CN102964516A - Monocomponent epoxide-modified acrylic resin and application thereof - Google Patents
Monocomponent epoxide-modified acrylic resin and application thereof Download PDFInfo
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- CN102964516A CN102964516A CN2012104080519A CN201210408051A CN102964516A CN 102964516 A CN102964516 A CN 102964516A CN 2012104080519 A CN2012104080519 A CN 2012104080519A CN 201210408051 A CN201210408051 A CN 201210408051A CN 102964516 A CN102964516 A CN 102964516A
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- acrylic resin
- antifouling
- resin modified
- component epoxy
- epoxy base
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Abstract
The invention provides a monocomponent epoxide-modified acrylic resin and an application thereof. A characteristic structural formula is shown in the specification, wherein in the formula, R1, R2, R3 is H or CH3; R4 as CH3, CH2CH3, CH2CH2CH3, CH(CH3)2, CH2CH2CH2CH3, CH2CH(CH3)2, C(CH3)3, CH2CH2OH or CH2CH2CH2OH; R5 is CH3, CH2CH3, CH2CH2CH3,CH(CH3)2, CH2CH2CH2CH3, CH2CH(CH3)2, C(CH3)3, CH2CH2OH or CH2CH2CH2OH; m is 1 to 20; and n is 1 to 10000. The resin can be used as a connecting paint for hull antirust and antifouling. The connecting paint resin prepared by the monocomponent epoxide-modified acrylic resin has quite good adhesion intensity to an antirust priming paint and an antifouling finish.
Description
Technical field
The present invention relates to the acrylic resin modified and application of a kind of hull antirust antifouling connection lacquer technology, particularly a kind of single-component epoxy base.
Background technology
The present invention is applied in hull to comprise that a kind of single-component epoxy base of the antirust antifouling connection lacquer usefulness of hull underwater is acrylic resin modified.
Hull comprises that hull underwater coating mainly contains at present rust-inhibiting paint, connects lacquer and antifouling varnish composition.
The rust-inhibiting paint base-material mainly contains bituminous epoxy, chlorinated rubber pitch, chlorinated rubber and Resins, epoxy, because the rust-proof effect of single-component chlorinated rubber rust-inhibiting paint is poor and pitch has the shortcoming of carcinogenesis, thereby replaced by epoxy anti-rust paint gradually, therefore the rust-inhibiting paint base-material is mainly Resins, epoxy at present.
Antifouling finish paint mainly contains the Vinylite of insoluble type and the acrylate resin of chlorinated rubber and solvable type with base-material.Because insoluble type resin runs into seawater and do not dissolve, and the stain control agent in the coating surface is met seawater dissolving release, stays polynuclear plane at coating surface and makes surface irregularity, and incrustation also reduces shipping sail speed easily.And the slow corrosion of seawater is met on the acrylate resin of solvable type surface, constantly exposes new surface, the stripping stain control agent, and making films keeps smooth and didirtresistance.Therefore the antifouling varnish base-material mainly is acrylate resin at present.
Because rust-inhibiting paint is different with antifouling varnish binder resin structure, resin compatible is poor, in use occurs easily the attached power reduction of antifouling varnish, caducous phenomenon on the rust proof paint if antifouling paint directly is coated in.Usually in the middle of rust-inhibiting paint and antifouling varnish, add a transition and be connected lacquer, antirust antifouling varnish effectively is bonded together, in order to avoid the antifouling varnish early fallout.
At present antirust antifouling connection is both at home and abroad coated with lacquer and is mainly contained ethene connection lacquer, and chlorinated rubber connects lacquer, and the epoxy connection is coated with lacquer.Ethene is connected lacquer because binder resin is poorly soluble, and the strong solvent that building-up process is used such as tetracol phenixin etc. have very strong destruction to ozonosphere, bring environmental problem with chlorinated rubber, the adhesion strength to antirust antifouling coating is not high simultaneously, substantially need not at present.It mainly is Resins, epoxy that epoxy connects its binder resin of lacquer, although solved connection coating resins and epoxy rust-proofing primer poor adhesion problem, large with the antifouling top-coat resin textural difference of vinylformic acid, consistency is poor, still is prone to sticking power in the use procedure and reduces phenomenon.No. 4996112 patents of the U.S. have been announced a kind of epoxy organosilicon and connected coating resins, and are better with the antifouling finish paint sticking power of organosilicon, but are not suitable for the antifouling finish paint poor adhesive force of acryllic acid.This project improves the consistency of resin and epoxy rust-proofing primer resin by introducing pendant epoxide groups in the acrylic resin structure compatible with antifouling top-coat resin, improves the adhesion strength to antirust antifouling varnish, to remedy the deficiencies in the prior art.
Summary of the invention
Technical problem to be solved by this invention provides the acrylic resin modified and application of a kind of single-component epoxy base, can be good at solving the consistency that connects lacquer and epoxy rust-proofing primer and the antifouling finish paint of vinylformic acid, improve adhesion strength, prevent that antifouling varnish from adhesion strength in use occurring and descending, even the problem that comes off of antifouling varnish.
For the purpose that realizes solving the problems of the technologies described above, the present invention has adopted following technical scheme:
A kind of single-component epoxy base of the present invention is acrylic resin modified, and its structural formula is:
R in the formula
1, R
2, R
3Be H or CH
3R
4Be CH
3, CH
2CH
3, CH
2CH
2CH
3, CH (CH
3)
2, CH
2CH
2CH
2CH
3, CH
2CH (CH
3)
2, C (CH
3)
3, CH
2CH
2OH or CH
2CH
2CH
2OH; R
5Be CH
3, CH
2CH
3, CH
2CH
2CH
3, CH (CH
3)
2, CH
2CH
2CH
2CH
3, CH
2CH (CH
3)
2, C (CH3)
3, CH
2CH
2OH or CH
2CH
2CH
2OH; M is 1 ~ 20; N is 1 ~ 10000.
Further concrete, the acrylic resin modified oxirane value of single-component epoxy base is at 0.03～0.51eq/100g, and second-order transition temperature (Tg) is controlled at 10～100 ℃, and number-average molecular weight is 1000～100000.
The acrylic resin modified antirust antifouling connection lacquer of hull that can be used as of single-component epoxy base of the present invention is used.The acrylic resin modified mode by roller coat, brushing or spraying of single-component epoxy base is coated with the surface that is contained in rust-inhibiting paint, control wet-film thickness 10～250 μ m.
The acrylic resin modified preparation method of single-component epoxy base of the present invention is: in the 500ml four-hole bottle of agitator, reflux exchanger, constant pressure funnel and thermometer is housed, pass into nitrogen protection during reaction, to avoid the inhibition of oxygen; Four-hole bottle is placed constant temperature oil bath, after adding solvent, be heated to 60～110 ℃ of polymeric reaction temperatures, be added drop-wise in the four-hole bottle uniformly with constant pressure funnel after again (methyl) glycidyl acrylate, methacrylic ester and other acrylate monomer and initiator mixture being dissolved mutually.Drip 1～5h, after dropwising, continue insulation 3～8h, to improve transformation efficiency, make the basic complete reaction of monomer in the bottle, until reaction finishes.
By adopting technique scheme, the present invention has following beneficial effect:
The antirust antifouling connection lacquer of the hull of the acrylic resin modified preparation of a kind of single-component epoxy base of the present invention, with reference to national standard " paint and varnish pulls open the method adhesion test " (GB/T 5210-2006), its dry state sticking power is tested, and connecting coating resins has good adhesion strength to rust-proofing primer and antifouling finish paint.
Description of drawings
Fig. 1 is the polymkeric substance infrared spectrogram.
2996 cm in the infrared spectrogram of polymkeric substance
-1With 2950 cm
-1The absorption peak at place is respectively CH
3And CH
2The C-H stretching vibration; Wave number 1449 cm
-1The place is for C-H(methyl or methylene radical) flexural vibration, wave number 990 cm
-1The place is the characteristic peak of butyl ester; Wave number 1731 cm
-1The absorption peak at place is the characteristic peak (O=C-O) of ester group, wave number 1148 cm
-1, 1239 cm
-1Be the stretching vibration of C-O-C, the absorption peak at this two place has proved the existence of ester bond in the polyacrylate resin; Wave number 909 cm
-1With 843 cm
-1What locate is the absorption peak of epoxy group(ing), proves that the epoxide group monomer has been copolymerized on the resin backbone.
Embodiment
Below in conjunction with embodiment and accompanying drawing this patent is further explained.But the protection domain of this patent is not limited to concrete embodiment.
Embodiment 1
Polyreaction is to carry out in the 500ml four-hole bottle of agitator, reflux exchanger, constant pressure funnel and thermometer is housed, and passes into nitrogen protection during reaction, to avoid the inhibition of oxygen.Four-hole bottle is placed constant temperature oil bath, after adding the toluene solvant of 100g, be heated to 70 ℃ of polymeric reaction temperatures, be added drop-wise in the four-hole bottle uniformly with constant pressure funnel after again methyl methacrylate 40g, butyl acrylate 30g, glycidyl methacrylate 20g, hydroxyethyl methylacrylate 10g and initiator (AIBN) 3g mixture being dissolved mutually.Drip 2h, after dropwising, continue insulation 7h, to improve transformation efficiency, make the basic complete reaction of monomer in the bottle, until reaction finishes.
The acrylic resin modified polymkeric substance infrared spectrogram of single-component epoxy base is seen Fig. 1.
Embodiment 2
Polyreaction is to carry out in the 500ml four-hole bottle of agitator, reflux exchanger, constant pressure funnel and thermometer is housed, and passes into nitrogen protection during reaction, to avoid the inhibition of oxygen.Four-hole bottle is placed constant temperature oil bath, after adding the xylene solvent of 100g, be heated to 80 ℃ of polymeric reaction temperatures, be added drop-wise in the four-hole bottle uniformly with constant pressure funnel after the mixture dissolving with methyl methacrylate 40g, butyl methacrylate 30g, glycidyl methacrylate 20g, Rocryl 410 10g and initiator Diisopropyl azodicarboxylate (AIBN) 3g again.Drip 3h, after dropwising, continue insulation 6h, to improve transformation efficiency, make the basic complete reaction of monomer in the bottle, until reaction finishes.
Embodiment 3
Polyreaction is to carry out in the 500ml four-hole bottle of agitator, reflux exchanger, constant pressure funnel and thermometer is housed, and passes into nitrogen protection during reaction, to avoid the inhibition of oxygen.Four-hole bottle is placed constant temperature oil bath, after adding the N-BUTYL ACETATE solvent of 100g, be heated to 90 ℃ of polymeric reaction temperatures, be added drop-wise in the four-hole bottle uniformly with constant pressure funnel after the mixture dissolving with methyl methacrylate 40g, butyl methacrylate 30g, glycidyl methacrylate 20g, Rocryl 410 10g and initiator benzoyl peroxide (BPO) 3g again.Drip 5h, after dropwising, continue insulation 3h, to improve transformation efficiency, make the basic complete reaction of monomer in the bottle, until reaction finishes.
With reference to national standard " paint and varnish pulls open the method adhesion test " (GB/T 5210-2006), its dry state sticking power to be tested, experimental result sees Table 1, shows that connecting coating resins has good adhesion strength to rust-proofing primer and antifouling finish paint.
The embodiment coating system is according to the following steps preparation specifically: the thick epoxy rust-proofing primer (725-H44-61) of application one deck 200～250 μ m on steel plate at first, the acrylic resin modified resin of application epoxy group(ing) after 7 days, connecting application antifouling varnish (725-AFB2) on the coating resins in 7 days, then room temperature is placed and is carried out respectively the coating adhesion test after 7 days.
Now use antirust antifouling connection coating resins and embodiment effect comparison result such as table 1:
Table 1 coating system adhesion results
Claims (4)
1. a single-component epoxy base is acrylic resin modified, it is characterized in that: its structural formula is:
R in the formula
1, R
2, R
3Be H or CH
3R
4Be CH
3, CH
2CH
3, CH
2CH
2CH
3, CH (CH
3)
2, CH
2CH
2CH
2CH
3, CH
2CH (CH
3)
2, C (CH
3)
3, CH
2CH
2OH or CH
2CH
2CH
2OH; R
5Be CH
3, CH
2CH
3, CH
2CH
2CH
3, CH (CH
3)
2, CH
2CH
2CH
2CH
3, CH
2CH (CH
3)
2, C (CH3)
3, CH
2CH
2OH or CH
2CH
2CH
2OH; M is 1 ~ 20; N is 1 ~ 10000.
2. described single-component epoxy base is acrylic resin modified according to claim 1, it is characterized in that: the acrylic resin modified oxirane value of described single-component epoxy base is at 0.03～0.51eq/100g, second-order transition temperature (Tg) is controlled at 10～100 ℃, and number-average molecular weight is 1000～100000.
3. acrylic resin modified application as the antirust antifouling connection lacquer of hull of the described single-component epoxy base of claim 1.
4. according to claim 1 described application is characterized in that: the acrylic resin modified mode by roller coat, brushing or spraying of described single-component epoxy base is coated with the surface that is contained in rust-inhibiting paint, control wet-film thickness 10～250 μ m.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210408051.9A CN102964516B (en) | 2012-10-24 | 2012-10-24 | Monocomponent epoxide-modified acrylic resin and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210408051.9A CN102964516B (en) | 2012-10-24 | 2012-10-24 | Monocomponent epoxide-modified acrylic resin and application thereof |
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|---|---|
| CN102964516A true CN102964516A (en) | 2013-03-13 |
| CN102964516B CN102964516B (en) | 2015-06-24 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103674636A (en) * | 2013-09-11 | 2014-03-26 | 中国船舶重工集团公司第七二五研究所 | Detection method of epoxy/acrylic acid connecting paint gradient components |
| CN104046211A (en) * | 2013-04-25 | 2014-09-17 | 中国船舶重工集团公司第七二五研究所 | Epoxy modified acrylic resin gradient connection paint and preparation method thereof |
| CN105017914A (en) * | 2015-07-21 | 2015-11-04 | 厦门双瑞船舶涂料有限公司 | Method for preparing connection paint from rosin-modified acrylate |
| CN110724436A (en) * | 2019-10-24 | 2020-01-24 | 厦门双瑞船舶涂料有限公司 | Epoxy grafted acrylate self-layering connecting paint and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0846739A2 (en) * | 1996-12-05 | 1998-06-10 | Kansai Paint Co., Ltd. | Coating composition and method for application thereof |
| CN102030861A (en) * | 2010-11-09 | 2011-04-27 | 长春工业大学 | Method for preparing epoxy functional acrylate polymer |
| CN102050909A (en) * | 2009-10-28 | 2011-05-11 | 东丽纤维研究所（中国）有限公司 | Functionalized polymer and preparation method thereof |
-
2012
- 2012-10-24 CN CN201210408051.9A patent/CN102964516B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0846739A2 (en) * | 1996-12-05 | 1998-06-10 | Kansai Paint Co., Ltd. | Coating composition and method for application thereof |
| CN102050909A (en) * | 2009-10-28 | 2011-05-11 | 东丽纤维研究所（中国）有限公司 | Functionalized polymer and preparation method thereof |
| CN102030861A (en) * | 2010-11-09 | 2011-04-27 | 长春工业大学 | Method for preparing epoxy functional acrylate polymer |
Non-Patent Citations (2)
| Title |
|---|
| 王健等: "《防腐蚀涂料与涂装工》", 30 April 2006, article ""三 船舶防污漆"", pages: 98-100 * |
| 袁媛等: ""分散聚合法制备粉末涂料用丙烯酸酯树脂"", 《高分子材料科学与工程》, vol. 25, no. 5, 31 May 2009 (2009-05-31), pages 15 - 18 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104046211A (en) * | 2013-04-25 | 2014-09-17 | 中国船舶重工集团公司第七二五研究所 | Epoxy modified acrylic resin gradient connection paint and preparation method thereof |
| CN103674636A (en) * | 2013-09-11 | 2014-03-26 | 中国船舶重工集团公司第七二五研究所 | Detection method of epoxy/acrylic acid connecting paint gradient components |
| CN103674636B (en) * | 2013-09-11 | 2016-08-10 | 中国船舶重工集团公司第七二五研究所 | A kind of epoxy/acrylic acid connects the detection method of paint gradient composition |
| CN105017914A (en) * | 2015-07-21 | 2015-11-04 | 厦门双瑞船舶涂料有限公司 | Method for preparing connection paint from rosin-modified acrylate |
| CN105017914B (en) * | 2015-07-21 | 2017-03-22 | 厦门双瑞船舶涂料有限公司 | Method for preparing connection paint from rosin-modified acrylate |
| CN110724436A (en) * | 2019-10-24 | 2020-01-24 | 厦门双瑞船舶涂料有限公司 | Epoxy grafted acrylate self-layering connecting paint and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN102964516B (en) | 2015-06-24 |
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