CN103073696A - Preparation method of light-resistant waterborne polyurethane - Google Patents
Preparation method of light-resistant waterborne polyurethane Download PDFInfo
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- CN103073696A CN103073696A CN2013100343312A CN201310034331A CN103073696A CN 103073696 A CN103073696 A CN 103073696A CN 2013100343312 A CN2013100343312 A CN 2013100343312A CN 201310034331 A CN201310034331 A CN 201310034331A CN 103073696 A CN103073696 A CN 103073696A
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 44
- 239000004814 polyurethane Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 46
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000004945 emulsification Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007908 nanoemulsion Substances 0.000 claims abstract description 13
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 12
- 239000004970 Chain extender Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 7
- 230000000176 photostabilization Effects 0.000 claims description 24
- 230000035484 reaction time Effects 0.000 claims description 12
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims description 10
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 10
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 claims description 10
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002086 nanomaterial Substances 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006096 absorbing agent Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000004255 Butylated hydroxyanisole Substances 0.000 claims description 5
- 239000004322 Butylated hydroxytoluene Substances 0.000 claims description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 235000019282 butylated hydroxyanisole Nutrition 0.000 claims description 5
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 5
- 229940043253 butylated hydroxyanisole Drugs 0.000 claims description 5
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 5
- 229940095259 butylated hydroxytoluene Drugs 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- HGRNRWNRNVPVMM-UHFFFAOYSA-N benzene-1,3-diol;benzoic acid Chemical compound OC1=CC=CC(O)=C1.OC(=O)C1=CC=CC=C1 HGRNRWNRNVPVMM-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
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- RDBMUARQWLPMNW-UHFFFAOYSA-N phosphanylmethanol Chemical compound OCP RDBMUARQWLPMNW-UHFFFAOYSA-N 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 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 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 229920000909 polytetrahydrofuran Polymers 0.000 abstract 1
- 238000010008 shearing Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- -1 Urethane aromatic isocyanate Chemical class 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 229920006264 polyurethane film Polymers 0.000 description 3
- 238000000576 coating method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Abstract
The invention discloses a preparation method of light-resistant waterborne polyurethane, which comprises the steps of mixing polytetramethylene ether glycol with diisocyanate in the presence of a dibutyltin dilaurate catalyst, stirring at 70-90 DEG C for reaction for 2-4h, obtaining a polyurethane prepolymer, adding a hydrophilic chain extender, a polyhydroxyl compound and butanone into the polyurethane prepolymer, stirring at 70-90 DEG C for reaction for 1.0-3.5 h, adding triethylamine for neutralizing, stirring for reaction for 40-60min, adding water for emulsification to form hydrophilic polyurethane, adding a nano emulsion into a hydrophilic polyurethane system, shearing and stirring for 40-60min under the condition that a pH value is 7, and obtaining light-resistant waterborne polyurethane. Prepared light-resistant waterborne polyurethane is environment-friendly and low in price, and can meet the demand of a market on a property of light-resistant polyurethane.
Description
Technical field
The present invention relates to a kind of preparation method of aqueous polyurethane, particularly a kind of preparation method of photostabilization aqueous polyurethane.
Background technology
Aqueous polyurethane is take water as dispersion medium, and is nonpoisonous and tasteless, free from environmental pollution, is widely used in the preparation of water-borne coatings, aqueous paint.But because the use field often contacts sunlight, contain harmful to light object in a large number UV-light in the solar ray, its wavelength 290 ~ 460nm, these UV-light are passed through redoxomorphism chemically, make material surface generation colour-change, affect appearance.
Urethane aromatic isocyanate commonly used is made raw material at present, but the easy yellowing of urethane of aromatic isocyanate preparation, can not satisfy the needs of varnish, white paint and outdoor decoration, therefore the normal aliphatic isocyanates that adopts prepares sunproof aqueous polyurethane dispersing liquid, but owing to lacking the rigidity phenyl ring in the aliphatic molecules structure, synthetic aqueous polyurethane hardness of film is lower, and water tolerance, poor solvent resistance are difficult to satisfying the market to the demand of sunproof polyurethane.
Summary of the invention
The present invention has adopted following technical scheme.
(1), under the condition that dibutyltin dilaurate catalyst exists, be 1.6:1 ~ 4.0:1 by the mol ratio of NCO/OH, PTMG is mixed with vulcabond, in 70 ~ 90 ℃ of lower stirring reaction 2 ~ 4h, obtain base polyurethane prepolymer for use as A; Described catalyst levels is 0.15 ~ 0.4% of PTMG and vulcabond gross weight;
(2), adding carboxyl-content in the A is the hydrophilic chain extender of A weight 1.5 ~ 4.2%, the stirring reaction time is 30 ~ 60min, the polyol that applies A weight 0.2 ~ 0.8% carries out crosslinked, the stirring reaction time is 30min, the butanone that adds A weight 10 ~ 30%, stirring reaction 1.0 ~ 3.5h under 70 ~ 90 ℃ of conditions presses COOH/NH
2Mol ratio be 0.5:1 ~ 1.4:1, add triethylamine and neutralize, stirring reaction 40 ~ 60min adds water and carries out emulsification, forms a kind of hydrophilic urethane B for subsequent use;
(3), emulsifying agent 10g is dissolved in the 50g water, add nano material 2 ~ 5g, uv-absorbing agent 1 ~ 5g, antioxidant 2 ~ 3g, shear agitation emulsification, stirring velocity 400 ~ 1500r/min, emulsification 30 ~ 60min gets nanoemulsions for subsequent use;
(4), the nanoemulsions that adds B solid content 20 ~ 40% in B, be that 7 condition down cut stirs 40 ~ 60min at pH, obtain photostabilization aqueous polyurethane C.
The number-average molecular weight M of PTMG
nBe 1000g/mol; Vulcabond is any one in hexamethylene diisocyanate, the isophorone diisocyanate; Chainextender is any one in dimethylol propionic acid, the dimethylolpropionic acid; Polyol is any one in tetrakis hydroxymetyl phosphonium sulfuric, the TriMethylolPropane(TMP); Emulsifying agent is any one of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, Sodium hexametaphosphate 99; Nano material is any one in nano zine oxide, nano silicon, the nano-sized iron oxide; Uv-absorbing agent is any two kinds mixture in salicylic acid phenyl ester, 2,4 dihydroxyl benzophenone, the single phenylformic acid resorcinol; Antioxidant is mixture any two kinds in butylated hydroxy anisole, butylated hydroxytoluene, the ethylenediamine tetraacetic acid (EDTA).
The present invention has following characteristics:
(1), prepared photostabilization aqueous polyurethane and material compatibility are good;
(2), the vulcabond of selecting has good photostabilization;
(3), nano material environmental protection, cheap, have and absorb ultraviolet function, prepared sunproof polyurethane can not raise the cost;
(4), to adopt polyol that urethane is carried out cross-linking modified, changes the characteristics of traditional sunproof polyurethane poor solvent resistance, poor mechanical property;
(5), nano material and UV light absorber absorb UV-light, oxygenant stops urethane oxidized, adopts nano material, UV light absorber, antioxidant performance synergistic effect, improves the photostabilization of urethane.
(4), embodimentFurther specify the present invention below in conjunction with example.
Example one
(1), in the four-hole boiling flask of the 500ml that stirring arm, thermometer, prolong are housed, PTMG 10.0g is mixed with isophorone diisocyanate 35.5g, under the condition that dibutyltin dilaurate catalyst 0.07g exists, in 70 ℃ of lower stirring reaction 2h, get the 45.3g base polyurethane prepolymer for use as;
(2), in base polyurethane prepolymer for use as, add hydrophilic chain extender dimethylol propionic acid 2.02g, the stirring reaction time is 30min, adding tetrakis hydroxymetyl phosphonium sulfuric 0.09g carries out crosslinked, and the stirring reaction time is 30min, adds butanone solvent 4.5g, stirring reaction 1.0h under 70 ℃ of conditions, add triethylamine 3.05g and neutralize, stirring reaction 40min adds water 150g and carries out emulsification, solid content is 24.9% hydrophilic polyurethane 202.5g, be transferred in the 500ml beaker for subsequent use;
(3), emulsifying agent 10g is dissolved in the 50g water, add nano-sized iron oxide 2g, 2,4-dihydroxy benaophenonel 0.5g, single phenylformic acid resorcinol 0.5g, butylated hydroxytoluene 1g, ethylenediamine tetraacetic acid (EDTA) 1g, emulsification pretreatment speed 400r/min, emulsification times 30min gets nanoemulsions for subsequent use;
(4), add nanoemulsions 10.1g in hydrophilic polyurethane, be that 7 condition down cut stirs 40min at pH, obtain the photostabilization aqueous polyurethane.
Example two
(1), in the four-hole boiling flask of the 500ml that stirring arm, thermometer, prolong are housed, PTMG 10.0g is mixed with hexamethylene diisocyanate 67.2g, under the condition that dibutyltin dilaurate catalyst 0.31g exists, in 90 ℃ of lower stirring reaction 4h, obtain the 77.5g base polyurethane prepolymer for use as;
(2), in base polyurethane prepolymer for use as, add hydrophilic chain extender dimethylolpropionic acid 10.71g, the stirring reaction time is 60min, adding TriMethylolPropane(TMP) 0.62g carries out crosslinked, and the stirring reaction time is 30min, adds butanone solvent 23.3g, stirring reaction 3.5h under 90 ℃ of conditions, apply triethylamine 5.22g and neutralize, stirring reaction 60min adds water 150g and carries out emulsification, solid content is 33.2% hydrophilic polyurethane 267.4g, be transferred in the 500ml beaker for subsequent use;
(3), Sodium dodecylbenzene sulfonate 10g is dissolved in the 50g water, add nano silicon 5g, salicylic acid phenyl ester 2.5g, 2,4-dihydroxy benaophenonel 2.5g, butylated hydroxy anisole 1.5g, butylated hydroxytoluene 1.5g, emulsification pretreatment speed 1500r/min, emulsification 60min gets nanoemulsions for subsequent use;
(4), add nanoemulsions 35.5g in hydrophilic polyurethane, be that 7 condition down cut stirs 60min at pH, obtain the photostabilization aqueous polyurethane.
Example three
(1), in the four-hole boiling flask of the 500ml that stirring arm, thermometer, prolong are housed, PTMG 10.0g is mixed with isophorone diisocyanate 62.2g, under the condition that dibutyltin dilaurate catalyst 0.20g exists, in 80 ℃ of lower stirring reaction 3 h, obtain base polyurethane prepolymer for use as 72.3g;
(2), in base polyurethane prepolymer for use as, add hydrophilic chain extender dimethylol propionic acid 6.2g, the stirring reaction time is 45min, continue to add tetrakis hydroxymetyl phosphonium sulfuric 0.36g, the stirring reaction time is 30min, adds butanone 14.5g, stirring reaction 2 h under 80 ℃ of conditions, add triethylamine 4.9g and neutralize, stirring reaction 50min adds water 160g and carries out emulsification, the formation solid content is 32.3% aqueous polyurethane 257.9g, is transferred in the 500ml beaker for subsequent use;
(3), Sodium hexametaphosphate 99 10g is dissolved in the 50g water, add nano zine oxide 3.5g, salicylic acid phenyl ester 1.5g, single phenylformic acid resorcinol 1.5g, butylated hydroxy anisole 1.25g, ethylenediamine tetraacetic acid (EDTA) 1.25g, emulsification pretreatment speed 950r/min, emulsification times 45min gets nanoemulsions for subsequent use;
(4), add nanoemulsions 25.0g in hydrophilic polyurethane, be that 7 condition down cut stirs 50min at pH, obtain the photostabilization aqueous polyurethane.
Example four
(1), in the four-hole boiling flask of the 500ml that stirring arm, thermometer, prolong are housed, PTMG 10.0g is mixed with hexamethylene diisocyanate 47.2g, under the condition that dibutyltin dilaurate catalyst 0.16g exists, in 80 ℃ of lower stirring reaction 3h, obtain the 57.0g base polyurethane prepolymer for use as;
(2), in base polyurethane prepolymer for use as, add hydrophilic chain extender dimethylolpropionic acid 5.25g, the stirring reaction time is 60min, adding TriMethylolPropane(TMP) 0.34g carries out crosslinked, and the stirring reaction time is 50min, adds butanone solvent 17.1g, stirring reaction 3.5h under 80 ℃ of conditions, add triethylamine 3.58g and neutralize, stirring reaction 50min adds water 150g and carries out emulsification, solid content is 28.4% hydrophilic polyurethane 233.3g, be transferred in the 500ml beaker for subsequent use;
(3), Sodium dodecylbenzene sulfonate 10g is dissolved in the 50g water, add nano silicon 3g, salicylic acid phenyl ester 1.5g, 2,4-dihydroxy benaophenonel 2.5g, butylated hydroxy anisole 2.5g, butylated hydroxytoluene 0.5g, emulsification pretreatment speed 950r/min, emulsification times 60min gets nanoemulsions for subsequent use;
(4), add nanoemulsions 19.5g in hydrophilic polyurethane, be that 7 condition down cut stirs 50min at pH, obtain the photostabilization aqueous polyurethane.
For the light fastness of quantitative description urethane, adopt spectrophotometer to detect, to obtain inverse difference △ E, the photostabilization of urethane is described.△ E has represented the colour-change degree, and △ E is larger, and color change is more obvious.In general, △ E value is the slight variation of 0～1.5 genus; △ E value is that 1.5～3.0 genus can be felt variation; △ E value be 3.0～6.0 belong to considerable changes (referring to Wang Fang, party's climax, Wang Liqin, the photodegradation of several organic historical relic's protection polymer coatings [J]. Northwest University's journal, 2005,35 (5): 56 ~ 58).The mechanical property of polyurethane film adopts elongation at break to weigh, and elongation at break is larger, and its mechanical property is better.The testing method of elongation at break see (Jiang Weiqi. leather finished product physical and chemical inspection [M]. China Light Industry Press, 1999,82 ~ 96).Example one is designated as respectively D, F, G, H to the sunproof polyurethane of example four gained, selects the sunproof polyurethane PODESENG 513MS on the market to compare with it.
The value of chromatism △ E of urethane changes under the table one UV-irradiation different time
| Time/min | PODESENG ?513MS | D | F | G | H |
| 90 | 0.7 | 0.2 | 0.5 | 0.3 | 0.1 |
| 150 | 0.9 | 0.6 | 0.7 | 0.3 | 0.1 |
| 270 | 1.0 | 0.7 | 0.8 | 0.4 | 0.3 |
| 330 | 1.1 | 0.7 | 0.8 | 0.5 | 0.4 |
| 390 | 1.3 | 0.8 | 0.9 | 0.6 | 0.6 |
| 450 | 1.5 | 0.9 | 0.9 | 0.7 | 0.7 |
| 510 | 1.8 | 1.0 | 1.0 | 0.8 | 0.9 |
| 540 | 2.1 | 1.1 | 1.2 | 0.8 | 0.9 |
| 600 | 2.3 | 1.2 | 1.2 | 1.1 | 1.0 |
Can find from table one, example one all in slight variation range, show good photostabilization, and the sunproof polyurethane on the market has belonged to and can feel variation to the prepared four kinds of urethane photostabilization of example four more than 510min.
Table two photostabilization aqueous polyurethane film elongation at break
| Classification | PODESENG 513MS | D | F | G | H |
| Elongation at break/% | 187.06 | 237.67 | 262.52 | 271.80 | 253.54 |
In the table two, the sunproof polyurethane film elongation at break of example one to four gained is larger than the elongation at break of the sunproof polyurethane in market.
Claims (9)
1. the preparation method of a photostabilization aqueous polyurethane is characterized in that:
(1), under the condition that dibutyltin dilaurate catalyst exists, be 1.6:1 ~ 4.0:1 by the mol ratio of NCO/OH, PTMG is mixed with vulcabond, in 70 ~ 90 ℃ of lower stirring reaction 2 ~ 4h, obtain base polyurethane prepolymer for use as A; Described catalyst levels is 0.15 ~ 0.4% of PTMG and vulcabond gross weight;
(2), adding carboxyl-content in the A is the hydrophilic chain extender of A weight 1.5 ~ 4.2%, the stirring reaction time is 30 ~ 60min, the polyol that applies A weight 0.2 ~ 0.8% carries out crosslinked, the stirring reaction time is 30min, the butanone that adds A weight 10 ~ 30%, stirring reaction 1.0 ~ 3.5h under 70 ~ 90 ℃ of conditions presses COOH/NH
2Mol ratio be 0.5:1 ~ 1.4:1, add triethylamine and neutralize, stirring reaction 40 ~ 60min adds water and carries out emulsification, forms a kind of hydrophilic urethane B for subsequent use;
(3), emulsifying agent 10g is dissolved in the 50g water, add nano material 2 ~ 5g, uv-absorbing agent 1 ~ 5g, antioxidant 2 ~ 3g, shear agitation emulsification, stirring velocity 400 ~ 1500r/min, emulsification 30 ~ 60min gets nanoemulsions for subsequent use;
(4), the nanoemulsions that adds B solid content 20 ~ 40% in B, be that 7 condition down cut stirs 40 ~ 60min at pH, obtain photostabilization aqueous polyurethane C.
2. the preparation method of a kind of photostabilization aqueous polyurethane as claimed in claim 1 is characterized in that: the number-average molecular weight M of PTMG
nBe 1000g/mol.
3. the preparation method of a kind of photostabilization aqueous polyurethane as claimed in claim 1 is characterized in that: vulcabond be in hexamethylene diisocyanate, the isophorone diisocyanate any one.
4. the preparation method of a kind of photostabilization aqueous polyurethane as claimed in claim 1, it is characterized in that: chainextender is any one in dimethylol propionic acid, the dimethylolpropionic acid.
5. the preparation method of a kind of photostabilization aqueous polyurethane as claimed in claim 1, it is characterized in that: polyol is any one in tetrakis hydroxymetyl phosphonium sulfuric, the TriMethylolPropane(TMP).
6. the preparation method of a kind of photostabilization aqueous polyurethane as claimed in claim 1 is characterized in that: emulsifying agent is any one of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, Sodium hexametaphosphate 99.
7. the preparation method of a kind of photostabilization aqueous polyurethane as claimed in claim 1, it is characterized in that: nano material is any one in nano zine oxide, nano silicon, the nano-sized iron oxide.
8. the preparation method of a kind of photostabilization aqueous polyurethane as claimed in claim 1, it is characterized in that: uv-absorbing agent is any two kinds mixture in salicylic acid phenyl ester, 2,4 dihydroxyl benzophenone, the single phenylformic acid resorcinol.
9. the preparation method of a kind of photostabilization aqueous polyurethane as claimed in claim 1, it is characterized in that: antioxidant is mixture any two kinds in butylated hydroxy anisole, butylated hydroxytoluene, the ethylenediamine tetraacetic acid (EDTA).
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436155A (en) * | 2013-09-09 | 2013-12-11 | 段宝荣 | Preparation method of light-resistant water-based polyurethane coating |
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| CN103436155B (en) * | 2013-09-09 | 2015-12-23 | 段宝荣 | A kind of preparation method of light-resistant waterborne polyurethane coating |
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| CN106221551A (en) * | 2016-08-30 | 2016-12-14 | 段宝荣 | Polyurethane coating preparation method with low VOC fire-retardant, waterproof |
| CN106221551B (en) * | 2016-08-30 | 2018-03-13 | 河北晨阳工贸集团有限公司 | Fire-retardant, waterproof and low VOC polyurethane coating preparation method |
| CN106590394A (en) * | 2016-11-25 | 2017-04-26 | 清远市美佳乐环保新材股份有限公司 | Process of preparing waterborne polyurethane optical coating through continuous method |
| CN107417881A (en) * | 2017-08-04 | 2017-12-01 | 合肥思敬齐化工材料有限责任公司 | A kind of preparation method of the aqueous polyurethane of ultraviolet radiation preventing |
| CN108822713A (en) * | 2018-07-15 | 2018-11-16 | 段宝荣 | The preparation method of light-resistant waterborne polyurethane coating and adhesive |
| CN109721704A (en) * | 2019-01-11 | 2019-05-07 | 北京理工大学 | A kind of light shield extinguishing waterborn polyurethane and preparation method thereof |
| CN114025959A (en) * | 2019-07-12 | 2022-02-08 | 陶氏环球技术有限责任公司 | Water-based composition |
| CN111303374A (en) * | 2020-04-02 | 2020-06-19 | 上海应用技术大学 | Brominated soybean oil modified pure water-based polyurethane nano-emulsion and preparation method thereof |
| CN113999360A (en) * | 2021-12-02 | 2022-02-01 | 太原理工大学 | Method for preparing flame-retardant waterborne polyurethane from waste polyester textile fabrics |
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