CN1329648A - Substance for bonding, coating and sealing, consisting of cyanoacrylates and aldehyde or ketone condensation products - Google Patents

Substance for bonding, coating and sealing, consisting of cyanoacrylates and aldehyde or ketone condensation products Download PDF

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Publication number
CN1329648A
CN1329648A CN99813954A CN99813954A CN1329648A CN 1329648 A CN1329648 A CN 1329648A CN 99813954 A CN99813954 A CN 99813954A CN 99813954 A CN99813954 A CN 99813954A CN 1329648 A CN1329648 A CN 1329648A
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Prior art keywords
cyanoacrylate
aldehyde
alcohol
weight
oxygen
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约翰·克莱因
贝恩德·博伊尔
沃尔夫岗·克劳克
沃尔夫岗·梅尔
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • C09J159/00—Adhesives based on polyacetals; Adhesives based on derivatives of polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • 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
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/005—Glue sticks

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paints Or Removers (AREA)

Abstract

Gel-forming condensation products of aldehydes or ketones can be used with polyols in cyanoacrylates to obtain dimensionally stable adhesives, coating and sealing substances. These are stable in storage and are especially suitable for bonding porous substrates such as paper or wood. They are particularly easy to handle when produced in the form of rub-off glue sticks.

Description

Be used for tackiness agent, coating and sealing agent by cyanoacrylate and aldehyde-or material of forming of ketone-condensation product
The present invention relates to a kind of composition as tackiness agent, coating and sealing agent, said composition is based on A) cyanoacrylate and B) mixture formed of the condensation product of aldehyde and ketone.
Patent DE4317886 discloses such cyanoacrylate adhesive.The grease derivative that exists with certain fatty alcohol or certain aliphatic carboxylic acid ester-formin that it contains 1 to 40 weight % is used to reduce the adhesion on the top layer.In this mixture, also add 10 to 100000ppm cationoid polymerisation promotor.Can list a series of materials particularly, formaldehyde and acetaldehyde and oxirane ether are wherein also arranged, as condensation product as the sorbyl alcohol of hydroxy-containing compounds.Can enumerate polyoxyethylene sorbitan ester and polyoxyethylene/sorbyl alcohol-adduct particularly.In order to make a kind of low-viscosity cyanoacrylate thickening or to have thixotropy, dissolve in or disperse to add a kind of thickening material, as polymethylmethacrylate, acrylic elastomer, derivatived cellulose or silicon ester.Add-on according to thickening material in this patent working example is 0 to 10 weight %.The shortcoming of said composition is, even when containing the thickening material of high density, cyanoacrylate adhesive is still very rare, therefore is not suitable as sealing agent or bonding porous base material, and is also inconvenient when generally using.
From prior art, the purpose of this invention is to provide a kind of cyanoacrylate compositions that improves use properties, it has the good use properties as tackiness agent, coating and sealing, at first is at room temperature to have enough stability in storagies.Production process is also very simple in addition.
The objective of the invention is that feature by each claim realizes.In order to produce the composition at 20 ℃ of dimensionally stables, it is mainly based on the application of the gelinite of the condensation product that contains aldehydes or ketones and polyvalent alcohol in cyanoacrylate.
The connotation of dimensionally stable is, it is that 1.5cm, length are, horizontal positioned in the sleeve that opens wide of 5cm that the right cylinder composition is placed on diameter at 20 ℃, composition can not change owing to own wt makes shape in 20 ℃, 10 days, the outstanding sleeve of stock column this moment is at least less than 10mm, preferably less than 0.1mm.Stock column stability maximum can not be depressed the friction condition that occurs above general goods glue rod on paper outside slight on the other hand.
The certain aldehydes or ketones and the condensation product of polyvalent alcohol are that the gelinite that is fit to forms thing.
The compound that application contains at least a acetal or ketal functional group forms thing as gelinite.Such compound makes by condensation reaction, usually also can by polyalcohols with (OH :=C=O) than being 1: 0.5 to 1: 0.01, preferred 1: 0.5 to 1: 0.1 ratio and aldehydes or ketones for example dewater under an acidic catalyst effect partially or completely and make.Also can make by the derivatives reaction of polyvalent alcohol and aldehydes or ketones according to acetal of the present invention and ketal, as by the elimination reaction together with the hydrogenchloride of the dichloride that replaces, or the alcohol of acetal or ketal is eliminated reaction and is made.Suitable compound has a fusing point and is at least 50 ℃, and preferably at least 100 ℃, more preferably at least 150 ℃.Wherein also can use the mixture of acetal and ketal.
It is at least a 1 that suitable polyvalent alcohol contains, 2-dibasic alcohol, 1,3-dibasic alcohol or 1,4-dibasic alcohol group.In addition they also can contain other functional group such as ether-, acid-, ester-, acid amides-, cyanogen-, hemiacetal-and halide functional group.As such polyvalent alcohol is as 1; 2-ethylene glycol; 1; ammediol; 1; the 2-propylene glycol; 2; the 3-butyleneglycol; 1; the 4-butyleneglycol; 2; 2-dimethyl-1; ammediol; 2; two (methylol)-1 of 2-; ammediol; 2-(brooethyl)-2-(methylol)-1; ammediol; 1; 3; the 4-trihydroxybutane; 1-phenyl-1,2, the 3-glycerol; 1; the 2-hexylene glycol; neopentyl glycol; 1; 4-dihydroxyl methylcyclohexane; the 2-methyl isophthalic acid, ammediol; 1,2; the 6-hexanetriol; 2-(2-hydroxyl-oxethyl)-1; 3, the 4-trihydroxybutane; glycerine; two-and Polyglycerine alcohol; two glyceryl alcohol diacetates; TriMethylolPropane(TMP); two-(TriMethylolPropane(TMP)); trimethylolethane; tetramethylolmethane; two ring [2.2.1]-2,3; 5; 6-tetrol in heptan; 2,2,3; the 3-tetrahydroxysuccnic acid; Dipentaerythritol; sorbyl alcohol; formin; Xylitol; inositol; glucitol; glucose; sucrose; starch; Mierocrystalline cellulose; xitix; polyvinyl acetate part or complete hydrolysis; 9,10-dihydroxystearic acid methyl ester; diacetyl sorbyl alcohol and methyl glucoside.
Preferred polyhydric alcohols is sorbyl alcohol, Xylitol and mannitol, more preferably sorbyl alcohol.
Suitable aldehydes or ketones contain aromatics at least a replacement or unsubstituted-, heteroaromatic-or aliphatic series ring.Can contain other functional group in addition, as ether-, ester-, acid amides-, cyanogen-and halogen group.
Suitable ketone is as cyclopentanone, pimelinketone, suberone, 1-(3, the 3-Dimethylcyclohexyl)-ethyl ketone, 1-cyclopropyl ethyl ketone, 3-methyl-5-propyl group hexamethylene-2-alkene-1-ketone, two cyclopropyl ketones, 4-tertiary butyl pimelinketone, dicyclohexyl ketone, the 4-methylcyclohexanone, 1-(1-methyl cyclopropyl)-ethyl ketone, (4-chloro-phenyl-)-cyclopropyl-ketone, 1-(1H-pyrroles-2-yl) ethyl ketone, 1-(2,4, the 6-trimethylphenyl)-ethyl ketone, 1-(2-furyl)-2-acetone, 1-(2-naphthyl)-ethyl ketone, 1-(2-thienyl)-1-acetone, 1-(4-bromophenyl)-ethyl ketone, 1 (4-p-methoxy-phenyl)-ethyl ketone, 1-(naphthyl)-ethyl ketone, 1,1-phenylbenzene-2-acetone, 1,2-phenylbenzene ethyl ketone, 1,3-phenylbenzene-2-acetone, 1-phenyl-butanone, 1-phenyl-1-decanone, 1-phenyl-1-ten diketone, 1-phenyl-1-hexanone, 1-phenyl-1-octanone, 1-phenyl-1-pentanone, 1-phenyl-1-penten-3-one, 1-phenyl-1-ten tetraketones, 1-phenyl-2-butanone, 1-phenyl-2-acetone, 1-pyrazinyl-ethyl ketone, 2,2,2-three fluoro-1-phenyl-ethyl ketones, 1-(2-furyl)-ethyl ketone, 1-(2-pyridyl)-ethyl ketone, 1-(2-thienyl)-ethyl ketone, 4-chloro-1-(4-fluorophenyl)-1-butanone, 4-phenyl-2-butanone, 1-phenyl-ethyl ketone, two-(2-hydroxyphenyl)-ketone, two-(4-chloro-phenyl-)-ketone, the cyclopentyl phenyl ketone, cyclopropyl (4-p-methoxy-phenyl)-ketone, cyclopropyl-(4-aminomethyl phenyl)-ketone, cyclopropyl-2-thienyl-ketone, cyclopropyl phenyl ketone, 1,5-phenylbenzene-1,4-pentadiene-3-ketone, phenyl-2-pyridyl-ketone, 2-bromo-1-(4-nitrophenyl)-ethyl ketone, 2-naphthyl phenyl-ketone, 3-chloro-1-phenyl-1-acetone, 4-(4-hydroxy phenyl)-2-butanone, 4-(4-p-methoxy-phenyl)-3-butene-2-ketone, 1-(4-pyridyl)-ethyl ketone, 1-(4-hydroxy phenyl)-ethyl ketone, 1-phenyl-1-acetone, 4-phenyl-3-butene-2-ketone, diphenylmethanone, 1-phenyl-2-butanone, 1-phenyl-2-butylene-1-ketone, two-(4-aminomethyl phenyl)-ketone, 2-methyl isophthalic acid-phenyl-1-acetone, 2-chloro-1-phenyl-ethyl ketone, cyclopropyl-(4-fluorophenyl)-ketone, 1-(p-methoxyphenyl)-2-acetone, cyclohexyl phenyl ketone and phenyl-(2-thienyl)-ketone.
Suitable aldehyde is as phenyl aldehyde, the 3-chlorobenzaldehyde, the 4-chlorobenzaldehyde, 2, the 6-dichlorobenzaldehyde, 2, the 4-dinitrobenzal-dehyde, 3, the 4-dichlorobenzaldehyde, the 3-fluorobenzaldehyde, the 4-bromobenzaldehyde, 2-methyl tetrahydrochysene phenyl aldehyde, the tetrahydrochysene phenyl aldehyde, 2-methyl-5-sec.-propyl cyclopentenes-1-aldehyde, 2,2,4-3-methyl cyclohexanol-4,6-diene-1-aldehyde, 3 (4)-methyl isophthalic acids-propyl group tetrahydrobenzene-3-aldehyde, 1,3 (4)-dimethyl tetrahydrobenzene-3-aldehyde, 2-methyl isophthalic acid-propyl group tetrahydrobenzene-3-aldehyde, 3-tetrahydrobenzene-1-aldehyde, 2,3,4,5,6-penta fluoro benzene formaldehyde, 2,4, the 6-tri hydroxybenzaldehyde, 4-toluene acetaldehyde, the 2-tolyl aldehyde, the 4-hydroxy benzaldehyde, the 3-tolyl aldehyde, 2-hydroxyl-1-naphthaldehyde, the 4-tolyl aldehyde, 3,5-dimethoxy-4 '-hydroxy benzaldehyde, phenylacrolein, the 3-nitrobenzaldehyde, the 2-amyl cinnamic aldehyde, 4-diethyl amino benzaldehyde, the 4-methoxybenzaldehyde, the 2-phenylpropionaldehyde, the 2-methoxycinnamic aldehyde, the 4-tolyl aldehyde, phenoxy acetaldehyde, methylpyrrole-2-aldehyde, 2,5-dimethoxy-tetrahydrofuran-3-aldehyde, 2,5-dipropyl-3,4-dihydropyrane-2-aldehyde, 2,5-diethyl-3,4-dihydropyrane-2-aldehyde, 2,5-di-isopropyl-3,4-dihydropyrane-2-aldehyde, 2,5-dimethyl-3,4-dihydropyrane-2-aldehyde, 2,5-dibutyl-3,4-dihydropyrane-2-aldehyde, thiophene-3-aldehyde, indoles-3-aldehyde, thiophene-3-aldehyde, pyridine-3-aldehyde, pyridine-4-aldehyde and N-methylpyrrole-2-aldehyde.
Preferred aldehyde is: phenyl aldehyde, 3-chlorobenzaldehyde and 3-fluorobenzaldehyde, more preferably phenyl aldehyde.
According to acetal of the present invention and ketal be as:
Two-oxygen-benzal base mannitol, two-oxygen-(2-benzyl chloride fork base) mannitol, two-oxygen-(4-nitro benzal base) mannitol, two-oxygen-(3-fluorine benzal base) mannitol, oxygen-benzal base sorbyl alcohol, two-oxygen-benzal base sorbyl alcohol diacetate, two-oxygen-(2-benzyl chloride fork base) sorbyl alcohol diacetate, three-oxygen-(4-benzyl chloride fork base) sorbyl alcohol, oxygen-benzal base threitol, oxygen-benzal base tartrate dimethyl esters, oxygen-cyclohexylidene base glycerol, oxygen-cyclohexylidene base xitix and oxygen-benzal base-9,10-dihydroxystearic acid methyl ester.
Preferred acetal or ketal are two-oxygen-benzal base mannitol, two-oxygen-(3-fluorine benzal base) mannitol and two-oxygen-benzal base sorbyl alcohol, preferred two-oxygen-benzal base sorbyl alcohol.
Aldehyde-or the condensation product content of ketone be 0.1 to 10 weight %, preferred 0.4 to 6 weight %, more preferably 1 to 3 weight % is based on the total amount of cyanoacrylate compositions.
Cyanoacrylate is basically based on common cyanoacrylate, promptly based on mono acrylic ester and/or dicyanogen methyl isophorone propylene ester.Their content is at least 29.5 weight %, preferably is at least 50 weight %, based on cyanoacrylate compositions.
" common single cyanoacrylate " is the compound with following structural formula:
H 2C=C (CN)-CO-O-R (I) wherein R is an alkyl, thiazolinyl, cycloalkyl, aryl, alkoxyalkyl, aralkyl or haloalkyl, be preferably with the two keys of 2 conjugated C-C-, 6-ring with a cyclic aliphatic, be with an aromatic nuclear, it is that Br that gone out by benzenesulfonamide derivative and preferred or Cr are as halogen, contain 1 to 18 carbon atom, preferred 2,3,4 carbon atoms, contain especially methyl-, ethyl-, n-propyl, sec.-propyl-, normal-butyl-, isobutyl--, amyl group-, hexyl-, cyclohexyl-, heptyl-, the 2-ethylhexyl-, n-octyl-, n-nonyl-, the oxidation nonyl-, positive decyl-, dodecyl, 2,2, the 2-trifluoroethyl-, the hexafluoro sec.-propyl-, allyl group-, methacrylic-, crot(on)yl-, propargyl-, benzyl-, phenyl-, cresylol-, the 2-chloroethyl-, the 3-chloropropyl-, the 2-chlorobutyl-, tetrahydrofurfuryl-, the 2-methoxy ethyl-, the butoxy ethoxyethyl group, 3-methoxyl group butyl and 2-ethoxyethyl group.Above-mentioned cyanoacrylate is very familiar to tackiness agent professional, can be with reference to Ullmann, and Encyclopaedia of Industrial Chemystry, Bd.Al, S.240, ChemicWeinheim press (1985) and patent US3254111.Preferred monomer be allyl group-, methoxy ethyl-, ethoxyethyl group-, methyl-, ethyl-, propyl group-, sec.-propyl-or 2-cyanogen butyl acrylate cores.
The dicyanogen methyl isophorone acrylate is the compound with following structural formula:
[H 2C=C (CN)-CO-O] 2R 1(II) R wherein 1Be a kind of 2 to 18 carbon atoms that contain, the alkylidene group of the straight or branched of preferred 6 to 12 carbon atoms, it also can contain heteroatoms, as halogen and the aliphatic or aromatic ring of oxygen.Preferred R 1It is a pure hydrocarbon.The dicyanogen methyl isophorone acrylate is pure especially, and this point is very important.Can satisfy this requirement by following production and purification process: the main and glycol generation transesterification reaction of single cyanoacrylate, reaction mixture is handled by fractional crystallization subsequently.
A kind of method of suitable production dicyanogen methyl isophorone acrylate is that 2-alpha-cyanoacrylate or its structural formula are:
H 2C=C (CN)-CO-O-R 2(III) alkyl ester, wherein R 2Be an alkyl that contains the straight or branched of 1 to 6 carbon atom, be with structural formula
[HO] 2R 1(IV) glycol, wherein R 1It is an alkylidene group that contains the straight or branched of 2 to 18 carbon atoms, it can also contain heteroatoms, as halogen and the aliphatic or aromatic ring of oxygen, transesterify generate dicyanogen methyl isophorone acrylate with structural formula II, carry out the purifying of reaction mixture subsequently by fractional crystallization.
Initial product is corresponding to the alpha-cyanoacrylate of the simple function group of structure III or its alkyl ester.To select to remove at an easy rate the alkyl of its correspondent alcohol when selecting alkyl.In general transesterification reaction, the very familiar this suitable possibility of professional.Preferably remove alcohol by distillation.So R 2Be a straight or branched alcohol residue that contains 1 to 6 carbon atom, preferably contain 1 or 2 carbon atom.The cyanoacrylate of simple function group is stable in common mode.
Described glycol (structural formula IV) is the primary alconol or the secondary alcohol of divalence, preferred primary alconol.Each hydroxy functional group can be placed on any position, but preferably be placed on α-/the Ω position.Glycol contains 2 to 18 carbon atoms, preferred 6 to 12 carbon atoms.Their arrangement can be straight chain, side chain or cyclic.Aliphatic residue can contain an aromatic functional group or except hydrogen atom and carbon atom, also have heteroatoms, as chlorine atom or Sauerstoffatom, is preferably the unitary form of polyoxyethylene glycol or polypropylene glycol.As concrete glycol is as hexylene glycol, ethohexadiol, decanediol and lauryl alcohol.
In reaction, use excessive cyanoacrylate.The cyanoacrylate of simple function group and the mol ratio of glycol were at least 2.0: 1.0, and preferred 2.5: 1.0, more preferably 2.2: 1.0.
By adding the effect of strong acid catalytic transesterification, particularly add sulfonic acid, preferably add aromatic sulfonic acid, as tosic acid.But also can add naphthene sulfonic acid, Phenylsulfonic acid and acid ion exchangers.The catalyst concentration of transesterification reaction, based on the amount of the cyanoacrylate of simple function group, should be between 1 and 20 weight %.
Transesterification reaction is carried out in solution in a conventional manner.Suitable solvent is aromatic hydrocarbons and halohydrocarbon.Preferred solvent is toluene and dimethylbenzene.The concentration of solution is 10 to 50 weight %, preferred 10 to 20 weight %.
The monohydroxy-alcohol that generates or the water of generation can be removed with known method, preferably distill out with solvent.The transformation efficiency of transesterification reaction can be with monitoring as the NMR-spectrometer.This reaction generally can last for hours., finish after being reflected at 10 to 15 hours as solvent and tosic acid under the situation as catalyzer at toluene, promptly no longer produce alcohol this moment.
Reaction mixture is very important.Under the situation of acid ion exchangers as catalyzer, filtering very simply.Under the situation as catalyzer, can remove catalyzer at solubility sulfonic acid such as tosic acid: use the mixture displacement toluene of forming by hexane, heptane or decane by solvent exchange.Behind the secondary fractional crystallization, obtain pure dicyanogen methyl isophorone acrylate.Spectroscopic analysis is measured its purity greater than 99% according to NMR.
Resulting dicyanogen methyl isophorone acrylate has conventional stablizer, can stably stored under common concentration, promptly in the time of 20 ℃ within 6 months its fusing point almost do not change.
But in the presence of alkali, the polymerization velocity of the dicyanogen methyl isophorone acrylate that obtains is very fast, and especially almost the speed with corresponding single polymerizable cyanoacrylate ester is the same.In the cyanoacrylate of simple function group, as long as there is trace water just enough.Just generate a kind of relatively better three-dimensional cross-linked polymkeric substance of thermal characteristics that has subsequently.
Therefore, according to the present invention, the dicyanogen methyl isophorone acrylate is used for the tackiness agent of known cyanoacrylate, is that the scope of basic usage quantity is 0.5 to 50 weight % with the total amount of cyanoacrylate compositions, preferred 1 to 10 weight %, more preferably 2 to 5 weight %.
Knownly not only obtain cyanoacrylate by a kind of anionic polymerization, and can obtain by the polymerization of free radical chain, therefore prevent that the ester component from two kinds of polymerization methodses taking place is favourable, the curing of ester so just can not take place prematurely, eliminated the difficulty in storing.In order to stop anionic polymerization, in tackiness agent according to the present invention, added a kind of negatively charged ion stopper.All negatively charged ion stoppers of using in the cyanoacrylate adhesive field all suit.As the negatively charged ion stopper can be a kind of sour gas, a kind of protonic acid or a kind of acid anhydride that is generated by them.Stopper according to tackiness agent preferred anionic of the present invention is a sulfurous gas, and preferred consumption is 0.001 to 0.5 weight % of tackiness agent total amount.Other applicable negatively charged ion stopper is nitrous oxide, hydrogen fluoride, hydrochloric acid, sulfuric acid, phosphoric acid, organic sulfonic acid and carboxylic acid and their acid anhydrides, five phosphorus oxide and acid chloride.In one of the present invention preferred embodiment, also can in tackiness agent, add the free radical chain stopper that consumption is 0.01 to 0.05 weight %.Any one in cyanoacrylate compositions exhausted free radical chain stopper all can use.The general oxybenzene compound of using is as quinhydrones, tert-butyl catechol, pyrocatechol and p methoxy phenol.Above-mentionedly be stabilized at 2-alpha-cyanoacrylate ether-ether preparation available on the market.In the time of if necessary, adjust the concentration of stablizer in the preparation that when using, can on market, obtain, this concerning professional without any difficulty.
Another preferred embodiment in, in order to improve viscosity (thickening material) or to change bond properties, in cyanoacrylate compositions of the present invention, add polymkeric substance.The amount that adds polymkeric substance is 1 to 60 weight % of total composition, preferred 10 to 50 weight %, more preferably 10 to 30 weight %.At first suitable polymer blend is based on vinyl ether, vinyl ester, and acrylate and methyl-propyl acid esters contain 1 to 22 carbon atom, the multipolymer of vinylbenzene or vinylbenzene and ethene, divinyl and trimeric polymkeric substance in its alcohol moiety.Vinylchlorid/the vinyl acetate copolymer that preferably contains 50 to 95 weight % vinylchlorid.Polymkeric substance can be liquid, resinoid or also can be solid state.Very weight is, does not suppress cyanoacrylate solidified impurity in the polymkeric substance that obtains after polymerization process finishes.When if polymkeric substance contains than high-moisture, must be when needing through super-dry.Molecular weight (Mw) can fluctuate in the scope of broad, should be Mw=1500 at least, and maximum is 1000000, otherwise the final viscosity of tackiness agent is too high.Also can use above-mentioned polymeric blends in addition.Particularly, the composition of lower molecular weight and high molecular weight product is best to forming the suitable final viscosity of tackiness agent.Suitable polymkeric substance on the vinyl acetate basis is as Mowilith type 20,30 and 60, Vinnapas type B1.5, B100, B17, B5, B500/20VL, B60, UW10, UW1, UW30, UW4 and UW50.Suitable polymers based on acrylate is as Acronal 4F and Laromer type 8912, PE55F and PO33F.At the suitable polymkeric substance based on methacrylic ester is as Elvacite2042, Neocryl type B724, B999731, B735, B811, B813, B817 and B722, Plexidon MW134, Plexigum type M825, M527, N742, N80, P24, P28 and PQ610.At the suitable polymkeric substance based on vinyl ether is as Lutonal A25.For thickening also can be used derivatived cellulose and silica gel.Ben is to add polybutylcyanoacrylate.
In order to reach and the application target corresponding effects, also can contain other auxiliary agent according to cyanoacrylate of the present invention in addition.At first be as disclosed polymerization promotor among the patent DE4317886, i.e. the derivative, particularly their ester and ether of polyalkylene oxides and they.Other polymerization promotor is hat fan and their derivative, silicon crown ether-compound and episulfide compounds.The add-on of polymerization promotor be the cyanoacrylate compositions total amount 10 to 100000ppm, preferred 30 to 10000ppm.Other promotor is cyclodextrin.
Can be added in patent DE19752893 or disclosed fat derivant in patent DE4317886 as softening agent.The carboxylicesters that wherein relates to grease and grease derivative, particularly fatty alcohol, aliphatic carboxylic acid esters, or isocyclic compound.Detailed data can be consulted above-mentioned patent document.Certainly also can use general softening agent, as phthalic ester, citrate, chloroparaffin and trimellitic acid ester.
For the solubleness that improves the aldehydes or ketones condensation product or in order easily these products to be processed into solution, can add solvent.In the suitable organic solvent as alcohol, ether, ketone and low-molecular-weight alkyl ester.Virahol, methoxypropanol, oxyethyl group propyl alcohol, ethoxy ethanol, propoxy-ethanol, butyl cellosolve, methylethylketone and N-N-methyl-2-2-pyrrolidone N-are particularly preferred.Solvent should be low as far as possible in the alpha-cyanoacrylate composition, can not influence the stability of shape like this, preferably less than 20 weight %.
Other auxiliary agent is activator, pigment, pigment, spices, sanitas, antiseptic-germicide and weighting agent.
Alpha-cyanoacrylate composition manufacturing method according to the present invention mainly be condensation product by cyanoacrylate and aldehydes or ketones and a kind of polyvalent alcohol by heating for dissolving, the solution by the cooling curing gained subsequently.Generally by a kind of acrylate and a kind of negatively charged ion stopper, at N 2As protection gas, be heated to 50 to 90 ℃, produce a kind of stable cyanoacrylate compositions.Dissolving or suspend into desirable component under high degree of agitation is until obtaining a kind of uniform mixture.Under 80 to 95 ℃, add condensation product in batches and continue dissolving down at 90 to 95 ℃.Mixture cooling is subsequently preferably reduced to about 80 ℃, filters, and is cast into desirable shape then.Composition solidifies usually after about 1 hour, the highly stable glue rod that can be used as of shape after about 24 hours.Though shape is very stable, yet cyanoacrylate compositions can be wiped on a kind of base material such as paper under light pressure.
On the basis of shape stability, cyanoacrylate compositions is fit to constitute required geometrical shape, particularly clavate.The columniform tackiness agent rod of preferred production.This shape is very suitable to later application.But also might constitute other shape, particularly have the geometrical shape of a symmetry axis or a plane of symmetry at least, as sphere, rectangular parallelepiped, pyrometric cone, cone, right cylinder, thin rod, band, plate, algae film and pad.Preferred two-dimensional coordinate is greater than the shape of third dimension coordinate.This shape is the pencil lead as clavate (hot melt rod) or wax crayon form.Primary surface or geometric element can be dihedral, special triangle, quadrangle or sexangle or circle (for example (circle or ellipsoidal).Diameter can reach 2 to 100mm and length can reach 150mm.The shape of cyanoacrylate compositions and weight can be very flexible according to the present invention, basically by the application purpose decision, and also easy to use.
Cyanoacrylate component by high rotating speed cutting processing can be produced the liquid cyanoacrylate compositions with strong thixotropic property.That cyanoacrylate compositions according to the present invention is suitable for is bonding, coating and sealing, and particularly bonding porous substrate is as leather, textiles, paper, cardboard, presspaper, timber and fur.According to cyanoacrylate compositions of the present invention, on the clavate basis, also can be applied to repair shoes, pvc pipe and synthetical nail.Bonding wound is particularly used the cyanoacrylate of long-chain, suits equally.Combine with primer, as fatty amine, also can bonding well polyalkenes hydrocarbon.Wherein primer can change into clavate with gel formation thing according to the present invention.Can produce coloured rod and master bar by adding pigment and/or pigment.Such thin rod is because solubilizing agent not, to the environmental protection particularly advantageous.Use a little binder can eliminate crack and aperture in the differing materials as filler.Both sides base thing adhesive coating is very practical method as the friction by the glue rod.It also is possible filling bonding to the crack in addition.
When using as sealing agent, cyanoacrylate compositions can solidify soon, and this is of great value.
It should be noted that can long-term storage according to cyanoacrylate compositions of the present invention.For example be placed in the common glue rod sleeve and at room temperature can place several weeks, can not reduce cohesive force in use.
Other advantage according to cyanoacrylate compositions of the present invention is, easy to use, safe (not can splash in eye or on the skin), can be used for big plane coating, the vertical base material of placing can bond.
The invention will be further described below in conjunction with embodiment.
At 2 to 5 ℃, the glue rod still can use after 6 months, and promptly denseness and bond properties keep fine.
At-18 ℃ after 9 months, the glue rod still can use, and promptly gel structure does not have destroyed and do not generate polymkeric substance.When being heated to 20 ℃, be easy to open the pipe lid.When doing test with paper, binding time and cohesive force almost do not change (until paper tear).Still keep stable more than 9 months-18 ℃ of storages, this is significant to medical use.The production of embodiment 1. cyanoacrylate compositions
Oneself stable cyanoacrylate is placed on one and fills N 2In the big flask of three necks of protection gas,, add polymethacrylate 50 ℃ of high degree of agitation in batches.Solution clarification and even after 10 minutes.
In order to form gel, elevated temperature to 85 ℃ and portion-wise addition two-oxygen-benzal base sorbyl alcohol its objective is for fear of generating grumeleuse.Jelling agent further dissolves after 10 minutes.When being cooled to about 80 ℃ undissolved particle filtration is removed.Still hot solution is poured in the general glue rod sleeve into cooling then, formation one solid piece after about 1 hour.Completion of processing can be used in second day, though repeatedly open and close lid after several weeks, it is still stable.2. check
A) in order to test stability in storage, at 50% time, cyanoacrylate compositions is placed in the glue rod sleeve, in its cohesive force to paper of all build-in tests at 23 ℃ and relative air humidity.
B) in order to measure the condensation cure time, cyanoacrylate compositions is wiped on the long paper slip of a 30cm, subsequently the second paper slip is directly sticked and pushes.Write down the time of following test then, paper tear when separating bonding coat through how long afterwards.
C) in order to test the tensile shear strength of vertical bonding coat, (a) drips 2 tackiness agent liquid on the substrate surface of 10 * 25mm, (b) wipes the tackiness agent of respective amount with the glue rod on substrate surface, direct then with the 2nd base material be pressed in gently it above.Stopped 2 days under 23 ℃ and 50% relative humidity, the sample of paper timber and non-timber type is by standard EN 205 test tensile shear strengths (speed 10 mm/min).
The result is the mean value of 5 test values.By following mode base material is carried out pre-treatment:
---paper timber: undressed;
---PMMA: the greasy processing of deoiling;
---ABS plastic: the greasy processing of deoiling;
---PVC: the greasy processing of deoiling; With
---A1 sheet: sandblast and handle and deoil greasy the processing.3. result
Test result is listed in the table 1.The result shows that every kind of situation has all reached required intensity, has also surpassed the intensity level of common cyanoacrylate adhesive in paper timber.
Composition of table 1 cyanoacrylate compositions (weight part) and performance
I. form ????B 1 ???????B 2
1 cyanoacrylate 2SO 23 phosphoric acid, methanesulfonic acid 4 polymethacrylates 5 two benzal base sorbierite II. performances are storage stability [week] b a)) binding time [second] c) tensile shear strength [MPa]-paper timber-PMMA-ABS plastic-A1 (sandblasting)-PVC 100 100++++ 550 1.8-＞10 in conjunction with 20 7.33TA, 7.75 7.01MB 6.11MB 8.10MB, 6.21 part MB, 14.75 7.08 14.59MB 4.90MB
Annotate: TA: material is broken
MB: material fractures
Part MB: material fractures in individual sample

Claims (9)

1. as the cyanoacrylate compositions of tackiness agent, coating and sealing agent, said composition be with
A) at least a cyanoacrylate and
B) condensation product of at least a aldehydes or ketones and polyvalent alcohol is the mixture on basis.
2. composition according to claim 1 is characterized in that containing the material of at least a following aldehydes or ketones family: phenyl aldehyde, 3-chlorobenzaldehyde and 3-fluorobenzaldehyde, preferred phenyl aldehyde.
3. composition according to claim 1 is characterized in that containing the material of at least a following polyvalent alcohol: sorbyl alcohol, Xylitol and mannitol, preferred sorbyl alcohol.
4. composition according to claim 1, it is characterized in that containing the material of the condensation product of at least a following aldehydes or ketones and polyvalent alcohol: two-oxygen-benzal base mannitol, two-oxygen-(3-fluorine benzal base) mannitol and two-oxygen-benzal base sorbyl alcohol, preferred two-oxygen-benzal base sorbyl alcohol.
5. composition according to claim 1 is characterized in that based on the total amount of cyanoacrylate compositions, it consists of
A) at least a cyanoacrylate of at least 99.8 to 29.5 weight %;
B) at least a aldehydes or ketones of 0.1 to 10 weight % and a kind of condensation product of polyvalent alcohol;
C) stablizer of 0.001 to 0.5 weight %;
D) thickening agents of 0 to 60 weight %, solvent, softening agent, weighting agent and other auxiliary agent.
6. composition according to claim 1 is characterized in that said composition has certain geometrical shape, preferred a kind of clavate.
7. according to each described composition manufacturing method in the claim 1 to 6, it is characterized in that, at first will be by component A) and the mixture heating up of B) forming make a solution, then with its cooling.
8. according to the application of each described composition in the claim 1 to 6, it can be used as tackiness agent, coating and sealing agent.
9. the application of composition according to claim 8, it can be used for bonding porous base material.
CN99813954A 1998-12-02 1999-11-30 Substance for bonding, coating and sealing, consisting of cyanoacrylates and aldehyde or ketone condensation products Pending CN1329648A (en)

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CN101765620B (en) * 2007-06-15 2012-06-27 马克斯-普郎克科学促进学会 Method of preparing organic porous solids and solids obtainable by this method
CN102197102A (en) * 2008-09-26 2011-09-21 汉高公司 Cyanoacrylate compositions in non-flowable forms
CN102197102B (en) * 2008-09-26 2014-11-26 汉高公司 Cyanoacrylate compositions in non-flowable forms
CN103083718A (en) * 2011-11-02 2013-05-08 中国人民解放军军事医学科学院毒物药物研究所 Biodegradable medical adhesive, and preparation method and purpose thereof
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