WO1982002048A1 - Addition polymerizable isocyanate-polyahl anaerobic adhesives - Google Patents

Addition polymerizable isocyanate-polyahl anaerobic adhesives Download PDF

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Publication number
WO1982002048A1
WO1982002048A1 PCT/US1981/001634 US8101634W WO8202048A1 WO 1982002048 A1 WO1982002048 A1 WO 1982002048A1 US 8101634 W US8101634 W US 8101634W WO 8202048 A1 WO8202048 A1 WO 8202048A1
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Prior art keywords
adhesive
addition polymerizable
polyahl
isocyanate
substrates
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PCT/US1981/001634
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English (en)
French (fr)
Inventor
Chemical Co Dow
Dwight K Hoffman
Kurt C Frisch
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Chemical Co Dow
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Filing date
Publication date
Priority claimed from US06/215,996 external-priority patent/US4320221A/en
Application filed by Chemical Co Dow filed Critical Chemical Co Dow
Publication of WO1982002048A1 publication Critical patent/WO1982002048A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
    • 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

Definitions

  • the instant invention relates to formulations useful as anaerobic adhesives.
  • Anaerobic adhesives are well known and have been in commercial use for several years. Most anaerobic adhesives are compositions containing a monomer, or combination of monomers, which will polymerize under certain conditions but not under other conditions. Those conditions generally favoring polymerization include the absence of oxygen and, if a redox initiator is used, the presence of metal ions. Oxygen acts as a polymerization inhibitor, and metal ions act as polymerization promoters.
  • isocyanate compounds are used in excess to reduce the amount of volatile and toxic monofunctional alkyl or aryl acrylate esters. Because of the tendency for polyisocyanates and polyahls to form network polymers (gel), the stoichiometry of the preceding reactions is limited.
  • the present invention is an anaerobic adhesive comprising an addition polymerizable polyethylenically unsaturatad compound, a curing amount of a polymerization initiator and a stabilizing amount of a polymerization inhibitor characterized in that the addition polymerizable polyethylenically unsaturated compound is the reaction product of an addition polymerizable ethylenically unsaturated isocyanate and a polyahl.
  • the relative proportions of the ingredients are such that the adhesive is stable to addition polymerization until the inhibitor is consumed at which time the adhesive polymerizes to form a solid material capable of bonding two substrates.
  • the present invention is a method of bonding two substrates at a bond site comprising (1) depositing an anaerobic adhesive comprising (A) an addition polymerizable polyethylenically unsaturated compound, (B) a curing amount of a polymerization initiator, and (C) a stabilizing amount of a polymerization inhibitor, at the bond site such that the adhesive contacts both substrates and (2) consuming the polymerization inhibitor, thereby polymerizing the adhesive to form a solid material that bonds the two substrates, characterized in that the addition polymerizable polyethylenically unsaturated compound is the reaction product of an addition polymerizable ethylenically unsaturated isocyanate and a polyahl.
  • the adhesive of the present invention does not have the stoichiometric problems inherent in the polyurethane adhesives of the prior art.
  • the polyahl and the monoisocyanate can be employed in any and all proportions without significant increases in viscosity.
  • An additional advantage of these adhesives is that the process is simple and the product will consistently have the same viscosity, within a narrow specification range, time after time.
  • This formulation flexibility will also allow higher levels of active hydrogen compound to be formulated into the system while maintaining a high efficiency of coupling. That is, at the same mole percent unsaturation, more molecules will contain both the moieties of the active hydrogen containing compound and the vinyl unsaturation of the isocyanate. Thus, the probability of phase separation is reduced.
  • the ability to formulate over a wider range also means that products can be modified as required so that they are useful for bonding a greater variety of substrates.
  • the addition of addition polymerizable monoisocyanates to polyactive hydrogen compounds can be accomplished quite easily.
  • the adducts are low viscosity liquids which do not require reactive diluents such as isobutylmethacrylate (typical in U.S. Patent No. 3,425,988) to reduce the resin to application viscosity.
  • Excellent adhesive strengths have been obtained with simple formulations, as shown in the examples.
  • the adhesive of this invention requires the reaction product of an ethylenically unsaturated monoisocyanata and a polyahl. This reaction product is then blended with other suitable components, including, but not limited to, an initiator and inhibitor ⁇
  • Suitable isocyanates include any addition polymerizable ethylenically unsaturated monoisocyanates. Examples include vinyl isocyanate and vinylbenzyl isocyanate. More desirable monomers include isocyanatoalkyl esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids. Preferred are isocyanato acrylates of the formula:
  • R 1 is a hydrogen or a carbon chain of from 1 to 5 carbon atoms and R 2 is a carbon chain of from 1 to 7 carbon atoms. More preferred is 2-isocyanatoethyl acrylate. Most preferred is 2-isocyanatoethyl methacrylate ( IEM).
  • polyahl generally includes any polyfunctional compounds having an average greater than 1 active hydrogen moiety which displays significant activity according to the Zerewitnoff test described by Woller in the Journal of American Chemical Society, Vol. 49, page 3181 (1927).
  • polyols polyamines, polyamides, polymercaptans and polyacids.
  • suitable compounds may be those with active hydrogens supplied from more than one type of active hydrogen moiety. Examples of these compounds include amino alcohols and mercapto alcohols.
  • suitable polyahls also specifically include those compounds having 3 or more active hydrogen moieties per molecule.
  • polyols examples include the polyol polyethers, the polyol polyesters, hydroxy functional acrylic polymers, hydroxyl-containing epoxy resins, polyhydroxy terminated polyurethane polymers, polyhydroxyl-containing phosphorus compounds and alkylene oxide adducts of polyhydric thioethers including polythioethers, acetals including polyacetals, aliphatic and aromatic polyols and thiols including polythiols, ammonia and amines . including aromatic, aliphatic and heterocyclic amines including polyamines as well as mixtures thereof.
  • Alkylene oxide adducts of compounds which contain two or more different groups within the above-defined classes may also be used such as amino alcohols which contain an amino group and a hydroxyl group. Also alkylene adducts of compounds which contain one -SH group and one -OH group as well as those which contain an amino group and a -SH group may be used.
  • Polyether polyols which are most advantageously employed as the polyahl in the practice of this invention are the polyalkylene polyether polycls including the polymerization products of alkylene oxides and other oxiranes with water or polyhydric alcohols having from two to eight hydroxyl groups.
  • Exemplary alcohols that are advantageously employed in making the polyether polyol include ethylene glycol, 1,3-propylene glycol,
  • polyhydric alcohol sugars such as glucose, sucrose, fructose and maltose as well as compounds derived from phenols such as 2,2-(4,4'-hydroxylphenyl)-propane, commonly known as bisphenol A, and bisphenol F. Also included are alkylene oxide derivatives of bisphenol A, bisphenol F, etc., and hydrolyzed derivatives of epoxy resins such as hydrolyzed D.E.R. ® 331 (available from The Dow Chemical Company).
  • Illustrative oxiranes that are advantageously employed in the preparation of the polyether polyol include simple alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and amylene oxide; glycidyl ethers such as t-butyl glycidyl ether and phenyl glycidyl ether and random or block copolymers of two or more of these oxiranes.
  • the polyalkylene polyether polyols may be prepared from other starting materials such as tetrahydrofuran and alkylene oxidetetrahydrofuran copolymers; epihalohydrins such as epichlorohydrin; as well as aralkylene oxides such as styrene oxide.
  • the polyalkylene polyether polyols may have primary, secondary or tertiary hydroxyl groups and, preferably, are polyethers prepared from alkylene oxides having from, two to six carbon atoms such as ethylene oxide, propylene oxide and butylene oxide.
  • the polyalkylene polyether polyols may be prepared by any known process such as, for example, the process disclosed by Wirtz in 1859 and Encyclopedia of Chemical Technology, Vol. 7, pp. 257-262, published by Interscience Publishers, Inc. (1951) or in U.S. Patent No. 1,922,459. Also suitable are polyether polyols and processes for preparing them that are described in Schick, M.
  • Polyether polyols which are most preferred include the alkylene oxide addition products of water, trimethylolpropane, glycerine, pentaerythritol, sucrose, sorbitol, propylene glycol and blends thereof having hydroxyl equivalent weights up to about 5,000.
  • Polyhydric thioethers which are sometimes advantageously condensed with alkylene oxides include the reaction product of thiodiglycol with alkylene oxides or dihydric alcohol such as disclosed above for the preparation of the hydroxyl-containing polyethers with any other suitable thioether glycol.
  • Polyhydroxyl-containing phosphorus compounds which are optionally used include those compounds disclosed in U.S. Patent No. 3,639,542.
  • Preferred polyhydroxyl-containing phosphorus compounds are prepared from alkylene oxides and acids of phosphorus having a P 2 O 5 equivalency of from 72 percent to 95 percent.
  • Polyacetals which are optionally reacted with alkylene oxides or other oxiranes include the reaction product of formaldehyde or other suitable aldehyde with a polyhydric alcohol or an oxirane such as those disclosed above. Polyacetals derived from acetone or from cyclic acetals are also suitably employed.
  • Aliphatic and aromatic thiols which are optionally reacted with alkylene oxides and other oxiranes include alkane thiols such as 1,2-ethane dithiol, 1,2-propane dithiol and 1,6-hexane dithiol; alkene thiols such as 2-butene-1,4-dithiol and alkyne thiols such as 3-hexyne-1,6-dithiol and arene thiols such as 1,4-benzene dithiol.
  • alkane thiols such as 1,2-ethane dithiol, 1,2-propane dithiol and 1,6-hexane dithiol
  • alkene thiols such as 2-butene-1,4-dithiol and alkyne thiols such as 3-hexyne-1,6-dithiol and arene thiols such as 1,4-
  • Acids and amides which are optionally reacted with alkylene oxides and other oxiranes include difunctional fatty acids such as hydroxystearic and d-hydroxystearic acid as well as amides such as fatty acid alkanol amides, e.g., lauroyl monoethanolamide; diacids such as adipic and terephthalic acid; sulfonamides and other acids and amides set forth in Schick, supra.
  • Amines which are optionally reacted with alkylene oxides and other oxiranes include aromatic amines such as aniline, o-chloroaniline, p-amino aniline, 1,5-diamino naphthalene, methylene dianiline, the condensation products of aniline and formaldehyde and 2, 4-diaminotoluene; aliphatic amines such as methylamine, triisopropanolamine, isopropanolamine, diisopropanolamine, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and 1,3-butylenediamine, and mixtures thereof.
  • aromatic amines such as aniline, o-chloroaniline, p-amino aniline, 1,5-diamino naphthalene, methylene dianiline, the condensation products of aniline and formaldehyde and 2, 4-diaminotoluene
  • suitable hydroxy-containing polyesters include those obtained from polycarboxylic acids and polyhydric alcohols.
  • suitable polycarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, thapsic acid, maleic acid, fumaric acid, glutaconic acid, alpha-hydromuconic acid, beta-hydromuconic acid, alpha-butyl-alpha-ethyl-glutaric acid, alpha,- beta-diethylsuccinic acid, isophthalic acid, terephthalic acid, hemimellitic acid and 1,4-cyclohexane-dicarboxylic acid.
  • polyhydric alcohol including both aliphatic and aromatic
  • Any suitable polyhydric alcohol including both aliphatic and aromatic may be used such as ethylene glycol, 1,3-propylene glycol, 1, 2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentane diol, 1,4-pentane diol, 1,3-pentane diol, 1,6-hexane diol, 1,7-heptane diol, glycerol, 1,1, 1-trimethylolpropane, 1,1,1-trimethylolethane, hexane-1, 2, 6-triol, alpha-methyl glycoside, pentaerythritol and sorbitol.
  • polyhydric alcohol compounds derived from phenols such as 2,2(4,4'-hydroxyphenyl)propane, commonly known as bisphenol A.
  • polyahls suitably employed include polylactones, hydroxy functional acrylic polymers such as polymers of hydroxyethyl acrylate and hydroxypropyl acrylate, polyvinyl acetate and other polymers of vinyl acetate and other ethylenically unsaturated carboxylic acids, hydroxyl-containing epoxy resins, urea-formaldehyde and melamine-formaldehyde resins, hydroxyl ⁇ -containing polycarbonates and polyurethanes, methylol resins, starches and other cellulosic polymers, esters of phosphoric, sulfonic, sulfuric and boric acid and polypeptides.
  • hydroxy functional acrylic polymers such as polymers of hydroxyethyl acrylate and hydroxypropyl acrylate
  • polyvinyl acetate and other polymers of vinyl acetate and other ethylenically unsaturated carboxylic acids hydroxyl-containing epoxy resins, urea-formaldehyde
  • Additional polyols include glycols such as, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, glycerine, 1,1,1-trimethylolpropane and pentaerythritol.
  • Polymercaptans include, for example, hydrogen sulfide, 1, 2-dimercaptoethane, 1, 3-dimercaptopropane and low molecular weight Thiokol polysulfide elastomers
  • Polyphenols include, for example, bisphenol A and bisphenol F.
  • Polyacids include, for example, adipic acid, sebaccic acid and terephthalic acid.
  • polyahls include, for example, compounds having mixed functionalities such as 2-mercaptoethanol, 2-aminoethanol and mercaptophenol.
  • polyols Of the above classes of polyahls; polyols, polymercaptans and polyamines are preferred. Polyols are particularly available and safe to handle, as well as easy to use. Glycols and glycol ethers are readily used in the invention.
  • Polyamines are particularly interesting because their products have an unusually long shelf life. Unlike other polyahls, polyamines react readily with isocyanate moieties, without the need for added catalyst. It is believed that this lack of catalyst in the amine/isocyanate reaction contributes to the long shelf life of these adhesives.
  • polyamine is intended to mean any polyahl wherein an average greater than one of the active hydrogen moieties is provided by amine ® Trademark groups.
  • a polyamine may generally be illustrated by the formula:
  • R 3 and R 4 are each a hydrogen or an organic group and R 5 is an organic group.
  • Aminatad polyglycols are examples of suitable polyamines. Other examples include, for example, ethylenediamine and 1,4-butylenediamine.
  • the isocyanate and polyahl should be reacted in a ratio such that the reactant is capable of being addition polymerized to a substantially solid material.
  • suitable polyahls specifically include those compounds having 3 or more active hydrogen moieties per molecule, in defining reaction ratios it is important to specify whether equivalent ratios or molecular ratios are being used. It is generally desirable, from a toxicological standpoint, to have a slight excess of active hydrogen moiety. From an adhesive standpoint, it is desirable to have at least 1 molecule of isocyanate for each molecule of polyahl. An excess of isocyanate is not unduly harmful to the adhesive properties. Preferably, there should be about one equivalent of isocyanare for each equivalent of polyahl.
  • ethylenically unsaturated isocyanates can be obtained by reacting the above-described ethylenically unsaturated isocyanates with monofunctional active hydrogen compounds having addition polymerizable ethylenic unsaturation.
  • exemplary examples include monohydroxy acrylic monomers such as 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate and the like. These reaction products may be used by themselves as anaerobic adhesives, but preferably are added to the reaction product of a vinyl isocyanate and polyahl. In one aspect, the reaction products of the monohydroxy acrylic monomers may be used as a diluent, decreasing the viscosity of the final product.
  • a catalyst will be needed to react the active hydrogen moiety and the isocyanate.
  • Suitable catalysts include those catalysts commonly used in the manufacture of urethane foams. These and other catalysts, and their use are well known to those skilled in the polyurethane art. Further information may be obtained, for example, in U.S. Patent No. 4,233,425.
  • the isocyanate-polyahl reaction product requires a free radical generating means capable of initiating addition polymerization of the reaction product.
  • Any free radical generating means such as a peroxygen compound, an azo compound, a UV source and/or a heat source which is suitably employed in the addition polymerization of ethylenically unsaturated monomers is suitably employed in the practice of this invention. Examples of such free radical generating means and conditions of use are set forth in U.S. Patent No. 3,043,820.
  • Preferred free radical generating means are chemical initiators, especially the peroxygen compounds such as hydrogen peroxide and the entire class of organic peroxides and hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide.
  • Such initiators or other free radical generating means are employed in a curing amount, that is, an amount sufficient to cause the desired polymerization of the reaction product.
  • the hydroperoxides such are preferably employed in amounts as low as 0.01 weight percent based on the weight of the reaction product, more preferably from 1 to 10 weight percent.
  • Accelerators are compounds which are believed to assist in the breakdown of the initiator and increase the rate of initiator breakdown.
  • Typical accelerators include tertiary amines such as N,N'-dimethylaniline; N,N' -dimethyl-p-toluidene; triethylamine; and imides such as benzoic sulfimide.
  • Such accelerators may be used in quantities of 0.01 to 15 percent by weight based on the weight of initiator, with 0.1 to 7 percent being preferred.
  • Metal ions are particularly effective and useful accelerators. While metal ions may be specifically added to the composition, a trace amount will possibly be present as an impurity. In any event, if the adhesive is applied to a metal substrate, the substrate will provide the metal ion source. The application of the adhesive to a metal is particularly advantageous in that it delays the breakdown of the initiator until the adhesive is actually being used. Examples of effective metal ions include, for example, Cu + , Fe ++ , Cr ++ and v ++ . The metal ions need be present only in catalytic (trace) amounts. Because the aforementioned initiators or combination of initiator and accelerators promote polymerization quite well, it is generally required to employ an inhibitor to prevent premature polymerization.
  • inhibitors examples include antioxidants including phenols such as 2 , 5-di-tert-butyl-4-methylphenol (lonol ® ), quinones such as benzoquinone, hydroquinones and other compounds that are known to inhibit addition polymerisation of ethylenically unsaturated monomers.
  • An effective amount of an inhibitor must be added to a useful adhesive formulation.
  • An "effective amount" of an inhibitor is an amount which will prevent premature polymerization of the formulation. Excess inhibitor will cause long cure times.
  • the inhibitor is a quinone or a hydroquinone which is preferably employed in an amount in the range from 5 to 10,000 ppm based on the formulation weight, more preferably from 50 to 1,000 ppm.
  • the adhesive of the instant invention is utilizable in a number of applications. Uses include adhesives and metal impregnation. Specific applications include locking threaded assemblies, sealing threaded, porous and flanged assemblies, strengthening ® Trademark cylindrical assemblies and structural bonding. Substrates to be bonded include metals, plastics, ceramics and glass. Potential medical applications include tooth and bone cementing sealants.
  • the oxygen which is present in the adhesive is quickly consumed by the initiator and the physical barrier of the threads prevents the infusion of new oxygen.
  • Adduct 2 lEM-Diethylene Glycol Adduct Using Dibutyltin Dilaurate
  • Diethylene glycol (106 g, 1 mole), lonol antioxidant (0.2 g) and dibutyltin dilaurate (0.2 g) were combined in the apparatus as described for Adduct 1
  • the mixture was heated to 70oC and IEM (295 g, 1.9 mole) was added over a 45-minute period. Additional dibutyltin dilaurate (0.1 g) was added after 6 hours. After 6-1/2 hours, more lonol antioxidant (0.2 g) was added and the product cooled. The 'final product was a clear viscous liquid.
  • Triethylene glycol 150 g, 1 mole
  • lonol antioxidant 0.2 g
  • dibutyltin dilaurate 0 .2 g
  • the mixture was heated to 70°C and IEM (295 g, 1.9 mole) was added over a 1-1/4-hour period. Additional dibutyltin dilaurate ( 0.1 g) was added after 7 hours .
  • Ethylenediamine (60.0 g, 2 equivalents active hydrogen) and lono l® antioxidant (0.15 g) were combined in the apparatus as described for Adduct 1.
  • the mixture was at room temperature and IEM (194 g, 1-9 moles) was added over a 1-hour period. The temperature rose to 125oC.
  • the final product was a solid which did not melt at 125°C.
  • Adduct 1 as an Adhesive
  • N,N' -dimethylaniline (0.05 g). This mixture was applied onto the uncleaned threads of 3/8 inch (9.5 mm) stainless steel cap screws and nuts. After 5 minutes, the torque needed to move the nuts was significantly increased, and after 15 minutes the nuts were unable to be moved by hand. After full cure, a prevailing torque of 3.5 pound-force-feet (4.7 N ⁇ m) (0.484 Kg-meters) was needed to remove the nut.
  • the IEM-tetraethylene glycol Adduct 1 was formulated according to Table I. In Table I , all parts are by weight. The formulated adhesives were then applied to cap screws as described in Example 1. Results were obtained as shown in Table II. ® Trademark TABLE I
  • Adduct 1 10.0 10.0 10.0 10.0 10.0
  • IEM-polyethylene glycol Adducts 1, 2 and 3 were formulated using the following recipe:
  • IEM-Polyamine Adduct Formulation A polyamine, Jeffamine ® D400 available from Jefferson Chemical Co. (120.24 g, dried over a molecular sieve) was reacted with 94.02 g IEM which had been blended with 0.11 g lonol ® inhibitor. The amine was added dropwise to the IEM at a rate such that the temperature of the reaction mixture did not exceed 50°C. An infrared spectograph showed that the reaction was complete. The product was a translucent amber viscous liquid. Accelerated aging tests showed the product to have excellent shelf stability.
  • the first reaction product was formulated with 2.0 percent cumene hydroperoxide and 500 ppm lonol ® . When placed in an 82oC bath, the formulation gelled in 20 minutes.
  • IEM-Polyol Adhesive Formulation IEM 145.2 g was reacted with tetraethylene glycol (90.0 g) in the presence of 0.235 g zinc octoate and a total of 0.227 g lonol and 0.225 g Dabco (triethylenediamine).
  • the product was formulated with 2.0 percent cumene hydroperoxide and 500 ppm lonol ® . This formulation gelled in less than 3 minutes when placed in an 82°C bath.

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PCT/US1981/001634 1980-12-12 1981-12-09 Addition polymerizable isocyanate-polyahl anaerobic adhesives WO1982002048A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US21599780A 1980-12-12 1980-12-12
US06/215,996 US4320221A (en) 1980-12-12 1980-12-12 Addition polymerizable isocyanate-polyol anaerobic adhesives
US215997801212 1980-12-12
US215996 1980-12-12

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EP0111259A3 (en) * 1982-12-09 1985-09-25 Henkel Kommanditgesellschaft Auf Aktien Process for the preparation of compounds containing (meth)acrylic-acid esters, (meth)acrylic-acid esters and anaerobically curable adhesives and putty-like masses
EP0160709A1 (en) * 1982-09-07 1985-11-13 The Dow Chemical Company Addition polymerizable urethane-based anaerobic adhesives made from tin (II) organoesters
EP0934007A4 (forum.php) * 1996-10-08 1999-09-22
US6656550B1 (en) 1996-10-08 2003-12-02 Alan M. Zamore Dilatation device of uniform outer diameter
US20180022848A1 (en) * 2015-04-03 2018-01-25 Henkel IP & Holding GmbH (meth)acrylate-functionalized extended isosorbide
US12378340B2 (en) 2019-06-13 2025-08-05 3M Innovative Properties Company Crosslinkers and curable compositions including the same

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DE3688578T2 (de) * 1985-07-31 1993-10-28 Ciba Geigy Polyvinylalkoholderivate und vernetzte Hydrogelkontaktlinsen.

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Publication number Priority date Publication date Assignee Title
EP0160709A1 (en) * 1982-09-07 1985-11-13 The Dow Chemical Company Addition polymerizable urethane-based anaerobic adhesives made from tin (II) organoesters
EP0111259A3 (en) * 1982-12-09 1985-09-25 Henkel Kommanditgesellschaft Auf Aktien Process for the preparation of compounds containing (meth)acrylic-acid esters, (meth)acrylic-acid esters and anaerobically curable adhesives and putty-like masses
EP0934007A4 (forum.php) * 1996-10-08 1999-09-22
US6656550B1 (en) 1996-10-08 2003-12-02 Alan M. Zamore Dilatation device of uniform outer diameter
US20180022848A1 (en) * 2015-04-03 2018-01-25 Henkel IP & Holding GmbH (meth)acrylate-functionalized extended isosorbide
US12378340B2 (en) 2019-06-13 2025-08-05 3M Innovative Properties Company Crosslinkers and curable compositions including the same

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JPS6153391B2 (forum.php) 1986-11-17
JPS57502004A (forum.php) 1982-11-11
AU555141B2 (en) 1986-09-11
EP0066614A1 (en) 1982-12-15
EP0066614A4 (en) 1983-03-17
AU8004682A (en) 1982-07-01

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