CN101759847B - Preparation method of high-activity dumbbell type ultraviolet light curing resin - Google Patents
Preparation method of high-activity dumbbell type ultraviolet light curing resin Download PDFInfo
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- CN101759847B CN101759847B CN2009102641606A CN200910264160A CN101759847B CN 101759847 B CN101759847 B CN 101759847B CN 2009102641606 A CN2009102641606 A CN 2009102641606A CN 200910264160 A CN200910264160 A CN 200910264160A CN 101759847 B CN101759847 B CN 101759847B
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Abstract
The invention provides a preparation method of high-activity dumbbell type ultraviolet light curing resin, which belongs to the technical field of ultraviolet light curing resin. The invention adopts a polybasic acid as a major ingredient, and uses the polybasic acid as a connector of a dumbbell rod and a load for forming preformed polymers through the reaction of polyether polylol or polyester polylol with the certain molecular weight, then the preformed polymers and a material with both epoxy groups and double bonds react for forming rein capable of being cured by ultraviolet light, and both ends of the rein respectively comprise a plurality of functional base groups. The resin can solve the problem of low light curing activity of the traditional polyester acrylic acid resin, can obviously improve the existing brittle light curing resin, and simultaneously has good weather resisting property.
Description
Technical field
Design of a kind of new polyester bar or polyethers bar type dumbbell shaped polyene-based functional group UV-cured resin and preparation method thereof belongs to the UV-cured resin technical field.
Background technology
Along with the whole world flourish to the pay attention to day by day of environment protection and green science and technology, UV-curing technology because of its effectively control air pollute particularly that the discharging of volatile organic matter (VOC) more and more comes into one's own.It is advantages such as film forming is compared with traditional coating, and it has, and curing speed is fast, film performance good, energy expenditure low and environmentally friendly by form cross-linked structure fast under UV-irradiation.
The resin of existing ultraviolet light polymerization mainly comprises epoxy acrylate, amino acrylates, polyester acrylate, urethane acrylate and phenolic aldehyde acrylate etc., they all have certain shortcoming, fragility as the big resin of functionality is too big, and most resin all is the material of difunctionality, has the bad problem of curing performance again.As the epoxy acrylate of current application amount maximum, its laser curing velocity is fast, hardness is high, chemical-resistant is good, but its fragility is big, and weathering resistance is bad.Therefore polyester acrylate normal and other hardened resin system amalgamation use because of performances such as its snappiness are good is subjected to the favor of industry, and market outlook are wide.
But the polyester acrylate light-cured resin remains in certain shortcoming at present: (1) polyester acrylate is based on two functionality resins, and this directly causes active decline of photocuring of gained resin, and curing of coating speed is slow, well film forming.(2) need to finish by the method for hydroxyl polyester and vinylformic acid direct esterification under comparatively high temps in synthetic the production, the esterification transformation efficiency is lower, and easily produces gelatin phenomenon, and production technique is wayward.(3) isocyanic ester of PAUR acrylate mainly is that the toluene diisocynate that contains phenyl ring is calculated (TDI), and this makes that its weathering resistance is relatively poor, and is higher with the isocyanic ester cost that does not contain phenyl ring.
Summary of the invention
The objective of the invention is to design high conversion rate of esterification, polyfunctionality high reactivity, high performance polyester type acrylate, this UV-cured resin can be used separately, also can carry out the snappiness modification with the bigger resin amalgamation of fragility, can be applicable to the field of high adhesive force, high temperature tolerance, high-weatherability requirement, substitute expensive urethane acrylate.
Its mentality of designing is: adopt the method for dumbbell shaped molecular structure, increase average functionality, solve the active low problem of ultraviolet light polymerization of traditional polyester type acrylic resin; Introduce the dumbbell " bar " of polymer polarity, aliphatic chain, solve and reach the high adhesive force effect of high-flexibility of holding concurrently.This resin synthetic mainly comprises two key steps (1) and reacts under the effect of catalyzer by polyester or polyether glycol and polyprotonic acid, forms the prepolymer that contains a plurality of carboxyls of dumbbell shaped; (2) with these prepolymers by with certain material that had not only contained epoxy group(ing) but also contained double bond structure under the effect of catalyzer, finally form required dumbbell type ultraviolet light curing resin.
Technical scheme of the present invention: a kind of preparation method of dumbbell type ultraviolet light curing resin of polyester type, step is:
(1) esterification: with polyester diol or polyether Glycols is raw material, adds in the solvent, adds catalyzer, feeds N
2, electronic stirring, the oil bath heat temperature raising adds polyprotonic acid then, and adding mode and input amount are: feed N
2, being heated to 80 ℃, first adds earlier the feed intake 30%-35% of quality of raw material polyester diol or polyether Glycols; Be heated to reflux temperature, carry out esterification dehydration reaction 1-1.5h; Add the feed intake 25%-30% of quality of polyester diol or polyether Glycols again, back flow reaction 1-1.5h; Add the feed intake 20%-30% of quality of polyester diol or polyether Glycols again, back flow reaction 1-1.5h; Control reaction temperature is carried out when reflux temperature; Note the water yield in the water trap during the 3rd batch of back flow reaction, when the water yield in the water trap during near design load, water yield design load is that raw material polyester diol or polyether Glycols mole number multiply by 36g, the acid number of material in the assaying reaction device, acid number reaches preset value, be the twice that the acid number amount reaches raw material hydroxyl value quantity, stopped reaction; Be cooled to 60-70 ℃, obtain the thick polymkeric substance of reserving carboxyl that contains, be designated as polymer A, wait until and be used for next step building-up reactions;
Described polyester diol, its hydroxyl value are 110-190mgKOH/g; Or polyether Glycols, its hydroxyl value is 80-150mgKOH/g;
Solvent for use is selected toluene, dimethylbenzene, hexanaphthene, N for use, one or more in dinethylformamide, the methyl-sulphoxide; Add-on is the 20%-30% of raw material polyester diol or polyether Glycols quality;
Catalyst system therefor is selected triphenyl phosphorus or p-methyl benzenesulfonic acid for use, and add-on is the 0.2%-0.9% of raw material polyester diol or polyether Glycols quality;
(2) in containing the reactor of polymer A, add catalyzer triphenyl phosphorus, triethylamine, N, a kind of in the N-dimethyl benzylamine, add-on is the 0.2%-0.8% of polymer A quality; Add a kind of in hydroquinone of polymerization retarder, the 4-methoxyl group phenol, add-on is the 0.1%-0.7% of polymer A quality, to not only contain two keys but also contain the material glycidyl methacrylate or the vinylformic acid hexahydrophthalic acid 2-glycidyl ester of epoxy group(ing), consumption is raw material polyester diol or polyether Glycols quality 1-3 a times, add in the dropping funnel, in reactor, feed N
2, the liquid in the addition funnel makes the carboxyl reaction in epoxy group(ing) and the polymer A, and control reaction temperature is between 75-85 ℃, the time that control drips is added dropwise to complete the acid number of back detection architecture at 25-45min, and acid number is reduced to 5mgKOH/g, stopped reaction, vacuum extracts reaction solvent, discharging; Get shallow white viscous liquid, be polyester bar type dumbbell type ultraviolet light curing resin or polyethers bar type dumbbell type ultraviolet light curing resin.
Beneficial effect of the present invention:, just can synthesize the resin that molecular structure is the uV curable of dumbbell shaped by above reaction.The dumbbell bar of the intermediate chain structure of this resin is polyester or polyethers, by changing the length of " bar ", can change its snappiness, hydrophilic etc.Because all there is the active unsaturated group of Duoing than two traditional functionality polyester acrylates at two, has improved reactive behavior greatly.And because temperature of reaction low (traditional temperature of reaction is about 115 ℃), greatly reduce the danger of gelation in the reaction process in the past.
Embodiment
Embodiment 1:
In four neck flasks, add poly-(oxalic acid 1.2-propylene glycol ester) (hydroxyl value is about 120mgKOH/g) of 60g terminal hydroxy group; Add dimethylbenzene 15g, p-methyl benzenesulfonic acid 0.28g feeds N
2, being heated to about 80 ℃, first adds trimellitic acid 1,2-anhydride 20g earlier, is heated to reflux temperature, carries out esterification dehydration reaction 1h; Add trimellitic acid 1,2-anhydride 16g again, back flow reaction 1h; Add trimellitic acid 1,2-anhydride 13.3g again, back flow reaction 1h, the stopped reaction when acid number of measurement system reaches 110mgKOH/g.Be cooled to 70 ℃, continue next step reaction.In above-mentioned four neck flasks, add triethylamine 0.5g, 4-methoxyl group phenol 0.25g.Add glycidyl methacrylate 73g in dropping funnel, control reaction temperature is about 80 ℃, and the time that control drips is at 35min.After dripping off, at 80 ℃ of left and right sides insulation reaction 1-1.5h, the acid number in reaction system is reduced to below the 5mgKOH/g, stopped reaction.Vacuumize at last except that removal xylene, get shallow white viscous liquid product.This is a polyester bar type dumbbell type ultraviolet light curing resin, and the dumbbell head has 4 vinyl unsaturated functional groups.
Embodiment 2:
In four neck flasks, add 50g polyether Glycols (hydroxyl value is about 112mgKOH/g), dimethylbenzene 15g, triphenyl phosphorus 0.25g feeds N
2, being heated to about 80 ℃, first adds 1,2 earlier, and 4-hexanaphthene tricarboxylic acid 16g is heated to reflux temperature, carries out esterification dehydration reaction 1.5h; Add 1,2 again, 4-hexanaphthene tricarboxylic acid 14g, back flow reaction 1.5h; Add 1,2 again, 4-hexanaphthene tricarboxylic acid 13g, back flow reaction 1.5h, the stopped reaction when acid number of measurement system reaches 110mgKOH/g.Be cooled to about 70 ℃, continue next step reaction.In above-mentioned four neck flasks, add N, N-dimethyl benzylamine 0.5g, Resorcinol 0.3g.Add vinylformic acid hexahydrophthalic acid 2-glycidyl ester 143g in dropping funnel, control reaction temperature is about 80-83 ℃, and the time that control drips is about 45min.After dripping off, at 85 ℃ of left and right sides insulation reaction 1-1.5h, the acid number in reaction system is reduced to below the 5mgKOH/g, stopped reaction.Vacuumize at last except that removal xylene, get shallow white viscous liquid product.This is a polyethers bar type dumbbell type ultraviolet light curing resin, and the dumbbell head has 4 vinyl unsaturated functional groups.
Claims (2)
1. the preparation method of the dumbbell type ultraviolet light curing resin of a polyester type is characterized in that:
Add 60g terminal hydroxy group poly-(oxalic acid 1.2-propylene glycol ester) in four neck flasks, its hydroxyl value is 120mgKOH/g; Add dimethylbenzene 15g, p-methyl benzenesulfonic acid 0.28g feeds N
2, control is heated to 80 ℃, and first adds trimellitic acid 1,2-anhydride 20g earlier, is heated to reflux temperature, carries out esterification dehydration reaction 1h; Add trimellitic acid 1,2-anhydride 16g again, back flow reaction 1h; Add trimellitic acid 1,2-anhydride 13.3g again, back flow reaction 1h, the stopped reaction when acid number of measurement system reaches 110mgKOH/g; Be cooled to 70 ℃, continue next step reaction; In above-mentioned four neck flasks, add triethylamine 0.5g, 4-methoxyl group phenol 0.25g, in dropping funnel, add glycidyl methacrylate 73g, control reaction temperature is at 80 ℃, the time that control drips after dripping off, is controlled at 80 ℃ of insulation reaction 1-1.5h at 35min, acid number in reaction system is reduced to below the 5mgKOH/g, stopped reaction; Vacuumize at last except that removal xylene, get shallow white viscous liquid product polyester bar type dumbbell type ultraviolet light curing resin, the dumbbell head has 4 vinyl unsaturated functional groups.
2. the preparation method of the dumbbell type ultraviolet light curing resin of a polyester type is characterized in that:
Add the 50g polyether Glycols in four neck flasks, its hydroxyl value is 112mgKOH/g, dimethylbenzene 15g, and triphenyl phosphorus 0.25g feeds N
2, control is heated to 80 ℃, and first adds 1,2 earlier, and 4-hexanaphthene tricarboxylic acid 16g is heated to reflux temperature, carries out esterification dehydration reaction 1.5h; Add 1,2 again, 4-hexanaphthene tricarboxylic acid 14g, back flow reaction 1.5h; Add 1,2 again, 4-hexanaphthene tricarboxylic acid 13g, back flow reaction 1.5h, the stopped reaction when acid number of measurement system reaches 110mgKOH/g; Be cooled to 70 ℃, continue next step reaction; In above-mentioned four neck flasks, add N, N-dimethyl benzylamine 0.5g, Resorcinol 0.3g.Add vinylformic acid hexahydrophthalic acid 2-glycidyl ester 143g in dropping funnel, control reaction temperature is at 80-83 ℃, and the time that control drips is at 45min, after dripping off, be controlled at 85 ℃ of insulation reaction 1-1.5h, the acid number in reaction system is reduced to below the 5mgKOH/g, stopped reaction; Vacuumize at last except that removal xylene, get shallow white viscous liquid product polyethers bar type dumbbell type ultraviolet light curing resin, the dumbbell head has 4 vinyl unsaturated functional groups.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009102641606A CN101759847B (en) | 2009-12-31 | 2009-12-31 | Preparation method of high-activity dumbbell type ultraviolet light curing resin |
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| CN2009102641606A CN101759847B (en) | 2009-12-31 | 2009-12-31 | Preparation method of high-activity dumbbell type ultraviolet light curing resin |
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| CN101759847A CN101759847A (en) | 2010-06-30 |
| CN101759847B true CN101759847B (en) | 2011-12-21 |
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| CN106432703B (en) * | 2016-09-26 | 2018-11-02 | 华南理工大学 | A kind of highly filled hydroxy polyester resin and the preparation method and application thereof |
| CN114561002A (en) * | 2022-03-21 | 2022-05-31 | 孝感市易生新材料有限公司 | Preparation method and application of urethane-based modified polyester acrylate |
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