CN1101366A - Composition of photosensitive polymerizing resin - Google Patents
Composition of photosensitive polymerizing resin Download PDFInfo
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- CN1101366A CN1101366A CN 94113864 CN94113864A CN1101366A CN 1101366 A CN1101366 A CN 1101366A CN 94113864 CN94113864 CN 94113864 CN 94113864 A CN94113864 A CN 94113864A CN 1101366 A CN1101366 A CN 1101366A
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- ether
- methyl
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- Macromonomer-Based Addition Polymer (AREA)
Abstract
The resin has photosensitive trigger action, can take part in polymerization and is suitable for photosensitive anaerobic adhesive. The photosensitive adhesive and photosenstive anaerobic adhesive are generally made of (methyl) acrylic resin and photosensitizer. A resin has both benzoin ether radial (photosensitivity) and (methyl) acrylyl radial (polymerizability) in its molecule.
Description
Photosensitivity tackiness agent (abbreviation light-sensitive emulsion) is with its quick solidifying, solvent-free, single-component, need not heat, save the energy and be suitable for advantage such as automation application and obtain to develop rapidly, meanwhile, anaerobism tackiness agent (abbreviation anaerobic glue) is as the important industrial tackiness agent of a class, be widely used in the locking of part in the engineering goods, sealing and bonding, anaerobic glue with photosensitivity also early there is report and uses, yet the composition of light-sensitive emulsion or photosensitivity anaerobic glue generally all adds photoinitiator more in addition by various (methyl) acrylate that participate in Raolical polymerizable and is formed, photoinitiator causes (methyl) acrylic ester polymerization when illumination, and just photoinitiator and polymerisable monomer are two other components of branch.Attempt photosensitivity and polymerizability be combined in the exploration in a part bibliographical information was once arranged, 593 pages of Japan's " technical chemistry magazine " 1967 70 volumes are disclosed be with st-yrax with the acrylate chloride reaction with among the st-yrax group introducing acrylate, make vinylformic acid benzoin ester resin, structural formula is:
This resin has photo sensitized initiation simultaneously and participates in the function of polyreaction.Can be applied in (DE 2743979,1979.) on the sealing tape.
The objective of the invention is to attempt to find the resin that has photo sensitized initiation simultaneously and participate in the polyreaction function, made higher photosensitive active photosensitivity anaerobic glue.
Because the photo sensitized initiation of st-yrax compound is to be cracked into free radical by Norrish I type mechanism, the substituting group relation is very big on its activity and the alpha-carbon atom, for making the st-yrax compound that higher photosensitive activity be arranged, the stronger electronics substituent of giving should be arranged on alpha-carbon atom, according to this viewpoint, there is benzoin ether higher photosensitive activity to be arranged on the alpha-carbon atom than st-yrax to the electronics base.The present invention is when preparation photosensitivity anaerobic glue, adopt a kind of resin that has benzoin ether unit structure (photosensitivity) and (methyl) acrylic acid groups (polymerizable and anaerobism) at intramolecularly, its intramolecularly has the photo sensitized initiation group simultaneously and participates in the unsaturated double-bond group of Raolical polymerizable, can be used as photosensitivity initiator and polymerizing resin and use, the chemical structure of this resin is:
In the formula: R
1Be hydrogen or methyl, R
2Be C
1～C
4Alkyl, n=1～3(preferred value n=1), X is that the group of various chemical structures also can be vacancy, the alpha-carbon atom of benzoin ether can link to each other with (methyl) acryloyl group etc. by alkyl in the molecule.
The preparation of this structural resin can be adopted dual mode:
(1) .(methyl) reactant of acryl and bifunctional active reaction thing (X part in the molecule) and α hydroxyalkyl benzoin ether prepared in reaction get.
(2). adopt (methyl) acrylate chloride and α hydroxyalkyl benzoin ether prepared in reaction (this moment, the X part did not exist).
Can participate in polymer-based group is acryloyl or methacryloyl; can use hydroxyl ethyl ester, hydroxypropyl acrylate, multicondensed ethylene glycol base ester or the acyl chlorides of acrylic or methacrylic acid as reactant; the photosensitivity initiating group is a α hydroxyalkyl benzoin ether group; can participate in reacting and obtaining as reactant with various α hydroxyalkyl benzoin ethers; wherein hydroxyalkyl can be methylol, hydroxyethyl (n equals 0 as with hydroxyl the time), and ether is methyl ether, ether, isopropyl ether etc.With (1) method is example; polymerizable group can adopt acryloyl or methacryloyl; in order there to be bigger anaerobism should adopt methacryloyl, can use (methyl) acrylic acid hydroxyl ester, be reaction raw materials as hydroxyl ethyl ester, hydroxypropyl acrylate and multicondensed ethylene glycol ester etc.But X partly is the polyfunctional group reactant in the molecule, as toluene di-isocyanate (T (TDI), two isocyanic acid ditans (MDI), diisocyanato-Hexane (HDI) or the like vulcabond is reaction raw materials, in order to obtain higher photosensitive activity, the benzoin ether that the benzoin ether group should adopt the α hydroxyalkyl to replace is a reaction raw materials, wherein hydroxyalkyl is methylol, hydroxyethyl etc., and ether is methyl ether, ether, isopropyl ether or the like.Be applied to carry out in the anaerobic glue above-mentioned resin photosensitive and the curing performance test, wherein the anaerobic glue performance test is: test under room temperature (23 ± 2 ℃) with M10 steel bolt and nut, after the gluing assembling, placing and solidify, is the set time when reaching with pointing the stubborn motionless time.At the appointed time carry out the torsional strenght test, survey the breakdown torque of different set times and on average ease out moment of torsion (mean value of 1/4,1/2,3/4,1 all places moment of torsion reading).Stability test is that the 10ml high-pressure polyethylene bottle that about 5ml glue is housed is deposited in 80 ℃ of baking ovens, checks that the time that gel appears in glue represents stability.
Embodiment one:
This example is synthetic for the acrylate that contains the benzoin methyl ether structure.Take by weighing α methylol benzoin methyl ether 20.5g, toluene 13g, dibutyl tin laurate 0.02g is in reaction flask, under logical nitrogen atmosphere, add toluene di-isocyanate (T (80/20) 16.0g,, add Propylene glycol monoacrylate 41.6g again in 90～95 ℃ of reactions three hours, in 80 ℃ of reactions, moments later add Resorcinol 0.01g, 80 ℃ of coreactions three hours, underpressure distillation was sloughed toluene and is promptly got resin.
Embodiment two:
This example is that photosensitive polymerizing resin of the present invention should be as the test of photosensitivity anaerobic glue.
This example adopts practical locking to test with the methacrylic ester anaerobic glue.The anaerobic glue trade mark is " 250 ", and it consists of by containing 40 parts of weights of double methyl methacrylate triethylene glycol ester, and 60 parts of weights of methacrylate E-44 Resins, epoxy (bisphenol A-type) ester reach an amount of institute of redox initiator and stablizer and are mixed with.To add the acrylate that contains the benzoin ether structure (the being called for short BEA down) 0.01mol/L for preparing by embodiment one again for anaerobic glue " 250 " in the same old way.Uv irradiation uses 1000W ultraviolet lamp (power density 80W/cm) apart from 14cm.Test-results is: anaerobic glue keeps original anaerobism solidified curing speed and good mechanical strength performance after adding BEA.After the UV irradiation, to harden (and " 250 " the glue surface that does not add BEA is unhardened) at the lip-deep unnecessary glue of bolt, the set time shortens and has accelerated curing speed and had excellent mechanical intensity.In addition, add anaerobic gelatin behind the photosensitive resin of the present invention under lucifuge 80 ℃ gel does not take place through 1 hour, test again with this glue that heated, still keep good curing speed and physical strength, stability better (seeing Table 1) is described.(methyl) acrylate that contains the benzoin ether structure of the present invention has photo sensitized initiation and can participate in the polymeric performance and can be used for forming the photosensitivity anaerobic glue.
Table 1 adds the influence of BEA to anaerobic glue
Annotate: Tb=breakdown torque, Tp=on average ease out moment of torsion.UV lamp 1000W is apart from 14cm.
Claims (4)
1, a kind of photosensitive polymerizing resin that is used for the photosensitivity anaerobic adhesive.Have the photo sensitized initiation group in its molecule simultaneously and participate in the Raolical polymerizable group; it is characterized in that the photosensitivity initiating group is a α hydroxyalkyl benzoin ether group; participating in polymer-based group is acryloyl or methacryloyl; the alpha-carbon atom of benzoin ether can link to each other with (methyl) acryloyl group by alkyl in the molecule, and chemical structural formula is
In the formula: R
1Be hydrogen or methyl;
R
2Be C
1～C
4Alkyl;
n=1～3；
X is the group or the vacancy of various chemical structures.
2, according to the resin described in the claim 1, it is characterized in that participating in polymer-based group, can obtain as reactant with the hydroxyethyl of acrylic or methacrylic acid, hydroxypropyl, multicondensed ethylene glycol base ester etc. or acyl chlorides.
3, according to the resin described in the claim 1, it is characterized in that the photosensitivity initiating group, can obtain as reactant with various α hydroxyalkyl benzoin ethers, wherein hydroxyalkyl can be methylol, hydroxyethyl etc., and ether is methyl ether, ether and isopropyl ether etc.
4,, it is characterized in that the n value in the described chemical structural formula equals 1 according to the resin described in the claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94113864A CN1045981C (en) | 1994-11-07 | 1994-11-07 | Composition of photosensitive polymerizing resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94113864A CN1045981C (en) | 1994-11-07 | 1994-11-07 | Composition of photosensitive polymerizing resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1101366A true CN1101366A (en) | 1995-04-12 |
| CN1045981C CN1045981C (en) | 1999-10-27 |
Family
ID=5036856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94113864A Expired - Fee Related CN1045981C (en) | 1994-11-07 | 1994-11-07 | Composition of photosensitive polymerizing resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1045981C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057787C (en) * | 1996-11-15 | 2000-10-25 | 北京市天山新材料技术公司 | Anaerobic glue and preparation method |
| 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 |
| CN101897650B (en) * | 2009-05-31 | 2013-05-08 | 北京实德隆科技发展有限公司 | Double-curing fiber post resin adhesive and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2743979C3 (en) * | 1977-09-30 | 1981-09-10 | Beiersdorf Ag, 2000 Hamburg | Process for the production of products coated with a self-adhesive composition based on crosslinked polyacrylic acid derivatives |
| JPS60146233A (en) * | 1984-01-10 | 1985-08-01 | Asahi Chem Ind Co Ltd | Novel photopolymerizable composition |
-
1994
- 1994-11-07 CN CN94113864A patent/CN1045981C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057787C (en) * | 1996-11-15 | 2000-10-25 | 北京市天山新材料技术公司 | Anaerobic glue and preparation method |
| 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 |
| CN101897650B (en) * | 2009-05-31 | 2013-05-08 | 北京实德隆科技发展有限公司 | Double-curing fiber post resin adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1045981C (en) | 1999-10-27 |
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