GB2085883A - Polyether orthoformates and silicates useful as polymerization catalysts in cyanoacrylate adhesive compositions - Google Patents
Polyether orthoformates and silicates useful as polymerization catalysts in cyanoacrylate adhesive compositions Download PDFInfo
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- GB2085883A GB2085883A GB8132634A GB8132634A GB2085883A GB 2085883 A GB2085883 A GB 2085883A GB 8132634 A GB8132634 A GB 8132634A GB 8132634 A GB8132634 A GB 8132634A GB 2085883 A GB2085883 A GB 2085883A
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- United Kingdom
- Prior art keywords
- adhesive compositions
- cyanoacrylate
- group
- independently
- lower alkyl
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- 239000000203 mixture Substances 0.000 title abstract description 22
- 239000002685 polymerization catalyst Substances 0.000 title description 10
- 239000004830 Super Glue Substances 0.000 title description 8
- 229920000570 polyether Polymers 0.000 title description 3
- 239000004721 Polyphenylene oxide Substances 0.000 title description 2
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 title description 2
- 150000004760 silicates Chemical class 0.000 title 1
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052710 silicon Chemical group 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 23
- -1 isopropy] Chemical group 0.000 claims description 15
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- TUEYHEWXYWCDHA-UHFFFAOYSA-N ethyl 5-methylthiadiazole-4-carboxylate Chemical compound CCOC(=O)C=1N=NSC=1C TUEYHEWXYWCDHA-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 241001582429 Tetracis Species 0.000 claims 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 239000007983 Tris buffer Substances 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 29
- 230000001070 adhesive effect Effects 0.000 abstract description 29
- 229920001651 Cyanoacrylate Polymers 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 2
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 10
- 239000002023 wood Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Chemical group 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000002905 orthoesters Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- RXCVUXLCNLVYIA-UHFFFAOYSA-N orthocarbonic acid Chemical class OC(O)(O)O RXCVUXLCNLVYIA-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- AHJWSRRHTXRLAQ-UHFFFAOYSA-N tetramethoxymethane Chemical compound COC(OC)(OC)OC AHJWSRRHTXRLAQ-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyethers (AREA)
- Polymerization Catalysts (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Multiple arm podands of the formula <IMAGE> wherein B represents a carbon or silicon atom; R<2> each independently represents a lower alkyl group; and n, m, p and q each independently represent an integer of from about 2 to 50, or of the formula: <IMAGE> wherein B represents a silicon atom, R1 represents a hydrogen atom or a lower alkyl group, R2 each independently represents a lower alkyl group and m, n and p each independently represents an integer of from about 2 to 50 are useful as polymerisation catalysts in cyanoacrylate-based adhesive compositions.
Description
1
SPECIFICATION
Multiple arm podands useful as polymerization catalysts in cyanoacrylate adhesive compositions GB 2 085 883 A 1 The present invention relates to polymerization catalysts useful in rapid- setting a-cyanoacrylate-based 5 adhesive compositions having good storage stability and a very fast setting time on wood and other substrates with a porous/acid surface. This Application is a divisional of an Application No. 8106727 filed March 4th 1981, serial No. 2075522.
a-cyanoacrylates of general formula CN CH2 C COOR 1 .are rapid-setting adhesives which are ideally suited forthe adhesion of a large number of materials. The parts can be joined in an extremely shorttime of only a few seconds and the adhesive joints produced in this way have good mechanical strength characteristics. The adhesives are hardened by anionic polymerization initiated by even small traces of extremely weak basic-acting compounds (Lewis bases) such as, for 20 example, water or methanol.
When using such a-cyanocrylate adhesives on wood, leather and other porous/acid surfaces, there is the problem that the anionic polymerization of the a-cyanoacrylate is inhibited in spite of the high moisture content which should in fact aid the polymerization. As a result, the adhesive setting time is too long for practical use. In addition, such adhesives tend to penetrate the pores of the surfaces to be adhered to one another, so that in the case of porous material, the strength of the adhesive joint is impaired due to the protracted setting time.
However, because the distinct advantage of a-cyanoacrylate based adhesives is their short setting time, numerous measures have been attempted to reduce the setting times on wood and similar materials. One of these measures involves treating one of the wood surfaces to be joined with a primer and the other with an 30 a-cyanoacrylate adhesive composition. Polymerization occurs on contacting the treated surfaces together.
The required added operation of applying a primer is a serious disadvantage to such process. Another measure involves reducing the quantity of acid stabilizers present for satisfactory storage stability of the a-cyanoacrylate adhesive compositions. However, although this reduces the setting time, such adhesive compositions have an increased tendency to prematurely harden during storage.
Therefore, polymerization catalysts have been proposed which are suitable for use in sing le-component systems and which reduce the setting times of such (x-cyanoacrylate adhesives without excessively impairing their storage stability. According to DE-OS 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 compound from the group of macrocyclic polyethers and their analogs. The most serious disadvantage of 40 such accelerators relates to their synthesis which, even when the dilution principle is used, only supplies the desired product in low yields, because the tendency to produce intermolecular linkage which form chains is greater than that for intramolecular linkages which form macrocycles. Further, U.S. Patent 4,170,585 suggests the addition of approximately 0.0001 to 20% by weight of a polyethylene glycol with a degree of polymerization of at least 3 or a non-ionic surfactant with a polyethyleneoxy content (degree of polymerization also at least 3) or mixtures thereof to a-cyanoacrylate- based adhesive compositions. These compounds, however, have the disadvantage in that they have a great tendency to contain water and low molecular weight polyethylene glycol ether which are difficult to remove and spontaneously initiate -polymerization when the compounds are added to a-cyanoacrylates.
The two specifications discussed above also describe in detail the disadvantages commonly associated 50 with a-cyanoacrylate adhesives when used on wood, leather and other porous/acid surfaces as mentioned above.
It has now been surprisingly found thatthe above difficulties and disadvantages of the prior art polymerization catalysts can be obviated bythe use of certain compounds described in our aforesaid Application No. 8106727 as polymerization catalysts contained in a- cyanoacrylate-based adhesive composi- 55 tions. These compounds can be easily prepared in high yield and purity, are free from polymerization initiating substances, require only limited concentrations in the resulting adhesive compositions based on a-cyanoacrylate and lead to greatly reduced setting times on wood and other porous/acid surfaces. It has also been found that the susceptibility to water can be still further reduced by the addition of suitable compounds described in our aforesaid Application No. 8106727 which result in improved storage stability of 60 such adhesive compositions.
In our aforesaid Application No. 8106727 we have described and claimed adhesive compositions based on a-cyanoacrylate and containing a polymerisation catalyst.
The generally known ot-cyanoacrylates which serve as a basis for the adhesive composition are of general formula:
T GB 2085883 A 2 ".,' CN CH2 C '11 1 COOR 5 wherein R is straight or branched-chain aikyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyi, and the like as well as a halogen atom or alkoxy group substituted alkyl such as 2-chlorethyl, 3-chloropropyl, 2-chlorobuty], trifluoroethy], 2- methoxyethyl, 3-methoxybutyl, 2-ethoxyethyl group and the like; a straight or branched-chain alkenyl group such as allyl, methally], crotyl and the like; a straight or branched-chain alkynyl gorup, such as propargyl and the like; cycloalkyl group such as cyclohexyl, and the like; an aryl group, such as benzy], phenyl and the like; or an aralkyl group, such as cresyl and the like. Further, German published application DE-OS 2,816,836 refers to a large number of suitable a-cyanoacrylates which are incorporated herein by reference. The adhesive compositions, in addition, contain conventional additives such as polymerisation inhibitors, thickeners, plasticizers, perfumes, dyes, 15 pigments, etc. These additives are conventionally known, form part of the prior art and examples of them are described in the herein-above mentioned references.
The compounds found useful as polymerization catalysts in the adhesive compositions described in our aforesaid Application No. 8106727 are open-chain, podands having multiple arms each containing donor atoms. The podands are compounds selected from the group of compounds of general formula:
X 4_\ A-\ 1- 0 1 n Y - R - A 25- -,-,X //- A \ 1 25 0 'm - R X 0 Y - R 2 30 R B // --X 0 Y - R 2 11 X 0 2 oo"ooooo,0,0jp Y - R 35 X +\ /In--\y IZ2 0 Y - R2 40 2 B-. - X - Y - R iii /jqY R 2 In the compounds 1, A represents a central chemical moiety capable of forming a one or two atom bridge between X units; and when A is the central chemical moiety, X represents oxygen, sulphur or N-CH3, preferably oxygen; Y represents oxygen, sulphur, N-CH3, or -N-, preferably oxygen; and R represents a short 56 chain hydrocarbon terminal group.
The present invention is however concerned with compounds 11 and III which are new compounds.
In compounds 11 and 111, B represents a central chemical moiety which is a carbon atom or a silicon atom, R' represents a hydrogen atom or a lower alkyl group; R 2 are each independently selected from a lower alkyl group. Generally, when R' and/or R 2 are an alkyl group it is preferred that each group contain no more than 4 56 carbon atoms such that, for example, each can independently be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and the like. Further, it is preferred that when B is carbon RI is hydrogen or alkyl as defined above and that when B is silicon R' is alkyl as defined above. In the compounds of the present inventon, each X and Y of such podands represents oxygen. The preferred orthoester podands 11 and III are, therefore, orthoformic, orthoacetic, orthocarbonic, orthomethylsiliconic and orthosilicic acid esters, as well as mixtures thereof.
The podand compounds 11 and III can have arms which are formed from polyalkylene groups, such as ethylene which have oxygen associated therewith, and are, preferably polyethylene glycol chains. The chain length of each of the chains can vary widely. The setting time of the adhesive compositions is influenced by the podand chain length with the setting time being reduced with increased number of units, such as ethylene oxide units, in the podand chain as defined by n, m, p and q. However, if the number of donor 65 j t 3 GB 2 085 883 A 3 atoms exceeds approximately 50 on each chain, there is no further significant acceleration of adhesion of the (x-cyanoacrylate to wood or other porous/acid substances.
The symbols n, m, p and q used herein-above to define the podands 1, 11 and III are each independently whole numbers between 2 and 50 and preferably between 3 and 20.
It has been unexpectedly found that the use of the adhesive compositions containing the polymerization catalyst according to the present invention cancels out the inhibition of polymerization of ot-cyanoacrylates when used on wood and other substrates with porous/acid surfaces which otherwise occurs. Due to the advantageous action of the polymerization catalysts presently described, it is only necessary to add small quantities of 0.01 to 10% by weight and preferably 0.01 to 5% by weight (based on the total weight of the adhesive compositions) to the a-cycloanoacrylate adhesives to obtain, for example, bonded wood joints 10 with excellent mechanical strength. In the case of all the adhesive joints made and stored at room temperature for 24 hours, the break in the sample material took place in the wood during the tensile shear strength test.
In addition, it has been unexpectedly found that the storage stability of a-cyanoacrylate adhesive compositions is enhanced when they contain the polymerization catalysts according to the present invention. It is well known that a-cyanoacrylate based adhesives tend to undergo premature polymerization and/or agglomeration to a greater or lesser extent. This behavior is particularly apparent when the adhesive is subjected to standardized accelerated aging tests at 700 C. However, it has been found that a-cyanoacrylate based adhesives which contain the subject poclands could undergo the standard accelerated ageing test (5 days at 70'C.) without forming agglomerates or modifying viscosity or adhesive characteristics.
A further unexpected and highly desired advantage of the orthoester podands according to the present invention is that they can be easily synthesized. This takes place in a high yield from inexpensive, low molecular weight starting substances and is particularly economical due to the easy elimination of undesired by-products.
Synthesis of the new compounds of the present invention can be performed using known process steps. 25 Synthesis of the orthocarbonic acid esters can be carried out by acid catalyzed reaction of lower alkyl esters (methyl, ethyl esters and the like) of the relevant ortho acids, accompanied by azeotropic distillation of the lower alcohols formed by means of a suitable carrier (e.g. benzene, toluene). The corresponding chlorosilanes can be reacted with a polyalkylene glycol, such as polyethylene glycol monoethers to prepare the alkylsiliconic acid esters and orthosilicic acid esters.
The following examples are given for illustrative purposes only and are not meant to be a limitation on the subject invention except as defined by the claims appended hereto. All parts and percentages are by weight unless otherwise indicated.
EXAMPLE 1
Podandll 15.9g of trimethyl orthoformate, 1 00g of anhydrous tetraethylene glycol monomethyl ether, 0.1 g of 4-methyl benzene sulphonic acid and 300 m] of anhydrous toluene were refluxed with the aid of a packed column with the top fitted. The azeotropic mixture comprising methanol and toluene boiling at 64'C. was distilled until there was no further drop in the boiling point of toluene (11 O'C) on switching over to total reflux. At the end of the reaction, the reaction mixture was cooled, the toluene solution obtained was extracted by shaking with aqeuous NaHCO3 solution, dried with Na2S04 and the solvent was distilled off in vacuo. 99.3g (97.6% of theory) of crude tris-(tetraethylene glycol monomethyl ether)-orthoformate (colourless liquid) were obtained.
The crude productwas distilled in high vacuum to remove unreacted tetraethylene glycol monomethyl ether. At a pressure of 8 x 10 mbar and an evaporator temperature of 1300C, firstly 11.8 g of the colourless liquid were distilled off. The residue was again distilled off at 5 X 10- 5 mbar/s50-260'C. and 84.99 (89.3%) of pure tris-(tetraethylene glycol monomethyl ethed-orthoformate were obtained.
This compound may be used in the manner described in our aforesaid Application No. 8106727.
EXAMPLE 2
PodandIll 37.3g of anhydrous polyethylene glycol-350-monomethylether, 2.9g of tetramethyl orthocarbonate, 150ml of anhydrous toluene and 50mg of 4-methyl benzene sulphonic acid were refluxed with the aid of a packed column with fitted top. The distillation of the reaction mixture was performed as in Example 1 above. 34.2g 55 (89.2%) of crude tetracis-(polyethylene g lyco 1-350-m ono m ethyl ether)- orthocarbonate were obtained.
By high vacuum distillation at a pressure of 2 x 10-5 mbar and an evaporator temperature of 140'C., 9.0 g of a distillate were obtained (which essentially comprised polyethylene glycol-350-monomethyl ether). The distillation residue consisted of 24.1g of pure tetracis-(polyethylene glycol-350-monomethyl ether)- orthocarbonate.
This compound may be used in the manner described in our aforesaid Application No. 8106727.
4 GB 2 085 883 A 4 EXAMPLE3
Podandffl 28g of anhydrous polyethylene glycol-350-monomethyl ether were placed in a vessel and accompanied by stirring. 3.4g of freshly distilled tetra-chlorosilane were added dropwise at 50C within 5 minutes. The reaction mixture was stirred for an additional 10 minutes at 5'C, then stirred for 3 hours at ambient temperature, and finally heated at800C. for an additional 4 hours. The crude product obtained (28.6g, 100%) was freed from lower boiling fractions in high vacuum.
At a pressure of 2 x 10-5 mbar and an evaporator temperature of 170'C., 3. 2g of a colourless liquid were distilled off. The residue consisted of 24. 1 g (84.6%) of tetracis-(polyethylene glycol-350-monomethyl 10 ethedorthosilicate.
This compound may be used as described in our aforesaid Application No. 8106727.
While the invention has been described in connection with certain preferred embodiments, it is not intended to limit the invention to the particular form set forth, but, on the contrary, it is intended to cover such alternatives, modifications and equivalents as defined by the appended claims.
Claims (6)
1. A compound having the general formula:
0z 2 20 0 0 R R2 25 2 0 0 R c R2 q 0 q 0 wherein B represents a carbon or silicon atom; R 2 each independently represents a lower alkyl group; and n, m, p and q each independently represent an integer of from about 2 to 50, or of the formula:
-_01 n-----"O-R 2 35 RI- -1 -- -f-041 0 --R 2 \.I- - - --'.O ---R 2 p 40 wherein B represents a silicon atom, R' represents a hydrogen atom or a lower alkyl group, R 2 each independently represents a lower alkyi group and m, n and p each independently represents an integer of from about 2 to 50.
2. A compound according to claim 1, wherein each R' and R' group is independently selected from 45 methyl, ethyl, n-propyl, isopropy], n-butyl, isobutyl and t-butyl.
3. A compound according to claim 1 or2wherein n, m, p and q are each from 3to 20.
4. Tris(tetraethyleneglycol monomethyl ether)-orthoformate.
5. Tetracis(polyethylene glycol-350-mono-methyl ether)orthocarbonate.
6. Tetracis(polyethyleneglycol-350-mono-methyI ether)orthosilicate.
Printed for Her Majesty's Stationery Office, by Croydon Printing Company Limited, Croydon, Surrey, 1982.
Published by The Patent Office, 25 Southampton Buildings, London. WC2A lAY, from which copies may be obtained.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0132080A AT365623B (en) | 1980-03-10 | 1980-03-10 | CYANOACRYLATE ADHESIVE COMPOSITION |
| DE19803025127 DE3025127C2 (en) | 1980-07-03 | 1980-07-03 | Cyanoacrylate adhesive composition. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2085883A true GB2085883A (en) | 1982-05-06 |
| GB2085883B GB2085883B (en) | 1984-06-13 |
Family
ID=25595523
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8132634A Expired GB2085883B (en) | 1980-03-10 | 1981-03-04 | Polyether orthoformates and silicates useful as polymerization catalysts in cyanoacrylate adhesive compositions |
| GB8106727A Expired GB2075522B (en) | 1980-03-10 | 1981-03-04 | Cyanoacrylate adhesive composition |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8106727A Expired GB2075522B (en) | 1980-03-10 | 1981-03-04 | Cyanoacrylate adhesive composition |
Country Status (8)
| Country | Link |
|---|---|
| JP (2) | JPH02167245A (en) |
| AU (2) | AU546896B2 (en) |
| BR (1) | BR8101401A (en) |
| ES (1) | ES8302064A1 (en) |
| FR (1) | FR2477566A1 (en) |
| GB (2) | GB2085883B (en) |
| IT (1) | IT1211003B (en) |
| NL (1) | NL186644C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6945691B1 (en) * | 2020-06-29 | 2021-10-06 | 日本航空株式会社 | Manual display device and manual display method |
-
1981
- 1981-03-04 GB GB8132634A patent/GB2085883B/en not_active Expired
- 1981-03-04 GB GB8106727A patent/GB2075522B/en not_active Expired
- 1981-03-05 AU AU68101/81A patent/AU546896B2/en not_active Ceased
- 1981-03-09 IT IT8120210A patent/IT1211003B/en active
- 1981-03-09 NL NLAANVRAGE8101115,A patent/NL186644C/en not_active IP Right Cessation
- 1981-03-09 FR FR8104629A patent/FR2477566A1/en active Granted
- 1981-03-10 BR BR8101401A patent/BR8101401A/en not_active IP Right Cessation
- 1981-03-10 ES ES500239A patent/ES8302064A1/en not_active Expired
-
1985
- 1985-07-17 AU AU45115/85A patent/AU576605B2/en not_active Ceased
-
1989
- 1989-08-21 JP JP1213117A patent/JPH02167245A/en active Granted
-
1990
- 1990-12-29 JP JP2417016A patent/JPH04208291A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| NL186644B (en) | 1990-08-16 |
| ES500239A0 (en) | 1983-01-01 |
| AU576605B2 (en) | 1988-09-01 |
| NL186644C (en) | 1991-01-16 |
| JPH04208291A (en) | 1992-07-29 |
| JPH0364490B2 (en) | 1991-10-07 |
| AU546896B2 (en) | 1985-09-26 |
| FR2477566A1 (en) | 1981-09-11 |
| JPH02167245A (en) | 1990-06-27 |
| BR8101401A (en) | 1981-09-15 |
| AU4511585A (en) | 1985-12-05 |
| NL8101115A (en) | 1981-10-01 |
| AU6810181A (en) | 1981-09-17 |
| GB2075522B (en) | 1984-02-01 |
| IT1211003B (en) | 1989-09-29 |
| GB2085883B (en) | 1984-06-13 |
| IT8120210A0 (en) | 1981-03-09 |
| ES8302064A1 (en) | 1983-01-01 |
| FR2477566B1 (en) | 1985-02-22 |
| GB2075522A (en) | 1981-11-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19960304 |