CN1328103A - Trigger used for anaerobic adhesive and its anaerobic adhesive - Google Patents
Trigger used for anaerobic adhesive and its anaerobic adhesive Download PDFInfo
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- CN1328103A CN1328103A CN 01114865 CN01114865A CN1328103A CN 1328103 A CN1328103 A CN 1328103A CN 01114865 CN01114865 CN 01114865 CN 01114865 A CN01114865 A CN 01114865A CN 1328103 A CN1328103 A CN 1328103A
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- Prior art keywords
- superoxide
- anaerobic glue
- tertiary amine
- anaerobic
- peroxide
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- 239000000853 adhesive Substances 0.000 title claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 9
- -1 hydrazine-saccharine Chemical class 0.000 claims abstract description 70
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 239000003292 glue Substances 0.000 claims description 69
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 17
- 150000003512 tertiary amines Chemical class 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 12
- 230000002829 reductive effect Effects 0.000 claims description 12
- 239000003352 sequestering agent Substances 0.000 claims description 12
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 9
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 9
- UICBCXONCUFSOI-UHFFFAOYSA-N n'-phenylacetohydrazide Chemical group CC(=O)NNC1=CC=CC=C1 UICBCXONCUFSOI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical group C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 5
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- 150000004053 quinones Chemical class 0.000 claims description 3
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- 229930192627 Naphthoquinone Natural products 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004056 anthraquinones Chemical class 0.000 claims description 2
- 150000004054 benzoquinones Chemical class 0.000 claims description 2
- 150000002791 naphthoquinones Chemical class 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000000470 constituent Substances 0.000 description 7
- 108010010803 Gelatin Proteins 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- FOAUQQDOLGYUFX-UHFFFAOYSA-N 7,8,15,16-tetraoxadispiro[5.2.5^{9}.2^{6}]hexadecane Chemical compound C1CCCCC21OOC1(CCCCC1)OO2 FOAUQQDOLGYUFX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013521 mastic Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
An improved initiator for anaerobic adhesive features that for the oxide-substituted hydrazine-saccharine initiator system, its oxidant and reducer are the combination of more than one comound to make the anaerobic adhesive have better solidifying performance and higher storage stability (3-5 years).
Description
The present invention relates to a kind of composition and anaerobic glue thereof of trigger used for anaerobic adhesive.
Anaerobic glue is the mastic sealant that has been widely used in various engineering goods productions and maintenance.The essentially consist of anaerobic glue; comprise the monomer that contains the active methyl acryloyl group or oligomer, initiator, stopper, also normal as required sequestrant, properties-correcting agent (for example thixotropy agent, oilness agent, toughner, intensity are adjusted agent, thickening material, reactive thinner, coupling agent or the like) and dyestuff, spices or the like of adding.
The most frequently used representative anaerobic glue initiator (being redox system); mainly comprise: oxygenant (comprising the various alkyl hydroperoxide ROOH, the peresters RCO-OOR ' that contain single and many peroxidation base and hydrocarbyl superoxide ROOR ' etc.), reductive agent (organic replacement hydrazine or tertiary amine), promotor (as o-benzoic sulfimide, i.e. asccharin) etc.And from numerous redox systems, being employed two more or more famous individual system substantially is superoxide-tertiary amine-asccharin (being called for short amine system down) and superoxide-replacement hydrazine-asccharin (being called for short the hydrazine system down) two classes, and this is the technology of the seventies in 20th century with regard to having begun to use.
Typical initiator is formed early existing many patent reports, and the work in this regard of happy safe (Loctite) company is significant.For example reported the redox system of forming by isopropyl benzene hydroperoxide, organic replacement hydrazine (many kinds are representative with 1-acetyl-2-phenylhydrazine), asccharin at 1976 (J51-144438) and 1981 (US4287330); 1976 (US3988299) and 1977 (US4007323) reported respectively by superoxide, N, N ' diethyl-p-tlouidine and N, the redox system that the combination of N ' dimethyl Ortho Toluidine, asccharin are formed; In addition, (J53-084042,1978) are introduced and are added acidic cpd such as toxilic acid or vinylformic acid again.
Form introduction as for the anaerobic glue that belongs to superoxide-replacement hydrazine-asccharin system (hydrazine system), representational have: patent (US4180640) embodiment had introduced the anaerobic glue of being made up of methacrylic acid multicondensed ethylene glycol ester, isopropyl benzene hydroperoxide, pyrodin, asccharin, toxilic acid or vinylformic acid etc. in 1979.It is that monomer, isopropyl benzene hydroperoxide are that oxygenant, pyrodin are that reductive agent, asccharin are promotor and have added the anaerobic glue that sequestrant (EDTA tetra-na salt etc.), vinylformic acid, ethylene glycol, stopper, gaseous oxidation silicon (as thixotropic agent and thickening material) etc. are formed that the embodiment of nineteen eighty-three patent (USP4380613) has introduced by oligomers such as polyurethane-type methacrylic ester and methacrylic ester dibasic acid esters.Unit and worker that above-mentioned technology is development, produce anaerobic glue know already, and the representative of still with practical value so far and the anaerobic glue formula technique that also is employed.
Aspect superoxide-tertiary amine in trigger used for anaerobic adhesive-asccharin system, existing some report about combination, two kinds of different structure N of usefulness except aforementioned patent, N ' dialkyl group replaces Tolylamine (N, N ' diethyl-p-tlouidine and N, N ' dimethyl Ortho Toluidine) beyond combination is used always, also relevant for adding that on the basis of aryl tertiary amine a certain amount of replacement hydrazine improves the report of curing performance (as USP3987234,1976), other has data also to report at isopropyl benzene hydroperoxide, N, N ' dialkyl replaces Tolylamine, can add pyrodin again in the system of asccharin, in addition, more early stage 1972 of anaerobic glue development, (US3634379) reported N ' diethyl-p-tlouidine at hydroperoxide that belongs to the amine initiator system and N, in the system that asccharin is formed two kinds of superoxide are made up.
Reported in the patent and can be used as oxygenant, though the compound that reductive agent and promotor are used has a lot, but relate to the array mode except that aforesaid, most of patents all are at oxygenant, reductive agent adopts the wherein mode of certain simplification compound respectively, the system that particularly belongs to superoxide-replacement hydrazine-asccharin is more like this, one of possible reason is in this system, no matter be Oxidizing and Reducing Agents, use single compound to have practicality respectively, and the method that is adopted so far by domestic and international many anaerobic glue producers, in the anaerobic glue of current home sale, much be the better simply system that belongs to this superoxide-replacement hydrazine-asccharin.But, in fact still there is some not enough and have much room for improvement aspect, be apparent that when storage at normal temperature the active decline of glue is still very fast, so that active storage period is not long, most document announcements are 1 year, indivedual 1.5～2 years.
From the occasion of using, wish that it can comparatively fast solidify in use, but when storage at normal temperature, but require bottled glue to deposit the long period and still can keep greater activity.Because each constituent of anaerobic glue even and air between, exist mutual restriction and the actual reason that is in the fine balance state, when longer-term was stored, each constituent reacted to each other or overbalance, and the activity of anaerobic glue just descends and makes that curing speed descends until not solidifying when using.Package stability for anaerobic glue, the factor of influence is more, among forming, except the influence of monomer, stopper and various additives, more important and crucial is that its initiator system is the influence that redox system is formed, i.e. the influence of the aspects such as oxygenant, reductive agent and promotor in anaerobic gelatin is formed.
The object of the invention provides a kind of trigger used for anaerobic adhesive, by the improvement that anaerobic glue initiator (redox system) is formed, to obtain preferable anaerobic glue curing performance and shelf-stable performance.
Another object of the present invention provides the anaerobic glue that contains this initiator.
The present invention is based on and improves existing anaerobic glue initiator system, the redox system of superoxide-replacement hydrazine-asccharin particularly, Oxidizing and Reducing Agents (or respectively) employing simultaneously makes anaerobic glue obtain preferable curing performance and package stability more than the method for a compound combination with this.
Trigger used for anaerobic adhesive system provided by the invention comprises oxygenant, reductive agent and promotor, counts by weight, comprising:
0～10 part of alkyl hydrogen peroxide (R (OOH) n, n 〉=1),
0～10 part of hydrocarbyl superoxide (R (OO) nR ', n 〉=1 or R '-OO-R-OO-R "),
0.1～3 part of organic replacement hydrazine,
0～0.5 part of tertiary amine,
0.1～4 part of o-benzoic sulfimide (being asccharin);
Wherein R, R ', R " represent various alkyl;
Maximum consumptions are 0 in alkyl hydrogen peroxide, hydrocarbyl superoxide and the tertiary amine.
Anaerobic glue provided by the invention comprises (methyl) acrylate monomer and/or oligomer, initiator, stopper, counts by weight, and its composition comprises:
100 parts of (methyl) acrylate monomer and/or oligomers,
0～10 part of alkyl hydrogen peroxide (R (OOH) n, n 〉=1),
0～10 part of hydrocarbyl superoxide (R (OO) nR ', n 〉=1 or R '-OO-R-OO-R "),
0.1～3 part of organic replacement hydrazine,
0～0.5 part of tertiary amine,
0.1～4 part of o-benzoic sulfimide (being asccharin),
0.005～0.1 part of stopper,
0.005～1.0 part of sequestrant;
Wherein R, R ', R " represent various alkyl,
Maximum consumptions are 0 in alkyl hydrogen peroxide, hydrocarbyl superoxide and the tertiary amine.
A kind of composition of comparatively ideal anaerobic glue comprises:
100 parts of (methyl) acrylate monomer and/or oligomers,
0.5～3 part of alkyl hydrogen peroxide (R (OOH) n, n 〉=1),
0.5～4 part of hydrocarbyl superoxide (R (OO) nR ', n 〉=1 or R '-OO-R-OO-R "),
0.1～1 part of organic replacement hydrazine,
0.05～0.5 part of tertiary amine,
0.1～3.2 part of o-benzoic sulfimide (being asccharin),
0.01～0.05 part of stopper,
0.01～0.1 part of sequestrant;
During optimal anaerobic glue was formed, the alkyl hydrogen peroxide was a tertbutyl peroxide, and hydrocarbyl superoxide is selected from two cyclohexylidene diperoxy things and 2,5-dimethyl-2,5-(di-tert-butyl peroxide) hexane, organic replacement hydrazine are 1-acetyl-2-phenylhydrazine, and tertiary amine is a tri-n-butylamine.
Wherein oxygenant alkyl hydrogen peroxide is to contain one or more hydrogen peroxide-based in the molecule (compound OOH) is as tertbutyl peroxide, isopropyl benzene hydroperoxide etc.
The oxygenant hydrocarbyl superoxide is for containing one or more peroxies (compound OO-), as ditertiary butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-(di-tert-butyl peroxide) hexane and two cyclohexylidene diperoxy things and three cyclohexylidenes, three superoxide etc. especially can be two cyclohexylidene diperoxy things and three cyclohexylidenes, three superoxide.
Wherein the organic replacement hydrazine of reductive agent can be selected from the organic replacement hydrazine that uses in the prior art, as 1-acetyl-2-phenylhydrazine.
The reductive agent tertiary amine can be selected from aromatic nitrile base, especially aliphatic tertiary amines such as aliphatic tertiary amine such as tri-n-butylamine that prior art uses, triethylamine, trolamine and xylidine.
As anaerobic glue, monomer whose and oligomer should be the compound that contains unsaturated double-bond, are mainly methacrylic ester, have anaerobism and intramolecularly and contain a minimum methacryloyl, generally include with molecule to be no less than two methacryloyl persons for good.Optionally also can add some other the compound that contains unsaturated double-bond.
Stopper is the stopper that prior art is used, and is generally phenols and quinones, as Resorcinol, benzoquinones, naphthoquinones, anthraquinone etc.
Sequestrant is the sequestrant that prior art is used, as disodium salt, trisodium salt and the tetra-na salt etc. of ethylene dinitrilotetra-acetic acid.
The present invention is based in the anaerobic glue initiator system, and oxygenant, reductive agent etc. are formed the method that all adopts (or adopting respectively) to make up more than a compound, obtains preferable curing performance and package stability in the hope of making anaerobic glue.It is generally acknowledged, because anaerobic glue is when storage at normal temperature, each constituent of initiator system, but be to be in actual being among the process that constantly reacts to each other and consume among a kind of fine balance, when certain composition consumes comparatively fast and produce too much non-active ingredient, just some imbalance may appear, at this moment, anaerobic gelatin package stability and the curing speed when using just change, it is the performance possible deviation of glue, curing speed occurring descends, gelatin viscosity changes even gel, and the factor of anaerobic glue stability is not limited to initiator system and reason is quite complicated though influence, and initiator system is considerable.In recent years existing foreign patent has been reported the research about the better oxygenant of performance, reductive agent and promotor aspect.The then discrepant a plurality of compounds combinations of the similar and performance of employing effect of the present invention, because the complementary or collaborative influence of performance between the compound, just helping equilibrated and keep, also is to can be used as to improve the anaerobic gelatin performance and reach a stable approach of longer-term.
The present invention is based on and improves existing anaerobic glue initiator system, belongs to the improvement to the redox system (hydrazine system) of superoxide-replacements hydrazine-asccharin, thus in the reductive agent still based on organic hydrazine, the consumption of tertiary amine is unsuitable too much.
The tertbutyl peroxide that uses among the present invention and 2 particularly, 5-dimethyl-2,5-(di-tert-butyl peroxide) hexane, two cyclohexylidene diperoxy things and the combination of three cyclohexylidenes, three superoxide have outstanding effect as oxygenant to stability and the curing performance that improves glue.The English of two cyclohexylidene diperoxy things is called Dicyclohexylidene diperoxide, on the structure is to link to each other with two-OO-between two cyclohexylidene bases, and its structural formula is:
R is that cyclohexylidene is to change to come or a kind of two polyperoxides of ad hoc approach synthetic (Dimeric peroxide) from cyclohexanone peroxide (Cyclohexanone peroxide), trimeric three cyclohexylidenes three superoxide also are available in addition, its synthetic method is at J.Org.Chem., vol35 (9), the existing introduction in 3059,1970.And another kind of peroxidase 12,5 dimethyl 2,5 (di-tert-butyl peroxide) hexanes also have report to can be used as oxygenant in the anaerobic glue patent, and its structural formula is:
R is the tertiary butyl, and R ' is a methyl
As anaerobic glue, monomer whose and oligomer should be methacrylic ester, have anaerobism and intramolecularly and contain a minimum methacryloyl, include with molecule generally that to be no less than two methacryloyl persons be main.In an embodiment of the present invention, specific that used at home widespread use and be the contriver at development at the end of the seventies monomer identical as trial target with the GY-340 anaerobic glue that obtains state award for inventions.
The adding of stopper is necessary, and the stopper that prior art is used all is an available to the present invention, and commonly used have phenols and a quinones.
In order to reduce the detrimentally affect of metal ion in the glue, also added sequestrant in the glue of the present invention, the sequestrant that the present invention uses also is to use in the prior art, and the representative sequestrant of prior art is disodium salt, trisodium salt and the tetra-na salt of ethylene dinitrilotetra-acetic acid (being EDTA).Because EDTA separates than indissoluble in glue, the present invention is made into EDTA the aqueous solution of polyvalent alcohol (as glycerine or ethylene glycol) earlier just to join among the glue, its ratio and consumption can change according to actual needs, the EDTA among the embodiment: polyvalent alcohol: the ratio of water is 1: 4: 5 (weight).
In addition, also can add acidic cpd in the initiator system of anaerobic glue, acidic cpd can be accelerated glue and solidify, as toxilic acid, vinylformic acid, methacrylic acid and chloracetic acid etc. as a kind of secondary accelerator.
Various modifications (interpolation) agent and dyestuff, the spices etc. that often are added in anaerobic glue because of being that the needs that will look different anaerobic glues add or lack, and in the embodiment that the present invention uses as proof test, do not add these constituents.
The physical data report, at room temperature mostly be 1 year the active storage period of anaerobic glue, reach 1.5～2 years individually, and the present invention relates generally to the composition of anaerobic glue initiator system (being redox system), in initiator system of the present invention is formed, its Oxidizing and Reducing Agents can adopt (maybe can adopt respectively) aforementioned more than a combination of compounds method all, the anaerobic gelatin room temperature storage still had good curing performance in 3～5 years, show that anaerobic glue of the present invention is when keeping the fast setting performance, have longer active storage period, have excellent application value.
Embodiment 1
The preparation of some required constituent in the glue: double methyl methacrylate triethylene glycol ester is for being entrainer with methacrylic acid, Triethylene glycol at toluene, is prepared into through over-churning, neutralization, vacuum piptonychia benzene, and wherein iron level after testing.The bisphenol A epoxide resin double methyl methacrylate, for methacrylic acid and E-44 Resins, epoxy in the presence of catalyzer, 110～120 ℃ of reactions make.Two cyclohexylidene diperoxy things were then used cyclohexanone peroxide processing transformation structure such as chloric acid and were prepared.
Anaerobic gelatin in the embodiment of the invention (being parts by weight) composed as follows:
The constituent consumption
Prescription 1 prescription 2
Double methyl methacrylate triethylene glycol ester 60.0 60.0
E-44 epoxy methacrylic acid diester 40.0 40.0
1-acetyl-2-phenylhydrazine 0.5 0.5
Tri-n-butylamine 0.1 0.1
Asccharin 2.0 2.0
Toxilic acid 1.0 1.0
EDTA solution 0.5 0.5
Resorcinol 0.02 0.02
Tertbutyl peroxide 2.0 2.0
2,5 dimethyl 2,5 (di-tert-butyl peroxide) hexanes-3.0
Two cyclohexylidene diperoxy things 2.0-
With above-mentioned each constituent, be mixed with anaerobic glue by prescription with the routine operation method, being respectively charged into and depositing in volume is in the new LDPE (film grade) bottle of 100ml, leaves 1/2 to 1/3 space in the bottle.
Fill a prescription 2 actual be a improvement to superoxide-the replacements hydrazine-asccharin initiator system that uses in the past, used oxygenant of the present invention etc. and formed by not only method that compound makes up.Prescription 1 has more adopted the combination of two cyclohexylidene diperoxy things of general also little use in anaerobic glue as superoxide.
Embodiment 2
Prescription 1 and each 4～5ml of prescription 2 glues with embodiment 1 are respectively charged in the 10ml high-pressure polyethylene bottle of the about 1cm of diameter, are placed in 80 ℃ of air thermostat containers and test, and take out behind 6h, and all the glue outward appearance is constant, does not find the gel quav body in the glue.
Embodiment 3
The about 7ml of prescription 1 glue with embodiment 1, leave in the 10ml high-pressure polyethylene bottle, in 50 ℃ of air thermostat containers, take out behind the 10d, carry out 23 ℃ of locking tests of room temperature of M10 steel screw element, deposit Pretesting for 50 ℃ and refer to that the solid time is 15min, the average torque of self-vulcanizing 1h (1/4 week, 1/2 week, 3/4 week and 1 week the place read the mean value of torque value, down with) 3.9Nm, 50 ℃ then are respectively 10min and 4.2Nm after depositing.
Embodiment 4
Carry out the test of embodiment 1 prescription 2 glues with embodiment 3 same procedure, 50 ℃ are deposited the solid time of preceding finger is 15min, and the average torque of self-vulcanizing 1h is 4.3Nm, then is respectively 15min and 4.25Nm after depositing.
Embodiment 5
Form the glue of preparation according to embodiment 1 prescription 2, get 50ml, leave in the 100ml high-pressure polyethylene bottle, place 3 years at normal temperatures after, glue is not found gel, carries out the locking test of M10 steel screw element, detects when 30min, has referred to solid.Average torque during self-vulcanizing 1d is 2.9Nm.
Claims (12)
1, a kind of trigger used for anaerobic adhesive system comprises oxygenant, reductive agent and promotor, counts by weight, comprising:
0～10 part of alkyl hydrogen peroxide (R (OOH) n, n 〉=1),
0～10 part of hydrocarbyl superoxide (R (OO) nR ', n 〉=1 or R '-OO-R-OO-R "),
0.1～3 part of organic replacement hydrazine,
0～0.5 part of tertiary amine,
0.1～4 part of o-benzoic sulfimide,
Wherein R, R ', R " represent various alkyl;
Maximum consumptions are 0 in alkyl hydrogen peroxide, hydrocarbyl superoxide and the tertiary amine.
2, a kind of anaerobic glue that contains initiator described in the right requirement 1 comprises (methyl) acrylate monomer and/or oligomer, initiator, stopper, counts by weight, and its composition comprises:
100 parts of (methyl) acrylate monomer and/or oligomers,
0～10 part of alkyl hydrogen peroxide (R (OOH) n, n 〉=1),
0～10 part of hydrocarbyl superoxide (R (OO) nR ', n 〉=1 or R '-OO-R-OO-R "),
0.1～3 part of organic replacement hydrazine,
0～0.5 part of tertiary amine,
0.1～4 part of o-benzoic sulfimide,
0.005～0.1 part of stopper,
0.005～1.0 part of sequestrant;
Wherein R, R ', R " represent various alkyl,
Maximum consumptions are 0 in alkyl hydrogen peroxide, hydrocarbyl superoxide and the tertiary amine.
3,, it is characterized in that its composition comprises according to the anaerobic glue described in the claim 2:
100 parts of methacrylate monomer and/or oligomers,
0.5～3 part of alkyl hydrogen peroxide (R (OOH) n, n 〉=1),
0.5～4 part of hydrocarbyl superoxide (R (OO) nR ', n 〉=1 or R '-OO-R-OO-R "),
0.1～1 part of organic replacement hydrazine,
0.05～0.5 part of tertiary amine,
0.1～3.2 part of o-benzoic sulfimide,
0.01～0.05 part of stopper,
0.01～0.1 part of sequestrant.
4, according to the anaerobic glue described in the claim 3, it is characterized in that wherein the alkyl hydrogen peroxide is a tertbutyl peroxide, hydrocarbyl superoxide is selected from two cyclohexylidene diperoxy things and 2,5-dimethyl-2,5-(di-tert-butyl peroxide) hexane, organic replacement hydrazine is 1-acetyl-2-phenylhydrazine, and tertiary amine is a tri-n-butylamine.
5,, it is characterized in that described alkyl hydrogen peroxide is selected from tertbutyl peroxide, isopropyl benzene hydroperoxide according to the anaerobic glue described in claim 2 or 3.
6, according to the anaerobic glue described in claim 2 or 3, it is characterized in that described hydrocarbyl superoxide is selected from ditertiary butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-(di-tert-butyl peroxide) hexane, two cyclohexylidene diperoxy things and three cyclohexylidenes, three superoxide.
7,, it is characterized in that described hydrocarbyl superoxide is selected from two cyclohexylidene diperoxy things and three cyclohexylidenes, three superoxide according to the anaerobic glue described in the claim 6.
8,, it is characterized in that described tertiary amine is selected from aliphatic tertiary amine and aromatic nitrile base according to the anaerobic glue described in claim 2 or 3.
9, the anaerobic glue described in according to Claim 8 is characterized in that described tertiary amine is selected from tri-n-butylamine, triethylamine, trolamine and xylidine.
10,, it is characterized in that described stopper is selected from phenols and quinones according to the anaerobic glue described in claim 2 or 3.
11,, it is characterized in that described stopper is selected from Resorcinol, benzoquinones, naphthoquinones and anthraquinone according to the anaerobic glue described in the claim 10.
12,, it is characterized in that described sequestrant is selected from the disodium salt of ethylene dinitrilotetra-acetic acid, trisodium salt and tetra-na salt according to the anaerobic glue described in claim 2 or 3.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011148659A CN1164621C (en) | 2001-06-29 | 2001-06-29 | Trigger used for anaerobic adhesive and its anaerobic adhesive |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011148659A CN1164621C (en) | 2001-06-29 | 2001-06-29 | Trigger used for anaerobic adhesive and its anaerobic adhesive |
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| Publication Number | Publication Date |
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| CN1328103A true CN1328103A (en) | 2001-12-26 |
| CN1164621C CN1164621C (en) | 2004-09-01 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100463924C (en) * | 2006-03-20 | 2009-02-25 | 广州市坚红化工厂 | Anaerobic oxygen rubber initiating agent and anaerobic oxygen rubber having same |
| CN101735734B (en) * | 2008-11-04 | 2012-05-16 | 广东恒大新材料科技有限公司 | Anaerobic adhesive initiator composite and anaerobic adhesive containing initiator |
| CN102703018A (en) * | 2012-05-30 | 2012-10-03 | 朱立超 | Adhesive and preparation method thereof |
| CN107722842A (en) * | 2017-11-07 | 2018-02-23 | 广东三和控股有限公司 | A kind of quick-drying, high stability anaerobic adhesive and preparation method thereof |
| CN111925756A (en) * | 2019-05-13 | 2020-11-13 | 湖州欧美化学有限公司 | Initiator composition for anaerobic adhesive, anaerobic adhesive and preparation method thereof |
-
2001
- 2001-06-29 CN CNB011148659A patent/CN1164621C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100463924C (en) * | 2006-03-20 | 2009-02-25 | 广州市坚红化工厂 | Anaerobic oxygen rubber initiating agent and anaerobic oxygen rubber having same |
| CN101735734B (en) * | 2008-11-04 | 2012-05-16 | 广东恒大新材料科技有限公司 | Anaerobic adhesive initiator composite and anaerobic adhesive containing initiator |
| CN102703018A (en) * | 2012-05-30 | 2012-10-03 | 朱立超 | Adhesive and preparation method thereof |
| CN102703018B (en) * | 2012-05-30 | 2014-06-25 | 朱立超 | Adhesive and preparation method thereof |
| CN107722842A (en) * | 2017-11-07 | 2018-02-23 | 广东三和控股有限公司 | A kind of quick-drying, high stability anaerobic adhesive and preparation method thereof |
| CN111925756A (en) * | 2019-05-13 | 2020-11-13 | 湖州欧美化学有限公司 | Initiator composition for anaerobic adhesive, anaerobic adhesive and preparation method thereof |
| CN111925756B (en) * | 2019-05-13 | 2022-10-21 | 湖州欧美化学有限公司 | Initiator composition for anaerobic adhesive, anaerobic adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1164621C (en) | 2004-09-01 |
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