsule size 1-3 21st NaOH
■ ■■■ -. ■. 297 1-3 22nd Ethylenediamine 297-590 <1 23 Ethylenediamine 297 <i ^: 2M Glycerine / 10% 297-590 1-3 25th Quaternary ammo
sodium salt, 1 % 297-540 > 1 26th IM10-1680

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Claims (8)

P a t e η t a η s ρ r ü c h e 1. Storable, curable polythiol polymer composition that is one-liquid Polythiol polymer and an effective amount of at least one latent one Contains hardening agent for the polymer, characterized in that it contains mechanically breakable capsules in which an activator * for the curing agent with an essentially impermeable to the components of the polymer mass © and non-reacting shell is encapsulated, the total amount of activator contained in the capsules being sufficient, activate the hardener. 2. Polythiol polymer composition according to claim I _9, characterized in that it contains water as an activator. 3. Polythiol polymer composition according to claim 1 and 2 _S, characterized in that it contains capsules a size of about 100 to about ¹ 1,000 .u. 4. Polythiol polymer composition according to claim 1 to 3, characterized gekennzeichfc net that they have capsules with an activator content of about 25 to 95 liters by weight and a frangibility of about 0.1 to 5 pounds (45 to 2,268 g) per capsule. 5. polythiol polymer composition according to claim 1 to 4, characterized in that that as a liquid polythiol polymer, polyalkylene polysulphide polythiol polymers, Polysulfide polymers with -SSH end groups and a large number of sulfur atoms in the polysulfide groups, blocked Polysulphide polymers with a large number of sulfur atoms in the polyulphide groups, Polyether polythiol polymers, hydrocarbon polythiol 109809/2002 203625Q polymers, polyurethane polythiol polymers, polythioether polythiol polymers or geminal dithioether polythiol polymers. 6 .. Polythiol polymer composition according to claim 1 to 5, characterized in that it is calcium peroxide, calcium orthoplumbate, as the latent curing agent Manganese dioxide, lithium peroxide, or barium peroxide Zinc peroxide contains « 7, polythiol polymer composition according to claim 6, characterized in that that they are calcium peroxide as a latent hardener, as a liquid Polythiol polymer contains an alkylene polysulfide polythiol polymer and water as an activator. 8. polythiol polymer composition according to claim 7, characterized in that it contains capsules in a size of about 1,000 to M. OOOyU. 109809/2002> ORlGlNALiNSPEGTEO