CA1207096A - Cyanoacrylate adhesive composition - Google Patents
Cyanoacrylate adhesive compositionInfo
- Publication number
- CA1207096A CA1207096A CA000439775A CA439775A CA1207096A CA 1207096 A CA1207096 A CA 1207096A CA 000439775 A CA000439775 A CA 000439775A CA 439775 A CA439775 A CA 439775A CA 1207096 A CA1207096 A CA 1207096A
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- Canada
- Prior art keywords
- group
- general formula
- adhesive composition
- sulfonic acid
- cyclization
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
Abstract
CYANOACRYLATE ADHESIVE COMPOSITION
ABSTRACT OF THE INVENTION
Adhesive composition consisting of?-cyanoacrylate, one or more sulphonic acid derivatives as stabilizers and conventional additives. The stabilizers are sulphonic acid derivatives having the general formula (I) in which R1 is a trimethylsilyl group, R2 a halogen atom, an alkyl group, a perfluoroalkyl group, a cycloalkyl group or an aryl group or R1 and R2 together, accompanied by cyclization, represent a group of the general formula (II) in which Z is a substituted or unsubstituted phenylene radical. Preferred are combinations of compounds in which in one R1 is a trimethylsilyl group and in the other R1 and R2 form the aforementioned ring group.
(Dihydroxy)-organylboranes and bis(dihydroxyboryl)-derivatives can be used as costabilizers. The storage stability obtained with the stabilizers according to the invention is excellent, without impairing the setting rate and the strength of the bonds obtained.
ABSTRACT OF THE INVENTION
Adhesive composition consisting of?-cyanoacrylate, one or more sulphonic acid derivatives as stabilizers and conventional additives. The stabilizers are sulphonic acid derivatives having the general formula (I) in which R1 is a trimethylsilyl group, R2 a halogen atom, an alkyl group, a perfluoroalkyl group, a cycloalkyl group or an aryl group or R1 and R2 together, accompanied by cyclization, represent a group of the general formula (II) in which Z is a substituted or unsubstituted phenylene radical. Preferred are combinations of compounds in which in one R1 is a trimethylsilyl group and in the other R1 and R2 form the aforementioned ring group.
(Dihydroxy)-organylboranes and bis(dihydroxyboryl)-derivatives can be used as costabilizers. The storage stability obtained with the stabilizers according to the invention is excellent, without impairing the setting rate and the strength of the bonds obtained.
Description
~Z~7(1 9~
BACKGROUND OF INVENTION
The present invention relates to a ~-cyanoaerylate-based adhesive composition having good storage stability.
d-cyanoacrylates of general formula CN
,. /
C~2 = C (IV) COOR
are rapid-setting adhesives which are suited for an extraordinarily rapid adhesion of a large number of materials like rubber, plastics, metal, leather and wood in various teehnieal areas like machine eonstruetion, apparatus construetion, eleetrieal engineering, jewelery industry, watch-maker industry, household ete. The parts ean be joined in an extremely short time of only a few seconds and the adhesive joints produced in this way have good mechanical strengths characteristics. These adhesives harden by anionie polymerization initiated by even small traees of extremely weak basic-acting eompounds (Lewis bases) such as for example, water or methanol. Due to the extreme reactivity of these adhesives usually inhibition of premature polymerization whieh has an adverse effect on storage stability is required. Accordingly, in the past acidic gases like sulphur dioxide, nitrogen monoxide, carbon dioxide, hydrogen fluoride etc., have been added to these adhesives. Furthermore, proton acids including mineral acids like hydrochloric acid, sulphuric acid and polyphosphoric acid, anhydrides like phosphoric anhydride , sulfonic acids and carboxylic acids like ~r~
7~6 acetic acid, itaconic acid and benzenesulfonic acid have been used as stabilizers. Typical patents relating to the aforementioned stabilizers are US-PS 2 765 332, US-PS
BACKGROUND OF INVENTION
The present invention relates to a ~-cyanoaerylate-based adhesive composition having good storage stability.
d-cyanoacrylates of general formula CN
,. /
C~2 = C (IV) COOR
are rapid-setting adhesives which are suited for an extraordinarily rapid adhesion of a large number of materials like rubber, plastics, metal, leather and wood in various teehnieal areas like machine eonstruetion, apparatus construetion, eleetrieal engineering, jewelery industry, watch-maker industry, household ete. The parts ean be joined in an extremely short time of only a few seconds and the adhesive joints produced in this way have good mechanical strengths characteristics. These adhesives harden by anionie polymerization initiated by even small traees of extremely weak basic-acting eompounds (Lewis bases) such as for example, water or methanol. Due to the extreme reactivity of these adhesives usually inhibition of premature polymerization whieh has an adverse effect on storage stability is required. Accordingly, in the past acidic gases like sulphur dioxide, nitrogen monoxide, carbon dioxide, hydrogen fluoride etc., have been added to these adhesives. Furthermore, proton acids including mineral acids like hydrochloric acid, sulphuric acid and polyphosphoric acid, anhydrides like phosphoric anhydride , sulfonic acids and carboxylic acids like ~r~
7~6 acetic acid, itaconic acid and benzenesulfonic acid have been used as stabilizers. Typical patents relating to the aforementioned stabilizers are US-PS 2 765 332, US-PS
2 794 788, US-PS 2 756 251, VS-PS 2 912 454, US-PS
2 926 188, US-PS 3 728 375, US-PS 3 993 678 and DE-OS
23 07 834 Reference is also made to US-PS 3 652 635, DE-OS 21 28 985, DE-OS 20 42 334, DE-OS 18 07 895 and DE-OS 21 18 701, which propose organic sulfonic acids, sulfonic anhydrides, aliphatic or aromatic sultons and aliphatic sulfocarboxylic anhydrides as stabilizers for ~-cyanoacrylate-based adhesives.
However, gaseous stabilizers are only suited to a limited degree for effective stabilization of ~-cyanoacrylates, since metering in the liquid adhesive is difficult and during storage undefined amounts can prematurely escape.
When using higher concentrations of acidic gases or non-gaseous acids the curing rate of the ~-cyanoacrylates rapidly decreases. On the other hand when using too low concentrations no sufficient stabilization is achieved.
It has now been surprisingly found that the above difficulties and disadvantages of the prior art stabilizers can be avoided or the stabilizing action can be improved by using as stabilizers certain sulfonic acid derivatives and preferably combinations of such sulfonic acid derivatives. It has also surprisingly been found that storage stability can frequently be still further improved by combining these stabilizers with compounds from the group consisting of (dihydroxy)-organylboranes and bis-(dihydroxyboryl)-derivatives.
~l2C~7~9~;
DETAILED DESCRIPTION OF INVENTION
The present invention is directe~ to adhesive compositions based on ~-cyanoacrylate and which contain S one or more sulfonic acid derivatives as stabilizer and may contain conventional additives as described herein and in the appended claims. Preferred embodiments, which may additionally contain a costabilizer, are also described herein and in the appended subclaims.
The generally known ~-cyanoacrylates which serve as a basis for the adhesive compositions according -to the invention are of general formula:
~ CN
\ COOR (IV) wherein R is a straight or branched-chain alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-bu-tyl, isobutyl, pentyl, hexyl and the like as well as a halogen atom subs-tituted alkyl group such as 2-chloroethyl, 3-chloropropyl, 2-chloro-butyl, trifluoroethyl, and the like; a straight or branched-chain alkenyl group, such as allyl, methallyl, crotyl and the like; a straight or branched-chain alkinyl group such as propargyl and the like; a cycloalkyl group such as cyclohexyl and the like; a tetrahydrofurfuryl groupi an ether group X-O-Y or X-O-X-O-Y, in which X is a saturated alkylene group having 2 to 4 carbon atoms and Y is an alkyl group having 2 -to 6 carbon atoms such as 2-methoxyethyl, 3-methoxybutyl, 2-ethoxyethyl and the like; an aralkyl group such as benzyl or an aryl group such as phenyl, cresyl and the like. Further, German ~2¢~'7~96i ~5--published applica~ion DE-OS 28 16 836 refers to a large number of suitable ~-cyanoacrylates.
The subject stabilizers contained in the adhesive compositions according to the invention are sulfonic acid derivatives of general formula o R1 _ o - S - R2 (I) wherein R1 is a trimethyl silyl group Si(CH3)3, R is a halogen atom, a straight or branched-chain alkyl group having 1 to 10 carbon atoms, a perfluoroalkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group or R or R2 together and accompanied by cyclization stand for a group of general formula o - C - Z - (II) in which Z is with R being an alkyl group with 1 to 4 carbon atoms, an oxyalkyl group with 1 to 7 carbon atoms or a nitro group, m having a value between 0 and 3.
In a preferred embodiment the adhesive compositions according to the invention contain combinations of compounds according to general formula I. Thus, prefer-ably compounds in which Rl stands for a trimethyl silyl ~., ~, 12~7C)~6 group are combined with a compound in which Rl and R2,accompanied by cyclization, form a group of general formula II. When using such combinations oE sulfonic acid derivatives, Z can also be -CR4 -CR5 in the group of general formula II, R4 and R5 being the same or different and stand for hydrogen or alkyl radicals. Like -the other sulfonic acid derivatives used according to the invent-ion, the latter can also be combined with (dihydroxy)-organylboranes or bis(dihydroxyboryl)-derivatives of general formula R ~B(OH)2~ m (III) wherein m is 1 or 2 and depending from m R6 is a straight or branched-chain alkyl or alkylene group having 1 to 12 carbon atoms, which can contain halogen atoms, a cyclo-hexyl or cyclohexylene group, an aralkyl or aralkylene group or an aryl or arylene group. The adhesive compositions containing the sulfonic acid derivatives according to the invention, their combinations or their combinations with compounds of general formula III
are characterized by an excellent storage stability, whilst retaining very good setting times and strengths of the bonds.
The compounds which are suitable alone or in combination as stabilizers can, as solid or liquid substances, be predissolved in a simple manner in a specific monomer quantity. By means of the thus ob-tained stabilizer solution, and~-cyanoacrylate quantity obtained by depolymizeration of polycyanoacrylate and subsequent , .
_7_ ~ ~7Q96 distillative puri:Eication can then be stabilized in the desired manner depending on the requisite s-torage stability and setting time. The resulting adhesive mixtures show an excellen-t storage stability, aceompanied by short setting times on various substrates.
Examples of typical compounds according to general formula I in which R stands for a trimethylsilyl group (trimethylsilyl sulfonates) and which are suitable for the purposes of the present invention are inter alia tri-methylsilyl methane sulfonate, trimethylsilyl trifluoro-methane sulfonate, trimethylsilyl nonafluorobutane sulfonate, trimethylsilyl heptadecane sulfonate, tri-methylsilyl benzene sulfonate, trimethylsilyl toluenesulfonate and trimethylsilyl chlorosulfonate.
Stabilizers according to general formula I in which Rl and R2, accompanied by cyclization, form the group with general formula II and which are suitable according to the invention are inter ali.a 2-sulfobenzoic cycloanhydride,
2 926 188, US-PS 3 728 375, US-PS 3 993 678 and DE-OS
23 07 834 Reference is also made to US-PS 3 652 635, DE-OS 21 28 985, DE-OS 20 42 334, DE-OS 18 07 895 and DE-OS 21 18 701, which propose organic sulfonic acids, sulfonic anhydrides, aliphatic or aromatic sultons and aliphatic sulfocarboxylic anhydrides as stabilizers for ~-cyanoacrylate-based adhesives.
However, gaseous stabilizers are only suited to a limited degree for effective stabilization of ~-cyanoacrylates, since metering in the liquid adhesive is difficult and during storage undefined amounts can prematurely escape.
When using higher concentrations of acidic gases or non-gaseous acids the curing rate of the ~-cyanoacrylates rapidly decreases. On the other hand when using too low concentrations no sufficient stabilization is achieved.
It has now been surprisingly found that the above difficulties and disadvantages of the prior art stabilizers can be avoided or the stabilizing action can be improved by using as stabilizers certain sulfonic acid derivatives and preferably combinations of such sulfonic acid derivatives. It has also surprisingly been found that storage stability can frequently be still further improved by combining these stabilizers with compounds from the group consisting of (dihydroxy)-organylboranes and bis-(dihydroxyboryl)-derivatives.
~l2C~7~9~;
DETAILED DESCRIPTION OF INVENTION
The present invention is directe~ to adhesive compositions based on ~-cyanoacrylate and which contain S one or more sulfonic acid derivatives as stabilizer and may contain conventional additives as described herein and in the appended claims. Preferred embodiments, which may additionally contain a costabilizer, are also described herein and in the appended subclaims.
The generally known ~-cyanoacrylates which serve as a basis for the adhesive compositions according -to the invention are of general formula:
~ CN
\ COOR (IV) wherein R is a straight or branched-chain alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-bu-tyl, isobutyl, pentyl, hexyl and the like as well as a halogen atom subs-tituted alkyl group such as 2-chloroethyl, 3-chloropropyl, 2-chloro-butyl, trifluoroethyl, and the like; a straight or branched-chain alkenyl group, such as allyl, methallyl, crotyl and the like; a straight or branched-chain alkinyl group such as propargyl and the like; a cycloalkyl group such as cyclohexyl and the like; a tetrahydrofurfuryl groupi an ether group X-O-Y or X-O-X-O-Y, in which X is a saturated alkylene group having 2 to 4 carbon atoms and Y is an alkyl group having 2 -to 6 carbon atoms such as 2-methoxyethyl, 3-methoxybutyl, 2-ethoxyethyl and the like; an aralkyl group such as benzyl or an aryl group such as phenyl, cresyl and the like. Further, German ~2¢~'7~96i ~5--published applica~ion DE-OS 28 16 836 refers to a large number of suitable ~-cyanoacrylates.
The subject stabilizers contained in the adhesive compositions according to the invention are sulfonic acid derivatives of general formula o R1 _ o - S - R2 (I) wherein R1 is a trimethyl silyl group Si(CH3)3, R is a halogen atom, a straight or branched-chain alkyl group having 1 to 10 carbon atoms, a perfluoroalkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group or R or R2 together and accompanied by cyclization stand for a group of general formula o - C - Z - (II) in which Z is with R being an alkyl group with 1 to 4 carbon atoms, an oxyalkyl group with 1 to 7 carbon atoms or a nitro group, m having a value between 0 and 3.
In a preferred embodiment the adhesive compositions according to the invention contain combinations of compounds according to general formula I. Thus, prefer-ably compounds in which Rl stands for a trimethyl silyl ~., ~, 12~7C)~6 group are combined with a compound in which Rl and R2,accompanied by cyclization, form a group of general formula II. When using such combinations oE sulfonic acid derivatives, Z can also be -CR4 -CR5 in the group of general formula II, R4 and R5 being the same or different and stand for hydrogen or alkyl radicals. Like -the other sulfonic acid derivatives used according to the invent-ion, the latter can also be combined with (dihydroxy)-organylboranes or bis(dihydroxyboryl)-derivatives of general formula R ~B(OH)2~ m (III) wherein m is 1 or 2 and depending from m R6 is a straight or branched-chain alkyl or alkylene group having 1 to 12 carbon atoms, which can contain halogen atoms, a cyclo-hexyl or cyclohexylene group, an aralkyl or aralkylene group or an aryl or arylene group. The adhesive compositions containing the sulfonic acid derivatives according to the invention, their combinations or their combinations with compounds of general formula III
are characterized by an excellent storage stability, whilst retaining very good setting times and strengths of the bonds.
The compounds which are suitable alone or in combination as stabilizers can, as solid or liquid substances, be predissolved in a simple manner in a specific monomer quantity. By means of the thus ob-tained stabilizer solution, and~-cyanoacrylate quantity obtained by depolymizeration of polycyanoacrylate and subsequent , .
_7_ ~ ~7Q96 distillative puri:Eication can then be stabilized in the desired manner depending on the requisite s-torage stability and setting time. The resulting adhesive mixtures show an excellen-t storage stability, aceompanied by short setting times on various substrates.
Examples of typical compounds according to general formula I in which R stands for a trimethylsilyl group (trimethylsilyl sulfonates) and which are suitable for the purposes of the present invention are inter alia tri-methylsilyl methane sulfonate, trimethylsilyl trifluoro-methane sulfonate, trimethylsilyl nonafluorobutane sulfonate, trimethylsilyl heptadecane sulfonate, tri-methylsilyl benzene sulfonate, trimethylsilyl toluenesulfonate and trimethylsilyl chlorosulfonate.
Stabilizers according to general formula I in which Rl and R2, accompanied by cyclization, form the group with general formula II and which are suitable according to the invention are inter ali.a 2-sulfobenzoic cycloanhydride,
3,4-dimethyl-2-sulfobenzoic cycloanhydride, 5-methoxy-2-sulobenzoic cycloanhydride, 5-ethoxy-2-sulfobenzoic cycloanhydride, 5-isopropyloxy-2-sulfobenzoic cyclo-anhydride and 5-nitro-2-sulfobenzoic cycloanhydride.
These compounds can be used as effective inhibitors of anionie polymerization without other additives. However, 3-sulfopropionic cycloanhydride is only used in combi-nation with compounds of general formula I, in which Rl standsfora trimethylsilyl group, and/or with (dihydroxy)-organylboranes or bis(dihydroxyboryl)-derivatives. All these compounds in which R and R form a ring closure, contain the group - C - Z - (II) so that the following structural formula is obtained:
~ S ~
Z O
~ ..~
o wherein Z has the aforementioned meaning. In other words, they are sulfocarboxylic cycloanhydrides.
Examples of costabilizers from the group of (dihydroxy)-organylboranes suitable accordiny to the invention and which can only be used in combination with sulfonic acid derivatives, are inter alia (dihydroxy)-ethylborane, (dihydroxy)-n-propylborane, (dihydroxy)-trifluoropropyl-borane, (dihydroxy)-n-butylborane, (dihydroxy)-t-butyl-borane, (dihydroxy)-n-pentylborane, (dihydroxy)-n-hexyl-borane, (dihydroxy)-cyclohexylborane, (dihydroxy)-n-dodecylborane, (dihydroxy)-benzylborane, (dihydroxy)-p-tolylborane, (dihydroxy)-o-trifluoromethylphenylborane, (dihydroxy)-o-ethylphenylborane, (dihydroxy)-mesityl-borane, (dihydroxy)-p-carboxyphenylborane, (dihydroxy)-o-me-thoxyphenylborane, (dihydroxy)-o-chlorophenylborane and (dihydroxy)-o-nitrophenylborane. In addition, there are bis(dihydroxyboryl)-derivatives such as bis(l,4-di-hydroxyboryl)-benzene and optionally the benzene nucleus can have one or more substituents.
Some examples of stabilizer combinations suitable accord-ing to the invention are o-sulfobenzoic cycloanhydride ~2G'70~ff g combined wi-th trimethylsilyl benzene sulfonate, 3-sulfo-propionic anhydride combined with a trimethylsilyl sulfonate, o-sulfobenzoic cycloanhydride combined wi-th a (dihydroxy)-alkyl or preferably (dihydroxy)-aryl borane, which can be termed as alkyl or aryl boronic acids, 3-sulfopropionic anhydride combined with (dihydroxy)-phenylborane (benzene boronic acid) and trimethylsilyl benzene sulfonate combined with a (dihydroxy)-alkyl borane or (dihydroxy)-aryl borane, such as benzene boronic acid.
The stabilizers according to the invention as well as their combinations are used in a quantity of 0.0001 to 0.1% by weight and preferably 0.001 to 0.05% by weight, based on theo~-cyanoacrylate monomers. A percentage composition of 20 to 80% by weight, preferably 40 to 60%
by weight, based on the quantity of the first stabilizer used, has proved advantageous for the stabilizer combinations. The (dihydroxy)-organylboranes and bis(di-hydroxyboryl)-derivatives used as costabilizers, based on the weight of -the sulfonic acid derivative used, can be used in such a quantity that the weight ratio of costabilizer to stabilizer is 0.5:1 to 10:1.
The stabilizers and costabilizers used according to the invention are either commercially available or are prepared according to known processes.
Trimethylsilyl sulfonates, i.e. compounds of general formula I in which R is a trimethylsilyl group, are obtained by heating the sulfonic acids with trimethyl-chlorosilane or under mild conditions in certain cases by reacting aryl trimethylsilane with the corresponding ~2~7096 sulfonic aeids (D. Habich, F. Effenberger, Synthesis, 1978, 755; ~l. Emde et al, Synthesis, 1982, 1).
Compounds of general formula I, in which Rl and R2, aceompanied by cyclization, form the group of formula II, i.e. aromatic cyclic sulfocarboxylic anhydrides can be prepared merely by heating the free acid or accompanied by the addition of phosphorous pentoxide and by treatment with aeetyl chloride. According to another process, aromatic carboxylic cycloanhydrides are obtained by reacting ammonium salts of o-sulfocarboxylie acids with thionyl chloride (cf. Organic Synthesis Collective, Vol.
1, 495, (1941)). The cyclic anhydrides of aliphatic sulfocarboxylic acids, i.e. Z is -CR2 - CR2 -, suitable as stabilizers in eombination with trimethyl-silyl sulfonates and/or (dihydroxy)-organylboranes or bis(dihydroxyboryl)-derivatives can be prepared by photo-ehemical sulfochlorination of the corresponding carboxy-lic acids with sulfonyl chloride.
Alkyl or aryl boronie aeids, i.e. (dihydroxy)-organyl-boranes are generally obtained by reacting trihalogen boranes with Grignard reagents and subsequent hydrolysis.
A second generally used method consists of the hydrolysis of the products obtained by photochemieal reaetion of tribromoboranes and alkyl benzene. Functional groups such as e.g. nitro groups on aromatic (dihydroxy)-organyl-boranes must be subsequently introduced. The bis(di-hydroxyboryl)-derivatives are obtained by hydrolysis of the corresponding organyl-bis(dihaloboranes) or organyl-bis(dialkyloxyboranes) or by reacting tris(alkyloxy)-boranes with difunctional Grignard reagents (Gmelin:
~l2~'7Q~i Handbuch der Anorganisehen Chemie, supplement to 8th edition, Vol. 48, part 16, 167).
Surprisingly, through the combination of the compounds suitable as stabilizers according to -the invention with one another or with compounds of general formula III, a significant synergistic stabilizing effee-t is obtained.
Although the reasons for this have not as yet been elarified, it is assumed that the synergistie stabilizing effect is based on the different reaetivity features of the stabilizers aeeording to the invention.
As mentioned before the adhesive eombinations aeeording to the invention may also contain conventional additives.
As ~-cyanoacrylates are also capable of radieally initiated polymerization, it is advantageous to add to the adhesive eompositions according to the invention common inhibitors for the radical polymerization. Such inhibitors are for example quinone, hydroquinone, p-methoxyphenol, pyrogallol, p-tert.-butyl cateehol and 2,6-di-tert.-butyl-p-cresol. These inhibitors can be added in a concentration of about 0.001 to 1~ by weight based on the total weigh-t of the adhesive composition.
Depending on the intended use, the adhesive compositions according to the invention may contain further convent-ional additives such as thickeners, plasticizers, polymers, aceelerators, perfumes, dyes, pigments, further copolymerizable monomers and solvents. Thus, for example when joining porous materials it is desired to increase the viscosity by adding a thickener to avoid that the adhesive penetrates the pores of the surfaces to be adhered to one another. Furthermore, the setting times of the adhesives aecording to the invention especially i2~7096 on porous/acidic surfaces (e.g. wood) can be rec~uced by polymerization catalysts like podands as disclosed in German published applications DE-OS 30 25 127 and DE-OS
31 09 220 which are herein incorporated by reference.
Such modifications are sufficiently described in the literature.
The following examples are given for illustrative purposes only and are nGt meant to be a limitation on the subject invention except as defined by the claims append-ed hereto. All parts and percentages are by weight unless otherwise indicated.
Example 1 Several stabilizers according to the invention in the quantities stated in Table I were added to freshly distilled ethyl- ~-cyanoacrylate containing 0.01~ by weight hydroquinone and 30 ppm SO2. The obtained adhesives were tested for their long term stability at room temperature and in an accelerated ageing -test at 50C. ~As a measure for the stability serves the change of viscosity of the liquid adhesives. The viscosity in mPa.s is determined with a capillary viscosimeter. The results are also given in Table I.
There were only insignificant changes to the good setting times of the adhesives through storage.
Substantially the same results were obtained in tests in which ethyl-~-cyanoacrylate was wholly or partly re-placed by methyl-, C3-C20-alkyl, cycloalkyl-, alkoxy-alkyl-, alkoxyalkoxyalkyl- and phenyl-d~-cyanoacrylate as well as mixtures thereof.
~za7~6 Table I
Stabilizer S-torage Stability Added O
Type Amount RT 50 C
(ppm) Trimethylsilyl Longer Longer methane than than sulfonate 100 6 months 20 days Trimethylsilyl benzene sulfonate 100 " "
Trimethylsilyl p-toluene sulfonate 100 " "
o-sulfobenzoic cycloanhydride 100 " "
No additive - 10 days 3 days Example 2 The stabilize.rs used in example 1 were replaced by various combinations of stabilizers .according to the invention. The obtained adhesives were stored and tested in the same manner as in example 1.
Again there were only negligible changes to the short setting times on various substrates as a result of storage. The results of the storage stability tests are given in Table II.
~2~7~g6 Table II
S-tabilizer Combination Storage Stabilit-y Added Type Amount RT 50 C
(ppm) No additive - lO days 3 da~ys Trimethylsilyl benzene sulfonate 50 Longer than l.onger than o-sulfobenzoic cycloanhydride 50 6 Months 30 days Trimethylsilyl benzene sulfGnate 50 3-sulfopropionic "
anhydride 50 o-sulfobenzoic cycloanhydride 80 benzene boroniC
acid 400 3-sulfopropionic anhydride 80 benzeneboronic ll "
acid 400 Trimethylsilyl benzene sulfonate 80 benzene boronic " "
acid 500 Example 3 An adhesive mixture, which was stable in storage, was prepared from freshly distilled ethyl~ -cyanoacrylate, containing 0.01% by weight of hydroquinone and 30ppm S02, using several stabilizers and stabilizer combinations according to the invention. The obtained adhesives were thickened with polymethyl methacrylate (PMM~) with a molecular weight dis-tribution of 400,000 to 500,000.
Further a polymerization accelerating podand was added -to accelerate setting on porous/acidic surfaces (cf.
Table III).
Table III
Stabilizer Thickener Podand Type AddedPMMA Polyethylene Amount(% by weight) glycol-400-(PPM)dimethyl ether (% by weight) 1. No additive - 8 0.5 2. Trimethylsilyl benzene sulfonate 100 8 0.5 15 3, 0-sulfobenzoic cycloanhydride100 8 0.5
These compounds can be used as effective inhibitors of anionie polymerization without other additives. However, 3-sulfopropionic cycloanhydride is only used in combi-nation with compounds of general formula I, in which Rl standsfora trimethylsilyl group, and/or with (dihydroxy)-organylboranes or bis(dihydroxyboryl)-derivatives. All these compounds in which R and R form a ring closure, contain the group - C - Z - (II) so that the following structural formula is obtained:
~ S ~
Z O
~ ..~
o wherein Z has the aforementioned meaning. In other words, they are sulfocarboxylic cycloanhydrides.
Examples of costabilizers from the group of (dihydroxy)-organylboranes suitable accordiny to the invention and which can only be used in combination with sulfonic acid derivatives, are inter alia (dihydroxy)-ethylborane, (dihydroxy)-n-propylborane, (dihydroxy)-trifluoropropyl-borane, (dihydroxy)-n-butylborane, (dihydroxy)-t-butyl-borane, (dihydroxy)-n-pentylborane, (dihydroxy)-n-hexyl-borane, (dihydroxy)-cyclohexylborane, (dihydroxy)-n-dodecylborane, (dihydroxy)-benzylborane, (dihydroxy)-p-tolylborane, (dihydroxy)-o-trifluoromethylphenylborane, (dihydroxy)-o-ethylphenylborane, (dihydroxy)-mesityl-borane, (dihydroxy)-p-carboxyphenylborane, (dihydroxy)-o-me-thoxyphenylborane, (dihydroxy)-o-chlorophenylborane and (dihydroxy)-o-nitrophenylborane. In addition, there are bis(dihydroxyboryl)-derivatives such as bis(l,4-di-hydroxyboryl)-benzene and optionally the benzene nucleus can have one or more substituents.
Some examples of stabilizer combinations suitable accord-ing to the invention are o-sulfobenzoic cycloanhydride ~2G'70~ff g combined wi-th trimethylsilyl benzene sulfonate, 3-sulfo-propionic anhydride combined with a trimethylsilyl sulfonate, o-sulfobenzoic cycloanhydride combined wi-th a (dihydroxy)-alkyl or preferably (dihydroxy)-aryl borane, which can be termed as alkyl or aryl boronic acids, 3-sulfopropionic anhydride combined with (dihydroxy)-phenylborane (benzene boronic acid) and trimethylsilyl benzene sulfonate combined with a (dihydroxy)-alkyl borane or (dihydroxy)-aryl borane, such as benzene boronic acid.
The stabilizers according to the invention as well as their combinations are used in a quantity of 0.0001 to 0.1% by weight and preferably 0.001 to 0.05% by weight, based on theo~-cyanoacrylate monomers. A percentage composition of 20 to 80% by weight, preferably 40 to 60%
by weight, based on the quantity of the first stabilizer used, has proved advantageous for the stabilizer combinations. The (dihydroxy)-organylboranes and bis(di-hydroxyboryl)-derivatives used as costabilizers, based on the weight of -the sulfonic acid derivative used, can be used in such a quantity that the weight ratio of costabilizer to stabilizer is 0.5:1 to 10:1.
The stabilizers and costabilizers used according to the invention are either commercially available or are prepared according to known processes.
Trimethylsilyl sulfonates, i.e. compounds of general formula I in which R is a trimethylsilyl group, are obtained by heating the sulfonic acids with trimethyl-chlorosilane or under mild conditions in certain cases by reacting aryl trimethylsilane with the corresponding ~2~7096 sulfonic aeids (D. Habich, F. Effenberger, Synthesis, 1978, 755; ~l. Emde et al, Synthesis, 1982, 1).
Compounds of general formula I, in which Rl and R2, aceompanied by cyclization, form the group of formula II, i.e. aromatic cyclic sulfocarboxylic anhydrides can be prepared merely by heating the free acid or accompanied by the addition of phosphorous pentoxide and by treatment with aeetyl chloride. According to another process, aromatic carboxylic cycloanhydrides are obtained by reacting ammonium salts of o-sulfocarboxylie acids with thionyl chloride (cf. Organic Synthesis Collective, Vol.
1, 495, (1941)). The cyclic anhydrides of aliphatic sulfocarboxylic acids, i.e. Z is -CR2 - CR2 -, suitable as stabilizers in eombination with trimethyl-silyl sulfonates and/or (dihydroxy)-organylboranes or bis(dihydroxyboryl)-derivatives can be prepared by photo-ehemical sulfochlorination of the corresponding carboxy-lic acids with sulfonyl chloride.
Alkyl or aryl boronie aeids, i.e. (dihydroxy)-organyl-boranes are generally obtained by reacting trihalogen boranes with Grignard reagents and subsequent hydrolysis.
A second generally used method consists of the hydrolysis of the products obtained by photochemieal reaetion of tribromoboranes and alkyl benzene. Functional groups such as e.g. nitro groups on aromatic (dihydroxy)-organyl-boranes must be subsequently introduced. The bis(di-hydroxyboryl)-derivatives are obtained by hydrolysis of the corresponding organyl-bis(dihaloboranes) or organyl-bis(dialkyloxyboranes) or by reacting tris(alkyloxy)-boranes with difunctional Grignard reagents (Gmelin:
~l2~'7Q~i Handbuch der Anorganisehen Chemie, supplement to 8th edition, Vol. 48, part 16, 167).
Surprisingly, through the combination of the compounds suitable as stabilizers according to -the invention with one another or with compounds of general formula III, a significant synergistic stabilizing effee-t is obtained.
Although the reasons for this have not as yet been elarified, it is assumed that the synergistie stabilizing effect is based on the different reaetivity features of the stabilizers aeeording to the invention.
As mentioned before the adhesive eombinations aeeording to the invention may also contain conventional additives.
As ~-cyanoacrylates are also capable of radieally initiated polymerization, it is advantageous to add to the adhesive eompositions according to the invention common inhibitors for the radical polymerization. Such inhibitors are for example quinone, hydroquinone, p-methoxyphenol, pyrogallol, p-tert.-butyl cateehol and 2,6-di-tert.-butyl-p-cresol. These inhibitors can be added in a concentration of about 0.001 to 1~ by weight based on the total weigh-t of the adhesive composition.
Depending on the intended use, the adhesive compositions according to the invention may contain further convent-ional additives such as thickeners, plasticizers, polymers, aceelerators, perfumes, dyes, pigments, further copolymerizable monomers and solvents. Thus, for example when joining porous materials it is desired to increase the viscosity by adding a thickener to avoid that the adhesive penetrates the pores of the surfaces to be adhered to one another. Furthermore, the setting times of the adhesives aecording to the invention especially i2~7096 on porous/acidic surfaces (e.g. wood) can be rec~uced by polymerization catalysts like podands as disclosed in German published applications DE-OS 30 25 127 and DE-OS
31 09 220 which are herein incorporated by reference.
Such modifications are sufficiently described in the literature.
The following examples are given for illustrative purposes only and are nGt meant to be a limitation on the subject invention except as defined by the claims append-ed hereto. All parts and percentages are by weight unless otherwise indicated.
Example 1 Several stabilizers according to the invention in the quantities stated in Table I were added to freshly distilled ethyl- ~-cyanoacrylate containing 0.01~ by weight hydroquinone and 30 ppm SO2. The obtained adhesives were tested for their long term stability at room temperature and in an accelerated ageing -test at 50C. ~As a measure for the stability serves the change of viscosity of the liquid adhesives. The viscosity in mPa.s is determined with a capillary viscosimeter. The results are also given in Table I.
There were only insignificant changes to the good setting times of the adhesives through storage.
Substantially the same results were obtained in tests in which ethyl-~-cyanoacrylate was wholly or partly re-placed by methyl-, C3-C20-alkyl, cycloalkyl-, alkoxy-alkyl-, alkoxyalkoxyalkyl- and phenyl-d~-cyanoacrylate as well as mixtures thereof.
~za7~6 Table I
Stabilizer S-torage Stability Added O
Type Amount RT 50 C
(ppm) Trimethylsilyl Longer Longer methane than than sulfonate 100 6 months 20 days Trimethylsilyl benzene sulfonate 100 " "
Trimethylsilyl p-toluene sulfonate 100 " "
o-sulfobenzoic cycloanhydride 100 " "
No additive - 10 days 3 days Example 2 The stabilize.rs used in example 1 were replaced by various combinations of stabilizers .according to the invention. The obtained adhesives were stored and tested in the same manner as in example 1.
Again there were only negligible changes to the short setting times on various substrates as a result of storage. The results of the storage stability tests are given in Table II.
~2~7~g6 Table II
S-tabilizer Combination Storage Stabilit-y Added Type Amount RT 50 C
(ppm) No additive - lO days 3 da~ys Trimethylsilyl benzene sulfonate 50 Longer than l.onger than o-sulfobenzoic cycloanhydride 50 6 Months 30 days Trimethylsilyl benzene sulfGnate 50 3-sulfopropionic "
anhydride 50 o-sulfobenzoic cycloanhydride 80 benzene boroniC
acid 400 3-sulfopropionic anhydride 80 benzeneboronic ll "
acid 400 Trimethylsilyl benzene sulfonate 80 benzene boronic " "
acid 500 Example 3 An adhesive mixture, which was stable in storage, was prepared from freshly distilled ethyl~ -cyanoacrylate, containing 0.01% by weight of hydroquinone and 30ppm S02, using several stabilizers and stabilizer combinations according to the invention. The obtained adhesives were thickened with polymethyl methacrylate (PMM~) with a molecular weight dis-tribution of 400,000 to 500,000.
Further a polymerization accelerating podand was added -to accelerate setting on porous/acidic surfaces (cf.
Table III).
Table III
Stabilizer Thickener Podand Type AddedPMMA Polyethylene Amount(% by weight) glycol-400-(PPM)dimethyl ether (% by weight) 1. No additive - 8 0.5 2. Trimethylsilyl benzene sulfonate 100 8 0.5 15 3, 0-sulfobenzoic cycloanhydride100 8 0.5
4. Trimethylsilyl benzene sulfonate 50 o-sulfobenzoic 8 0.5 cycloanhydride 50 20 5~ o-sulfobenzoic cycloanhydride 80 benzene boronic 8 0.5 acid 300 The lon~ term stability of these adhesives was tested by storing samples of the stabilized, accelerated product in an oven heated to 50C. The change of viscosity as a measure for the stability is plotted in Figure l. After 20 days of accelerated ageing the stabilized ~- cyano-acrylate-based adhesives according to the invention only exhibited a slight viscosity increase and saveshort setting times on various substrates before and also after accelerated ageing.
. ,~
. ,~
Claims (10)
1. An?-cyanoacrylate-based adhesive composition containing as stabilizer one or more sulfonic acid derivatives of the following general formula (I) in which R1 stands for a trimethylsilyl group Si(CH3)3, R2 is a halogen atom, a straight or branched-chain alkyl group having 1 to 10 carbon atoms, a perfluoroalkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group or R1 and R2 together, accompanied by cyclization, stand for a group of formula (II) in which Z is wherein R3 is an alkyl group having 1 to 4 carbon atoms, an oxyalkyl group having 1 to 7 carbon atoms or a nitro group and m has a value between 0 and 3.
2. The adhesive composition of claim 1 which as co-stabilizer additionally contains one or more compounds from the group consisting of (dihydroxy)-organylboranes and bis(dihydroxyboryl)-derivatives of general formula (III) in which m is 1 or 2 and depending from m R6 is a straight or branched-chain alkyl or alkylene group having 1 to 12 carbon atoms, which can contain halogen atoms, a cyclohexyl or cyclohexylene group, an aralkyl or aralkylene group or an aryl or arylene group.
3. The adhesive composition of claim 1 which contains as stabilizers both a sulfonic acid derivative of general formula I, in which R1 is Si(CH3)3, and a sulfonic acid derivative of general formula I, in which R1 and R2, accompanied by cyclization, are the group of general formula II.
4. The adhesive composition of claim 2 which contains as stabilizers both a sulfonic acid derivative of general formula I, in which R1 is Si(CH3)3, and a sulfonic acid derivative of general formula I, in which R1 and R2, accompanied by cyclization, are the group of general formula II.
5. The adhesive composition of claim 2 wherein in the sulfonic acid derivative, in which the radicals are R1 and R2, accompanied by cyclization, form the group with general formula II, Z stands for -CR? -CR? -, in which R4 and R5 can be the same or different and stand for hydrogen or alkyl radicals.
6. The adhesive composition of claim 3 wherein in the sulfonic acid derivative, in which the radicals are R1 and R2, accompanied by cyclization, form the group with general formula II, Z stands for -CR? -CR? -, in which R4 and R5 can be the same or different and stand for hydrogen or alkyl radicals.
7. The adhesive composition of claim 4 wherein in the sulfonic acid derivative, in which the radicals are R1 and R2, accompanied by cyclization, form the group with general formula II, Z stands for -CR? -CR? -, in which R4 and R5 can be the same or different and stand for hydrogen or alkyl radicals.
8. The adhesive composition of claims 1, 2 or 3 which additionally contains small amounts of a gaseous stabilizer such as SO2 and/or common inhibitors for the radical polymerization.
9. The adhesive composition of claims 4 or 5 which additionally contains small amounts of a gaseous stabilizer such as SO2 and/or common inhibitors for the radical polymerization.
10. The adhesive composition of claims 6 or 7 which additionally contains small amounts of a gaseous stabilizer such as SO2 and/or common inhibitors for the radical polymerization.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3239776.3 | 1982-10-27 | ||
| DE19823239776 DE3239776A1 (en) | 1982-10-27 | 1982-10-27 | CYANACRYLATE ADHESIVE COMPOSITION |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1207096A true CA1207096A (en) | 1986-07-02 |
Family
ID=6176716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000439775A Expired CA1207096A (en) | 1982-10-27 | 1983-10-26 | Cyanoacrylate adhesive composition |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4565883A (en) |
| JP (1) | JPS5998178A (en) |
| CA (1) | CA1207096A (en) |
| DE (1) | DE3239776A1 (en) |
| FR (1) | FR2535335B1 (en) |
| GB (3) | GB2129003B (en) |
| IT (1) | IT1169902B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3406708C2 (en) * | 1984-02-24 | 1986-01-02 | Teroson Gmbh, 6900 Heidelberg | Anaerobic curing adhesive or sealant composition |
| DE3414805A1 (en) * | 1984-04-19 | 1985-10-24 | Bayer Ag, 5090 Leverkusen | STABILIZED ADHESIVES |
| JPH0826288B2 (en) * | 1986-02-26 | 1996-03-13 | 高圧ガス工業株式会社 | α-Cyanoacrylate adhesive composition |
| GB8729140D0 (en) * | 1987-12-14 | 1988-01-27 | Lingner & Fischer Gmbh | Adhesive |
| US5328944A (en) * | 1992-07-14 | 1994-07-12 | Loctite Corporation | Cyanoacrylate adhesives with improved cured thermal properties |
| US5424343A (en) * | 1992-10-08 | 1995-06-13 | Loctite Corporation | Thermally resistant cyanoacrylates employing substituted napthasultone additive |
| US5288794A (en) * | 1992-10-23 | 1994-02-22 | Loctite Corporation | Cyanoacrylate adhesives with improved cured thermal properties utilizing substituted aromatic additive |
| JP2005162850A (en) * | 2003-12-02 | 2005-06-23 | Koatsu Gas Kogyo Co Ltd | Adhesive for thermoplastic elastomer |
| US8173622B2 (en) | 2007-08-15 | 2012-05-08 | Medtronic, Inc. | Antimicrobial compounds having protective or therapeutic leaving groups |
| ATE516332T1 (en) * | 2007-08-30 | 2011-07-15 | Sika Technology Ag | USE OF A LATENT ACID TO IMPROVE ADHESION |
| EP3116962B1 (en) | 2014-03-10 | 2019-10-30 | 3M Innovative Properties Company | Conformable coating composition |
| BR112017000440A2 (en) | 2014-07-14 | 2017-10-31 | 3M Innovative Properties Co | conformal coating compositions, conformal film, multilayer article and copolymers? |
| TWI752043B (en) * | 2016-06-28 | 2022-01-11 | 日商東亞合成股份有限公司 | 2-cyanoacrylate-based adhesive composition |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA914693A (en) * | 1972-11-14 | Intercontinental Chemical Company | Cyanoacrylate adhesive composition | |
| US2794788A (en) * | 1952-11-01 | 1957-06-04 | Eastman Kodak Co | Adhesive compositions containing alkyl esters of cyanoacrylic acid |
| US2765332A (en) * | 1954-02-11 | 1956-10-02 | Eastman Kodak Co | Stabilized alpha-cyanoacrylate adhesive compositions |
| US2756251A (en) * | 1954-03-23 | 1956-07-24 | Eastman Kodak Co | Preparation of monomeric alpha-cyanoacrylates |
| US2926188A (en) * | 1957-05-06 | 1960-02-23 | Rohm & Haas | Process for preparing alpha-cyanoacrylates |
| US3576877A (en) * | 1967-11-07 | 1971-04-27 | Pennwalt Corp | Nitro-n,n-dialkyl aniline-n-oxides |
| CH540329A (en) * | 1967-11-10 | 1973-08-15 | Intercontinental Chem Co Ltd | adhesive |
| BE788670R (en) * | 1968-04-08 | 1973-03-12 | Johnson & Johnson | COMPOSITIONS |
| US3652635A (en) * | 1968-08-09 | 1972-03-28 | Toa Gosei Chem Ind | Stabilized alpha-cyanoacrylate adhesive compositions |
| US3632564A (en) * | 1970-07-08 | 1972-01-04 | Harry Elmer Albert | Process for inhibiting popcorn polymer formation |
| DE2118701A1 (en) * | 1971-04-17 | 1972-10-26 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Adhesives based on substd olefines and cyanoacrylates - - stabilised by addn of sulphocarboxylic acid anhydrides |
| US3728375A (en) * | 1971-05-12 | 1973-04-17 | Eastman Kodak Co | Cyanoacrylate adhesive compositions |
| DE2128985C3 (en) * | 1971-06-11 | 1981-10-29 | Schering Ag Berlin Und Bergkamen, 1000 Berlin | Stabilized adhesives |
| JPS5652949B2 (en) * | 1972-02-18 | 1981-12-15 | ||
| US3993678A (en) * | 1974-02-26 | 1976-11-23 | Minnesota Mining And Manufacturing Company | Stabilized alpha-cyanoacrylate compositions |
| US4041063A (en) * | 1975-11-18 | 1977-08-09 | Johnson & Johnson | Modified cyanoacrylate monomers and methods of preparation |
| JPS53129231A (en) * | 1977-04-19 | 1978-11-11 | Toagosei Chem Ind Co Ltd | Adhesion composition |
-
1982
- 1982-10-27 DE DE19823239776 patent/DE3239776A1/en active Granted
-
1983
- 1983-10-11 US US06/540,725 patent/US4565883A/en not_active Expired - Fee Related
- 1983-10-25 JP JP58198433A patent/JPS5998178A/en active Pending
- 1983-10-25 GB GB08328432A patent/GB2129003B/en not_active Expired
- 1983-10-26 IT IT23468/83A patent/IT1169902B/en active
- 1983-10-26 FR FR8317091A patent/FR2535335B1/en not_active Expired
- 1983-10-26 CA CA000439775A patent/CA1207096A/en not_active Expired
-
1984
- 1984-11-07 GB GB08428110A patent/GB2148312B/en not_active Expired
- 1984-11-07 GB GB08428111A patent/GB2148313B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2535335B1 (en) | 1985-11-22 |
| GB2129003A (en) | 1984-05-10 |
| GB2129003B (en) | 1986-06-18 |
| GB8428111D0 (en) | 1984-12-12 |
| IT1169902B (en) | 1987-06-03 |
| GB2148312A (en) | 1985-05-30 |
| GB8328432D0 (en) | 1983-11-23 |
| FR2535335A1 (en) | 1984-05-04 |
| US4565883A (en) | 1986-01-21 |
| GB2148313A (en) | 1985-05-30 |
| GB2148312B (en) | 1986-07-23 |
| GB2148313B (en) | 1986-07-23 |
| JPS5998178A (en) | 1984-06-06 |
| GB8428110D0 (en) | 1984-12-12 |
| DE3239776C2 (en) | 1987-01-02 |
| DE3239776A1 (en) | 1984-05-03 |
| IT8323468A1 (en) | 1985-04-26 |
| IT8323468A0 (en) | 1983-10-26 |
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