CN101538345A - Dendritic hyper-branched polymer, preparation method and application thereof - Google Patents
Dendritic hyper-branched polymer, preparation method and application thereof Download PDFInfo
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- CN101538345A CN101538345A CN200910045779A CN200910045779A CN101538345A CN 101538345 A CN101538345 A CN 101538345A CN 200910045779 A CN200910045779 A CN 200910045779A CN 200910045779 A CN200910045779 A CN 200910045779A CN 101538345 A CN101538345 A CN 101538345A
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Abstract
The invention discloses a dendritic hyper-branched polymer, a preparation method and application thereof. The homo-polymerized or co-polymerized dendritic hyper-branched polymer is obtained by taking poly-alkenyl monomers or poly-alkenyl monomers and mono-alkenyl monomers as raw materials to carry out polymerization in the presence of radical initiator and chain transfer agent. The invention comprises the following components by the weight percentage: 69% to 92% of poly-alkenyl monomers or poly-alkenyl monomers and mono-alkenyl monomers, 0.05% to 2% of radical initiator and 7% to 30% of chain transfer agent. In the invention, the monomer conversion rate of polymers is 40% to 90%, and the number average molecular weight of polymers is 2,000 to 6,000. Compared with the prior art, the invention has the advantages of various material sources, high product branching coefficient and short production period, therefore, the invention is applicable to industrialized production on a large scale. The photo-curable coatings which are obtained by mixing the dendritic hyper-branched polymer of the invention, photo initiator and photo-initiation additive are applicable to coil coatings, board coatings, and film coatings for electronic products.
Description
Technical field
The present invention relates to a kind of dendritic hyper-branched polymer, Preparation method and use.
Background technology
Have highly branched structure, this polymkeric substance is difficult to crystallization, and no chain twines, and shows good solubility and low solution viscosity.The dendritic hyper-branched polymer molecular surface contains a large amount of terminal group functional group, makes it can mix the back with light trigger, light-initiated auxiliary agent as photo-cured coating, is used for the coil lacquer, the lacquer of filming of plank lacquer and electronic product.
In the prior art, U.S. Pat 6,713,584B1 has reported a kind of synthetic method of branched polymer,, carry out copolyreaction with a kind of polyfunctional group vinyl monomer and conventional vinyl monomer by traditional radical polymerization and obtain target product as chain-transfer agent with mercaptan.But in this method, the consumption of polyfunctional group vinyl monomer is limited (ratio is less than 50%), otherwise polymerisate can be cross-linked to form gel.The multipolymer degree of branching that this method obtains is not high, and the carbon-carbon double bond content in the multipolymer is few, and curing speed is slow.Still the bibliographical information that does not have at present the high branching homopolymer that contains a large amount of unsaturated double-bonds.
Summary of the invention
The technical problem that the present invention solves provides a kind of preparation method of dendritic hyper-branched polymer, promptly in polymerization process, strengthen inactivation by chain transfer reaction, the radically homo or the copolyreaction of control polyfunctional group vinyl monomer, acquisition has the hyper branched polymer of dendritic structure.To overcome the not high shortcoming of the degree of branching in the prior art.
Technical conceive of the present invention is such: with polyene-based monomer or polyene-based monomer and mono alkenyl monomer is raw material, carries out polymerization in the presence of radical initiator, chain-transfer agent, obtains the dendritic hyper-branched polymer of homopolymerization or copolymerization.
Component of the present invention and weight percentage comprise polyene-based monomer or polyene-based monomer and mono alkenyl monomer: 69-92%, initiator: 0.05-2%, chain-transfer agent: 7-30%.
Method of the present invention comprises the steps:
Homopolymerization:, in the presence of toluene solvant, radical initiator Diisopropyl azodicarboxylate and chain-transfer agent,, obtain containing the high branching homopolymer of two keys at 60-80 ℃ of following homopolymerization 1-5 hour with the polyene-based monomer.
Copolymerization:, in the presence of radical initiator Diisopropyl azodicarboxylate and chain-transfer agent,, obtain containing the high branched copolymers of two keys at 60-80 ℃ of following copolyreaction 1-5 hour with multiple polyene-based monomer and mono alkenyl monomer.
According to the present invention, said polyene-based monomer is a kind of in dimethacrylate, diacrylate, the Vinylstyrene; Said mono alkenyl monomer is a kind of in butyl acrylate, Ethyl acrylate, the Isooctyl acrylate monomer; The volume ratio of monomeric quality of homopolymerization polyene-based and toluene solvant is 1: 0-2.5, g/ml.
The said chain-transfer agent of the present invention is a kind of in butanethiol, positive Dodecyl Mercaptan and the tert-dodecyl mercaptan, the add-on of Quality Initiative transfer agent, can obtain the monomeric high branching homopolymer of polyene-based, obtain dendritic hyper-branched polymer by radical polymerization, in copolyreaction with the monomeric ratio of polyene-based greater than 50%, improved the degree of branching of multipolymer greatly.By suitable control, effectively avoid the appearance of gel in the polyreaction for level of response.
The dendritic hyper-branched polymer that preparation method of the present invention obtains mixes as photo-cured coating with light trigger, light-initiated auxiliary agent, can be used for the coil lacquer, the lacquer of filming of plank lacquer and electronic product.
The dendritic hyper-branched polymer monomer conversion that obtains with preparation method of the present invention is 40-90%.Use gpc analysis, polymkeric substance number-average molecular weight Mn is 2000-6000, identifies the structure of product with the method for nucleus magnetic resonance (NMR).
The present invention's beneficial effect compared with prior art:
1. method polyene-based monomer of the present invention can homopolymerization, also can polyene-based monomer and mono alkenyl monomer copolymerization, and the monomeric ratio of polyene-based can surpass 50%, the degree of branching height of product during copolymerization;
2. method chain-transfer agent wide material sources of the present invention can be sulfur alcohol compounds, also can use the free radical chain transfer agent, or the catalytic type chain-transfer agent;
3. method mild condition of the present invention, easy and simple to handle, with short production cycle, be suitable for large-scale industrial production.
4. the more similar non-high branched substances of dendritic hyper-branched polymer that obtains of the present invention has better laser curing velocity, improves curing of coating efficient greatly.
Embodiment
The invention will be further elaborated below by embodiment, its objective is to understand the present invention ground content better, but protection scope of the present invention is not subjected to the restriction of embodiment.
Embodiment 1
In the reactor that has stirring, heating, thermometer, add 10g ethylene glycol dimethacrylate (EGDMA) respectively, 15ml toluene, 0.2g Diisopropyl azodicarboxylate (AIBN), the 2g butanethiol, heat temperature raising when stirring keeps 65 ℃ of reactions of temperature 2.5hr, obtains heavy-gravity polyethylene glycol dimethacrylate (poly-EGDMA) solution 23g, recording monomer conversion with the precipitator method is 90%, gpc analysis Mn=5650.
Embodiment 2
In the reactor that has stirring, heating, thermometer, add 104g Vinylstyrene (DVB) respectively, 2.08g Diisopropyl azodicarboxylate (AIBN), 8.08g lauryl mercaptan, 2hr, obtain heavy-gravity polydivinylbenezene (poly-DVB) solution 114g, recording monomer conversion with the precipitator method is 44%, gpc analysis Mn=3807.
Embodiment 3
In the reactor that has stirring, heating, thermometer, add 104g Vinylstyrene (DVB) respectively, 1.04g Diisopropyl azodicarboxylate (AIBN), 8.08g lauryl mercaptan, heat temperature raising when stirring, keep 70 ℃ of reactions of temperature 3hr, obtain heavy-gravity polydivinylbenezene (poly-DVB) solution 113g, recording monomeric transformation efficiency with the precipitator method is 56%, gpc analysis Mn=4875.
Embodiment 4
In the reactor that has stirring, heating, thermometer, add the 108g molecular weight respectively and be the oligopolymer (PEGDA-200) of 200 glycol diacrylate, 1.0g Diisopropyl azodicarboxylate (AIBN), the 21g lauryl mercaptan, heat temperature raising when stirring, keep 65 ℃ of reactions of temperature 2hr, obtain heavy-gravity (poly-EGDMA) solution 130g, recording monomeric transformation efficiency with the precipitator method is 50%, gpc analysis, Mn=2060.
Embodiment 5
In the reactor that has stirring, heating, thermometer, add the 60g molecular weight respectively and be the oligopolymer (PEGDA-200) of 200 glycol diacrylate, 40g Isooctyl acrylate monomer (EHA), 0.1g Diisopropyl azodicarboxylate (AIBN), the 36g lauryl mercaptan, heat temperature raising when stirring keeps 65 ℃ of reactions of temperature 3.5hr, obtains heavy-gravity (poly-EGDMA-co-EHA) solution 136g, recording monomeric transformation efficiency with the precipitator method is 41%, gpc analysis Mn=3520.
Claims (7)
1. a dendritic hyper-branched polymer is characterized in that, comprises following component, and its content is in weight percentage:
Polyene-based monomer or polyene-based monomer and mono alkenyl monomer 69-92%;
Initiator 0.05-2%;
Chain-transfer agent 7-30%.
2. dendritic hyper-branched polymer according to claim 1 is characterized in that, the polyene-based monomer is a dimethacrylate; A kind of in diacrylate, the Vinylstyrene.
3. dendritic hyper-branched polymer according to claim 1 is characterized in that, the mono alkenyl monomer is a kind of in butyl acrylate, Ethyl acrylate, the Octyl acrylate.
4. dendritic hyper-branched polymer according to claim 1 is characterized in that, chain-transfer agent is a kind of in butanethiol, positive Dodecyl Mercaptan, the tert-dodecyl mercaptan.
5. the preparation method of the described dendritic hyper-branched polymer of claim 1 is characterized in that, comprises the steps:
Homopolymerization: with the polyene-based monomer, in the presence of toluene solvant, radical initiator Diisopropyl azodicarboxylate and chain-transfer agent, under 60-80 ℃, carry out 1-5 hour homopolymerization, obtain containing the high branching homopolymer of two keys;
Copolymerization: with multiple polyene-based monomer and mono alkenyl monomer, in the presence of radical initiator Diisopropyl azodicarboxylate and chain-transfer agent, under 40-80 ℃, carry out 1-5 hour copolyreaction, obtain containing the high branched copolymers of two keys.
6. dendritic hyper-branched polymer according to claim 5 is characterized in that, the volume ratio of monomeric quality of homopolymerization polyene-based and toluene solvant is 1: 0-2.5, g/ml.
7. the purposes of the described dendritic hyper-branched polymer of claim 1 is mixed as photo-cured coating with light trigger, light-initiated auxiliary agent, at preparation coil lacquer, and the application in the lacquer of filming of plank lacquer and electronic product.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153354A (en) * | 2015-10-18 | 2015-12-16 | 长春工业大学 | Preparation method of highly-branched polymer |
| CN106479333A (en) * | 2016-10-09 | 2017-03-08 | 华南理工大学 | A kind of ultraviolet light polymerization hybrid super-hydrophilic coating and preparation method thereof |
| WO2018197884A1 (en) * | 2017-04-26 | 2018-11-01 | The University Of Liverpool | Polymers |
| CN109535967A (en) * | 2018-11-14 | 2019-03-29 | 常州大学 | A kind of preparation method of environment-friendly type high impact resistance coating |
| CN110662772A (en) * | 2017-04-26 | 2020-01-07 | 利物浦大学 | Branched polymers |
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| CN1292805A (en) * | 1998-03-12 | 2001-04-25 | 伊尼奥斯丙烯酸英国有限公司 | Polymer composition |
| US20060116492A1 (en) * | 2004-12-01 | 2006-06-01 | 3M Innovative Properties Company | Branched polymer |
| US20060116476A1 (en) * | 2004-12-01 | 2006-06-01 | 3M Innovative Properties Company | Hybrid thermosetting composition |
| EP1940884A1 (en) * | 2005-10-07 | 2008-07-09 | E.I.Du pont de nemours and company | High temperature polymerization process for making branched acrylic polymers, caprolactone-modified branched acrylic polymers, and uses thereof |
| CN101415733A (en) * | 2006-04-06 | 2009-04-22 | 巴斯夫欧洲公司 | Process for preparing an aqueous polymer dispersion |
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2009
- 2009-02-05 CN CN200910045779A patent/CN101538345A/en active Pending
Patent Citations (5)
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| CN1292805A (en) * | 1998-03-12 | 2001-04-25 | 伊尼奥斯丙烯酸英国有限公司 | Polymer composition |
| US20060116492A1 (en) * | 2004-12-01 | 2006-06-01 | 3M Innovative Properties Company | Branched polymer |
| US20060116476A1 (en) * | 2004-12-01 | 2006-06-01 | 3M Innovative Properties Company | Hybrid thermosetting composition |
| EP1940884A1 (en) * | 2005-10-07 | 2008-07-09 | E.I.Du pont de nemours and company | High temperature polymerization process for making branched acrylic polymers, caprolactone-modified branched acrylic polymers, and uses thereof |
| CN101415733A (en) * | 2006-04-06 | 2009-04-22 | 巴斯夫欧洲公司 | Process for preparing an aqueous polymer dispersion |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153354A (en) * | 2015-10-18 | 2015-12-16 | 长春工业大学 | Preparation method of highly-branched polymer |
| CN106479333A (en) * | 2016-10-09 | 2017-03-08 | 华南理工大学 | A kind of ultraviolet light polymerization hybrid super-hydrophilic coating and preparation method thereof |
| WO2018197884A1 (en) * | 2017-04-26 | 2018-11-01 | The University Of Liverpool | Polymers |
| CN110662772A (en) * | 2017-04-26 | 2020-01-07 | 利物浦大学 | Branched polymers |
| CN110678490A (en) * | 2017-04-26 | 2020-01-10 | 利物浦大学 | Polymer and method of making same |
| JP2020517809A (en) * | 2017-04-26 | 2020-06-18 | ザ ユニバーシティ オブ リバプールＴｈｅ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｌｉｖｅｒｐｏｏｌ | polymer |
| CN110662772B (en) * | 2017-04-26 | 2022-04-08 | 利物浦大学 | Branched polymers |
| CN109535967A (en) * | 2018-11-14 | 2019-03-29 | 常州大学 | A kind of preparation method of environment-friendly type high impact resistance coating |
| CN109535967B (en) * | 2018-11-14 | 2022-01-25 | 常州大学 | Preparation method of environment-friendly high-impact-resistance coating |
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Application publication date: 20090923 |