CN100463924C - Anaerobic oxygen rubber initiating agent and anaerobic oxygen rubber having same - Google Patents
Anaerobic oxygen rubber initiating agent and anaerobic oxygen rubber having same Download PDFInfo
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- CN100463924C CN100463924C CNB2006100344512A CN200610034451A CN100463924C CN 100463924 C CN100463924 C CN 100463924C CN B2006100344512 A CNB2006100344512 A CN B2006100344512A CN 200610034451 A CN200610034451 A CN 200610034451A CN 100463924 C CN100463924 C CN 100463924C
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Abstract
The invention discloses an anaerobic rubber trigger based on tautomeric compound as accelerator, which is composed of peroxidate, tautomeric compound and organic acid, wherein the tautomeric compound and organic acid can be replaced by the compound with tautomeric structure and organic acid group. The invention also relates to anaerobic oxygen rubber with the trigger, wherein the trigger is mixed by acrylate or methyl acrylate monomer and/or oligomer and polymerization inhibitor according to certain proportion.
Description
Technical field
The present invention relates to a kind of initiator, relate to a kind of new anaerobic glue initiator specifically, also relate to the anaerobic glue that contains this initiator.
Background technology
Anaerobism gluing sealing agent is called for short anaerobic glue, is than a kind of gluing and the sealing agent of widespread use in the mechanical industry products production.The composition of anaerobic glue mainly comprises unsaturated monomer (is representative with the methyl acrylic ester), initiator (oxygenant, reductive agent or promotor etc.), stopper and other modification constituents and filler, spices, dyestuff, sequestrant etc.It is liquid that most of anaerobic glue products belong to, and these liquid anaerobic glues are stored in the polyethylene container made with the form of single liquid at ordinary times, are re-introduced into during application in the part that needs gluing or sealing.Owing to lack air (oxygen) in the gap of part, under the effect that the metal of inner initiator of glue and piece surface participates in, anaerobic glue reaches the purpose of gluing and sealing with the mode autopolymerization curing of radical chain reaction.Therefore, anaerobic glue will reach good gluing and sealing effectiveness, and it is one of gordian technique that its initiator is formed.
The initiator of anaerobic glue is a kind of redox (Redox) initiator, has for example just formed redox initiator by superoxide (oxygenant) and transition metal ion (reductive agent).Redox initiator is applied to already and variously carries out polymeric macromolecular material manufacturing processed with radical chain reaction, therefore all among practical application, it forms introducing in detail and discussing of early existing many documents to many kinds of initiator systems that comprise organic or inorganic.But because anaerobic glue is stored and the singularity of application requiring, the energy successful Application is but less relatively to the initiator system of anaerobic glue.Usually the initiator that is applicable to anaerobic glue all is made up of superoxide and promotor.Current more representative trigger used for anaerobic adhesive is formed superoxide-organic replacement hydrazine-asccharin (US4287330,1981.9.1; US 4321349,1982.3.23), and isopropyl benzene hydroperoxy--pyrodin-asccharin for example, superoxide-tertiary amine-asccharin (US 3988299,1976.10.26), and Tolylamine-asccharin of replacing of isopropyl benzene hydroperoxy--dialkyl group for example.The system of isopropyl benzene hydroperoxy-(CHP) wherein-pyrodin (APH)-asccharin particularly, the initiator system that current especially domestic and international anaerobic glue factory more generally uses is used as representational system or is called the system of " standard ".In these initiators, all be superoxide as oxygenant, and use different organic hydrazine classes or amine respectively, and adopt asccharin (o-benzoic sulfimide) as co-accelerator (Co-accelerator) as promotor (Accelerator).In recent years the patent or the research report that also have the alternative compounds of novel promotor or asccharin, for example replaced asccharin to be used for anaerobic glue initiator (US4764239 with the butyl asccharin, 1988.8.16), and use sulfimide and sulfamide compound as promotor (US6958368,2005.10.25), the anaerobic glue initiator that has obtained not contain asccharin is formed.In addition, also there is research to replace the patent report of promotor such as organic replacement hydrazine or tertiary amine in the initiator with new compound, (WO 03078537 for example to substitute original dialkyl Tolylamine with aromatic diamines, 2003.9.25) and with phenylglycocoll (Phenylglycine) and derivative thereof (US 6897277,2005.5.24) as a kind of composition of promotor.
Though tautomeric compound does not have report to serve as the anaerobic glue initiator so far, report is arranged about its redox initiator that is used for polyreaction then the time.For example letex polymerization can be used (Die Makromol.Chem.1209 such as α keto-alcohol, enol, 1947-48) participate in initiation reaction, the redox system that acrylic ester polymerization is used also can be combined (USSR 159023,1963) by the organic acid salt-enolization compound of superoxide-transition metal.
Summary of the invention
The objective of the invention is to utilize tautomeric compound to develop a kind of new anaerobic glue initiator, this initiator can make anaerobic glue solidify rapidly.Another purpose is to develop a kind of anaerobic glue that contains this initiator.
We are oxygenant with a certain proportion of superoxide, and tautomerism compound is a promotor, or adds organic acid again, form a kind of new initiator, and this initiator can make anaerobic glue solidify rapidly.In addition with the integral part of this initiator, mix with a certain proportion of acrylate or methacrylate monomer and/or oligomer and stopper, obtain a kind of anaerobic glue that practical intensity is arranged, thereby realized purpose of the present invention.
Anaerobic glue initiator of the present invention, its essentially consist comprises superoxide and contains the compound of tautomeric structure, according to the mass fraction, by 0.1～10 part of superoxide, 0.1～5 part of tautomerism compound and 0～8 part of composition of organic acid, or tautomerism compound wherein and organic acid are had 0.1～5 part of replacement of compound of tautomeric structure and organic acid group simultaneously by intramolecularly.
The anaerobic glue that contains above-mentioned initiator, it is formed according to the mass fraction, contains 100 parts of acrylate or methacrylate monomer and/or oligomers, 0.1～10 part of superoxide, 0.1～5 part of tautomerism compound, 0.01～0.20 part of 0～8 part of organic acid and stopper.
The anaerobic glue that contains above-mentioned initiator, it is formed according to the mass fraction, preferably contains 100 parts of acrylate or methacrylate monomer and/or oligomers, 0.5～5 part of superoxide, 0.2～3 part of tautomerism compound, 0.01～0.20 part of 0～5 part of organic acid and stopper.
0.1～5 part of replacement of compound that tautomerism compound during above-mentioned anaerobic glue is formed and organic acid can have tautomeric structure and organic acid group simultaneously with intramolecularly, preferably 0.5～3 part.
Described acrylate or methacrylate monomer, oligomer can be polymerisable monomer, the oligomers that many kinds of being widely used in anaerobic glue now contain unsaturated link(age), wherein representational is in the simple function group ester, bifunctional ester, polyfunctional group ester of methacrylic acid one or more, for example methacrylic acid multicondensed ethylene glycol ester, methacrylic acid epoxy ester, polyurethane-type methacrylic ester, methacrylic acid hydroxyethyl ester, hydroxypropyl methacrylate, methacrylic acid trihydroxymethylpropanyl ester, methacrylic acid C
8～C
16Alcohol ester etc.Some double bond containing compounds, unsaturated polyester also can be used as anaerobic glue of the present invention and partly form in addition, for example phthalic acid two propylene esters, vinylbenzene, benzene divinyl, Octyl acrylate, unsaturated polyester etc.Monomer that the present invention is used and oligomer all can be bought from the market, and methacrylic acid triethyleneglycol ester wherein and methacrylate triethyleneglycol ester also can be easily with conventional method preparations.
Described superoxide can be the hydrocarbyl superoxide that contains single or multiple peroxy-OO-, the alkyl hydroperoxy-that contains single or multiple hydroperoxy-base-OOH or peracid that contains CO-OOR or peresters etc., for example benzoyl peroxide, dicumyl peroxide, ditertiary butyl peroxide, 2,5 dimethyl 2, the diperoxy thing of 5 (di-tert-butyl peroxide) hexane, cyclohexylidene or three superoxide etc., benzoyl peroxide preferably, described superoxide all can be bought from the market.
Described tautomerism compound can be the compound that on the α carbon of intramolecularly carbonyl the ketone of hydrogen atom is arranged or contain enol, for example contains CO-CHOH, CO-CH, CO-CH in the molecule
2-CO, the compound of group such as COH=CH or COH=COH, methyl-oxalacetic ester preferably, st-yrax or mda etc., described organic acid can be carboxylic acid or sulfonic compound, trichoroacetic acid(TCA) for example, dichloro acetic acid, Mono Chloro Acetic Acid, methacrylic acid, vinylformic acid, toxilic acid or Phenylsulfonic acid etc., preferably trichoroacetic acid(TCA) or toxilic acid, the compound that described intramolecularly has tautomeric structure and organic acid group simultaneously can be a hydroxyl acrylic, oxyacetic acid or oxaloacetic acid etc., hydroxyl acrylic preferably, methyl-oxalacetic ester wherein can prepare with conventional method, for example the sodium Metal 99.5 silk is added in the solution of oxalic acid diethyl ester and anhydrous diethyl ether, add anhydrous ethyl acetate again, after the sodium dissolving, the mashed prod extracting and the purifying that contain yellow crystal that obtain are obtained, and remaining tautomerism compound and intramolecularly have the compound of tautomeric structure and organic acid group simultaneously and all can buy from the market.
Described stopper can be quinhydrones, quinone, phenols or sulfur-bearing or nitrogen compound, for example Resorcinol, benzoquinones, naphthoquinones, anthraquinone etc., and described stopper all can be bought from the market.
The preparation method who contains the anaerobic glue of above-mentioned initiator is with the dissolving or mix mutually of each component method routinely except the superoxide, adds superoxide at last and prepares.
The anaerobic glue that contains initiator of the present invention, can also add when needing property-modifying additive such as liquid state than macromolecular cpd and superpolymer, reactive thinner, softening agent etc., secondary accelerator is as compound of containing thiol group or benzenesulfonimide etc., sequestrant such as ethylenediamine tetraacetic acid (EDTA) and its esters etc., organic filler such as ethylene waxes and polytetrafluoroethylene powder etc., mineral filler such as white carbon black, titanium dioxide, mica etc., dyestuff, spices etc., whether these components need how much will require on the actual performance of different anaerobic glue products decide, and the affiliation that adds of these components has influence on the consumption that initiator system is formed with consumption.
When the superoxide in the anaerobic glue adopts benzoyl peroxide, adopt st-yrax, oxalyl diethyl ester, mda etc. all to have tangible initiated polymerization for promotor, exist organic acid (particularly trichoroacetic acid(TCA) and toxilic acid) Shi Zegeng that velocity of initiation is had tangible favourable influence, promotor is adopted when having the compound (as hydroxyl acrylic) of tautomerism and carboxylic acid structure simultaneously in the molecule, has tangible initiated polymerization too.
Initiator of the present invention can make anaerobic glue solidify rapidly when using, and the anaerobic glue that obtains has practical intensity, thereby has good practical prospect.
Embodiment
Embodiment 1:
Methacrylic acid triethyleneglycol ester and methacrylate triethyleneglycol ester prepare with conventional laboratory method, methacrylic acid and triglycol with stoichiometric quantity, with toluene is entrainer, adds stopper and make the methacrylic acid triethyleneglycol ester behind esterification, neutralization and vacuum piptonychia benzene.
With methacrylic acid triethyleneglycol ester 100g (containing Resorcinol 0.02g in addition), st-yrax 1g and trichoroacetic acid(TCA) 1g be dissolving and mixing mutually, add benzoyl peroxide 3g then, after mixing, glue divides in the polyethylene bottle of the 100mL that packs into immediately, leave the space (air) of half approximately in the bottle, be experimental group 1.In addition with methacrylic acid triethyleneglycol ester 100g (containing Resorcinol 0.02g in addition), isopropyl benzene hydroperoxy-3g, pyrodin 0.5g, asccharin 1.0g and toxilic acid 1.0g, after mixing, glue divides in the polyethylene bottle of the 100mL that packs into immediately, leaves the space (air) of half approximately in the bottle, be comparative group, it then is the representativeness composition of current application that the initiator of this comparative group is formed.
(room temperature) torsional strenght of (beginning) gel time of the steel test piece of test anaerobic glue and the test of M10 steel bolt.The method of measuring (beginning) gel time of steel test piece is a kind of off-gauge relative test method: with No. 30 steel through the lap shear test piece of sand papering (20mm * 60mm * 2mm).Under the room temperature, drip two, three ends of pressing the glue of specified mix preparation at the test piece faying surface, again another test piece is sticked and compress, the overlap joint area is about 15mm * 20mm, the time of record beginning gel, promptly ought mentioning wherein (under), a slice test piece is to plumbness, and the time of the no longer downward free landing of another test piece of overlap joint is (beginning) gel time of steel test piece.Other tests are tested (overlap joint) shearing resistance in specified set time with material-testing machine for carrying out the bonding back of similar overlap joint; (room temperature) torsional strenght method of measuring the test of M10 steel bolt is similar to MIL-S-46163.Write down the breakdown torque (T that specifies set time
b) and peak torque (T
Max) and average torque (T
p, promptly 1/4 week, 1/2 week, 3/4 week and 1 all places read the mean value of torque value) measured value.The results are shown in Table 1.
The gel time of the anaerobic glue of table 1 experimental group 1 and the anaerobic glue of comparative group and steel bolt torque intensity contrast
Embodiment 2
The prescription of according to the form below 2 is mixed into the anaerobic glue of experimental group 2 to experimental group 10 respectively.
The prescription of each experimental group of table 2
Wherein methyl-oxalacetic ester is synthetic in testing laboratory, 23g sodium Metal 99.5 silk joins in the solution of 146g oxalic acid diethyl ester and 600g anhydrous diethyl ether, slowly add the 88g anhydrous ethyl acetate, after the sodium dissolving, obtain containing the mashed prod of yellow crystal, behind extracting and the purifying yellow liquid, boiling point about 131 ℃ (3.2kPa).Other component is a commercial goods reagent.
Each experimental group is carried out steel test piece test and M10 bolt torque intensity.The results are shown in Table 3.
The gel time of the anaerobic glue of table 3 experimental group 1～10 and steel bolt torque intensity contrast
Embodiment 3:
Prescription by table 4 is mixed into the anaerobic glue of experimental group 11 to experimental group 15.Measure the gel time of each experimental group, the results are shown in Table 4.
The gel effect of the anaerobic glue of table 4 when initiator content is very low
Claims (8)
1. anaerobic glue initiator, its essentially consist comprises superoxide and contains the compound of tautomeric structure, according to the mass fraction, by 0.1～10 part of superoxide, 0.1～5 part of tautomerism compound and 0～8 part of composition of organic acid, or tautomerism compound wherein and organic acid are had 0.1～5 part of replacement of compound of tautomeric structure and organic acid group simultaneously by intramolecularly, described organic acid is carboxylic acid or sulfonic compound, and described tautomerism compound is to contain CO-CHOH, CO-CH in the molecule
2The compound that the compound of-CO, COH=CH or COH=COH group, described intramolecularly have tautomeric structure and organic acid group simultaneously is hydroxyl acrylic, oxyacetic acid or oxaloacetic acid.
2. according to a kind of anaerobic glue initiator of claim 1, it is characterized in that described superoxide is the hydrocarbyl superoxide that contains single or multiple peroxy-OO-, the alkyl hydroperoxy-that contains single or multiple hydroperoxy-base-OOH or peracid that contains CO-OOR or peresters.
3. according to a kind of anaerobic glue initiator of claim 1 or 2, it is characterized in that described superoxide is benzoyl peroxide, dicumyl peroxide, ditertiary butyl peroxide, 2,5 dimethyl 2, the diperoxy thing or three superoxide of 5 (di-tert-butyl peroxide) hexane, cyclohexylidene, described organic acid is trichoroacetic acid(TCA), dichloro acetic acid, Mono Chloro Acetic Acid, methacrylic acid, vinylformic acid, toxilic acid or Phenylsulfonic acid.
4. according to a kind of anaerobic glue initiator of claim 1 or 2, it is characterized in that described superoxide is a benzoyl peroxide, described tautomerism compound is methyl-oxalacetic ester, st-yrax or mda, described organic acid is trichoroacetic acid(TCA) or toxilic acid, and the compound that described intramolecularly has tautomeric structure and organic acid group simultaneously is a hydroxyl acrylic.
5. the anaerobic glue that contains any initiator in the claim 1～4, it is formed according to the mass fraction, contain 100 parts of acrylate or methacrylate monomer and/or oligomers, 0.1～10 part of superoxide, 0.1～5 part of tautomerism compound, 0.01～0.20 part of 0～8 part of organic acid and stopper, or tautomerism compound wherein and organic acid are had 0.1～5 part of replacement of compound of tautomeric structure and organic acid group simultaneously by intramolecularly.
6. according to the anaerobic glue of claim 5, it is characterized in that described superoxide is 0.5～5 part, described tautomerism compound is 0.2～3 part, described organic acid is 0～5 part, described stopper is 0.01～0.20 part, and the compound that described intramolecularly has tautomeric structure and organic acid group simultaneously is 0.5～3 part.
7. according to the anaerobic glue of claim 5 or 6, it is characterized in that described stopper is quinhydrones, quinone, phenols or sulfur-bearing or nitrogen compound.
8. according to the anaerobic glue of claim 5 or 6, it is characterized in that described stopper is Resorcinol, benzoquinones, naphthoquinones or anthraquinone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100344512A CN100463924C (en) | 2006-03-20 | 2006-03-20 | Anaerobic oxygen rubber initiating agent and anaerobic oxygen rubber having same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100344512A CN100463924C (en) | 2006-03-20 | 2006-03-20 | Anaerobic oxygen rubber initiating agent and anaerobic oxygen rubber having same |
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| Publication Number | Publication Date |
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| CN101041700A CN101041700A (en) | 2007-09-26 |
| CN100463924C true CN100463924C (en) | 2009-02-25 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102993990B (en) * | 2012-10-31 | 2014-04-23 | 安徽东方金河精密机械制造有限公司 | Anaerobic adhesive |
| CN109181556B (en) * | 2018-07-20 | 2021-08-31 | 东营咸亨工贸有限公司 | High-temperature-resistant high-pressure-resistant anticorrosive cured sealant and preparation method thereof |
| CN110373115B (en) * | 2019-07-22 | 2022-04-05 | 中国兵器工业第五九研究所 | UV anaerobic sealant suitable for quickly sealing small workpieces |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6210179A (en) * | 1985-07-09 | 1987-01-19 | Nippon Shokubai Kagaku Kogyo Co Ltd | Anaerobic adhesive composition |
| CN1101366A (en) * | 1994-11-07 | 1995-04-12 | 中国科学院广州化学研究所 | Composition of photosensitive polymerizing resin |
| CN1328103A (en) * | 2001-06-29 | 2001-12-26 | 中国科学院广州化学研究所 | Trigger used for anaerobic adhesive and its anaerobic adhesive |
-
2006
- 2006-03-20 CN CNB2006100344512A patent/CN100463924C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6210179A (en) * | 1985-07-09 | 1987-01-19 | Nippon Shokubai Kagaku Kogyo Co Ltd | Anaerobic adhesive composition |
| CN1101366A (en) * | 1994-11-07 | 1995-04-12 | 中国科学院广州化学研究所 | Composition of photosensitive polymerizing resin |
| CN1328103A (en) * | 2001-06-29 | 2001-12-26 | 中国科学院广州化学研究所 | Trigger used for anaerobic adhesive and its anaerobic adhesive |
Non-Patent Citations (2)
| Title |
|---|
| 厌氧胶用复合型氧化还原引发剂. 杨颖泰等.粘结，第24卷第1期. 2003 |
| 厌氧胶用复合型氧化还原引发剂. 杨颖泰等.粘结，第24卷第1期. 2003 * |
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