CN101423602A - Method for preparing ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer - Google Patents
Method for preparing ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer Download PDFInfo
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- CN101423602A CN101423602A CNA2008102439624A CN200810243962A CN101423602A CN 101423602 A CN101423602 A CN 101423602A CN A2008102439624 A CNA2008102439624 A CN A2008102439624A CN 200810243962 A CN200810243962 A CN 200810243962A CN 101423602 A CN101423602 A CN 101423602A
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Abstract
The invention provides a method for preparing a crosslinking active multi-allyl multi-arm star-shaped pre-polymer by ultra violet light, and belongs to the technical field of light-curing composite coating material. The invention relates to selecting methylol melamine monomers and N, N-dihydroxyethyl-3-amino acid methyl ester monomers to synthesize hydroxyl-terminated multi-arm polyester, and the arm length is relative to the amount of hydroxymethyl of tripolycyanamide and the added amount of N, N-dihydroxyethyl-3-amino acid methyl ester monomers, and the sealed end of acrylic acid hydroxy ester is adopted to prepare the active multi-allyl multi-arm star-shaped pre-polymer; and the pre-polymer which can be cured by the ultra violet light with high thermal stability, high rigidity, excellent wear resistance, color and luster retention at high temperature, rapider curing, chemical agent pollution resistance and weather resistance is obtained. The crosslinking active multi-allyl multi-arm star-shaped pre-polymer by the ultra violet light has low viscosity property, dose not need adding organic solvent or reactive diluent so as to facilitate environmental protection, and can realize automation coating by adopting an ultra violet light-curing technology, so that the pre-polymer is energy-saving and high efficient, and has remarkable environmental benefits, social benefits and economic benefits.
Description
Technical field
But the preparation method of ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer, but relate to a kind of ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer that can be used for timber, paper, density board, metal, glass surface, belong to the light solidifying coating technical field of composite materials with high thermal stability, high rigidity, high-wearing feature and high-weatherability.
Background technology
UV-light (UV) curing has capacity usage ratio height, suitable heat-sensitive substrate material, VOC free pollution, film forming speed is fast, film performance is high and the characteristics of suitable continuous mass production, belongs to environmentally friendly coating of new generation, and its society and environmental benefit are huge; Star-type polymer has characteristics such as three-dimensional highly branched structure and a large amount of end group and good solubility, low viscosity, high chemical reactivity, particularly owing in star-type polymer synthetic, do not need to carry out purifying or seldom need purifying, thereby preparation is simple, cost is lower, has obtained widespread use in paint field.
Have the thermostability height, the hardness height, excellent in abrasion resistance at high temperature keeps color and gloss, and curing speed faster, chemically-resistant medicament pollute and the resin of weathering resistance is the target of domestic and international coating circle pursuit always.The present invention mainly selects melamine methylol monomer and N for use, and N-dihydroxy ethyl-3-amido methyl propionate monomer synthesizes terminal hydroxy group multi-arm polyester, adopts the crylic acid hydroxy ester end-blocking to prepare high performance uv curable oligomer.
Summary of the invention
But the preparation method who the purpose of this invention is to provide a kind of ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer, select melamine methylol monomer and N for use, the multi-arm polyester of the synthetic terminal hydroxy group of N-dihydroxy ethyl-3-amido methyl propionate monomer adopts the crylic acid hydroxy ester end-blocking to prepare a kind of prepolymer of high performance uV curable.
Technical scheme of the present invention: but a kind of preparation method of ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer, and step is:
(1) preparation melamine methylol: 1: 6～1: 9 trimeric cyanamide of mol ratio and formaldehyde are placed the reactor of band stirring, transfer pH to 8.5～9.5 with triethylamine, react 3h down at 60～80 ℃ then, leave standstill at 50 ℃, crystallization separates out, suction filtration, washing, drying obtains melamine methylol;
(2) preparation N, N-dihydroxy ethyl-3-amido methyl propionate monomer: in reactor, add the 0.1mol methyl acrylate, 0.1mol diethanolamine and 10mL methyl alcohol, mixture is at room temperature and logical N
2Be warming up to 35 ℃ of maintenance 4h after stirring 30min under the situation, vacuumize then, obtain a kind of water white transparency oily thing N, N-dihydroxy ethyl-3-amido methyl propionate monomer to remove methyl alcohol;
(3) " accurate single stage method " synthetic terminal hydroxy group multi-arm polyester: the adding mol ratio is 1: 9～1: 18 melamine methylol and N in reactor, N-dihydroxy ethyl-3-amido methyl propionate monomer, the tosic acid that adds reactant weight 2%, mixture is at 60～90 ℃ and logical N
2Stirring reaction 18～24h under the situation, vacuumize the methyl alcohol of removing generation then, obtain a kind of melamine methylol and be nuclear, N, N-dihydroxy ethyl-3-amido methyl propionate is the faint yellow oily terminal hydroxy group multi-arm polyester of arm, and the methylol amount of brachium and trimeric cyanamide is inversely proportional to, and N, N-dihydroxy ethyl-monomeric add-on of 3-amido methyl propionate is relevant, and add-on multi-arm more is long long more;
(4) but the preparation ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer: in reactor, accurately take by weighing terminal hydroxy group multi-arm polyester, the MEHQ that adds terminal hydroxy group multi-arm weight polyester 0.2% is as stopper, under agitation slow dropwise addition of acrylic acid hydroxy ester, hydroxyl mol ratio in crylic acid hydroxy ester and the terminal hydroxy group multi-arm polyester is 1: 1, room temperature refluxes under nitrogen protection, adopt its acid number of 0.5mol/L standard K OH solution titration, the half that reaction is reduced to when beginning to react up to acid number stops; Then this reaction mixture is dissolved with methylene dichloride, add an amount of KOH and be neutralized to neutrality, separate, get its lower floor, add anhydrous MgSO with separating funnel
4Suction adds an amount of stopper MEHQ at last in this reaction product, reduce pressure to take out down in 70 ℃ and desolvate, but promptly had ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer.
Described melamine methylol is: the mixture of trimethylol melamine, tetra methylol trimeric cyanamide, pentamethylol melamine and hexamethylolmelamine.
Described terminal hydroxy group multi-arm polyester is: the star-like phenodiazine HPAE-2 of terminal hydroxy group multi-arm polyester, the star-like three nitrogen HPAE-3 of terminal hydroxy group multi-arm polyester, the star-like four nitrogen HPAE-4 of terminal hydroxy group multi-arm polyester, the mixture of star-like five nitrogen HPAE-5 of terminal hydroxy group multi-arm polyester and the star-like six nitrogen HPAE-6 of terminal hydroxy group multi-arm polyester.
Described crylic acid hydroxy ester is selected for use: Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate or Rocryl 410.
Beneficial effect of the present invention: but ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer of the present invention can be used in the photo-cured coating, has high thermal stability timber, paper, density board, metal, filming of glass surface, high rigidity, excellent abrasive, at high temperature keep color and gloss, curing speed faster, the chemically-resistant medicament pollutes and weathering resistance.But ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer of the present invention is easy to prepare, lower viscosity is arranged, needn't add organic solvent or reactive thinner, VOC free, help environmental protection, adopt UV-curing technology can realize automation paint, efficient energy-saving has tangible environmental benefit, social benefit and economic benefit.
Embodiment
Embodiment 1
With mol ratio is the reactor that the trimeric cyanamide of 1:6 and formaldehyde place band to stir, and transfers pH to 9 with triethylamine, then at 70 ℃ of reaction 3h down, leave standstill, crystallization separates out at 50 ℃, and suction filtration, washing, drying obtains methylolation trimeric cyanamide (HMM).
In reactor, add the 0.1mol methyl acrylate, 0.1mol diethanolamine and 10mL methyl alcohol, mixture is at room temperature and logical N
2Be warming up to 35 ℃ of maintenance 4h after stirring 30min under the situation, vacuumize then, obtain a kind of water white transparency oily thing N, N-dihydroxy ethyl-3-amido methyl propionate monomer to remove methyl alcohol.
" accurate single stage method " synthesizes terminal hydroxy group multi-arm polyester: adding mol ratio in reactor is melamine methylol and the N of 1:9, N-dihydroxy ethyl-3-amido methyl propionate monomer, and 2% tosic acid, mixture is at 70 ℃ and logical N
2Stir 22h under the situation, vacuumize the methyl alcohol of removing generation then, obtain a kind of melamine methylol and be nuclear, N, N-dihydroxy ethyl-3-amido methyl propionate is the faint yellow oily terminal hydroxy group multi-arm polyester of arm, the methylol amount and the N of brachium and trimeric cyanamide, N-dihydroxy ethyl-monomeric add-on of 3-amido methyl propionate is relevant.
In reactor, accurately take by weighing terminal hydroxy group multi-arm polyester, add 0.2% MEHQ as stopper, under agitator stirs slowly dropwise addition of acrylic acid hydroxyl ethyl ester (with the mol ratio of hydroxyl be 1: 1), room temperature refluxes under nitrogen protection.Adopt its acid number of 0.5mol/L standard K OH solution titration, the half that reaction is reduced to when beginning to react up to acid number stops.Then this reaction mixture is dissolved with methylene dichloride, add an amount of KOH and be neutralized to neutrality, separate, get its lower floor, add anhydrous MgSO with separating funnel
4Suction adds an amount of stopper MEHQ at last in this reaction product, reduce pressure to take out down in 70 ℃ and desolvate, but promptly had ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer.
Coating is at the stable existence of energy below 200 ℃, and hardness reaches 3H, ultraviolet lighting 5h nondiscoloration.
Embodiment 2
The mol ratio of trimeric cyanamide and formaldehyde is 1: 7, melamine methylol and N, and N-dihydroxy ethyl-monomeric mol ratio of 3-amido methyl propionate is 1: 10, other building-up processes are identical with embodiment 1.The prepolymer that obtains is added light trigger, be coated with on metal substrate, use ultra violet lamp 20s, filming has high hardness and wear resistance.
Embodiment 3
The mol ratio of trimeric cyanamide and formaldehyde is 1: 8.The adding mol ratio is 1: 12 melamine methylol and N earlier, and N-dihydroxy ethyl-3-amido methyl propionate monomer adds 3 parts of N behind the question response 1h, N-dihydroxy ethyl-3-amido methyl propionate monomer, and other building-up processes are identical with embodiment 1.
Embodiment 4
PH is 8 during the reaction of formaldehyde and trimeric cyanamide, and other building-up processes are identical with embodiment 1.
Embodiment 5
The temperature of reaction of formaldehyde and trimeric cyanamide is 65 ℃, and other building-up processes are identical with embodiment 1.
Embodiment 6
Melamine methylol and N, N-dihydroxy ethyl-3-amido methyl propionate monomer reaction temperature is 90 ℃, and the reaction times is 19h, and other building-up processes are identical with embodiment 1.The prepolymer viscosity that obtains reduces, and adds light trigger, is coated with on metal substrate, uses ultra violet lamp 25s, and filming has high hardness, wear resistance, glossiness.
Embodiment 7
Slow dropwise addition of acrylic acid hydroxypropyl acrylate in the terminal hydroxy group multi-arm polyester, other building-up processes are identical with embodiment 1.
Claims (4)
- But 1, a kind of preparation method of ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer is characterized in that:(1) preparation melamine methylol: 1: 6～1: 9 trimeric cyanamide of mol ratio and formaldehyde are placed the reactor of band stirring, transfer pH to 8.5～9.5 with triethylamine, react 3h down at 60～80 ℃ then, leave standstill at 50 ℃, crystallization separates out, suction filtration, washing, drying obtains melamine methylol;(2) preparation N, N-dihydroxy ethyl-3-amido methyl propionate monomer: in reactor, add the 0.1mol methyl acrylate, 0.1mol diethanolamine and 10mL methyl alcohol, mixture is at room temperature and logical N 2Be warming up to 35 ℃ of maintenance 4h after stirring 30min under the situation, vacuumize then, obtain a kind of water white transparency oily thing N, N-dihydroxy ethyl-3-amido methyl propionate monomer to remove methyl alcohol;(3) " accurate single stage method " synthetic terminal hydroxy group multi-arm polyester: the adding mol ratio is 1: 9～1: 18 melamine methylol and N in reactor, N-dihydroxy ethyl-3-amido methyl propionate monomer, the tosic acid that adds reactant weight 2%, mixture is at 60～90 ℃ and logical N 2Stirring reaction 18～24h under the situation, vacuumize the methyl alcohol of removing generation then, obtain a kind of melamine methylol and be nuclear, N, N-dihydroxy ethyl-3-amido methyl propionate is the faint yellow oily terminal hydroxy group multi-arm polyester of arm, and the methylol amount of brachium and trimeric cyanamide is inversely proportional to, and N, N-dihydroxy ethyl-monomeric add-on of 3-amido methyl propionate is relevant, and add-on multi-arm more is long long more;(4) but the preparation ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer: in reactor, accurately take by weighing terminal hydroxy group multi-arm polyester, the MEHQ that adds terminal hydroxy group multi-arm weight polyester 0.2% is as stopper, under agitation slow dropwise addition of acrylic acid hydroxy ester, hydroxyl mol ratio in crylic acid hydroxy ester and the terminal hydroxy group multi-arm polyester is 1: 1, room temperature refluxes under nitrogen protection, adopt its acid number of 0.5mol/L standard K OH solution titration, the half that reaction is reduced to when beginning to react up to acid number stops; Then this reaction mixture is dissolved with methylene dichloride, add an amount of KOH and be neutralized to neutrality, separate, get its lower floor, add anhydrous MgSO with separating funnel 4Suction adds an amount of stopper MEHQ at last in this reaction product, reduce pressure to take out down in 70 ℃ and desolvate, but promptly had ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer.
- But 2, each method of the system of ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer according to claim 1 is characterized in that described melamine methylol is: the mixture of trimethylol melamine, tetra methylol trimeric cyanamide, pentamethylol melamine and hexamethylolmelamine.
- But 3, the preparation method of ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer according to claim 1, it is characterized in that described terminal hydroxy group multi-arm polyester is: the star-like phenodiazine HPAE-2 of terminal hydroxy group multi-arm polyester, the star-like three nitrogen HPAE-3 of terminal hydroxy group multi-arm polyester, the star-like four nitrogen HPAE-4 of terminal hydroxy group multi-arm polyester, the mixture of star-like five nitrogen HPAE-5 of terminal hydroxy group multi-arm polyester and the star-like six nitrogen HPAE-6 of terminal hydroxy group multi-arm polyester.
- But 4, the preparation method of ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer according to claim 1, it is characterized in that described crylic acid hydroxy ester selects for use: Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate or Rocryl 410.
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| CN2008102439624A CN101423602B (en) | 2008-12-18 | 2008-12-18 | Method for preparing ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786995A (en) * | 2010-03-11 | 2010-07-28 | 浙江奥仕化学有限公司 | Method for preparing granular hexamethylol melamine |
| CN106117155A (en) * | 2016-06-23 | 2016-11-16 | 重庆建峰浩康化工有限公司 | A kind of trimethylol melamine and hexakis(hydroxymethyl)melamine co-production |
| CN107325061A (en) * | 2017-08-15 | 2017-11-07 | 重庆建峰浩康化工有限公司 | The production technology of pentamethylol melamine |
| CN109666118A (en) * | 2018-12-14 | 2019-04-23 | 江南大学 | A kind of preparation method of fire-retardant multi-arm type epoxy resin |
| CN115417968A (en) * | 2022-10-10 | 2022-12-02 | 世名(苏州)新材料研究院有限公司 | Hyperbranched polyurethane acrylate with isocyanuric acid as core and preparation method thereof |
-
2008
- 2008-12-18 CN CN2008102439624A patent/CN101423602B/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786995A (en) * | 2010-03-11 | 2010-07-28 | 浙江奥仕化学有限公司 | Method for preparing granular hexamethylol melamine |
| CN101786995B (en) * | 2010-03-11 | 2014-03-12 | 奥仕集团有限公司 | Method for preparing granular hexamethylol melamine |
| CN106117155A (en) * | 2016-06-23 | 2016-11-16 | 重庆建峰浩康化工有限公司 | A kind of trimethylol melamine and hexakis(hydroxymethyl)melamine co-production |
| CN107325061A (en) * | 2017-08-15 | 2017-11-07 | 重庆建峰浩康化工有限公司 | The production technology of pentamethylol melamine |
| CN109666118A (en) * | 2018-12-14 | 2019-04-23 | 江南大学 | A kind of preparation method of fire-retardant multi-arm type epoxy resin |
| CN109666118B (en) * | 2018-12-14 | 2021-02-09 | 江南大学 | Preparation method of flame-retardant multi-arm epoxy resin |
| CN115417968A (en) * | 2022-10-10 | 2022-12-02 | 世名(苏州)新材料研究院有限公司 | Hyperbranched polyurethane acrylate with isocyanuric acid as core and preparation method thereof |
| CN115417968B (en) * | 2022-10-10 | 2023-11-10 | 世名(苏州)新材料研究院有限公司 | Hyperbranched polyurethane acrylate with isocyanuric acid as core and preparation method thereof |
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| CN101423602B (en) | 2010-11-10 |
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Address after: No.8, Hongxing Road, Liangxi District, Wuxi City, Jiangsu Province Patentee after: Jiangnan University Address before: College of chemistry and material engineering Jiangnan University No. 1800 214122 Jiangsu city of Wuxi Province Li Lake Avenue Patentee before: Jiangnan University |
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