GB2069512A - Cyanoacrylate Adhesive Compositions - Google Patents
Cyanoacrylate Adhesive Compositions Download PDFInfo
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- GB2069512A GB2069512A GB8104882A GB8104882A GB2069512A GB 2069512 A GB2069512 A GB 2069512A GB 8104882 A GB8104882 A GB 8104882A GB 8104882 A GB8104882 A GB 8104882A GB 2069512 A GB2069512 A GB 2069512A
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- adhesive composition
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- branched chain
- weight
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- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 239000004830 Super Glue Substances 0.000 title abstract description 15
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 title description 4
- 239000000853 adhesive Substances 0.000 claims abstract description 56
- 230000001070 adhesive effect Effects 0.000 claims abstract description 56
- -1 alkenyl radicals Chemical class 0.000 claims abstract description 21
- 229920000570 polyether Polymers 0.000 claims abstract description 21
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 20
- 150000002240 furans Chemical class 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- TUCNEACPLKLKNU-UHFFFAOYSA-N acetyl Chemical compound C[C]=O TUCNEACPLKLKNU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000003426 co-catalyst Substances 0.000 claims description 16
- 229920001651 Cyanoacrylate Polymers 0.000 claims description 11
- 239000002023 wood Substances 0.000 claims description 8
- 239000002685 polymerization catalyst Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 2
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 claims description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims 1
- 125000005394 methallyl group Chemical group 0.000 claims 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 10
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract 1
- ARGCQEVBJHPOGB-UHFFFAOYSA-N 2,5-dihydrofuran Chemical class C1OCC=C1 ARGCQEVBJHPOGB-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002633 crown compound Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229940053009 ethyl cyanoacrylate Drugs 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical group [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 240000000731 Fagus sylvatica Species 0.000 description 1
- 235000010099 Fagus sylvatica Nutrition 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 244000186561 Swietenia macrophylla Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
A catalyst system for use in ???- cyanoacrylate adhesive compositions comprises at least one macrocyclic polyether together with a furan derivative of the following general formula <IMAGE> wherein R1 is a straight or branched chain alkyl or alkenyl radical or a cycloalkyl, phenyl, benzyl or acetyl radical and R2 and R3 independently of one another are hydrogen, straight and branched chain alkyl or alkenyl radicals or cycloalkyl, phenyl, benzyl or acetyl radicals or halogen. Such a system reduces the setting time, especially on porous and/or acid substrates and the adhesive composition has a reduced sensitivity to water.
Description
SPECIFICATION
Cyanoacrylate Adhesive Compositions
This invention relates to adhesive compositions of the a-cyanoacrylate type, and their use.
cu-Cyanoacrylates of the general formula
form rapidly hardening adhesives, whose hardening takes place by anionic polymerization which is started by even small traces of Lewis bases, such as e.g. moisture. When using such adhesives on wood, leather and other porous or acid surfaces, the problem occurs that the anionic polymerization of the a-cyanoacrylate is inhibited and as a result the setting time for the adhesive is too long for practical application. In addition, such adhesives tend to penetrate the pores of the surfaces to be adhered, so that in the case of the said materials the strength of the adhesive joint or bond is impaired by the longer setting time.Therefore, proposals have been made to reduce the setting time of such cyanoacrylate adhesives by adding polymerization catalysts and in this way to permit the use of the said adhesives also with the aforementioned materials. Thus, U.S. Patent No. 4,170,585 proposes the addition, to adhesive compositions based on a-cyanoacrylates, of approximately )0.0001 to 20% by weight of a polyethylene glycol with a degree of polymerization of at least 3 and/or an non-ionic surfactant possessing a polyethyleneoxy moiety (with a degree of polymerization also at least 3). According to
German Offenlegungsschrift 2,816,836, the setting time of a-cyanoacrylate adhesives is reduced by adding to the adhesive composition approximately 0.1 ppm or more of a macrocyclic polyether or an analog thereof.The two above-mentioned specifications also discuss in detail the abovementioned disadvantages of a-cyanoacrylate adhesives when used on wood, leather and other porous and/or acid surfaces. Finally, German Offenlegungsschrift 2,349,799 recommends the addition to a-cyanoacrylate adhesives of up to 50% by weight of lactones as plasticizers, which allegedly avoids the lengthening of the setting time caused by the plasticizers usually employed up to that time.
Although the use of macrocyclic polyether compounds as polymerization catalysts in a-cyanoacrylate adhesives leads to reduced setting times, the difficulty still remains that the presence of water in quantities above 200 ppm in such adhesive compositions, as in a-cyanoacrylate adhesive compositions in general, has a very adverse influence on the storage stability. In addition, in concentrations over 100 ppm such polyether compounds are only very sparingly soluble in - cyanoacrylates. In order to bring about dissolution and/or fine dispersion of the macrocyclic polyether compounds in a-cyanoacrylate mixtures, it is consequently necessary to stir the adhesive composition, accompanied by heating, for from a few hours to a few days, and the storage stability of such adhesive compositions is thereby reduced.
It has now surprisingly been found that the said difficulties when using macrocyclic polyether compounds as polymerization catalysts in a-cyanoacrylate adhesives can be avoided, the setting times and the sensitivity to water can be reduced, and the storage stability of such adhesives can be improved if in addition a suitable co-catalyst is used.
The invention therefore provides an adhesive composition comprising an a-cyanoacrylate and conventional additives and containing, as polymerization catalyst, at least one macrocyclic polyether or analog thereof, and additionally, as a co-catalyst, a furan derivative of general formula
in which R, is a straight or branched chain alkyl or alkenyl radical or a cycloalkyl, phenyl, benzyl or acetyl radical and R2 and R3 independently of one another are hydrogen, straight and branched chain alkyl or alkenyl radicals or cycloalkyl, phenyl, benzyl or acetyl radicals or halogen.
The generally known a-cyanoacrylates which form the basis for the adhesive compositions according to the invention are of general formula (III)
in which R is, e.g., a straight or branched chain alkyl group which can be substituted by halogen or alkoxy, or is a straight or branched chain alkenyl group, a straight or branched chain alkynyl group, a cycloalkyl group, an aralkyl group or an aryl group. More particularly R may be a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, allyl, methailyl, crotyl, propargyl, cyclohexyl, benzyl, phenyl, cresyl, 2-chloroethyl, 3-chloropropyi, 2-chlorobutyl, tnfluornethyl, 2-methoxyethyl, 3-methoxybutyl or 2-ethoxyethyl group (cf., inter alia, German Offenlegungsschrift 2, 816,836, which names a large number of suitable a-cyanoacrylates).
In addition, the adhesive compositions of the invention can contain conventional additives such as polymerization inhibitors, thickeners, plasticisers, perfumes, dyes, and pigments. Such additives form part of the prior art and are for example described in the above-mentioned specifications.
German Offenlegungsschrift 2,816,836 also provides a detailed description of macrocyclic polyether compounds from the group of macrocyclic polyethers and their analogs which description is imported by reference, such as 1 8-Crnwn-6 or 1 6Crown5, suitable for use as polymerization catalysts in a-cyano-acylate adhesives. These compounds are dissolved in any desired concentration in the furan derivative used according to the invention as the co-catalyst, and this dissolution takes place rapidly and without difficulty at room temperature. Suitable quantities of this solution are then introduced into the adhesive composition.The concentration of macrocyclic polyether compounds, based on the total weight of the adhesive composition, is approximately 0.1 ppm or higher, preference being given to concentrations of 1 ppm to 10% by weight and in particular 10 ppm to 5% by weight.
The quantity of macrocyclic polyether compound present in the a-cyano-acrylate adhesive is essentially determined by the sought degree of setting acceleration.
Furan derivatives especially suitable for use as co-catalysts according to the invention are the 5hydro-5-alkoxyfuran-2-ones (lì and 2,5-dialkoxy 2,5-dihydrofurans (II) of the formulae given above in which R1 can be a methyl, ethyl, n-propyl, iso-propyl, n-butyl, pentyl, hexyl, octyl, dodecyl or cyclohexyl radical and R2 and R3 independently of one another can be hydrogen, chlorine, bromine, methyl radicals and phenyl radicals.
The preparation of the furan derivatives of formulae I and II is known from the literature.
Based on total weight, the adhesive compositions of the invention contain approximately 1 ppm to 20% by weight and prefembly 10 ppm to 20% by weight of these furan derivatives.
Compared with adhesive compositions which only contain macrocyclic polyether compounds as the polymerization catalyst, the setting time, on wood and other substrates with a porous or acid surface, of adhesive compositions of the invention, which contain furan derivatives as co-catalysts, is, surprisingly, greatly reduced. In addition, for example, the addition of compound I in which R1 is a methyl radical and R2 and R3 are hydrogen leads to a greatly improved storage stability of the adhesive composition in relation to constancy of viscosity, and to agglomerate formation in the gas space of the containers. Storage at 700C for 5 days in a container causes neither a viscosity rise nor agglomerate formation in the gas space of the container.
Furthermore, the addition of, for example, a compound of formula I, in which R1, R2 and R3 stand for the above-mentioned radicals, reduces the sensitivity to water of a-cyanoacrylate adhesive compositions to a very decisive extent. Thus, a-cyanoacrylate adhesive compositions containing cocatalysts according to the invention are stable for several hours at extreme water contents of 1% and completely stable at lower water contents of e.g. 0.5%.
The following Examples illustrate the invention.
Examples 1 to 15
The following basic adhesive composition was prepared:
91.0% by weight of ethyl cyanoacrylate
8.5% by weight of thickener (polymethyl methacrylate)
0.005% by weight of radical stabilisers (hydroquinone)
traces of acid catalysts (SO2 and P205).
Adhesive compos7tions 1 to 1 5 were prepared from this basic composition and contained different quantities of macrocyclic polyether compound and furan derivative. The macrocyclic polyether compound used was 18-Crown-6, and compounds of general formulae I and II, in which R1 stands for a methyl radical and R2 and R3 for hydrogen, were used as the furane derivative. The contents of macrocyclic polyether compound and furan derivative in adhesive compositions 1 to 1 5 are given in
Table 1.
The setting times of adhesive compositions 1 te 1 5 were tested on different types of wood. The results are summarised in Table 2. The setting times were determined by a method wherein a ribbon of adhesive was applied to half of a substrate and then a second half of the substrate was placed above the first half with an overiap of 1 cm and was pressed down with a pressure of 5 kg/cm2 by means of a mechanical pressure applicator. The time which elapsed until the substrates could no longer be drawn apart with the fingers was recorded as the setting time (test piece dimensions: 1 00x25x7 mm).
Table 1
Adhesive Compositions with Different Contents of Macrocyclic Polyether Compound and Furan
Derivative
Example Crown compound, 18-Crown-6 Furan derivative No. {% by weight) {% by weight)
1
2 0.05
3 0.1
4 0.4 1
5 ~ 1.0
6 0.05 0.4 1
7 0.1 0.4 1
8 0.05 1.0 1
9 0.1 1.0 I
10 ~ 0.4 11
11 1.0 II
12 0.05 0.4 11
13 0.1 0.4 11
14 0.05 1.0 II
15 0.1 1.0 il Table 2
Setting Times of the Adhesive Compositions According to Table 1 on Different Types of Wood, in
Seconds
Adhesive
composition Pine Beech Spruce Mahogany Limba Teak Oak
Example No.
Moisture
content of
the wood in
% by weight *7.2 6.8 7.5 7.6 7.7 6.6 7.4
1 300 200 > 300 > 300 80 240 > 300
2 30 12 35 20 7 19 45 3 20 10 25 18 6 17 33
4 > 300 180 > 300 > 300 70 40 > 300 5 > 300 180 > 300 > 300 70 55 > 300
6 12 12 10 10 3 10 12
7 10 5 8 18 3 8 7
8 16 12 8 10 3 8 10
9 10 4 8 10 3 8 7
10 > 300 180 > 300 270 40 120 > 300
11 > 300 170 > 300 270 70 120 > 300
12 8 8 8 5 2 8 8
13 8 5 5 8 2 8 8
14 12 7 8 10 3 10 10
15 10 7 8 10 2 10 10
16** 80 15 80 40 8 60 120
*Determined by measuring the weight loss after storing for 24 hours at 1050C.
**1 6=commercial product (Cyanolit-732F) produced according to German Offenlegungsschrift
2,816,836.
In every case, after storing the adhered substrates (dimensions 100x25x7 mm, with 10 mm
overlap) for 24 hours at ambient temperature, failure occurred in the wood during the tensile shear
strength test.
The results in Table 2 clearly show that as a result of the addition of macrocyclic polyether
compounds in combination with furan derivatives I and II, the setting times were greatly improved
compared with adhesive compositions containing macrocyclic polyether compounds only. In all cases,
the adhesive compositions fulfil the requirement of withstanding accelerated ageing at 700C for 5 days
without undergoing significant changes.
The Crown compound was introduced rapidly and without difficulty at ambient temperature.
Example 17
Adhesive compositions with and without co-catalyst I (see above) were prepared and their
setting times on different substrates determined. The compositions used, and the measured setting
times, are given in Table 3 below.
Table 3
Setting Times of Different Substrates on Bonding by Means of a-cyanoacrylate Adhesive, with
the Addition of Co-catalyst I
with without
Adhesive composition co-catalystl co-catalyst I
Ethyl cyanoacrylate approx. 95% approx. 98% Thickener (PMMA) 2% 2%
Co-catalyst I 3% 0
Radical stabilizers
(hydroquinone) 0.05% 0.05%
Acid stabilizers (SO2, P205) 40-80 ppm 40-80 ppm
Setting times
Rigid PVC 3-5 sec. 3-5 sec.
Plasticized PVC 3-5 sec. 7-10 sec.
EPDM 3 sec. 5-8 sec.
ABS 3 sec. 8-10 sec.
SBR 3 sec. 7-8 sec.
It was found that on many substrates, particularly PVC, EDPM and SIR, the sole addition of the furan derivative I had an adhesion-promoting and accelerating effect. Thus, sliding away on the adhesive when making an adhesive joint was avoided through the immediate fixing of the substrates when co-catalyst I was present.
Example 18
10% solutions of water in tetrahydrofuran, dioxan and co-catalyst I were prepared. These solutions were in each case introduced in quantities of 10% into the basic adhesive composition according to Example I, so that the water content was 10/o. It was found that the first two solutions led to unstable adhesive compositions which spontaneously polymerized. In contrast, the adhesive composition containing the aqueous co-catalyst I was stable for several hours.
When performing the test in the same way, but using 5% solutions of water in tetrahydrofuran, dioxan and co-catalyst I, so that the water content of the adhesive composition was 0.5%, the same results were obtained, with the difference that the adhesive composition containing the aqueous co
catalyst I was now completely stable. These results clearly show that the furan derivatives according to the invention reduce the sensitivity to water of a-cyanoacrylate adhesives.
In conclusion, it is pointed out that the co-catalysts according to the invention offer the possibility of subsequently correcting even non-optimum batches in such a way that they are equivalent to excellent products.
Claims (11)
1. Adhesive composition comprising an a-cyanoacrylate and, as polymerization catalyst, at least one macrocyclic polyether or analog thereof, and as a co-catalyst, a furan derivative of the general formula:
in which R1 iSa straight or branched chain alkyl or alkenyl radical or a cycloalkyl, phenol, benzyl or acetyl radical and R2 and R3 independently of one another are hydrogen, straight and branched chain alkyl or alkenyl radicals or cycloalkyl, phenyl, benzyl or acetyl radicalsor halogen.
2. Adhesive composition according to claim 1, in which R, is methyl, ethyl, n-propyl, iso-propyl, n-butyl, pentyl, hexyl, octyl, dodecyl or cyclohexyl radical and R2 and R3 independently of one another are hydrogen chlorirre, bromine, methyl radicals or phenyl radicals.
3. Adhesive composition according to claim 1 or 2, which contains 1 ppm to 20% by weight of furan derivative based on the total weight of the adhesive composition.
4. Adhesive composition according to claim 3 containing 10 ppm to 20% by weight of the furan derivative.
5. Adhesive composition according to any one of claims 1 to 4, which contains 1 ppm to 10% by weight of the macrocyclic polyether compound, based on the total weight of the adhesive composition.
6. Adhesive composition according to claim 5 containing 10 ppm to 5% by weight of the macrocyclic polyether compound.
7. Adhesive composition according to any one of claims 1 to 6, in which the a-cyanoacrylate has the general formula:
in which R is a straight or branched chain alkyl group which can be substituted by halogen or alkoxy, or is a straight or branched chain alkenyl group, a straight or branched chain alkynyl group, a cycloalkyl group, an aralkyl group or an aryl group.
8. Adhesive composition according to claim 7, in which R is a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, allyl, methallyl, crotyl, propargyl, cyclohexyl, benzyl, phenyl, cresyl, 2- chloroethyl, 3-chloropropyl, 2-chlorobutyl, trifluoroethyl, 2-methoxyethyl, 3-methoxybutyl or 2 ethoxyethyl group.
9. Adhesive composition according to any one of claims 1 to 8 in which the macrocyclic poiyether compound is 18-Crown-6 or 16-Crown-S.
10. Adhesive composition according to claim 1 substantially as described in any one of Examples 6to9, 12to 15, 17or18.
11. Method of bonding wood or other material having a porous and/or acid surface which comprises applying to the surfaces to be bonded an adhesive composition as claimed in any one of claims 1 to 10, bringing the surfaces into contact and allowing the composition to set.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3006017A DE3006017C2 (en) | 1980-02-18 | 1980-02-18 | Cyanoacrylate adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2069512A true GB2069512A (en) | 1981-08-26 |
| GB2069512B GB2069512B (en) | 1983-11-02 |
Family
ID=6094912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8104882A Expired GB2069512B (en) | 1980-02-18 | 1981-02-17 | Cyanoacrylate adhesive compositions |
Country Status (4)
| Country | Link |
|---|---|
| DE (1) | DE3006017C2 (en) |
| FR (1) | FR2476112A1 (en) |
| GB (1) | GB2069512B (en) |
| IT (1) | IT1141975B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4695615A (en) * | 1984-11-21 | 1987-09-22 | Loctite (Ireland) Limited | Instant adhesive composition utilizing mixed functionality calixarenes as accelerators |
| US4906317A (en) * | 1983-11-10 | 1990-03-06 | Loctite Corporation | Instant adhesive composition and bonding method employing same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1467424A (en) * | 1973-06-16 | 1977-03-16 | Bostik Ltd | Adhesive compositions |
| JPS53129231A (en) * | 1977-04-19 | 1978-11-11 | Toagosei Chem Ind Co Ltd | Adhesion composition |
-
1980
- 1980-02-18 DE DE3006017A patent/DE3006017C2/en not_active Expired
-
1981
- 1981-02-13 IT IT19755/81A patent/IT1141975B/en active
- 1981-02-17 FR FR8103091A patent/FR2476112A1/en active Granted
- 1981-02-17 GB GB8104882A patent/GB2069512B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4906317A (en) * | 1983-11-10 | 1990-03-06 | Loctite Corporation | Instant adhesive composition and bonding method employing same |
| US4695615A (en) * | 1984-11-21 | 1987-09-22 | Loctite (Ireland) Limited | Instant adhesive composition utilizing mixed functionality calixarenes as accelerators |
Also Published As
| Publication number | Publication date |
|---|---|
| IT8119755A0 (en) | 1981-02-13 |
| IT1141975B (en) | 1986-10-08 |
| FR2476112A1 (en) | 1981-08-21 |
| DE3006017C2 (en) | 1982-06-03 |
| GB2069512B (en) | 1983-11-02 |
| DE3006017A1 (en) | 1981-08-20 |
| FR2476112B1 (en) | 1983-12-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940217 |