Urethane acrylate is the radiation curing performed polymer of using always, but because it has combustibility, thereby can not be used for the coating formula that particular requirement arranged to fire-retardant.Fire retardant commonly used at present contains haloid element mostly, can produce toxic gas during burning, the personnel of combustion site is suffocated, and environment is polluted; Conventional flame retardants generally is the low-molecular-weight organism or the inorganics of addition type, and add-on is very big usually; These a large amount of fire retardants that add can not form cross-linked network with the radiation curing prepolymer reaction, thereby the over-all properties of system is affected.Have the report of halogen-free flame retardants to overcome the above problems of preparation feedback type in recent years.
U.S. Pat 3,916,073 has reported the radiation-curable flame retardant coating of being made up of the phosphorous vinyl ester of polyfunctional group, nitrogenous vinyl ester, vinylbenzene, carbon black, inorganic filler and light trigger.But because this system is formed by small molecules, curing speed is slow and incomplete; Especially vinylbenzene can produce human body and poison and cause pollution to environment, limited its application in the base protection paint field greatly.
Japanese Patent JP 62,174,249A2 have reported with the multipolymer of quaternary amine substituted ethylene base monomer and vinyl monomer, polyethers, the blend of phosphoric acid grafting polymer material, obtain having the nitrogen phosphorus coordination system of flame retardant effect.But because this method adopts the blend step, raw-material consistency is had relatively high expectations, preparation process is more numerous and diverse.
U.S. Pat 5,045,385 and US 5,202,189 reported a kind of radiation-curable flame-proof composite material of forming at glass fibre, water glass and the resol of 10-15 micron by inertia ore, diameter, can be used as the base material of building infill wall and door and window.But because the existence of a large amount of inorganic additivess, the intensity of this matrix material reduces greatly, and it is embedded and can not be used for substrate surface to be used for base material.
U.S. Pat 5,218,030 and US 5,200,452 have reported with unsaturated polyester, Resins, epoxy as body, adopt antimony, bismuth and the 6th, seven, some elements of the eight subgroups radiation-curable flame-retardant system as flame-retardant additive, can be used as fire protection coating, fire-proof construction material.Its shortcoming is because the existence of a large amount of non-reacted fire retardants reduces the intensity of this material greatly, and the price height.
International monopoly WO 9,952, and 971A1 has reported that radiation-curable resin and fire retardant blend prepare the fire-resisting protection coating of material; So that but reach the fire-retardant purpose of ideal, and fire retardant generally occupies significant proportion in prescription, and this just requires the consistency height of resin and fire retardant, just can avoid being separated in the use; And the existence of a large amount of non-reacted fire retardants reduces the intensity of material greatly.
International monopoly WO 9,502,004 has reported by poly phosphate dibasic alcohol and vulcabond and hydroxy acrylate reaction and has made linear phosphorous urethane acrylate, adds the radiation-curable couting prescription that light trigger and multi-functional acrylate make as linking agent again.This method has realized the radiation curable halogen-free flame retardant coating, but because it is a linear molecule, must add a large amount of multi-functional acrylates as linking agent, regulation system viscosity and raising processing characteristics, but most of acrylate monomer has pungency, is detrimental to health to skin; And the affiliation that adds of acrylate monomer influences the solidification rate of system and the mechanical property of filming.
The purpose of this invention is to provide a kind of phosphorus contained ultra-branched polyurethane acrylate as fire retarding agent solidified by radiation and preparation method thereof, to overcome the above-mentioned defective of prior art.
The preparation method of phosphorus contained ultra-branched polyurethane acrylate as fire retarding agent solidified by radiation of the present invention; be characterised in that be response matrix with phosphoric acid and epoxy compounds at the phosphoric acid ester trivalent alcohol that 0-60 ℃ of reaction forms; by certain mole proportioning, add the monohydroxy end-caps of vulcabond or binary acyl chlorides and radiation-curable by " pre-polymerization method " or " single stage method ", catalyzer, stopper exist and protection of inert gas under react 2240-2275cm to the Fourier infrared spectrum in 0-80 ℃
-1Between disappear corresponding to the peak of isocyanic ester, promptly obtain phosphorus contained ultra-branched polyurethane acrylate as fire retarding agent solidified by radiation;
Described epoxy compounds comprises: oxyethane, propylene oxide, Racemic glycidol, glycidyl acrylate or glycidyl methacrylate;
Described vulcabond comprises: Toluene-2,4-diisocyanate, 4-vulcabond, Toluene-2,4-diisocyanate, 6-vulcabond, 4,4 '-diphenylmethanediisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, ethylbenzene vulcabond, 4,4 '-dicyclohexyl methane diisocyanate, 4,6-Xylene Diisocyanate, isophorone diisocyanate, PPDI, cyclohexyl diisocyanate, 3,3 '-dimethyl diphenyl-4,4 '-vulcabond or 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate;
Described binary acyl chlorides comprises: succinic chloride, phthalyl chloride, p-phthaloyl chloride, glutaryl chlorine, hexanedioyl chlorine or sebacoyl chloride;
The chemical formula of described radiation-curable monohydroxy end-caps can be expressed as HOR
1[R
2]
mIn the formula, R
1For containing the alkyl or aryl of 1-12 carbon; R
2Comprise acrylate, methacrylic ester, vinyl ether, allyl ethers, itaconic ester, crotonate or other radiation-curable group; M is 1,2 or 3;
Described catalyzer comprises dibutyltin dilaurate, stannous octoate, N-methylmorpholine or triethylenediamine; Consumption is a 0.1%-2% weight;
Described stopper comprises MEHQ, Resorcinol; Consumption is 500-4000ppm;
Described rare gas element comprises nitrogen, helium or argon gas;
Described " certain mole proportioning " refers to the molar ratio of vulcabond and phosphoric acid ester trivalent alcohol, when representing with B, and 1.5<B≤3.0; The molar ratio of monohydroxy end-caps and phosphoric acid ester trivalent alcohol is 2B-3;
Described " pre-polymerization method "; promptly earlier with the di-isocyanate reaction of phosphoric acid ester trivalent alcohol with certain mole proportioning; under catalyzer existence and protection of inert gas; 0-80 ℃ was reacted 5-10 hour; the monohydroxy end-caps that adds certain mole proportioning again; catalyzer, stopper exist and protection of inert gas under, 0-80 ℃ is reacted 2240-2275cm to the Fourier infrared spectrum
-1Between disappear corresponding to the peak of isocyanic ester;
Described " single stage method "; be about to the phosphoric acid ester trivalent alcohol and directly mix with the monohydroxy end-caps of vulcabond and radiation-curable, reacting 2240-2275cm to the Fourier infrared spectrum in 0-80 ℃ under catalyzer, stopper existence and the protection of inert gas by certain mole proportioning
-1Between disappear corresponding to the peak of isocyanic ester.
Characteristics of the present invention are to adopt first phosphoric acid and epoxy compounds prepared in reaction phosphoric acid ester trivalent alcohol, and introduce the performed polymer of radiation-curable; Adopt first with two functional group's isocyanic ester and the reaction of trifunctional phosphoric acid ester, prepare hyperbranched polyfunctional compound with the end capped method of simple function group compound again and be used for radiation-curable flame retardant coating performed polymer; The molecular weight of product and functionality can be regulated within the specific limits by the ratio that changes two functional group's isocyanic ester and trifunctional phosphoric acid ester.With U.S. Pat 3,916, the radiation-curable fire retardant of 073 method preparation is compared, and radiation-curable P contained compound fire retardant of the present invention is made up of macromole, and completion of cure and shrinking percentage are little in the solidification process, and the sticking power of filming is good; With Japanese Patent JP 62,174, the radiation-curable fire retardant of 249A2 method preparation is compared, and radiation-curable P contained compound fire retardant of the present invention need not blend in construction process, has simplified construction procedure; With U.S. Pat 5,218,030, US 5,200,452, US 5,045, and 385, US 5, the radiation-curable fire retardant of 202,189 methods preparations is compared, and radiation-curable P contained compound fire retardant raw material sources of the present invention are wider, more cheap and obtain easily; With international monopoly WO 9,952, the radiation-curable fire retardant of 971A1 method preparation is compared, because radiation-curable P contained compound fire retardant of the present invention is a kind of radiation-curable oligomer, can be used as the fire retardant body and directly use, range of application is broad more.With international monopoly WO 9,502, the linear phosphorous urethane acrylate of radiation-curable of 004 method preparation is compared, the hyperbranched phosphorous urethane acrylate of radiation-curable of the present invention is a multifunctional molecule, need not to sneak into small molecules multi-functional acrylate to the toxic effect of human body as linking agent, production process is more cleaned; And, can enhance productivity greatly and save the energy because it is hyperbranched structure, and solidification rate is faster; In addition, the functionality of the hyperbranched phosphorous urethane acrylate of radiation-curable of the present invention's preparation can be regulated within the specific limits, and then changes the physicals of solidifying the back coating, thereby can satisfy the performance requriements in different application field better.Do not see the report that the hyperbranched phosphorous polyurethane acrylate as fire retarding agent of such radiation-curable that adopts method therefor preparation of the present invention is arranged up to now as yet.
The hyperbranched phosphorous urethane acrylate preparation method its raw material source of radiation-curable of the present invention extensively, cheaply be easy to get is easy to suitability for industrialized production.The prepared hyperbranched phosphorous urethane acrylate of radiation-curable of the present invention has wide prospect in industrial application.
Further describe preparation method, radiation curing and the flame retardant properties thereof of the hyperbranched phosphorous polyurethane acrylate as fire retarding agent of radiation-curable of the present invention by the following examples.But the present invention is not limited to listed example.
Embodiment:
One, the preparation of intermediate product phosphoric acid ester trivalent alcohol
Embodiment 1. is with phosphoric acid and propylene oxide phosphoric acid ester trivalent alcohol
Employing is equipped with mechanical stirrer, is had the 250ml three-necked bottle reactor of nitrogen inlet and prolong, the adding weight concentration is 85% phosphoric acid 6.8g (0.059mol), slowly drip 27.9g (0.481mol) propylene oxide at ice bath and under continuing to stir, drip off the back and under ice bath, continue reaction one hour, get acid number less than 5mgKOH/g until reactant with 0.1N NaOH drips of solution location survey 30 ℃ of reactions again, the mixture that obtains vacuumizes under 80 ℃ removes remaining propylene oxide and the water in the phosphoric acid, obtains the flaxen liquid of 26.4g.
Products therefrom is through Infrared spectroscopy, at 1015cm
-1Very strong alkyl phosphate characteristic peak appears in the place, at 1200-1270cm
-1Between characteristic peak corresponding to C-O-C and P-O-C key appears.
Adopt the back titration method, measuring the product hydroxyl value with sodium hydroxide ethanol standardized solution is 361mgKOH/g, and the Theoretical Calculation hydroxyl value is 375mgKOH/g.
Through above-mentioned analysis as can be known, the present embodiment product is the phosphoric acid ester trivalent alcohol.Its reaction formula is:
N in the present embodiment
1+ n
2+ n
3=6.
Embodiment 2. phosphoric acid and propylene oxide phosphoric acid ester trivalent alcohol in varing proportions
Adopt the reaction conditions identical with embodiment 1, the adding weight concentration is 85% phosphoric acid 26.1g (0.226mol), and 130.5g (2.25mol) propylene oxide reaction, obtains the flaxen rarer liquid of 117.8g.Its reaction formula is the same listed, in the present embodiment n
1+ n
2+ n
3=7.3.
Two, the hyperbranched phosphorous urethane acrylate for preparing radiation-curable with intermediate product phosphoric acid ester trivalent alcohol
Embodiment 3. (represents the molar ratio of vulcabond and phosphoric acid ester trivalent alcohol with B, B=2.3) with the hyperbranched phosphorous urethane acrylate of " pre-polymerization method " preparation radiation-curable
Mechanical stirrer is equipped with in employing, oil bath and have nitrogen inlet, the 250ml three-necked bottle reactor of drying tube and dropping funnel, adding is by synthetic phosphoric acid ester trivalent alcohol 34.3g (0.066mol) and 70mg dibutyltin dilaurate among the embodiment 2,25 ℃ of following stirring at room also splash into 26.4g (0.151mol) Toluene-2,4-diisocyanate by dropping funnel, the 4-vulcabond, slowly be warmed up to 70 ℃ after dripping off, reacted 2 hours, add the 70mg MEHQ again, and, reacted 4 hours down at 70 ℃ by dropping funnel slow 12.2g (0.105mol) senecioate hydroxyl ethyl ester that drips in reactor.Reaction can be expressed as follows:
Products therefrom is through Infrared spectroscopy, at 2240-2275cm
-1Between the isocyanic ester characteristic peak disappear; At 1720cm
-1Acid amides I band appears in the place, at 1538cm
-1Acid amides II band appears, at 1200-1270cm
-1Acid amides III band appears in the place; At 810cm
-1Acrylate RCH=CH appears in the place
2Characteristic peak.
The two key assignments that adopt the bromide oxidation style to measure products therefrom are 1.38mmol/g, and theoretical two key assignments of product are 1.44mmol/g.
Toluene-2,4-diisocyanate in the present embodiment, the ratio B of 4-vulcabond and phosphoric acid ester trivalent alcohol is 2.3.
Embodiment 4. prepares the hyperbranched phosphorous urethane acrylate (B=1.8,2.8) of radiation-curable according to different ratios with " pre-polymerization method "
Adopt the reaction conditions identical, change Toluene-2,4-diisocyanate, the ratio of 4-vulcabond and phosphoric acid ester trivalent alcohol with embodiment 3.
With 23.7g (0.046mol) phosphoric acid ester trivalent alcohol and 14.3g (0.082mol) Toluene-2,4-diisocyanate, 4-vulcabond, the reaction of 3.2g (0.027) senecioate hydroxyl ethyl ester, the B value is 1.8 herein.
The two key assignments that adopt the bromide oxidation style to measure products therefrom are 0.61mmol/g, and theoretical two key assignments of product are 0.67mmol/g.
With 25.0g (0.048mol) phosphoric acid ester trivalent alcohol and 23.5g (0.135mol) Toluene-2,4-diisocyanate, 4-vulcabond, the reaction of 14.6g (0.126mol) senecioate hydroxyl ethyl ester, the B value is 2.8 herein.
The two key assignments that adopt the bromide oxidation style to measure products therefrom are 1.88mmol/g, and theoretical two key assignments of product are 1.99mmol/g.
Embodiment 5. prepares the hyperbranched phosphorous urethane acrylate (B=2.3) of radiation-curable with single stage method
The 250ml three-necked bottle reactor that employing is equipped with mechanical stirrer, oil bath and is had nitrogen inlet, drying tube and dropping funnel, adding is by synthetic phosphoric acid ester trivalent alcohol 26.4g (0.051mol), 50mg MEHQ and 50mg dibutyltin dilaurate among the embodiment 2,25 ℃ are descended stirring and splash into 20.3g (0.116mol) Toluene-2,4-diisocyanate continuously by dropping funnel, 4-vulcabond and 9.4g (0.081mol) senecioate hydroxyl ethyl ester, slowly be warming up to 70 ℃ after dripping off, reacted 5 hours.
Products therefrom is through Infrared spectroscopy, at 2240-2275cm
-1Between the isocyanic ester characteristic peak disappear; At 1720cm
-1Acid amides I band appears in the place, at 1538cm
-1Acid amides II band appears, at 1200-1270cm
-1Acid amides III band appears in the place; At 810cm
-1Acrylate RCH=CH appears in the place
2Characteristic peak.
The two key assignments that adopt the bromide oxidation style to measure products therefrom are 1.35mmol/g.
The number-average molecular weight that records product with QX-08 VPO tester is 1830.
Embodiment 6. prepares the hyperbranched phosphorous urethane acrylate (B=1.8,2.8) of radiation-curable according to different ratios with single stage method
Adopt the reaction conditions identical, change Toluene-2,4-diisocyanate, the ratio of 4-vulcabond and phosphoric acid ester trivalent alcohol with embodiment 5.
With 19.8g (0.038mol) phosphoric acid ester trivalent alcohol and 11.9g (0.068mol) Toluene-2,4-diisocyanate, 4-vulcabond, the reaction of 2.7g (0.023mol) senecioate hydroxyl ethyl ester, B is 1.8 herein.
The two key assignments that adopt the bromide oxidation style to measure products therefrom are 0.63mmol/g, and the number-average molecular weight that records product with QX-08 VPO tester is 2536.
With 16.7g (0.032mol) phosphoric acid ester trivalent alcohol and 15.7g (0.090mol) Toluene-2,4-diisocyanate, 4-vulcabond, the reaction of 9.7g (0.084mol) senecioate hydroxyl ethyl ester, B is 2.8 herein.
The two key assignments that adopt the bromide oxidation style to measure products therefrom are 1.87mmol/g, and the number-average molecular weight that records product with QX-08 VPO tester is 1035.
Three, the ultra-violet curing of the hyperbranched phosphorous urethane acrylate of radiation-curable and flame retardant properties are measured
The radiation curing of the hyperbranched phosphorous urethane acrylate of embodiment 7. radiation-curables
With the hyperbranched phosphorous urethane acrylate of radiation-curable of preparation among embodiment 5 and the embodiment 6 respectively with the light trigger α of 2% weight, alpha-alpha-dimethyl-Alpha-hydroxy methyl phenyl ketone (Darocur 1173) mixes, place half an hour at 80 ℃, stirring frequently mixes it, on sheet glass, paint the film of 200 micron thickness with spreader, place 10 centimetres of lamps apart from locating with Philip HPM-15 1000W ultraviolet lamp (UV) irradiation, wherein the sample of embodiment 5 is listed in the table 1 at the double bond conversion rate of different time, obtains the solidified coating of a hard transparent at last.Its hardness is listed in the table 2.
Table 1
Light application time (second) | 2 | 4 | 6 | 8 | 10 |
Double bond conversion rate (%) | 64.0 | 70.3 | 73.6 | 76.6 | 78.1 |
Table 2
The B value | 1.8 | 2.3 | 2.8 |
Pencil hardness | 4B | 3H | 4H |
Pendulum hardness (s) | 230 | 400 | 420 |
This product can solidify rapidly when electron beam or γ irradiation equally.
The mensuration of the hyperbranched phosphorous urethane acrylate cured film shrinking percentage of embodiment 8. radiation-curables with density bottle measure respectively solidify before and after the density of irradiation prescription and cured film not, can calculate the shrinking percentage of cured film according to density difference.The shrinking percentage of embodiment 5 is 8%, much smaller than the shrinking percentage (20-30%) of general curing system, illustrates that the sticking power of itself and base material is good.
The limiting oxygen index determination of the hyperbranched phosphorous urethane acrylate of embodiment 9. radiation-curables
With Toluene-2,4-diisocyanate, the senecioate hydroxyl ethyl ester of 4-vulcabond and twice molar weight, in the presence of 1000ppm MEHQ and 0.1% dibutyltin dilaurate, 70 ℃ were reacted 5 hours, obtained waxy solid under the room temperature, represented with ATA.The product of ATA and embodiment 5 and the aliphatic urethane acrylate Ebecryl 270 of U.S. UCB. S.A. (BE) Bruxelles Belgium are made a series of samples by a certain percentage, add 2wt% light trigger α respectively, alpha-alpha-dimethyl-Alpha-hydroxy methyl phenyl ketone (Darocur 1173), make long 14cm after the mixing, wide 6.5 ± 0.5mm, the sample rod of thick 3mm, place 10 centimetres of lamps apart from locating uv light irradiation with Philip HPM-151000W, solidified sample is measured its oxygen index with ZRY type limiting oxygen index determination instrument, and it the results are shown in table 3.
Table 3
The sample sequence number | Embodiment 5 products (wt%) | Ebecryl 270 (wt%) | ATA (wt%) | Phosphorus content (wt%) | Nitrogen content (wt%) | Phosphorus nitrogen total content (%) | Oxygen index |
1 | 100 | 0 | 0 | 2.8 | 5.8 | 8.6 | 27.0 |
2 | 75 | 0 | 25 | 2.1 | 6.1 | 8.2 | 26.5 |
3 | 75 | 12.5 | 12.5 | 2.1 | 5.7 | 7.8 | 25.5 |
4 | 75 | 25 | 0 | 2.1 | 5.3 | 7.4 | 25.0 |
5 | 50 | 0 | 50 | 1.4 | 6.4 | 7.8 | 26.0 |
6 | 50 | 25 | 25 | 1.4 | 5.6 | 7.0 | 24.0 |
7 | 50 | 50 | 0 | 1.4 | 4.8 | 6.2 | 22.8 |
8 | 25 | 0 | 75 | 0.7 | 6.6 | 7.3 | 25.5 |
9 | 25 | 37.5 | 37.5 | 0.7 | 5.4 | 6.1 | 23.0 |
10 | 25 | 75 | 0 | 0.7 | 4.3 | 5.0 | 21.5 |
11 | 0 | 0 | 100 | 0 | 6.9 | 6.9 | 24.5 |
12 | 0 | 50 | 50 | 0 | 5.3 | 5.3 | 21.0 |
13 | 0 | 100 | 0 | 0 | 3.7 | 3.7 | 19.5 |
Sample 2,3,4 or 5,6,7 or 8,9,10 or 11,12,13 all can be found in the comparison sheet 4, and the phosphorus content of each group is identical, and oxygen index descends with the decline of nitrogen content, illustrates that the nitrogen in the product has a promoter action to fire-retardant; Comparative sample 2,5,8,11 can find that though nitrogen content increases to some extent, oxygen index descends with the decline of phosphorus content, illustrates that the phosphorus in the product also has a promoter action to fire-retardant; The content of properly distributed phosphorus, nitrogen in the system of the present invention is because phosphorus-nitrogen synergistic effect has obtained the good flame effect.The nitrogenous phosphide of radiation-curable of the present invention can be used as fire retardant and is applied in the coatings such as material of construction, electronic product, textiles and electric wire.