CN104031544A - Preparation method of inflaming retarding type aqueous polyurethane coating - Google Patents
Preparation method of inflaming retarding type aqueous polyurethane coating Download PDFInfo
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- CN104031544A CN104031544A CN201410325222.0A CN201410325222A CN104031544A CN 104031544 A CN104031544 A CN 104031544A CN 201410325222 A CN201410325222 A CN 201410325222A CN 104031544 A CN104031544 A CN 104031544A
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- aqueous polyurethane
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- polyurethane coating
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- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000000979 retarding effect Effects 0.000 title abstract 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920002635 polyurethane Polymers 0.000 claims abstract description 31
- 239000004814 polyurethane Substances 0.000 claims abstract description 31
- -1 phosphoryl nafoxidine ester Chemical class 0.000 claims abstract description 24
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims abstract description 12
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 12
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- ODHCTXKNWHHXJC-VKHMYHEASA-N 5-oxo-L-proline Chemical compound OC(=O)[C@@H]1CCC(=O)N1 ODHCTXKNWHHXJC-VKHMYHEASA-N 0.000 claims abstract description 8
- 238000004945 emulsification Methods 0.000 claims abstract description 8
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- 239000004970 Chain extender Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000003063 flame retardant Substances 0.000 claims description 36
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 19
- 159000000013 aluminium salts Chemical class 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 11
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 238000002525 ultrasonication Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 4
- IKEIGECHKXPQKT-UHFFFAOYSA-N silicon phthalocyanine dihydroxide Chemical compound N1=C(C2=CC=CC=C2C2=NC=3C4=CC=CC=C4C(=N4)N=3)N2[Si](O)(O)N2C4=C(C=CC=C3)C3=C2N=C2C3=CC=CC=C3C1=N2 IKEIGECHKXPQKT-UHFFFAOYSA-N 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 4
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical group C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 claims description 3
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 claims description 3
- OZBIETPCMMGBGS-UHFFFAOYSA-N 1,1-dimethyl-2-propylhydrazine Chemical compound CCCNN(C)C OZBIETPCMMGBGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- ODHCTXKNWHHXJC-UHFFFAOYSA-N acide pyroglutamique Natural products OC(=O)C1CCC(=O)N1 ODHCTXKNWHHXJC-UHFFFAOYSA-N 0.000 abstract 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- MVLMPMUGCWJDLE-UHFFFAOYSA-M dibutylboron trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[B+]CCCC MVLMPMUGCWJDLE-UHFFFAOYSA-M 0.000 abstract 1
- 229950002366 nafoxidine Drugs 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 description 12
- 238000009835 boiling Methods 0.000 description 10
- 239000000779 smoke Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920006264 polyurethane film Polymers 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UCTWMZQNUQWSLP-VIFPVBQESA-N (R)-adrenaline Chemical compound CNC[C@H](O)C1=CC=C(O)C(O)=C1 UCTWMZQNUQWSLP-VIFPVBQESA-N 0.000 description 1
- 229930182837 (R)-adrenaline Natural products 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- VGHRAISFRBSOAL-UHFFFAOYSA-N [O].CCOC(N)=O Chemical compound [O].CCOC(N)=O VGHRAISFRBSOAL-UHFFFAOYSA-N 0.000 description 1
- 150000001398 aluminium Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960005139 epinephrine Drugs 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229940074869 marquis Drugs 0.000 description 1
- SWVGZFQJXVPIKM-UHFFFAOYSA-N n,n-bis(methylamino)propan-1-amine Chemical compound CCCN(NC)NC SWVGZFQJXVPIKM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a preparation method of an inflaming retarding type aqueous polyurethane coating. Under the condition that dibutylboron trifluoromethanesulfonate catalysts exist, 1,4-Bis(hydroxydimethylsily)benzene and hexamethylene diisocyanate are mixed by a weight ratio of 2:1 and react for 2-4 hours at 80-110 DEG C, then parathion is added into a reaction system, the reaction temperature is 80-110 DEG C, the reaction time is 40-60 minutes, and a polyurethane prepolymer is obtained; chain extenders and butanone are added into the polyurethane prepolymer and are stirred for 3-5 hours at 65-85 DEG C, trithylamine is added for neutral reaction for 10-40 minutes, water is added for emulsification, and aqueous polyurethane is formed; aluminum salt dispersion liquid, L-pyroglutamic acid, screw ring phosphoryl nafoxidine ester and N-aminoethyl-3-aminopropyl triethoxysilane are added into the aqueous polyurethane and are sheared and stirred for 40-80 minutes under the condition of pH being 7, and the inflaming retarding type aqueous polyurethane coating is obtained. The flammability and mechanical property of the obtained polyurethane coating are greatly improved.
Description
Technical field
The present invention relates to the preparation method of aqueous polyurethane coating, particularly a kind of preparation method of flame-retardant aqueous polyurethane coating.
Background technology
Aqueous polyurethane (claiming again waterbased urethane) is a kind of urethane resin that contains hydrophilic radical in the molecular chain of urethane, has very strong affinity with glassware for drinking water, adopts specific technique can make it in water, to disperse and form stable system.Aqueous polyurethane is mainly used in the aspects such as leather finish, textile printing and dyeing, paper-making industry, building coating, tackiness agent, steel moulder's paint, related is nearly all inflammable material, these materials as without fire-retardant finish, must become the potential safety hazard of initiation fire in use.Fire-retardantization of aqueous polyurethane is one of important directions of aqueous polyurethane functionalization.
The people such as Chen He [1] Chen He, Luo Yunjun, Li Jie. the synthetic and performance [J] of the flame-retardant modified aqueous polyurethane of hard section. polymer material science and engineering, 2008,24(6): 79 ~ 84 take dibromoneopentyl glycol as chainextender, by the mode of hard section of modification, ignition-proof element is incorporated in aqueous polyurethane, synthesizes the extinguishing waterborn polyurethane of a series of different modification degree.Oxygen index test discovery, the oxygen index of aqueous polyurethane increases with dibromoneopentyl glycol modification degree, and wherein the urethane oxygen index of 15% modification has reached 29.6%, makes urethane by the difficult combustion of flammable reduction.But the urethane of bromide fire retardant modification, when burning, produces a large amount of smog, also easy etching apparatus, is therefore subject to certain restrictions.And the extinguishing waterborn polyurethane that China sells in the market be take blend Compositional type as main, by adding a large amount of fire retardants, reach flame retardant effect, this method cost is higher and larger to the performance impact of urethane.
Phospho acid aluminium class is a kind of novel fire retardant, have non-volatile, the feature such as phosphorus content is high, Heat stability is good.Hypo-aluminum orthophosphate Heat stability is good, make its application product there is higher thermostability, at the material of processing, there is good mechanical property and good anti-marquis's property, the polymer composition that contains hypo-aluminum orthophosphate presents higher flame retardant resistance. because hypo-aluminum orthophosphate phosphorus content is high, there is the advantages such as Heat stability is good, fire-retardant effect be large.
Summary of the invention
A kind of flame-retardant aqueous polyurethane coating adopts poly-hydroxy organosilicon to replace traditional polyester polyol and polyether glycol and isocyanate reaction; select thiophos and trifluoromethanesulfonic acid two fourth boron concerted catalysiss to replace traditional dibutyl tin laurate; with Organo-silicon on Polyurethane performed polymer, carry out chain extension; add aluminium salt suppress the amount of being fuming of urethane and improve flame retardant resistance simultaneously; the burning of gained urethane produces fine and close protective layer, and the smog discharging is little.
The present invention has adopted following technical scheme.
A preparation method for flame-retardant aqueous polyurethane coating, is characterized in that:
(1) under the condition, existing at trifluoromethanesulfonic acid two fourth B catalysts, by 1, two (dimethyl hydroxyl the is silica-based) benzene of 4-mixes according to weight ratio 2:1 with hexamethylene diisocyanate, at 80 ~ 110 ℃, react 2 ~ 4h, add again thiophos in reaction system, 80 ~ 110 ℃ of temperature of reaction, reaction times 40 ~ 60min, obtains base polyurethane prepolymer for use as; Described catalyst levels is 1,0.3 ~ 0.7% of two (dimethyl hydroxyl the is silica-based) benzene of 4-and hexamethylene diisocyanate gross weight, thiophos is 1.0 ~ 1.4% of Isosorbide-5-Nitrae-bis-(dimethyl hydroxyl is silica-based) benzene and hexamethylene diisocyanate gross weight;
(2), in base polyurethane prepolymer for use as, add the chainextender of base polyurethane prepolymer for use as gross weight 1.4 ~ 2.8% and the butanone of base polyurethane prepolymer for use as weight 16 ~ 24%, stirring reaction 3 ~ 5h under 65 ~ 85 ℃ of conditions, add triethylamine to carry out neutralization reaction 10 ~ 40min, add water and carry out emulsification, form a kind of aqueous polyurethane standby; Described triethylamine is 10 ~ 30% of base polyurethane prepolymer for use as weight;
(3), add the dispersion agent of aluminium salt compound solution weight 1.5 ~ 1.8% in the aluminium salt compound solution that is 10% to mass concentration, in temperature, be that under 30 ℃, the pH condition that is 7, ultrasonication 20min, obtains aluminium salt dispersion liquid standby;
(4), N-aminoethyl-3-aminopropyl triethoxysilane of the volution phosphinylidyne Pyrrolidine ester of the aluminium salt dispersion liquid of aqueous polyurethane solid content 10 ~ 20%, the L-Glutimic acid of aqueous polyurethane solid content 1 ~ 2%, the urethane solid content 10 ~ 20% of water-based and aqueous polyurethane solid content 1 ~ 2% is joined in aqueous polyurethane, the condition down cut that is 7 at pH stirs 40 ~ 80min, obtains aqueous flame retardant polyurethane coating.
Chainextender is Diphenylsilanediol, 4, any one in two (dimethyl hydroxyl the is silica-based) phenyl ether of 4'-, silicon phthalocyanine dihydroxide; Aluminium salt compound is any one in diphenyl phosphonic acid aluminium, dipropyl phospho acid aluminium and diethyl phospho acid aluminium;
Dispersion agent is N, any one of N-dimethylamino propylamine, Sodium dodecylbenzene sulfonate, sodium polyacrylate, polyvinyl alcohol, cationic polyacrylamide, water glass, Sodium hexametaphosphate 99; Shear agitation speed 700 ~ 1200rpm.
The present invention has following characteristics:
(1) smog of comparing traditional flame retardant polyurethane release when prepared flame-retardant aqueous polyurethane coating burns significantly reduces, and fire-retardant cost performance is high;
(2) performed polymer synthetic in selected catalyst replaced the defect of the traditional obtained polyurethane film surface difference of dibutyl tin laurate, make product surface smooth smooth, good toughness.
(3) select organosilicon to make chainextender, performance nitrogen, phosphorus, silicon compound can form good tight zone, and aluminium salt compound has good smoke-suppressing, flame retardant resistance, accomplishes the optimum resistance combustion effect of fire-proof smoke-proof.
embodimentbelow in conjunction with example, further illustrate the present invention.
example one
(1), in the four-hole boiling flask of 500ml that stirring arm, thermometer, prolong are housed, add 0.3g trifluoromethanesulfonic acid two fourth boron, 1, two (dimethyl hydroxyl is silica-based) the benzene 66g of 4-and hexamethylene diisocyanate 33g, at 80 ℃, react 2h, add again thiophos 0.99g in four-hole boiling flask, 80 ℃ of temperature of reaction, reaction times 40min, obtains base polyurethane prepolymer for use as 99.8g;
(2), in base polyurethane prepolymer for use as, add Diphenylsilanediol 1.4g and butanone 16g, stirring reaction 3h under 65 ℃ of conditions, add triethylamine 9.98g to carry out neutralization reaction 10min, add water 160g and carry out emulsification, form a kind of solid content and be 35.4% aqueous polyurethane 282g, be transferred in 500ml beaker standby;
(3), in 50ml beaker, add 3g diphenyl phosphonic acid aluminium, 27g water and N, N-dimethylamino propylamine 0.45g, is that under 30 ℃, the pH condition that is 7, ultrasonication 20min, obtains aluminium salt dispersion liquid standby in temperature;
(4), aluminium salt dispersion liquid 10.1g, L-Glutimic acid 1g, volution phosphinylidyne Pyrrolidine ester 10.1g and N-aminoethyl-3-aminopropyl triethoxysilane 1g are joined in above-mentioned (2), under the condition that is 7 at pH, 700rpm down cut stirs 40min, obtains flame-retardant polyurethane coating.
example two
(1), in the four-hole boiling flask of 500ml that stirring arm, thermometer, prolong are housed, add 0.7g trifluoromethanesulfonic acid two fourth boron, 1, two (dimethyl hydroxyl is silica-based) the benzene 66g of 4-and hexamethylene diisocyanate 33g, at 110 ℃, react 4h, add again thiophos 1.39g in four-hole boiling flask, 110 ℃ of temperature of reaction, reaction times 60min, obtains base polyurethane prepolymer for use as 100.5g;
(2), in base polyurethane prepolymer for use as, add 4, two (dimethyl hydroxyl is silica-based) the phenyl ether 2.8g of 4'-and butanone 24.1g, stirring reaction 5h under 85 ℃ of conditions, add triethylamine 20.1g to carry out neutralization reaction 40min, add water 150g and carry out emulsification, form a kind of solid content and be 35% aqueous polyurethane 295g, be transferred in 500ml beaker standby;
(3) in temperature, be, in 50ml beaker, add 3g dipropyl phospho acid aluminium, 27g water and Sodium dodecylbenzene sulfonate 0.54g, that under 30 ℃, the pH condition that is 7, ultrasonication 20min, obtains aluminium salt dispersion liquid standby;
(4), aluminium salt dispersion liquid 20.7g, L-Glutimic acid 2.1g, volution phosphinylidyne Pyrrolidine ester 20.7g and N-aminoethyl-3-aminopropyl triethoxysilane 2.1g are joined in above-mentioned (2), under the condition that is 7 at pH, 1200rpm down cut stirs 80min, obtains flame-retardant polyurethane coating.
example three
(1), in the four-hole boiling flask of 500ml that stirring arm, thermometer, prolong are housed, add 0.5g trifluoromethanesulfonic acid two fourth boron, 1, two (dimethyl hydroxyl is silica-based) the benzene 66g of 4-and hexamethylene diisocyanate 33g, at 95 ℃, react 3h, add again thiophos 1.19g in four-hole boiling flask, 95 ℃ of temperature of reaction, reaction times 50min, obtains base polyurethane prepolymer for use as 100g;
(2), in base polyurethane prepolymer for use as, add silicon phthalocyanine dihydroxide 2.1g and butanone 20g, stirring reaction 4h under 75 ℃ of conditions, add triethylamine 15g to carry out neutralization reaction 25min, add water 150g and carry out emulsification, form a kind of solid content and be 35.8% aqueous polyurethane 285g, be transferred in 500ml beaker standby;
(3) in temperature, be, in 50ml beaker, add 3g diethyl phospho acid aluminium, 27g water and sodium polyacrylate 0.45g, that under 30 ℃, the pH condition that is 7, ultrasonication 20min, obtains aluminium salt dispersion liquid standby;
(4), aluminium salt dispersion liquid 15.3g, L-Glutimic acid 1.5g, volution phosphinylidyne Pyrrolidine ester 15.3g and N-aminoethyl-3-aminopropyl triethoxysilane 1.5g are joined in above-mentioned (2), under the condition that is 7 at pH, 950rpm down cut stirs 60min, obtains flame-retardant polyurethane coating.
example four
(1), in the four-hole boiling flask of 500ml that stirring arm, thermometer, prolong are housed, add 0.7g trifluoromethanesulfonic acid two fourth boron, 1, two (dimethyl hydroxyl is silica-based) the benzene 66g of 4-and hexamethylene diisocyanate 33g, at 110 ℃, react 4h, add again thiophos 1.39g in four-hole boiling flask, 110 ℃ of temperature of reaction, reaction times 60min, obtains base polyurethane prepolymer for use as 100.5g;
(2), in base polyurethane prepolymer for use as, add 4, two (dimethyl hydroxyl is silica-based) the phenyl ether 2.8g of 4'-and butanone 24.1g, stirring reaction 5h under 85 ℃ of conditions, add triethylamine 20.1g to carry out neutralization reaction 40min, add water 150g and carry out emulsification, form a kind of solid content and be 35% aqueous polyurethane 295g, be transferred in 500ml beaker standby;
(3) in temperature, be, in 50ml beaker, add 3g dipropyl phospho acid aluminium, 27g water and Sodium dodecylbenzene sulfonate 0.54g, that under 30 ℃, the pH condition that is 7, ultrasonication 20min, obtains aluminium salt dispersion liquid standby;
(4), aluminium salt dispersion liquid 20.7g, L-Glutimic acid 2.1g, volution phosphinylidyne Pyrrolidine ester 20.7g, N-aminoethyl-3-aminopropyl triethoxysilane 2.1g and tartaric acid epinephrine 0.2g are joined in above-mentioned (2), under the condition that is 7 at pH, 1200rpm down cut stirs 80min, obtains flame-retardant polyurethane coating.
example five
(1), in the four-hole boiling flask of 500ml that stirring arm, thermometer, prolong are housed, add 0.5g trifluoromethanesulfonic acid two fourth boron, 1, two (dimethyl hydroxyl is silica-based) the benzene 66g of 4-and hexamethylene diisocyanate 33g, at 95 ℃, react 3h, add again thiophos 1.19g in four-hole boiling flask, 95 ℃ of temperature of reaction, reaction times 50min, obtains base polyurethane prepolymer for use as 100g;
(2), in base polyurethane prepolymer for use as, add silicon phthalocyanine dihydroxide 2.1g and butanone solvent 20g, stirring reaction 4h under 75 ℃ of conditions, add triethylamine 15g to carry out neutralization reaction 25min, add water 150g and carry out emulsification, form a kind of solid content and be 35.8% aqueous polyurethane 285g, be transferred in 500ml beaker standby;
(3) in temperature, be, in 50ml beaker, add 3g diethyl phospho acid aluminium, 27g water and sodium polyacrylate 0.45g, that under 30 ℃, the pH condition that is 7, ultrasonication 20min, obtains aluminium salt dispersion liquid standby;
(4), by 3 of aluminium salt dispersion liquid 15.3g, L-Glutimic acid 1.5g, volution phosphinylidyne Pyrrolidine ester 15.3g, N-aminoethyl-3-aminopropyl triethoxysilane 1.5g and 0.5g, 3'-diamino bisphenol S joins in above-mentioned (2), under the condition that is 7 at pH, 950rpm down cut stirs 60min, obtains flame-retardant polyurethane coating.
Table one is films that example one of the present invention becomes to the prepared a kind of flame-retardant aqueous polyurethane of example five with table two.Flame retardant resistance is to weigh by smoke density method (maximum smoke density, reach the maximum smoke density time), oxygen index, vertical combustion index (flaming combustion time, flameless combustion time), and elongation at break characterizes its mechanical property.
The flame retardant resistance of table one flame-retardant aqueous polyurethane film
| Example one | Example two | Example three | Example four | Example five | Market PU-1 | |
| Maximum smoke density | 22 | 25 | 27 | 11 | 6 | 43 |
| Reach maximum smoke density time/s | 160 | 160 | 185 | 180 | 180 | 120 |
| Oxygen index | 25.4 | 24.7 | 25.8 | 26.8 | 26.6 | 23 |
| Flaming combustion time/s | 21.3 | 21.4 | 13.2 | 10.7 | 10.1 | 24 |
| Flameless combustion time/s | 0 | 0 | 0 | 0 | 0 | 0 |
The detection of table one indices is respectively according to following standard: smoke density is measured according to GB8323-2008, and oxygen index adopts GB/T5454-1997 < < textile combustion performance test-oxygen index method > > to measure; Flaming combustion time and flameless combustion time are to be measured by test-normal beam technique > > by GB/T 5455-1997 < < textile combustion.
As shown in Table 1, during flame-retardant aqueous polyurethane burning of the present invention, maximum smoke density significantly reduces, and reaches maximum smoke density time significant prolongation, and oxygen index obviously improves, and obviously shorten combustion time.
The elongation at break of table two flame-retardant aqueous polyurethane film
| Example one | Example two | Example three | Example four | Example five | Market PU-1 | |
| Elongation at break/% | 185.06 | 192.07 | 177.38 | ?192.69 | 193.54 | 164.1 |
Table two middle finger object detection method is with reference to [2] Jiang Weiqi. leather finished product physical and chemical inspection [M]. China Light Industry Press, 1999,82-96, the elongation at break of flame-retardant polyurethane of the present invention be improved significantly.
Claims (5)
1. a preparation method for flame-retardant aqueous polyurethane coating, is characterized in that:
(1) under the condition, existing at trifluoromethanesulfonic acid two fourth B catalysts, by 1, two (dimethyl hydroxyl the is silica-based) benzene of 4-mixes according to weight ratio 2:1 with hexamethylene diisocyanate, at 80 ~ 110 ℃, react 2 ~ 4h, add again thiophos in reaction system, 80 ~ 110 ℃ of temperature of reaction, reaction times 40 ~ 60min, obtains base polyurethane prepolymer for use as; Described catalyst levels is 1,0.3 ~ 0.7% of two (dimethyl hydroxyl the is silica-based) benzene of 4-and hexamethylene diisocyanate gross weight, thiophos is 1.0 ~ 1.4% of Isosorbide-5-Nitrae-bis-(dimethyl hydroxyl is silica-based) benzene and hexamethylene diisocyanate gross weight;
(2), in base polyurethane prepolymer for use as, add the chainextender of base polyurethane prepolymer for use as weight 1.4 ~ 2.8% and the butanone solvent of base polyurethane prepolymer for use as gross weight 16 ~ 24%, stirring reaction 3 ~ 5h under 65 ~ 85 ℃ of conditions, add triethylamine to carry out neutralization reaction 10 ~ 40min, add water and carry out emulsification, form a kind of aqueous polyurethane standby; Described triethylamine is 10 ~ 30% of base polyurethane prepolymer for use as weight;
(3), add the dispersion agent of aluminium salt compound solution weight 1.5 ~ 1.8% in the aluminium salt compound solution that is 10% to mass concentration, in temperature, be that under 30 ℃, the pH condition that is 7, ultrasonication 20min, obtains aluminium salt dispersion liquid standby;
(4), N-aminoethyl-3-aminopropyl triethoxysilane of the volution phosphinylidyne Pyrrolidine ester of the aluminium salt dispersion liquid of aqueous polyurethane solid content 10 ~ 20%, the L-Glutimic acid of aqueous polyurethane solid content 1 ~ 2%, the urethane solid content 10 ~ 20% of water-based and aqueous polyurethane solid content 1 ~ 2% is joined in aqueous polyurethane, the condition down cut that is 7 at pH stirs 40 ~ 80min, obtains flame-retardant aqueous polyurethane coating.
2. the preparation method of a kind of flame-retardant aqueous polyurethane coating as claimed in claim 1, is characterized in that: chainextender is Diphenylsilanediol, 4, any one in two (dimethyl hydroxyl the is silica-based) phenyl ether of 4'-, silicon phthalocyanine dihydroxide.
3. the preparation method of a kind of flame-retardant aqueous polyurethane coating as claimed in claim 1, is characterized in that: aluminium salt compound is any one in diphenyl phosphonic acid aluminium, dipropyl phospho acid aluminium and diethyl phospho acid aluminium.
4. the preparation method of a kind of flame-retardant aqueous polyurethane coating as claimed in claim 1, it is characterized in that: dispersion agent is N any one of N-dimethylamino propylamine, Sodium dodecylbenzene sulfonate, sodium polyacrylate, polyvinyl alcohol, cationic polyacrylamide, water glass, Sodium hexametaphosphate 99.
5. the preparation method of a kind of flame-retardant aqueous polyurethane coating as claimed in claim 1, is characterized in that: shear agitation speed is 700 ~ 1200rpm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105295474A (en) * | 2015-12-04 | 2016-02-03 | 常熟市裕华计量检测咨询服务有限公司 | Gas leakage measurement and detection device |
| CN111647118A (en) * | 2020-06-24 | 2020-09-11 | 苏州兴业材料科技南通有限公司 | Toughened flame-retardant phenolic resin and preparation method thereof |
| CN112646475A (en) * | 2020-12-31 | 2021-04-13 | 烟台大学 | Preparation and application methods of flame-retardant wear-resistant low-VOC (volatile organic compound) polyurethane coating |
| CN113248795A (en) * | 2021-06-16 | 2021-08-13 | 山东泰星新材料股份有限公司 | Preparation method of halogen-free flame retardant special for water-based PU adhesive |
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| CN107699040A (en) * | 2017-10-17 | 2018-02-16 | 浙江浦江永进工贸有限公司 | A kind of preparation method of polyurethane-type ink |
| CN114834112B (en) * | 2022-05-19 | 2024-03-29 | 青岛新材料科技工业园发展有限公司 | Puncture-resistant high-heat-insulation vacuum insulation panel and preparation method thereof |
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| WO2010034109A1 (en) * | 2008-09-26 | 2010-04-01 | Quantum Technical Services Ltd. | Flame retardant coating |
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| EP2623571A1 (en) * | 2010-09-28 | 2013-08-07 | Adeka Corporation | Aqueous polyurethane resin composition for flame retardant coated materials and coated products obtained by applying said composition |
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| CN112646475A (en) * | 2020-12-31 | 2021-04-13 | 烟台大学 | Preparation and application methods of flame-retardant wear-resistant low-VOC (volatile organic compound) polyurethane coating |
| CN112646475B (en) * | 2020-12-31 | 2021-10-15 | 烟台大学 | Preparation and application methods of flame-retardant wear-resistant low-VOC (volatile organic compound) polyurethane coating |
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| CN113248795B (en) * | 2021-06-16 | 2022-06-21 | 山东泰星新材料股份有限公司 | Preparation method of halogen-free flame retardant special for water-based PU adhesive |
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