GB2200124A - Cyanoacrylate adhesive compositions - Google Patents
Cyanoacrylate adhesive compositions Download PDFInfo
- Publication number
- GB2200124A GB2200124A GB08727837A GB8727837A GB2200124A GB 2200124 A GB2200124 A GB 2200124A GB 08727837 A GB08727837 A GB 08727837A GB 8727837 A GB8727837 A GB 8727837A GB 2200124 A GB2200124 A GB 2200124A
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- GB
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- Prior art keywords
- hydrocarbyl
- acyclic
- ch2c
- aryl
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 239000004830 Super Glue Substances 0.000 title claims description 7
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 title claims description 7
- 125000002015 acyclic group Chemical group 0.000 claims abstract description 14
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 9
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical group 0.000 claims abstract description 4
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002431 hydrogen Chemical group 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical group COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 6
- 229920001651 Cyanoacrylate Polymers 0.000 description 4
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 241000533901 Narcissus papyraceus Species 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal cations Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 description 1
- 229940053009 ethyl cyanoacrylate Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000002023 wood Substances 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)
Abstract
Instant adhesive compositions, particularly alpha-cyanoacrylate compositions, contain as accelerator an acyclic phenol-formaldehyde oligomer of the formula: <IMAGE> wherein n= 0 - 10, R<1> = CH2C(O)R<2>, or H, or -CH2COOH, at least 50% of the R<1> groups being -CH2C(O)R<2>, R<2> = hydrocarbyl, aryl, hydrocarbylaryl, hydrocarbyloxy, aryloxy, hydrocarbylaryloxy and substituted derivatives thereof, R = hydrogen, halogen, hydrocarbyl, aryl, hydrocarbylaryl, and a=1, b=0; or a=b=0; or a=b=1.
Description
"INSTANT ADHESIVE COMPOSITIONS UTILIZING FUNCTIONALISED PHENOL
FORMALDEHYDE OLIGOMERS AS ACCELERATORS; AND PREPARATION OF SUCH OLIGOMERS"
This invention relates to instant adhesive compositions, particularly cyanoacrylate compositions, which contain certain functionalised acyclic pkenol-formaldehyde oligomers as accelerators. The invention also relates to the preparation of such oligomers.
US Patent 4 556 700 Harris et al describes the use in cyanoacrylate adhesive compositions of calixarene compounds represented by the formula:
where R' is alkyl, alkoxy, substituted alkyl or substituted alkoxy; R2 H or alkyl; and n = 4, 6 or 8.
Calixarenes are macrocyclic phenol-formaldehyde condensation oligomers.
The synthesis of calixarenes is described in C. Gutsche, Acc. Chem. Res., 16, 161-170 (1983). Gutsche at pages 15163, 164 and 165 reports the formation as intermediate compounds of acyclic phenol-formaldehyde oligomers which are cyclisedto produce the calixarenes
McKervey et al., Chem.Soc., Chem. Commun., 1985, 388 refer to an acyclic pentaester of the formula:
wherein R = CH2CO2Et, now believed by the present inventors to have been the hexaester:
This compound is shown to have a very low level of phase transfer affinity for alkali metal cations. in contrast to the analogous calixarene esters (see Table 1).
It has hitherto been assumed that the ion transport properties of calixarenes, and their activity as accelerators in cyanoacrylate adhesive compositions, were dependent upon their macrocyclic structure.
However we have now surprisingly found that certain functionalised acyclic phenol-formaldehyde oligomers are useful as accelerators in cyanoacrylate adhesive compositions.
The present invention therefore provides an alpha-cyanoacrylate adhesive composition containing as accelerator an acyclic phenol-formaldehyde oligomer of the formula:
wherein n = 0 - 10,
R1 = CH2C(0)R2,2or H, or -CH2COOH, at least 50 b of the R1 groups being -CH2C(O)R2, R2 = hydrocarbyl, aryl, hydrocarbylaryl, hydrocarbyloxy, aryloxy, hydrocarbylaryloxy and substituted derivatives thereof,
R = hydrogen, halogen, hydrocarbyl, aryl, hydrocarbylaryl, and a=l, b=O; or a=b=O; or a=b=l.
Preferably 100% of the R1 groups are -CH2C(O)R2.
In the above formula, hydrocarbyl is suitably alkyl or alkenyl, especially having 1-10 carbon atoms, more particularly 1-5 carbon atoms. If R2 is a substituted derivative, it may suitably be substituted with one or more halo groups or substituted or interupted by one or more oxo groups.
Halogen may suitably be chlorine, fluorine, bromine or iodine. Aryl preferably has 6-20 carbon atoms* more especially 6-10 carbon atoms.
A particularly preferred acyclic oligomer is of the formula:
The acyclic oligomers may be prepared by the routes described as preliminary steps in the synthesis of cyclic oligomers in C. Gutsche, Acc.
Chem.Res. 1983, 16, 161-170 or in B. Dhawan and C. Gutsche, J. Org. Chem.
1983, 48, 1536-1539, particularly at page 1538, followed by substitution of appropriate side chains to form partly or fully etherified oligomers. The halogenated oligomers may be prepared by the routes described in Helvetica
Chimica Acta, Vol. 64. Fasc. 2 (1981)-Nr. 59 P 599 or in Helvetica Chimica
Acta. - Vol. 65. Fasc. 4 (1982)-Nr. 113 P 1221 again followed by substitution of appropriate side chains to form partly or fully etherified ol igomers.
The present invention provides new cyanoacrylate compositions for bonding wood and other de-activating surfaces such as paper, leather, ceramic, plastics and metals with chromate treated or acidic oxideXsurfaces. The inventive compositions are standard cyanoacrylate adhesive formulations to which have been added as accelerators, acyclic phenol-formaldehyde oligomers as defined above. The acyclic oligomers are employed in amounts conventional for cyanoacrylate accelerators, preferably at levels between about 0.1% and 2% by weight of the composition.
The standard cyanoacrylate compositions are as described in US Patent 4 556 700 Harris et al at column 2 line 18 - column 3 line 32, the contents of which are incorporated herein by reference.
The invention may be further understood with reference to the following non-limiting examples:
Example 1 Preparation
Following the Cornforth Procedure* 10.09 (0.066 mole) p-t-butylphenol was mixed with 10 mls 3N aqueous NaoH and 9.7g of 37f aqueous 7 formaldehyde solution. The mixture was heated at 50-55 C for 45 hours and then at 110-1200C for 2 hr to give an off white solid.
This solid was stirred with 100 ml IN HC1 for 1 hour to neutralise the base filtered and the solid washed with water to give after drying in a 110-1200C oven for 1 hour.l0.8 g (94% yield) of off-white oligomer powder;
*reference for Cornforth Procedure: Brit J. Pharmacol 10, p73, 1955 by
J.W. Cornforth, P.D'Arcy Hart, G.A. Nicholls, R.J.W. Rees and J.A.
Stock.
Example 2.
6.5 g (0.0094 mole) tetrameric open chain oligomer prepared as in
Example 1 was mixed with 13.4 g (0.080 mole) ethyl bromoacetate, 8.3g (0.060 mole) powdered anhydrous potassium carbonate and 100 mis dry analar acetone and the whole was refluxed with stirring under nitrogen for 72 hours. After this time the reaction mixture was cooled to room temperature and solids were filtered off. The volatiles were removed from the filtrate at reduced pressure to give 7.2 g of heavy pale yellow oil which was taken up in dichloromethane which was washed twice with 10% aqueous HCl and four times with water. The dichloromethane solution was then dried over dried magnesium sulphate and the volatiles were removed to give 6.9 g pale yellow oil product which was chromatographed on a neutral alumina column using dichloromethane as eluent. Removal of volatiles gave a colourless solid product m.pt.
67-68.50C identified as the etherified product:
by infra red spectroscopy and elemental analysis i.r. spectroscopy results: 1750 (S)C=O
Elemental Analysis results : (Calc'd for C69H960l8 C:68.29, H:7.97, Found Q67.5l, H:7.93).
Example 3.
Ethyl cyanoacrylate stabilised with 10 ppm BF3 was used as a base adhesive formulation. The additive shown below was dissolved in base adhesive at the indicated level and fixture times on copy paper and white deal were determined. The result below demonstrates the good accelerative activity for the functionalised acyclic oligomer:
TABLE
Fixture Time
Additive Amount Copy Paper White Deal
None - 60 seconds 5-6 minutes
Example 2 0.5% 30-40 seconds 30-40 seconds
Product.
Claims (6)
1. A cyanoacrylate adhesive composition containing as accelerator an acyclic phenol-formaldehyde oligomer of the formula:
wherein n = 0 - 10, R1 = CH2C(O)R2, or H or - CH2COOH, at least 50% of Rl groups being -CH2C(O)R, R2 = hydrocarbyl, aryl, hydrocarbylaryl, hydrocarbyloxy, aryloxy, hydrocarbylaryloxy and substituted derivatives thereof,
R = hydrogen, halogen, hydrocarbyl, aryl, hydrocarbylaryl, and a=l, b=O; or a=b=O; or a=b=l.
2. A composition according to claim 1 wherein R1 is CH2C(O)R2.
3. A composition according to..claim 1 or 2 wherein hydrocarbyl is alkyl or alkenyl having 1-10 carbon atoms.
4. A composition according to claim 3 wherein hydrocarbyl is alkyl or alkenyl having 1-
5 carbon atoms 5. A composition according to any of the preceding claims wherein the acyclic oligomer is of the formula:
6. A composition according to any of the preceding claims wherein the acyclic oligomer is employed at levels between about O.lg and 2% by weight of the composition.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IE314686 | 1986-12-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8727837D0 GB8727837D0 (en) | 1987-12-31 |
| GB2200124A true GB2200124A (en) | 1988-07-27 |
Family
ID=11037891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08727837A Withdrawn GB2200124A (en) | 1986-12-01 | 1987-11-27 | Cyanoacrylate adhesive compositions |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2200124A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6547917B1 (en) | 1998-12-23 | 2003-04-15 | Henkel Kommanditgesellschaft Auf Aktien | Activator for cyanoacrylate adhesives |
| US8198344B2 (en) | 2008-06-20 | 2012-06-12 | Adhezion Biomedical, Llc | Method of preparing adhesive compositions for medical use: single additive as both the thickening agent and the accelerator |
| US8293838B2 (en) | 2008-06-20 | 2012-10-23 | Adhezion Biomedical, Llc | Stable and sterile tissue adhesive composition with a controlled high viscosity |
| US20130034643A1 (en) * | 2011-08-01 | 2013-02-07 | Eric Turgeman | Device and method for preparing olive paste for oil extraction |
| US8609128B2 (en) | 2008-10-31 | 2013-12-17 | Adhezion Biomedical, Llc | Cyanoacrylate-based liquid microbial sealant drape |
| US8613952B2 (en) | 2007-11-14 | 2013-12-24 | Adhezion Biomedical, Llc | Cyanoacrylate tissue adhesives |
| US8652510B2 (en) | 2008-10-31 | 2014-02-18 | Adhezion Biomedical, Llc | Sterilized liquid compositions of cyanoacrylate monomer mixtures |
| US8729121B2 (en) | 2007-06-25 | 2014-05-20 | Adhezion Biomedical, Llc | Curing accelerator and method of making |
| US9018254B2 (en) | 2007-06-25 | 2015-04-28 | Adhezion Biomedical, Llc | Cyanoacrylate tissue adhesives with desirable permeability and tensile strength |
| US9254133B2 (en) | 2008-10-31 | 2016-02-09 | Adhezion Biomedical, Llc | Sterilized liquid compositions of cyanoacrylate monomer mixtures |
| US9309019B2 (en) | 2010-05-21 | 2016-04-12 | Adhezion Biomedical, Llc | Low dose gamma sterilization of liquid adhesives |
| US9421297B2 (en) | 2014-04-02 | 2016-08-23 | Adhezion Biomedical, Llc | Sterilized compositions of cyanoacrylate monomers and naphthoquinone 2,3-oxides |
-
1987
- 1987-11-27 GB GB08727837A patent/GB2200124A/en not_active Withdrawn
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6547917B1 (en) | 1998-12-23 | 2003-04-15 | Henkel Kommanditgesellschaft Auf Aktien | Activator for cyanoacrylate adhesives |
| US9018254B2 (en) | 2007-06-25 | 2015-04-28 | Adhezion Biomedical, Llc | Cyanoacrylate tissue adhesives with desirable permeability and tensile strength |
| US8980947B2 (en) | 2007-06-25 | 2015-03-17 | Adhezion Biomedical, Llc | Curing accelerator and method of making |
| US8729121B2 (en) | 2007-06-25 | 2014-05-20 | Adhezion Biomedical, Llc | Curing accelerator and method of making |
| US8613952B2 (en) | 2007-11-14 | 2013-12-24 | Adhezion Biomedical, Llc | Cyanoacrylate tissue adhesives |
| US9878041B2 (en) | 2007-11-14 | 2018-01-30 | Adhezion Biomedical, Llc | Cyanoacrylate tissue adhesives |
| US8603451B2 (en) | 2008-06-20 | 2013-12-10 | Adhezion Biomedical, Llc | Adhesive compositions for medical use: single additive as both the thickening agent and the accelerator |
| EP2679251A1 (en) | 2008-06-20 | 2014-01-01 | Adhezion Biomedical, LLC | Adhesive compositions for medical use: single additive as both the thickening agent and the accelerator |
| US8293838B2 (en) | 2008-06-20 | 2012-10-23 | Adhezion Biomedical, Llc | Stable and sterile tissue adhesive composition with a controlled high viscosity |
| US8198344B2 (en) | 2008-06-20 | 2012-06-12 | Adhezion Biomedical, Llc | Method of preparing adhesive compositions for medical use: single additive as both the thickening agent and the accelerator |
| US8652510B2 (en) | 2008-10-31 | 2014-02-18 | Adhezion Biomedical, Llc | Sterilized liquid compositions of cyanoacrylate monomer mixtures |
| US8609128B2 (en) | 2008-10-31 | 2013-12-17 | Adhezion Biomedical, Llc | Cyanoacrylate-based liquid microbial sealant drape |
| US9254133B2 (en) | 2008-10-31 | 2016-02-09 | Adhezion Biomedical, Llc | Sterilized liquid compositions of cyanoacrylate monomer mixtures |
| US9309019B2 (en) | 2010-05-21 | 2016-04-12 | Adhezion Biomedical, Llc | Low dose gamma sterilization of liquid adhesives |
| US8677894B2 (en) * | 2011-08-01 | 2014-03-25 | Olive X-Press Ltd. | Device for preparing olive paste for oil extraction |
| US20130034643A1 (en) * | 2011-08-01 | 2013-02-07 | Eric Turgeman | Device and method for preparing olive paste for oil extraction |
| US9421297B2 (en) | 2014-04-02 | 2016-08-23 | Adhezion Biomedical, Llc | Sterilized compositions of cyanoacrylate monomers and naphthoquinone 2,3-oxides |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8727837D0 (en) | 1987-12-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |