CN1147522C - Radiation-curable amino superbranching polyester and preparation process thereof - Google Patents
Radiation-curable amino superbranching polyester and preparation process thereofInfo
- Publication number
- CN1147522C CN1147522C CNB991176235A CN99117623A CN1147522C CN 1147522 C CN1147522 C CN 1147522C CN B991176235 A CNB991176235 A CN B991176235A CN 99117623 A CN99117623 A CN 99117623A CN 1147522 C CN1147522 C CN 1147522C
- Authority
- CN
- China
- Prior art keywords
- polyester
- unsaturated
- acid
- alcohol
- radiation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention provides radiation-solidifiable amino superbranched polyester and a preparation method thereof. The present invention is characterized in that firstly, dihydroxy amino ester is used as a chain extension monomer, polylol with multifunctional group molecules is added according to a certain proportion to be used as a nucleus, and the chain extension monomer reacts with the nucleus under the condition of the existence of a catalyst and inert gas to obtain terminal hydroxyl amino superbranched polyester; then, the terminal hydroxyl amino superbranched polyester is modified by propylene acidification or methyl propylene acidification to generate unsaturated dual-bond terminal group polyester with high branching degree. The radiation-solidifiable amino superbranched polyester has the excellent performance of low viscosity, high activity, etc. The radiation-solidifiable amino superbranched polyester can be used as oligomer for coating materials and adhesives, and can be quickly solidified to form a film under the condition of radiation of ultraviolet light or electronic beams at room temperature.
Description
The present invention relates to hyper-branched polyester, particularly radiation-curable hyper-branched polyester and preparation method thereof.International monopoly 96/07688 (R
Nby B., Shi W.F., WO96/07688,1996) reported elder generation with polyvalent alcohol and aryl polycarboxylic acid anhydride reactant, the preparation functional end-group is the hyper-branched polyester of carboxyl; Then with unsaturated epoxy compound to its modification, obtain the radiation-curable hyper-branched polyester of double-key end group: also can generate the hyper-branched polyester of double double key number further with the pendant hydroxyl group of the above-mentioned product of unsaturated acid anhydride esterification.This hyper-branched polyester is that the progressively esterification by different compounds obtains, because phenyl ring near " nuclear ", makes the reaction compartment steric hindrance increase, causes the polydispersity coefficient increase again; And the end group double key number of this hyper-branched polyester is at most four times of " nuclear " functionalized molecule degree in theory, thereby the degree of branching and molecular weight are restricted, and can not obtain high procreation for hyper-branched polyester, has also just limited its scope of application.
International monopoly 93/18079 (Hardeman G., WO93/18079,1993) having reported that with polyvalent alcohol be " nuclear ", is the chain extension monomer with aryl polybasic acid anhydride saturated rings oxygen compound, by synthetic high many carboxyls or the poly-hydroxy hyper-branched polyester of multiplying generation of the alternation response between two chain extension monomers.This method makes preparation process numerous and diverse owing to adopt two kinds of monomer alternation response procreations to increase on the one hand, makes the molecular weight of product wider distribution on the other hand, influences applicable performance and Application Areas.
International monopoly 93/17060 (Hult A.et al, WO93/17060,1993) has been reported with polyvalent alcohol and has been " nuclear ", is monomer with the monocarboxylic acid that contains at least 2 hydroxyls, the synthetic hyperbranched aliphatic polyester of terminal hydroxy group.Because it uses the carboxylic acid that contains hydroxyl to be monomer, causes containing intensive ester bond in the molecular structure, the chemical resistance of filming when making this terminal hydroxy group hyper-branched polyester be used for formulation for coating material is relatively poor, thereby has limited to some Application Areas.
United States Patent (USP) 5,136,014,5,183,862 and 5,270,402 (Garret D.F., U.S.Pat.No.5136 014,1992,5 813 862 and 5 270 402, and 1993) relate to by α the R that β unsaturated alkyl ester and amino alcohol reaction generate
1O
2CR
2N (R
3OH)
2Type dihydroxyl amido ester monomer is by the so-called nothing of method preparation " nuclear " terminal hydroxy group hyper-branched polyester from polycondensation; Also can carry out end capping with fatty acid anhydride, acyl chlorides or isocyanic ester etc.This hyper-branched polyester is not owing to add " nuclear " in the building-up process, and the polymer molecule of generation is single armed branch shape, and its molecular weight and polymolecularity all are difficult to control; And this viscosity with single armed structure polyester is bigger, need add solvent during use with diluted system, thereby bring problem of environmental pollution; And the hyper-branched polyester of saturated group end capping is used for conventional hot setting adhesive, rheological property conditioning agent and coating dispersant, and limitation is arranged in the application, uses inconveniently, and power consumption is high.
Conventional coating, tackiness agent, printing ink and the employed oligomer of fibre reinforced composites are usually by saturated line style molecular composition, its viscosity increases fast with the increase of molecular chain length, must add a large amount of volatile solvents to bring problem of environmental pollution to satisfy construction requirement; Also all has viscosity higher and be used for traditional linear polyesters of UV-light or low-energy electron beam radiation curing system such as epoxy acrylate, urethane acrylate, polyester acrylate etc., usually add single, multi-functional acrylate's monomer as thinner to reduce system viscosity, but most of acrylate monomers are volatile, toxicity big and have very strong irritating smell, are detrimental to health; And the affiliation that adds of acrylate monomer greatly influences the solidification rate of system and is coated with film dynamic performance.
The preparation method who the purpose of this invention is to provide a kind of amino superbranching polyester, and further its end group is carried out the method that modification prepares radiation-curable amino superbranching polyester, to overcome the above-mentioned defective of prior art.
The preparation method of amino superbranching polyester of the present invention, be characterised in that with dihydroxyl amido ester be the chain extension monomer, add a certain proportion of multifunctional molecule polyvalent alcohol and be " nuclear ", under catalyzer existence and protection of inert gas, under agitation in 90-160 ℃ of thermotonus 2-10 hour; The byproduct of generation is removed in underpressure distillation, promptly obtains highly branched terminal hydroxy group amido polyester.
Described dihydroxyl amido ester has R
1O
2CR
2N (R
3OH)
2The type molecular structure, in the formula, R
1And R
3Be respectively the alkyl or aryl that contains 1-12 carbon, R
2Be (CH
2)
2Or (CH
2CHCH
3); It comprises N, N-dihydroxy ethyl-3-amine-methyl propionate, N, N-dihydroxy ethyl-3-amine-ethyl propionate, N, N-dihydroxy ethyl-4-amine-methyl-butyrate, N, N-dihydroxy pentyl-3-amine-methyl propionate, N, N-dihydroxyphenyl ethyl-3-amine-methyl propionate, N, N-dihydroxypropyl-3-amine-methyl propionate.
The multifunctional molecule polyvalent alcohol of described conduct " nuclear " comprises dibasic alcohol, trivalent alcohol, tetravalent alcohol or other polyvalent alcohol; Wherein dibasic alcohol comprises aliphatic dihydroxy alcohol, alicyclic dibasic alcohol or aromatic diol; Aliphatic dihydroxy alcohol comprises 1, ammediol, 1,2-ethylene glycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, dihydroxy methylpropane, 1,1-dimethyl-1, ammediol, 2-propyl group-2-methyl isophthalic acid, ammediol, 2-butyl-2-ethyl-1, ammediol, 2,2-diethyl-1, ammediol, 1, the 2-propylene glycol, 1, the 3-butyleneglycol, 2,2,4-trimethylammonium-1,3-pentanediol, trimethylammonium-1, the 6-hexylene glycol, the 2-methyl isophthalic acid, ammediol, one two (ethylene glycol) that contract, two three (ethylene glycol) that contract, polyoxyethylene glycol, one two (propylene glycol) that contract, two three (propylene glycol) that contract, polypropylene glycol; Alicyclic dibasic alcohol comprises cyclohexanedimethanol, ring formaldehyde dimethyl acetal; Aromatic diol comprises 1,4-xylylene dicarbaldehyde, 1-phenyl-1; Described trivalent alcohol comprises TriMethylolPropane(TMP), trimethylolethane, tri hydroxy methyl butane, 3,5,5-trimethylammonium-2,2-dihydroxymethyl-1-hexanol, glycerol, 1,2,6-hexanetriol; Described tetravalent alcohol comprises tetramethylolmethane, contract TriMethylolPropane(TMP), glycol ether, contract trimethylolethane and other alicyclic, aromatic series tetravalent alcohol; Described polyvalent alcohol such as dipentaerythritol.
Described " certain proportion " is meant the molar reactive proportioning between " nuclear " and the monomer; When preparation first was multiplied for the terminal hydroxy group amino superbranching polyester, its value was 1/m; When preparation was equal to or greater than the terminal hydroxy group amino superbranching polyester of the s-generation, its value was 1/ (mn
X-1+ mn
X-2+ ... + mn+m), wherein m is the functionality of core molecule, and n is the functionality that monomer contains hydroxyl, and x is the procreation algebraically of terminal hydroxy group amino superbranching polyester, 1≤x≤20; Ratio by control certain " nuclear " among the present invention can prepare the 1-20 procreation amino superbranching polyester in generation; General desirable 2≤x≤10.
Described catalyzer is selected from tosic acid, sulfuric acid, metallic tin compound, as tin protochloride, dibutyl tin protoxide or dibutyl tin laurate ester; Consumption is 0.1-1wt%.
Radiation-curable amino superbranching polyester of the present invention is the high degree of branching polyester with the unsaturated double-bond end group of terminal hydroxy group amino superbranching polyester acrylated or methacrylic acidifying modification generation.
Described terminal hydroxy group amino superbranching polyester acrylated or methacrylic acidifying modification can be adopted " direct method ", promptly by the terminal hydroxy group amino superbranching polyester with contain and can make with unsaturated end-caps (I) reaction of the functional group of hydroxyl reaction; Perhaps adopt " indirect method ", promptly earlier by the terminal hydroxy group amino superbranching polyester with contain can with bifunctional saturated compound (II) reaction of hydroxyl reaction, with unsaturated end-caps (III) reaction, make its end group become radiosensitive reactive double bond again.
Described unsaturated end-caps (I) comprises unsaturated monocarboxylic acid acid anhydride, unsaturated monocarboxylic acid, unsaturated acyl chlorides or unsaturated isocyanate; Wherein the unsaturated monocarboxylic acid acid anhydride comprises acrylic anhydride, methacrylic anhydride; Unsaturated monocarboxylic acid comprises vinylformic acid, methacrylic acid; Unsaturated acyl chlorides comprises acrylate chloride, methacrylic chloride; Unsaturated isocyanate comprises vinyl toluene isocyanic ester, Jia Jibingxisuanyizhi isocyanic ester and by the unsaturated isocyanate of saturated vulcabond and 1/2 normal unsaturated oxy-compound prepared in reaction; Wherein saturated vulcabond comprises tolylene diisocyanate, hexamethylene diisocyanate, phenylbenzene methylene isocyanic ester and isophorone diisocyanate; Unsaturated oxy-compound comprises Hydroxyethyl acrylate, hydroxyethyl methylacrylate and tridecylene alcohol.
Described bifunctional saturated compound (II) comprises ring two saturated acid anhydrides and saturated vulcabond; Wherein encircle two saturated acid anhydrides such as Succinic anhydried, Tetra hydro Phthalic anhydride and Pyroglutaric acid; Saturated vulcabond comprises tolylene diisocyanate, hexamethylene diisocyanate, phenylbenzene methylene isocyanic ester and isophorone diisocyanate.
Described unsaturated end-caps (III) comprises unsaturated epoxy compound, as glycidyl acrylate, glycidyl methacrylate, and unsaturated oxy-compound, as Hydroxyethyl acrylate, hydroxyethyl methylacrylate.
The preparation method of radiation-curable amino superbranching polyester of the present invention is characterised in that the terminal hydroxy group amino superbranching polyester is adopted " direct method " or " indirect method " modification; So-called " direct method " modification, being about to amino superbranching polyester is dissolved in the solvent, slowly be added dropwise to the unsaturated end-caps with the hydroxyl equimolar amount while stirring, in the presence of catalyzer and stopper, 20-130 ℃ of thermotonus to acid number and hydroxyl value all less than the 10mgKOH/g polyester; Extraction process is removed the by product of generation; So-called " indirect method " modification, the bifunctional saturated compound that can react with it that is about to amino superbranching polyester and its hydroxyl equimolar amount is dissolved in the solvent, in the presence of catalyzer, 30-100 ℃ of thermotonus to hydroxyl value less than the 10mgKOH/g polyester, add stopper again, slowly be added dropwise to the unsaturated end-caps with bifunctional saturated compound equimolar amount, 80-120 ℃ of thermotonus to acid number less than the 10mgKOH/g polyester; Last underpressure distillation removes desolvates and by product, promptly gets radiation-curable amino superbranching polyester.
Solvent of the present invention comprises N, dinethylformamide, toluene, dioxane, ethyl acetate, N-Methyl pyrrolidone, butanone, dimethylbenzene, tetrahydrofuran (THF).
When adopting " direct method " modification, described catalyzer is selected from tosic acid, sulfuric acid, oil of mirbane, metallic tin compound such as tin protochloride, dibutyl tin protoxide or dibutyl tin laurate ester, and consumption is 0.5-2wt%; If use the unsaturated monocarboxylic acid modification, temperature of reaction is 70-130 ℃, and the reaction times is 2-7 hour; If use unsaturated acid anhydride, unsaturated acyl chlorides or unsaturated isocyanate modification, temperature of reaction is 20-50 ℃, and the reaction times is 0.5-3 hour; The extraction solvent for use comprises ether, methylene dichloride, chloroform or ethyl acetate.
When adopting " indirect method " modification, the temperature of the first step reaction is advisable with 30-100 ℃, and the reaction times was advisable with 2-4 hour; Described catalyzer is selected from tosic acid, sulfuric acid, oil of mirbane and metallic tin compound, and as tin protochloride, dibutyl tin protoxide or dibutyl tin laurate ester, consumption is 0.3-2wt%; The temperature of second step reaction is advisable with 80-120 ℃, and the time of reaction was advisable with 5-14 hour, and described catalyzer comprises tertiary amine, and as xylidine, dimethyl benzylamine, dimethyl aminopyridine and dimethylethanolamine, consumption is 1-3wt%.
Rare gas element of the present invention comprises nitrogen, helium or argon gas.
It is monomer that characteristics of the present invention are to adopt first dihydroxyl amido ester, with polyvalent alcohol is " nuclear ", by dispersing growth mechanism, promptly adopt building-up process from inside to outside, from the center core molecule, in the monomer reactive group and last generation functional group reactions, progressively outwards procreation, synthetic terminal hydroxy group amino superbranching polyester; Take " direct method " or " indirect method " that its end group is carried out modification then; Utilize the inventive method can prepare the radiation-curable amino superbranching polyester of number of chemical structure end group according to the performance requriements of differing materials.Compare with the radiation-curable hyper-branched polyester that the method for international monopoly 96/07688 prepares, because the present invention can prepare the amino superbranching polyester and the multiple acrylated method of modifying of multiplying generation more, thereby prepared product category is more, the scope of application is wide, Application Areas is wide.Do not see as yet up to now the report that adopts used monomeric such radiation-curable hyper-branched polyester of the present invention and preparation method thereof is arranged.
Compare with the method for international monopoly 93/17060, because the monomer that the present invention uses is dihydroxyl amido ester, the amino superbranching polyester molecular structure that is obtained contains the amido and the ester group of equal amount, being used for coating system as oligomer has increased anti-hydrolytic performance, has overcome the international monopoly 93/17060 method relatively poor problem of chemical resistance of filming when using the carboxylic acid that contains hydroxyl to be used for formulation for coating material as monomer synthetic aliphatics hyper-branched polyester.
With United States Patent (USP) 5,136,014,5,183,862 and 5,270, the method of nothing " nuclear " the single armed dendroid terminal hydroxy group hyper-branched polyester that pass through of 402 reports prepares from polycondensation method is compared, because the present invention has taked to add " nuclear " method, what obtain is the amino superbranching polyester of subglobular structure, has overcome the unmanageable problem of molecular weight and polymolecularity, and makes resin viscosity be lower than the resin formula of being prepared by the above-mentioned polyester of same molecular amount, so need not or add thinner on a small quantity and can be coated with, levelling, thus the environmental problem that causes owing to solvent solved.Because the hyper-branched polyester of the saturated group end capping of above-mentioned patented method can only be used for conventional solvent type heat-curing tackiness agent, rheological property conditioning agent, coating dispersant etc., thereby environmental pollution and the high problem of power consumption have been brought; And the present invention is on the basis of synthetic terminal hydroxy group amino superbranching polyester, make its terminal hydroxyl become the acrylic double bond of radiation sensitive by chemical modification again, and be distributed in the molecule sphere, thereby the amino superbranching polyester oligomer of these radiation-curables has very high activity, and radiation curing at room temperature, the solidification rate of the resin system that they are formed is much higher than traditional line style radiation-curable resin, thereby has reduced energy consumption, has improved production efficiency.
Among the present invention as the amino superbranching polyester of intermediate product, have high functionality, approximate spherically symmetric three-dimensional structure, intramolecularly and intermolecular no chain winding and sphere have the terminal hydroxy group feature of very easily modification, except that can be used to further acrylated or the methacrylic acidifying modification high degree of branching polyester with preparation unsaturated double-bond end group, also the useful as drug slowly-releasing is put carrier or support of the catalyst and rheological property conditioning agent.
Accompanying drawing 1 and accompanying drawing 2 are respectively the desirable molecular formula that the third generation and the 4th generation has the amino superbranching polyester of terminal hydroxy group.
Compare with existing radiation curing oligomer, radiation-curable amino superbranching polyester of the present invention is because the numerous reactive activity double key of the structure of its almost spherical and its surface, be used for coating, adhesive prescription as oligomer, have the premium properties such as low viscosity, high activity and coating low-shrinkage, can reduce the use of volatile organic solvent and polyfunctional group dilution property monomer, thereby solve that existing Radiation-curing system need use environmental pollution that more monomer causes and owing to the problem of the higher cured film that causes of its shrinkage factor and base material poor adhesive force; Because the high activity of material of the present invention and can be at room temperature with ultraviolet light or low energy electron beam irradiation rapid curing film forming, can greatly enhance productivity and save the energy.
The used raw material sources of radiation-curable amino superbranching polyester preparation method of the present invention extensively, cheaply be easy to get are easy to suitability for industrialized production. The prepared radiation-curable amino superbranching polyester oligomer of the present invention has wide prospects for commercial application.
Following examples further describe the preparation method of radiation-curable amino superbranching polyester of the present invention and the application in radiation-curable couting.But the present invention is not limited to listed example.
Embodiment:
AB
2The monomeric preparation of type
Embodiment 1.N, the N-dihydroxy ethyl-monomeric preparation of 3-amine-methyl propionate
Employing is equipped with magneton agitator and oil bath and is had nitrogen inlet and the 250ml four-necked bottle reactor of prolong, adds 8.6g (0.10mol) methyl acrylate, 10.5g (0.10mol) diethanolamine and 10ml methyl alcohol, and mixture is at room temperature and logical N
2Stir under the situation and be warming up to 35 ℃ of maintenances 4 hours after 30 minutes, vacuumize then, obtain a kind of water white transparency oily thing to remove methyl alcohol.
The synthetic monomer is through Infrared spectroscopy, at 1445cm
-1, 990cm
-1, 910cm
-1Methyl acrylate C=C of place and the N-H of 939cm-1 place characteristic peak all disappear.Adopt the German Foss Heraeus CHN-O-RAPID of company elemental analyser to measure monomer component C, H, N content results such as table 1.
Table 1
| Element | C(wt％) | H(wt％) | N(wt％) |
| Theoretical value | 50.26 | 8.90 | 7.33 |
| Measured value | 49.34 | 9.39 | 7.62 |
According to ultimate analysis and monomeric Infrared spectroscopy as can be known, this water white transparency oily thing is N, N-dihydroxy ethyl-3-amine-methyl propionate monomer; Productive rate is 94%.
The preparation of terminal hydroxy group amino superbranching polyester
Embodiment 2. synthetic s-generation terminal hydroxy group amino superbranching polyesters
Adopt the reactor identical, adding 1.34g (0.01mol) TriMethylolPropane(TMP), 5.74g (0.03mmol) synthetic N in embodiment 1, N-dihydroxy ethyl-3-amine-methyl propionate monomer and 35.4mg tosic acid with embodiment 1.Mixture reacted 2 hours down at 120 ℃, and the methyl alcohol of generation was removed in underpressure distillation in 1 hour then, obtained the faint yellow oily thing of 6.4g.
In this reactor, continue to add 11.50g (0.06mol) N, N-dihydroxy ethyl-3-amine-methyl propionate monomer and 23mg tosic acid, continue reaction 2 hours down at 120 ℃, the methyl alcohol of generation was removed in underpressure distillation in 1 hour then, obtain the faint yellow oily thing of 14.4g, be s-generation terminal hydroxy group amino superbranching polyester.
Adopt the back titration method, measuring the product hydroxyl value with sodium hydroxide ethanol standardized solution is 432mgKOH/g, and the Theoretical Calculation hydroxyl value is 420mgKOH/g.Employing is that to record the many distribution coefficients of molecular weight be 1.02 for the GPC-LC chromatographic instrument of stationary phase post with the styragel microballoon.
Table 2 is listed the productive rate and the color of the resulting product of reaction different time under the differing temps; The viscosity of product under differing temps when table 3 is 750 rev/mins for adopting QNX type rotational viscosimeter and rotating speed.
Table 2
| Temperature of reaction (℃) | Reaction times (h) | Productive rate (%) | The product color |
| 100 | 7 | 84 | Yellow |
| 120 | 5 | 92 | Faint yellow |
| 150 | 3 | 90 | Pale brown look |
Table 3
| Temperature (℃) | 50 | 55 | 60 | 65 |
| Viscosity (cps) | 4300 | 2950 | 2500 | 1600 |
Embodiment 3. synthetic third generation terminal hydroxy group amino superbranching polyesters
In the reactor of embodiment 2, continue to add 22.95g (0.12mol) N, N-dihydroxy ethyl-3-amine-methyl propionate monomer and 30mg tosic acid, continue reaction 3 hours down at 100 ℃, the methyl alcohol of generation was removed in underpressure distillation in 1 hour then, obtain the faint yellow oily thing of 38.62g, be third generation amino superbranching polyester.Productive rate is 91%.
The desirable molecular structure of third generation amino superbranching polyester as shown in Figure 1.
Recording hydroxyl value is 387mgKOH/g, and theoretical hydroxyl value is 403mgKOH/g; Employing is that to record the many distribution coefficients of molecular weight be 1.04 for the GPC-LC chromatographic instrument of stationary phase post with the styragel microballoon.
Table 4 for adopt QNX type rotational viscosimeter, when rotating speed is 750 rev/mins, the viscosity of product under differing temps.
Table 4
| Temperature (℃) | 50 | 55 | 60 | 65 |
| Viscosity (cps) | 4500 | 3100 | 2700 | 1850 |
Embodiment 4. synthetic the 5th generation the terminal hydroxy group amino superbranching polyester
Adopt the reactor identical with embodiment 1, add 0.67g (0.005mol) TriMethylolPropane(TMP), 88.90g (0.465mol) N, N-dihydroxy ethyl-3-amido methyl propionate monomer and 0.5g tosic acid, mixture was 140 ℃ of reactions 5 hours, the methyl alcohol of generation was removed in underpressure distillation in 2 hours then, obtained 82.25g yellow transparent oily matter, be the 5th generation the terminal hydroxy group amino superbranching polyester.
Employing is that to record the many distribution coefficients of molecular weight be 605 for the GPC-LC chromatographic instrument of stationary phase post with the styragel microballoon.
The preparation of radiation-curable amino superbranching polyester
Embodiment 5. prepares radiation-curable polyester (HPAE-2-MAA) with methacrylic acid anhydride modification terminal hydroxy group amino superbranching polyester
Employing is equipped with magneton agitator and oil bath and is had nitrogen inlet and the 250ml four-necked bottle reactor of prolong, dropping funnel, adding slowly drips 9.25g (0.06mol) methacrylic anhydride by synthetic s-generation terminal hydroxy group amino superbranching polyester 8.46g (0.005mol) and 35mg MEHQ among the embodiment 2 by dropping funnel in reactor.Mixture is dissolved in methylene dichloride with product in reaction under 25 ℃ after 2 hours, is neutralized to neutrality with aqueous sodium hydroxide solution, uses distilled water flush away sodium hydroxide again; Behind methylene dichloride re-extract product like this three times, the methylene dichloride in the layer that deoils is taken out in underpressure distillation, obtains thick liquid, is third generation radiation-curable amino superbranching polyester (HPAE-2-MAA).
The desirable molecular structure of third generation radiation-curable amino superbranching polyester as shown in Figure 2.
The two key assignments that adopt the bromide oxidation style to measure product are the 4.54mmol/g polyester, and theoretical two key assignments of product should be the 5.04mmol/g polyester.
The productive rate and the color of the resulting product of differential responses temperature and time are listed in the table 5.The rotary viscosity of product under differing temps listed in table 6.
Table 5
| Temperature of reaction (℃) | Reaction times (h) | Productive rate (%) | The |
| 10 | 2 | 78 | Yellowish |
| 25 | 1 | 85 | Little Huang |
| 40 | 0.5 | 80 | Yellowish |
Table 6
| Temperature (℃) | 20 | 30 | 40 | 50 | 60 | 70 |
| Viscosity (cps) | 2300 | 1250 | 410 | 314 | 172 | 99 |
Embodiment 6. prepares radiation-curable polyester (HPAE-2-AA) with acrylic acid modified terminal hydroxy group amino superbranching polyester.
Get the 250ml four-necked bottle, device for mechanical agitator, nitrogen inlet, dropping funnel, water-and-oil separator and oil bath, add s-generation terminal hydroxy group amino superbranching polyester 7.825g (0.005mol) and be dissolved in the 60ml toluene solvant, add 49mg MEHQ and 0.12g oil of mirbane again, under 80 ℃ while stirring slowly by dropping funnel dropwise addition of acrylic acid 4.32g (0.06mol) in reactor, be warming up to 120 ℃ after dripping, the water that generates is removed by backflow, react to acid number less than the 10mgKOH/g polyester.After toluene is taken out in last underpressure distillation, obtain yellow thick liquid, be radiation-curable polyester (HPAE-2-AA).
The two key assignments that record product are the 4.73mmol/g polyester, and theoretical two key assignments are the 5.42mmol/g polyester.
The productive rate and the color of resulting product of differential responses time are listed in table 7 under differing temps.
Table 7
| Temperature of reaction (℃) | Reaction times (h) | Productive rate (%) | The product color |
| 100 | 7 | 81 | Yellow |
| 120 | 4 | 87 | Yellow |
| 160 | 2 | 79 | Pale brown look |
Embodiment 7. prepares radiation-curable polyester (HPAE-2-TDI) with the unsaturated isocyanate modification terminal hydroxy group amino superbranching polyester that tolylene diisocyanate and Hydroxyethyl acrylate reaction generate.
Adopt the reaction unit identical with embodiment 5,17g (0.1mol) tolylene diisocyanate is added in the four-necked bottle, splash into 11.6g (0.05mol) Hydroxyethyl acrylate while stirring, 30 ℃ of controlled temperature are to finish down to monomer dropping, be warming up to 50 ℃, reacted 2 hours, and obtained containing the acrylate of isocyanate groups.Product is cooled to below 30 ℃, in reactor, drip the s-generation terminal hydroxy group amino superbranching polyester 6.5g (0.004mol) that is dissolved in methylene dichloride again by dropping funnel, be warming up to 40 ℃ of reactions after dropwising after 3 hours, methylene dichloride is removed in underpressure distillation, obtain faint yellow thick material, be radiation-curable polyester (HPAE-2-TDI).
Recording the two key assignments of product is the 2.1mmol/g polyester, and theoretical two key assignments should be the 2.38mmol/g polyester.
Embodiment 8. prepares the polyester (HPAE-2-SA) of radiation-curable earlier again with glycidyl methacrylate modification terminal hydroxy group amino superbranching polyester with Succinic anhydried.
Adopt the reaction unit identical with embodiment 1, add s-generation terminal hydroxy group amino superbranching polyester 7.825g (0.005mol) and Succinic anhydried 6.0g (0.06mol), and add the 20ml tetrahydrofuran (THF) as solvent, add the 70mg tin protochloride as catalyzer, mixture reacted 3 hours down at 60 ℃, tetrahydrofuran (THF) is removed in underpressure distillation then, obtains yellow thick liquid, is the terminal hydroxy group amino superbranching polyester.
The color and the level of response of different temperature of reaction and time products therefrom are listed in table 8.
Table 8
| Temperature of reaction (℃) | Reaction times (h) | Level of response (%) | The product color |
| 30 | 4 | 85 | Yellow |
| 60 | 3 | 92 | Yellow |
| 100 | 2 | 88 | Pale brown look |
Adopt the reaction unit identical with embodiment 5, get the above-mentioned terminal hydroxy group amino superbranching polyester that makes of 14.45g (0.005mol), dissolve in 20ml N, dinethylformamide, add stopper MEHQ 46mg and catalyzer 0.23g (1%wt) N, the N-dimethyl benzylamine slowly is added dropwise to 8.55g (0.06mol) glycidyl methacrylate by dropping funnel in reactor, be warming up to 100 ℃, react to acid number less than the 10mgKOH/g polyester.N is removed in underpressure distillation then, and dinethylformamide obtains yellow thick liquid, is the polyester (HPAE-2-SA) of radiation-curable.
The two key assignments that record product are the 2.4mmol/g polyester, and theoretical two key assignments should be the 2.68mmol/g polyester.
The color and the level of response of different temperature of reaction and time products therefrom are listed in table 9.
Table 9
| Temperature of reaction (℃) | Reaction times (h) | Level of response (%) | The product color |
| 80 | 14 | 82 | Yellow |
| 100 | 12 | 90 | Yellow |
| 120 | 8 | 89 | Pale brown look |
Embodiment 9. prepares the polyester (HPAE-2-PA) of radiation-curable earlier again with glycidyl methacrylate modification terminal hydroxy group amino superbranching polyester with Tetra hydro Phthalic anhydride.
Adopt the reaction unit identical with embodiment 1, get the s-generation amino superbranching polyester 7.825g (0.005mol) of terminal hydroxy group, add 8.9g (0.06mol) Tetra hydro Phthalic anhydride and 20ml tetrahydrofuran (THF) as solvent, add the 70mg dimethyl benzylamine as catalyzer, mixture reacted 4 hours down at 80 ℃, tetrahydrofuran (THF) is removed in underpressure distillation then, obtains fragrant carboxyl end group amino superbranching polyester, and product is little yellow crystals shape material.
The color and the level of response of different temperature of reaction and time products therefrom are listed in table 10.
Table 10
| Temperature of reaction (℃) | Reaction times (h) | Level of response (%) | The product color |
| 30 | 4 | 80 | Faint yellow |
| 80 | 3 | 87 | Little yellow |
| 100 | 2 | 88 | Yellow |
Adopt the reaction unit identical with embodiment 5, get above-mentioned little yellow crystals shape fragrance carboxyl end group amino superbranching polyester 17.33g (0.005mol), dissolve in 20ml N, dinethylformamide, add stopper MEHQ 52mg and catalyzer 0.26gN, the N-dimethyl benzylamine, slowly be added dropwise to 8.55g (0.06mol) glycidyl methacrylate, be warming up to 100 ℃, react to acid number less than the 10mgKOH/g polyester, N is removed in underpressure distillation then, dinethylformamide, obtain yellow thick liquid, be the polyester (HPAE-2-PA) of radiation-curable.
The two key assignments that record product are the 2.14mmol/g polyester, and theoretical two key assignments are the 2.37mmol/g polyester.
The color and the level of response of different temperature of reaction and time products therefrom are listed in table 11.
Table 11
| Temperature of reaction (℃) | Reaction times (h) | Level of response (%) | The product color |
| 80 | 14 | 85 | Yellow |
| 100 | 12 | 92 | Yellow |
| 120 | 8 | 92 | Pale brown look |
The viscosity characteristics of the amino superbranching polyester of embodiment 10. radiation-curables
Add 10% and the 20%HDDA polyfunctional monomer in the hyperbranched oligomer HPAE-2-MAA, adopt QNX type rotational viscosimeter, when rotating speed is 750 rev/mins, record the numerical value (cps) that its viscosity changes along with temperature and monomeric adding, list in table 12.
Table 12
The ultra-violet curing of the amino superbranching polyester of radiation-curable
| HDDA (wt％) | 20℃ | 25℃ | 30℃ | 35℃ | 40℃ | 45℃ | 50℃ | 55℃ | 60℃ | 65℃ | 70℃ |
| 0 | 2400 | 2200 | 1300 | 900 | 400 | 280 | 200 | 140 | 100 | 80 | 60 |
| 10 | 940 | 710 | 420 | 300 | 200 | 150 | 110 | 82 | 54 | 42 | 34 |
| 20 | 560 | 390 | 250 | 200 | 140 | 100 | 80 | 48 | 37 | 30 | 24 |
The ultra-violet curing of embodiment 11. amino superbranching polyesters (HPAE-2-MAA) resin is got amino superbranching polyester (HPAE-MAA) 5g of radiation-curable, light trigger α, alpha-alpha-dimethyl-Alpha-hydroxy methyl phenyl ketone (Darocure 1173) 150mg (3%wt), mix, on sheet glass, paint the film of 100 micron thickness with spreader, sample places 10 centimetres of lamps apart from locating to use the PhilipHPM-151000W uv light irradiation, light application time was respectively 2,4,8,10 seconds, obtain the cured film of different double bond conversion rates, list in table 13.Table 14 has been listed the calculated value and the experimental value of the ultra-violet curing shrinking percentage of amino superbranching polyester HPAE-2-MAA resin.
Table 13
| Light application time (second) | 2 | 4 | 6 | 8 | 10 |
| Double bond conversion rate (%) | 75.0 | 80.3 | 82.6 | 84.6 | 85.1 |
Table 14
| Sample | Double bond conversion rate (%) | Maximum contraction rate (100% transformation efficiency) | Shrinkage from mold dimensions (consideration transformation efficiency) | Actual measurement shrinking percentage (%) |
| NHP-2-MAA | 72.0 | 13.0 | 9.4 | 8.9 |
Claims (7)
1, a kind of preparation method of amino superbranching polyester is characterised in that with dihydroxyl amido ester be the chain extension monomer, adds a certain proportion of polyvalent alcohol and is " nuclear ", under catalyzer existence and protection of inert gas, under agitation in 90-160 ℃ of thermotonus 2-10 hour; The by product of generation is removed in underpressure distillation, promptly obtains highly branched terminal hydroxy group amido polyester;
Described dihydroxyl amido ester has R
1O
2CR
2N (R
3OH)
2The type molecular structure, in the formula, R
1And R
3Be respectively the alkyl or aryl that contains 1-12 carbon, R
2Be (CH
2)
2Or (CH
2CHCH
3);
The multifunctional molecule polyvalent alcohol of described conduct " nuclear " comprises dibasic alcohol, trivalent alcohol, tetravalent alcohol or other polyvalent alcohol;
Described " certain proportion " is meant the molar reactive proportioning between " nuclear " and the monomer; When preparation first was multiplied for the terminal hydroxy group amino superbranching polyester, its value was 1/m; When preparation was equal to or greater than the terminal hydroxy group amino superbranching polyester of the s-generation, its value was 1/ (mn
X-1+ mn
X-2+ ... + mn+m), wherein m is the functionality of core molecule, and n is the functionality that monomer contains hydroxyl, and x is the procreation algebraically of terminal hydroxy group amino superbranching polyester, 1≤x≤20;
Described catalyzer is selected from tosic acid, sulfuric acid, tin protochloride, dibutyl tin protoxide or dibutyl tin laurate ester; Consumption is 0.1-1wt%.
2, the preparation method of amino superbranching polyester according to claim 1, feature is that used chain extension monomer dihydroxyl amido ester is selected from N, N-dihydroxy ethyl-3-amine-methyl propionate, N, N-dihydroxy ethyl-3-amine-ethyl propionate, N, N-dihydroxy ethyl-4-amine-methyl-butyrate, N, N-dihydroxy pentyl-3-amine-methyl propionate, N, N-dihydroxyphenyl ethyl-3-amine-methyl propionate and N, N-dihydroxypropyl-3-amine-methyl propionate.
3, the preparation method of amino superbranching polyester according to claim 1, feature is that the multifunctional molecule polyvalent alcohol of described conduct " nuclear " is selected from the aliphatic dihydroxy alcohol in the dibasic alcohol, alicyclic dibasic alcohol or aromatic diol; Comprise 1 in the aliphatic dihydroxy alcohol, ammediol, 1,2-ethylene glycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, dihydroxy methylpropane, 1,1-dimethyl-1, ammediol, 2-propyl group-2-methyl isophthalic acid, ammediol, 2-butyl-2-ethyl-1, ammediol, 2,2-diethyl-1, ammediol, 1, the 2-propylene glycol, 1, the 3-butyleneglycol, 2,2,4-trimethylammonium-1,3-pentanediol, trimethylammonium-1, the 6-hexylene glycol, the 2-methyl isophthalic acid, ammediol, one two (ethylene glycol) that contract, two three (ethylene glycol) that contract, polyoxyethylene glycol, one two (propylene glycol) that contract, two three (propylene glycol) that contract, polypropylene glycol; Comprise cyclohexanedimethanol, ring formaldehyde dimethyl acetal in the alicyclic dibasic alcohol; Comprise 1 in the aromatic diol, 4-xylylene dicarbaldehyde, 1-phenyl-1; Comprise TriMethylolPropane(TMP), trimethylolethane, tri hydroxy methyl butane, 3,5 in the trivalent alcohol, 5-trimethylammonium-2,2-dihydroxymethyl-1-hexanol, glycerol, 1,2,6-hexanetriol; Comprise tetramethylolmethane, contract TriMethylolPropane(TMP), glycol ether, contract trimethylolethane and other alicyclic, aromatic series tetravalent alcohol in the tetravalent alcohol; And the dipentaerythritol in the polyvalent alcohol.
4, a kind of preparation method of radiation-curable amino superbranching polyester is characterised in that the terminal hydroxy group amino superbranching polyester is adopted " direct method " or " indirect method " modification; Last underpressure distillation removes desolvates and by product;
So-called " direct method " modification, being about to the terminal hydroxy group amino superbranching polyester is dissolved in the solvent, slowly be added dropwise to the unsaturated end-caps (I) with its hydroxyl equimolar amount while stirring, in the presence of catalyzer and stopper, 20-130 ℃ of thermotonus to acid number and hydroxyl value all less than the 10mgKOH/g polyester; Extraction process is removed the byproduct of generation;
So-called " indirect method " modification, promptly be dissolved in the solvent earlier with the terminal hydroxy group amino superbranching polyester with the bifunctional saturated compound (II) of its hydroxyl equimolar amount, in the presence of catalyzer, 30-100 ℃ of thermotonus to hydroxyl value less than the 10mgKOH/g polyester, add stopper again, slowly be added dropwise to the unsaturated end-caps (III) with bifunctional saturated compound equimolar amount, 80-120 ℃ of thermotonus to acid number less than the 10mgKOH/g polyester;
Described solvent comprises N, dinethylformamide, toluene, dioxane, ethyl acetate, N-Methyl pyrrolidone, butanone, dimethylbenzene or tetrahydrofuran (THF);
Described unsaturated end-caps (I) comprises unsaturated monocarboxylic acid acid anhydride, unsaturated monocarboxylic acid, unsaturated acyl chlorides or unsaturated isocyanate; Described bifunctional saturated compound (II) comprises ring two saturated acid anhydrides and saturated vulcabond; Described unsaturated end-caps (III) comprises unsaturated epoxy compound and unsaturated oxy-compound;
When adopting " direct method " modification, described catalyzer is selected from tosic acid, sulfuric acid, oil of mirbane, metallic tin compound such as tin protochloride, dibutyl tin protoxide or dibutyl tin laurate ester, and consumption is 0.5-2wt%; If use the unsaturated monocarboxylic acid modification, temperature of reaction is 70-130 ℃, and the reaction times is 2-7 hour; If use unsaturated acid anhydride, unsaturated acyl chlorides and unsaturated isocyanate modification, temperature of reaction is 20-50 ℃, and the reaction times is 0.5-3 hour; The extraction solvent for use comprises ether, methylene dichloride, chloroform or ethyl acetate;
When adopting " indirect method " modification, the temperature of the first step reaction is 30-100 ℃, reaction times 2-4 hour; Described catalyzer is selected from tosic acid, sulfuric acid, oil of mirbane, metallic tin compound such as tin protochloride, dibutyl tin protoxide or dibutyl tin laurate ester, and consumption is 0.3-2wt%; The temperature of second step reaction is 80-120 ℃, and reaction times 5-14 hour, it was xylidine, dimethyl benzylamine, dimethyl aminopyridine or dimethylethanolamine that described catalyzer is selected from tertiary amine, and consumption is 1-3wt%.
5, as the preparation method of radiation-curable amino superbranching polyester as described in the claim 4, be characterised in that described unsaturated end-caps (I) comprises acrylic anhydride, the methacrylic anhydride in the unsaturated monocarboxylic acid acid anhydride; Vinylformic acid in the unsaturated monocarboxylic acid, methacrylic acid; Acrylate chloride in the unsaturated acyl chlorides, methacrylic chloride; Vinyl toluene isocyanic ester in the unsaturated isocyanate, Jia Jibingxisuanyizhi isocyanic ester and by the unsaturated isocyanate of saturated vulcabond and 1/2 normal unsaturated oxy-compound prepared in reaction, wherein saturated vulcabond comprises tolylene diisocyanate, hexamethylene diisocyanate, phenylbenzene methylene isocyanic ester and isophorone diisocyanate; Unsaturated oxy-compound comprises Hydroxyethyl acrylate, hydroxyethyl methylacrylate and tridecylene alcohol.
6,, be characterised in that described bifunctional saturated compound (II) comprises Succinic anhydried, Tetra hydro Phthalic anhydride and the Pyroglutaric acid in the ring two saturated acid anhydrides as the preparation method of radiation-curable amino superbranching polyester as described in the claim 4; Tolylene diisocyanate in the saturated vulcabond, hexamethylene diisocyanate, phenylbenzene methylene isocyanic ester and isophorone diisocyanate.
7, as the preparation method of radiation-curable amino superbranching polyester as described in the claim 4, be characterised in that described unsaturated end-caps (III) comprises glycidyl acrylate, the glycidyl methacrylate in the unsaturated epoxy compound, and the Hydroxyethyl acrylate in the unsaturated oxy-compound, hydroxyethyl methylacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991176235A CN1147522C (en) | 1999-08-06 | 1999-08-06 | Radiation-curable amino superbranching polyester and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991176235A CN1147522C (en) | 1999-08-06 | 1999-08-06 | Radiation-curable amino superbranching polyester and preparation process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1248586A CN1248586A (en) | 2000-03-29 |
| CN1147522C true CN1147522C (en) | 2004-04-28 |
Family
ID=5280173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991176235A Expired - Fee Related CN1147522C (en) | 1999-08-06 | 1999-08-06 | Radiation-curable amino superbranching polyester and preparation process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1147522C (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305921C (en) * | 2005-08-04 | 2007-03-21 | 上海交通大学 | Temperature sensing superbranching polymer and its preparation method |
| CN1935872B (en) * | 2005-09-23 | 2010-08-18 | 长兴化学工业股份有限公司 | Radiation curable alkoxy silanized superbranched polyester acrlate and its preparing method |
| CN100368538C (en) * | 2005-11-14 | 2008-02-13 | 湛江师范学院 | Preparation method of superbranched polymer gel immobilized yeast vector |
| CN101041742B (en) * | 2007-04-11 | 2010-05-19 | 西北师范大学 | Over-branched polyamine ester/lanthanum/montmorillonite nano composite material and preparation thereof |
| CN101899175B (en) * | 2010-06-04 | 2012-07-04 | 上海工程技术大学 | Hyperbranched expandable flame retardant rubber material and preparation method thereof |
| CN102002134B (en) * | 2010-11-05 | 2012-02-08 | 江苏超力建材科技有限公司 | Hyperbranched polymer, hyperbranched type water reducing agent of polycarboxylic acid series and preparation method and application thereof |
| CN102060988B (en) * | 2010-11-08 | 2012-07-04 | 济南大学 | Hydroxy-terminated hyperbranched polyamine-ester polymer and application thereof in microfluidic chip |
| GB2499944B (en) * | 2010-11-15 | 2018-05-02 | Shanghai Weikai Optoelectronics New Mat Co Ltd | Crosslinkable curing super-branched polyester and cured product and preparation method thereof |
| MX352375B (en) * | 2011-04-15 | 2017-11-22 | Basf Se | Hyperbranched polyesters in printing inks. |
| CN102924679B (en) * | 2012-11-12 | 2014-08-13 | 长兴化学工业(中国)有限公司 | Epoxy resin modified waterborne hyperbranched polyurethane and preparation method thereof |
| CN103113569B (en) * | 2013-01-13 | 2015-04-22 | 株洲时代电气绝缘有限责任公司 | Hyper-branched unsaturated resin and application thereof |
| CN104192968B (en) * | 2014-08-28 | 2016-08-17 | 中山市宏科化工有限公司 | A kind of hyperbranched type heavy metal chelating agent and preparation method thereof |
| CN106519158B (en) * | 2016-10-26 | 2019-02-19 | 江南大学 | A kind of end group is the preparation method of the hyperbranched poly (urethane-amine) of hydroxyl, interior branch unit with vinyl |
| CN107266687B (en) * | 2017-07-11 | 2019-11-22 | 上海维凯光电新材料有限公司 | Anti-pollution auxiliary agent for ultraviolet-curing paint |
| CN107245129B (en) * | 2017-08-07 | 2019-04-02 | 南方医科大学 | A kind of hydrophilic unsaturated aliphatic polyester and its preparation method and application |
| CN109957083B (en) * | 2017-12-25 | 2021-06-29 | 江苏百赛飞生物科技有限公司 | Unsaturated polyol, photocurable polyurethane prepared from unsaturated polyol and preparation methods of unsaturated polyol and photocurable polyurethane |
| CN108314773B (en) * | 2018-03-14 | 2021-02-02 | 广州市嵩达新材料科技有限公司 | Low-viscosity hyperbranched polyurethane acrylic resin and preparation method and application thereof |
| CN112063127A (en) * | 2020-09-14 | 2020-12-11 | 深圳市中塑新材料有限公司 | Spraying-free polybutylene terephthalate and fiber composite material and preparation method thereof |
| CN116333571B (en) * | 2023-02-21 | 2024-05-17 | 金桥德克新材料股份有限公司 | Composite for protecting aluminum material and preparation method thereof |
-
1999
- 1999-08-06 CN CNB991176235A patent/CN1147522C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1248586A (en) | 2000-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1147522C (en) | Radiation-curable amino superbranching polyester and preparation process thereof | |
| EP3374456A1 (en) | Curable polymers | |
| CN101037497A (en) | Preparation method of special epoxy resin for aqueous ultraviolet solidifying coating | |
| EP1144479A3 (en) | Modified hyperbranched polyester polymers, processes for preparing them and uses of them | |
| CN1371409A (en) | Fast-dry, high solid coatings based on modified alkyd resins | |
| CN1023867C (en) | Coating composition and method for preparing same | |
| EP2794718B1 (en) | Process for producing polyesters | |
| CN101665568A (en) | Epoxy end group hyperbranched poly (amide-ester) and preparation method | |
| CN86105264A (en) | Powder coating compositions | |
| CN104017496A (en) | Ultraviolet light polymerized low polymer synthesized by utilizing rosin derivatives and preparation method of polymer | |
| CN1176129C (en) | Phosphorus contained ultra-branched polyurethane acrylate as fire retarding agent solidified by radiation and its preparing process | |
| JP2764324B2 (en) | Method for producing polycarbonate acrylate resin or polycarbonate methacrylate resin | |
| Ming et al. | Low surface energy polymeric films from partially fluorinated photocurable solventless liquid oligoesters | |
| CN111978512A (en) | High-functionality epoxy acrylate and preparation method thereof | |
| CN1296047A (en) | Solidifiable compositions | |
| CN1139634C (en) | Solidifiable composition based on polymer containing free carboxy | |
| CN115960365A (en) | Biological terminal hydroxyl hyperbranched polyester, hyperbranched UV (ultraviolet) curing resin, and preparation method and application thereof | |
| CN101983959B (en) | Multifunctional acrylic ester monomer for photopolymerization and preparing method thereof | |
| WO1997025386A1 (en) | Solvent-free, low-emission hardenable coating means | |
| Cui et al. | Facile method to prepared photoinitiated cationic curable plant oil and its enhancement on the impact strength of cycloaliphatic diepoxide | |
| JP2000239317A (en) | Partial esterification of polyvinyl alcohol | |
| WO1999010409A1 (en) | Radiation-polymerizable composition and printing inks containing same | |
| CN111499661A (en) | Preparation method of tin oxide complex diisooctanoate | |
| CN111019418A (en) | Multifunctional cardanol-based UV curing reactive diluent and preparation method and application thereof | |
| CN115746249A (en) | Castor oil-based waterborne UV-cured polyurethane acrylate as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |