CN1618849A - Low free tolylene diisocynate polyurethane solidifying agent and its preparation method - Google Patents
Low free tolylene diisocynate polyurethane solidifying agent and its preparation method Download PDFInfo
- Publication number
- CN1618849A CN1618849A CN 200410015135 CN200410015135A CN1618849A CN 1618849 A CN1618849 A CN 1618849A CN 200410015135 CN200410015135 CN 200410015135 CN 200410015135 A CN200410015135 A CN 200410015135A CN 1618849 A CN1618849 A CN 1618849A
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- Prior art keywords
- raw material
- toluene diisocyanate
- curing agent
- component
- defoamer
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 59
- 239000004814 polyurethane Substances 0.000 title claims abstract description 28
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title description 9
- 125000005628 tolylene group Chemical group 0.000 title 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 22
- 239000013530 defoamer Substances 0.000 claims description 17
- 239000012046 mixed solvent Substances 0.000 claims description 17
- 150000002148 esters Chemical class 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 12
- 150000001555 benzenes Chemical class 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- 230000001143 conditioned effect Effects 0.000 claims description 5
- -1 esters 2,4-tolylene diisocyanate Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 4
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 4
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 4
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 4
- 125000005375 organosiloxane group Chemical group 0.000 claims description 4
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- YOEZZCLQJVMZGY-UHFFFAOYSA-N octane-4,5-diol Chemical compound CCCC(O)C(O)CCC YOEZZCLQJVMZGY-UHFFFAOYSA-N 0.000 claims description 3
- 229940059574 pentaerithrityl Drugs 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 claims description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 2
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 claims description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 2
- AJMSSRFLFILJLF-UHFFFAOYSA-N 4-propyloctane-4,5-diol Chemical compound CCCC(O)C(O)(CCC)CCC AJMSSRFLFILJLF-UHFFFAOYSA-N 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- POFSNPPXJUQANW-UHFFFAOYSA-N hexane-3,4-diol Chemical compound CCC(O)C(O)CC POFSNPPXJUQANW-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- 208000005156 Dehydration Diseases 0.000 claims 3
- 239000002253 acid Chemical class 0.000 claims 1
- 150000002527 isonitriles Chemical class 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 abstract 1
- 150000007824 aliphatic compounds Chemical class 0.000 abstract 1
- 239000002518 antifoaming agent Substances 0.000 abstract 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 11
- 238000000576 coating method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 239000010408 film Substances 0.000 description 6
- 239000004922 lacquer Substances 0.000 description 5
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 5
- 239000012467 final product Substances 0.000 description 3
- 238000013008 moisture curing Methods 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 150000003673 urethanes Chemical class 0.000 description 3
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000000207 volumetry Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Abstract
A low-freedom toluene diisocyanate as the solidifying agent of polyurethane paint is prepared from toluene diisocyanate or the mixture of two kinds of toluene diisocyanate, the mixture of ester solvent and benzene solvent, trihydroxymethyl propane, aliphatic compound, low-molecular polyether, defoaming agent and leveling agent through direct synthesis.
Description
Technical field:
A kind of low free toluene diisocyanate polyurethane curing agent relates to epoxy flooring coating with moisture cure urethanes solidifying agent and preparation method thereof, particularly made the polyurethane curing agent that free toluene diisocyanate content meets the regulation among the standard GB 18581-2001 with direct synthesis technique.
Prior art:
The polyethers of low molecular mass and tolylene diisocyanate reaction, making end group is polyurethane resin coating polyisocyanate curing agent component commonly used for the polyisocyanate curing agent of-NCO base.Adopt the hypergolic polyurethane resin coating of this polyethers-tolylene diisocyanate solidifying agent and hydroxy-containing component preparation, paint film has good wearability, surface hardness and snappiness, and the gloss of film height also has good elasticity.This polyethers-tolylene diisocyanate solidifying agent also can be made the polyurethane resin coating of moisture-curable separately and use.But the free toluene diisocyanate content of domestic this product is usually up to 3.0%～5.0% at present, coatings formulated is very big to the human injury in construction process, environmental pollution is serious, and does not meet state compulsory standard GB18581-2001 " limits of harmful substances in the indoor decorating material solvent type woodwork coating " polyurethane coating free toluene diisocyanate content and can not surpass 0.7% regulation.
Summary of the invention:
The object of the invention is what the shortcoming synthetic method prior art at existing polyurethane curing agent existed, a kind of low free toluene diisocyanate polyurethane curing agent and preparation method thereof is provided, it need not increase extra investment and post-processed equipment, direct synthesis of polyurethane solidifying agent, and can reduce the content (single component is less than 0.7%) of the free toluene diisocyanate in the solidifying agent, and institute's synthetic solidifying agent use properties is unaffected.
The object of the present invention is achieved like this: raw material of the present invention and content (weight percent) are that (A) tolylene diisocyanate 18～25%; (B) ester class and benzene class mixed solvent 35～65%; (C) TriMethylolPropane(TMP) 2～4%; (D) contain 1 above hydroxyl, molecular weight at 60～150 fatty compounds 3～5%; (E) low molecular polyether 10～15%; (F) defoamer 0.2～0.5%, flow agent 0.1～0.3%.
Preparation process is: the component (D) after will dewater respectively earlier, component (E), component (F) and 1/3rd component (B) adding reactor, add after stirring (C), heat up, stir, dissolve the acidity that the back adds phosphoric acid conditioned reaction system fully Deng (C), add then (A), heat up, insulation each once more than, the percentage composition that detects the NCO group is 3.7～4.5% o'clock, add raw material (F) and cooling raw material 2/3rds dehydration (B) afterwards immediately, discharging is filtered in cooling.
Preparation process described in the utility model is: (D), (E) after will dewater respectively earlier, with 1/3rd (B) adding reactor, back adding (C) stirs, be warming up to 50～70 ℃, stirred 10～20 minutes, dissolve the acidity that the back adds phosphoric acid conditioned reaction system fully Deng (C), press formula ratio then and add (A), be warming up to 70～90 ℃, reaction 2h; Be warmed up to 90～110 ℃ of insulations 2～6 hours, the weight percentage that detects the NCO group is to add raw material (F) and cooling raw material (1/3rd through dewatering (B)) at 3.7～4.5% o'clock immediately, be cooled to below 60 ℃, filter, discharging is promptly produced free toluene diisocyanate content less than 0.7% low free toluene diisocyanate polyurethane curing agent.
Raw material (A) is selected from one of following in the present invention prescription: 2,4 toluene diisocyanate, 2,6-tolylene diisocyanate, 2,4 toluene diisocyanate and 2, any proportioning mixture of 6-tolylene diisocyanate.Preferred following a kind of or two kinds: 2,4 toluene diisocyanate or 2,4 toluene diisocyanate and 2, the mixture of 6-tolylene diisocyanate, the weight percent of 2,4 toluene diisocyanate is about 80% in the mixture.
The optional boiling point of raw material among the present invention (B) esters solvent is less than 200 ℃ esters solvent, can be selected from one of following: the mixture of vinyl acetic monomer, n-propyl acetate, Iso Butyl Acetate, n-butyl acetate, isobutyl acetate, vinyl acetic monomer and any proportioning of N-BUTYL ACETATE.The mixture of preferred vinyl acetic monomer, N-BUTYL ACETATE, vinyl acetic monomer and any proportioning of N-BUTYL ACETATE; Benzene kind solvent mainly is toluene and dimethylbenzene and the mixture of the two, preferably the two mixture.
It is one of following that raw material among the present invention (D) selects for use 1～2 hydroxyl, the fatty compounds of molecular weight between 60～200 to be selected from: 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, Pentyl alcohol, 1-methyl butanol, 1-ethyl-1-propanol, n-Octanol, sec-n-octyl alcohol, 2-ethyl-1-hexanol, neopentyl glycol, 1, the 2-propylene glycol, 1, ammediol, 1,3-butyleneglycol, 1,4-butyleneglycol, diethyl ethylene glycol, 2,3-butyleneglycol, dipropyl ethylene glycol one contract two different glycol, dipropylene glycol, tripropyl ethylene glycol, tetramethylolmethane etc.Preferred one of following: 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, Pentyl alcohol, dipropyl ethylene glycol one contract two different glycol, dipropylene glycol, tetramethylolmethane etc.
It is one of following that raw material among the present invention (E) low molecular polyether can be selected from: dihydroxyl polyoxygenated propyl ether, N-204, N-201, N-215, N-210, N-220, N-235; Trihydroxy-oxidation propyl ether, N-303, N-330 etc.One of preferred following: N-201, N-215, N-210, N-303 etc.
Defoamer among the present invention and flow agent are optional one of following: do not contain organo-siloxane type defoamer EFKA-2020, EFKA2526, EFKA2720 and the modified polyorganosiloxane defoamer Taiwan modest company of moral moral product 5500,6600 etc.; Polyether-modified polydimethylsiloxane flow agent BYK-331, BYK-344 and AFKA company do not contain organo-siloxane type flow agent EFKA-3777, EFKA3277 etc.
Technique effect of the present invention is: on the one hand, free toluene diisocyanate content meets the highest standard of among the GB18581-2001 free tolylene diisocyanate monomer content in the polyurethane coating being done fully in the polyurethane curing agent of gained of the present invention, its NCO content is 3.7～4.5%, and contained free toluene diisocyanate monomer is 0.5～0.7% or lower; On the other hand, the different preparation process method that is used to reduce free toluene diisocyanate has: falling-film evaporator, wiped film evaporator, distil process, different solvent extraction, molecular sieve adsorption etc.These processes and method all need extra investment and complex operating steps.Now external bigger polyurethane production company such as Bayer, just adopt wiped film evaporator to reduce free tolylene diisocyanate monomer content in the polyurethane curing agent, this method is more effective, but increase the bigger investment of this equipment claimed, non-general enterprise can bear, and the present invention adopts synthesized solidified dose of single component free toluene diisocyanate content of direct one-step synthesis less than 0.7%, and this is the leap again on the polyurethane curing agent synthetic technology; The 3rd, the polyethers of gained of the present invention/tolylene diisocyanate affixture solidifying agent is of light color, viscosity is low, good stability, paint film property is constant even be better than traditional moisture solidification polyurethane solidifying agent joins the lacquer performance.
For technique effect of the present invention is described, below just the moisture cure urethanes solidifying agent of gained of the present invention and the testing data tabulation of the every performance of traditional moisture solidification polyurethane solidifying agent are made comparisons as follows, the polyethers of gained of the present invention/TMP/ tolylene diisocyanate affixture is called for short " SUPE-10 ", and traditional moisture solidification polyurethane solidifying agent is called for short " PT-50 ":
| Explanation | 1, free toluene diisocyanate % adopts vapor-phase chromatography to detect.2, contain 120 ℃ of employings admittedly, the method for oven dry in 2 hours detects.3, viscosity adopts and is coated with-4 glasss of surveys, and the S/ of unit is coated with-4,25 ℃.Viscosity (1) is initial viscosity, and viscosity (2) is the detection viscosity of storage at normal temperature after 7 days.4, the dimethylbenzene tolerance is to add dimethylbenzene in per 1 part of solidifying agent to be checked to little turbid dimethylbenzene amount |
Join the lacquer result:
| Project | ??SUPE-10( ????I) | ??SUPE-10( ????II) | ??SUPE-10( ????III) | ????PT-50(I) | PT-50(II) |
| Surface drying, h | ????2.5 | ????2.6 | ????2.5 | ????4.5 | ????4.0 |
| Do solid work h | ????24 | ????24 | ????24 | ????28 | ????27 |
| Gloss (60 °), % | ????96 | ????96 | ????95 | ????96 | ????96 |
| Hardness (pencil) | ????2H | ????2H | ????2H | ????2H | ????2H |
| Sticking power | One-level | One-level | One-level | One-level | One-level |
The invention will be further described below in conjunction with embodiment.
Specific embodiment:
The abbreviation of using in the embodiment is described as follows:
TDI100-contains the 2,4 toluene diisocyanate of 100% weight percentage.
TDI80/20-contains the 2,4 toluene diisocyanate of 80% weight percentage, 20% 2, the 6-tolylene diisocyanate.
The TMP-TriMethylolPropane(TMP).
Embodiment one:
At one agitator is housed, in the 1000ml four-hole boiling flask of thermometer and temperature detection instrument, add 107.3 gram polyethers-1000,20.9 restrain a mixed solvent that contracts two different two pure and mild 125 gram dimethylbenzene and butyl esters, slowly add 14.6 gram TMP while stirring, heat temperature raising to 60 ± 2 ℃, stirred 15 minutes, add phosphoric acid regulation system acidity then, add 150 gram TDI80/20 and be warming up to 80 ± 2 ℃, be incubated follow-up continuous 100 ± 2 ℃ of insulations 3 hours that are warming up in 2 hours, the weight percentage that detects NCO is 4.0～4.5 o'clock, admittedly contain this moment is about 45%, about free TDI content 0.6%, add flow agent and defoamer, the mixed solvent that adds 350 gram dimethylbenzene and butyl ester at last is cooled to 40 ℃ and gets final product discharging.
Embodiment two:
At one agitator is housed, in the 1000ml four-hole boiling flask of thermometer and temperature detection instrument, add 109.1 gram polyethers-2000,20.9 the mixed solvent of gram isoamyl two pure and mild 130 gram dimethylbenzene and butyl ester, slowly add 15.2 gram TMP while stirring, heat temperature raising to 60 ± 2 ℃, stirred 15 minutes, add phosphoric acid regulation system acidity then, add 155 gram TDI80/20 and be warming up to 90 ± 2 ℃, be incubated after 4 hours, the weight percentage that detects NCO is 4.0～4.5 o'clock, and contain this moment admittedly is about 45%, free TDI content about 0.6%, add flow agent and defoamer, the mixed solvent that adds 340 gram dimethylbenzene and butyl ester at last is cooled to 40 ℃ and gets final product discharging.
Embodiment three:
At one agitator is housed, in the 1000ml four-hole boiling flask of thermometer and temperature detection instrument, add 137.3 gram polyethers-1000, mixed solvent with 135 gram dimethylbenzene and butyl ester, slowly add 23.1 gram TMP while stirring, heat temperature raising to 60 ± 2 ℃, stirred 15 minutes, add 154.5 gram TDI100 and be warming up to 80 ± 2 ℃, be incubated after 4～5 hours, the weight percentage that detects NCO is 4.0～4.5 o'clock, admittedly contain this moment is about 45%, about free TDI content 0.6%, add flow agent and defoamer, the mixed solvent that adds 300 gram dimethylbenzene and butyl ester at last is cooled to 40 ℃ and gets final product discharging.
Embodiment four:
Join lacquer by moisture cure urethanes solidifying agent and epoxypaint that embodiment two obtains by 1: 1～1.2, on the Portland cement floor, make build become 1～3 micron,, obtain coated products after 1 week of hardening in drying at room temperature with the wool Cylinder coating brush.It is as follows to detect paint film property by the chemical industry standard HG/T 2004-91 of the People's Republic of China (PRC) (concrete floor is with coating with lacquer):
| Project | Index | |
| Standard | Actual detected | |
| Hardness is not less than sticking power, level is not more than opacifying power, g/m is not more than water tolerance (24h) wear resistance, g is not more than abrasion resistance, inferior being not less than | 2B is 0 70 non-foaming, do not come off 0.040 10000 | B 0 65 48h are non-foaming, do not come off 0.013 20000 |
By embodiment four as can be seen, the two-pack terrace paint performance of solidifying agent that the present invention developed and epoxypaint preparation meets concrete floor lacquer standard fully.
In above-mentioned embodiment, the percentage composition of NCO group is to detect with the dibutylamine volumetry, and the content of free tolylene diisocyanate is to use gas chromatographic detection in the affixture.
Claims (12)
1, a kind of low free toluene diisocyanate polyurethane curing agent is characterized in that its raw material is formed and content (weight percent) is:
(A) tolylene diisocyanate is 18～25% parts;
(B) ester class and benzene class mixed solvent are 35～65% parts;
(C) TriMethylolPropane(TMP) is 2～4% parts;
(D) contain 1 above hydroxyl, molecular weight 3～5% parts of 60～150 fatty compoundss;
(E) low molecular polyether is 10～15% parts;
(F) 0.2～0.5% part of defoamer, 0.1～0.3% part of flow agent.
2, a kind of low free toluene diisocyanate polyurethane curing agent according to claim 1, it is characterized in that: described raw material (A) tolylene diisocyanate is 2,4-tolylene diisocyanate or 2,6-toluene two isocyanides or acid esters 2,4-tolylene diisocyanate and 2, the 6-tolylene diisocyanate arbitrarily than mixture.
3, a kind of low free toluene diisocyanate polyurethane curing agent according to claim 1, it is characterized in that: raw material (B) ester class and benzene class mixed solvent are boiling point less than 200 ℃ ester class and benzene class mixed solvent, wherein benzene kind solvent is selected toluene, dimethylbenzene or the mixing of the two for use, and esters solvent is selected the mixture of vinyl acetic monomer, n-propyl acetate, Iso Butyl Acetate, n-butyl acetate, isobutyl acetate, vinyl acetic monomer and any proportioning of N-BUTYL ACETATE for use.
4, a kind of low free toluene diisocyanate polyurethane curing agent according to claim 3, it is characterized in that: esters solvent percentage composition (accounting for the percentage composition of solidifying agent) is 10-25% in raw material (B) esters solvent and the benzene class mixed solvent, and the percentage composition of benzene kind solvent (accounting for the percentage composition of solidifying agent) is 25-40%.
5, a kind of low free toluene diisocyanate polyurethane curing agent according to claim 1 is characterized in that it is to contain 1 hydroxyl, molecular weight at 60～150 fatty compounds or contain 2 hydroxyls, molecular weight at 60～150 fatty compounds at 60～150 fatty compounds that raw material (D) contains 1 above hydroxyl, molecular weight.
6, low free toluene diisocyanate polyurethane curing agent according to claim 5, it is characterized in that: raw material (D) is 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, Pentyl alcohol, 1-methyl butanol, 1-ethyl-1-propanol, n-Octanol, sec-n-octyl alcohol, 2-ethyl-1-hexanol, neopentyl glycol, 1, the 2-propylene glycol, 1, ammediol, 1,3-butyleneglycol, 1,4-butyleneglycol, diethyl ethylene glycol, 2,3-butyleneglycol, dipropyl ethylene glycol one contract two different glycol, dipropylene glycol, tripropyl ethylene glycol or tetramethylolmethane.
7, described a kind of low free toluene diisocyanate polyurethane curing agent according to claim 1, it is characterized in that: described raw material (E) low molecular polyether is a dihydroxyl polyoxygenated propyl ether: one of N-201, N-215, N-210, N-303, or trihydroxy-oxidation propyl ether, N-303 or N-330.
8, a kind of low free toluene diisocyanate polyurethane curing agent according to claim 1 is characterized in that: defoamer is selected for use and is not contained a kind of in organo-siloxane type defoamer EFKA-2020, EFKA2526, EFKA2720 or the modified polyorganosiloxane defoamer 5500,6600 or two kinds; Flow agent be polyether-modified polydimethylsiloxane flow agent BYK-331, BYK-344 or do not contain organo-siloxane type flow agent EFKA-3777, EFKA3277 one of them.
9, a kind of manufacture method of low free toluene diisocyanate polyurethane curing agent, it is characterized in that: the component (D) after will dewatering respectively earlier contains 1 above hydroxyl, molecular weight is at 60～150 fatty compounds, component (E) low molecular polyether, component (F) defoamer, flow agent and 1/3rd component (B) ester class and benzene class mixed solvent add reactor, back adding (C) TriMethylolPropane(TMP) stirs, heat up, stir, dissolve the acidity that the back adds phosphoric acid conditioned reaction system fully Deng (C), add then (A), heat up, the insulation each once more than, the percentage composition that detects the NCO group is 3.7～4.5% o'clock, add raw material (F) defoamer part immediately, (B) ester class and benzene class mixed solvent after flow agent part and 2/3rds dehydrations of cooling raw material, cooling, filter discharging.
10, the manufacture method of a kind of low free toluene diisocyanate polyurethane curing agent according to claim 10, it is characterized in that: the component (D) after will dewatering respectively earlier contains 1 above hydroxyl, molecular weight is at 60～150 fatty compounds, component (E) low molecular polyether, component (F) defoamer, flow agent and 1/3rd component (B) ester class and benzene class mixed solvent add reactor, back adding (C) TriMethylolPropane(TMP) stirs, be warming up to 50～70 ℃, stirred 10～20 minutes, dissolve the acidity that the back adds phosphoric acid conditioned reaction system fully Deng (C), add (A) tolylene diisocyanate then, be warming up to 70～90 ℃, reaction 1～3h; Be warmed up to 90～110 ℃ of insulations 3～5 hours, the percentage composition that detects the NCO group is 3.7～4.5% o'clock, adds raw material (F) defoamer, flow agent and cooling raw material 2/3rds dehydrations (B) ester class and benzene class mixed solvent afterwards immediately, cools to below 60 ℃, filter discharging.
11. the manufacture method of a kind of low free toluene diisocyanate polyurethane curing agent according to claim 10, it is characterized in that: the component (D) after will dewatering respectively earlier contains 1 above hydroxyl, molecular weight is at 60～150 fatty compounds, component (E) low molecular polyether, component (F) defoamer, flow agent and 1/3rd component (B) ester class and benzene class mixed solvent add reactor, back adding (C) TriMethylolPropane(TMP) stirs, be warming up to 60 ± 2 ℃, stirred 15 minutes, dissolve the acidity that the back adds phosphoric acid conditioned reaction system fully Deng (C), press formula ratio then and add (A) tolylene diisocyanate, be warming up to 80 ± 2 ℃, reaction 2h; Be warmed up to 100 ℃ of insulations 3～5 hours, the percentage composition that detects the NCO group is 3.7～4.5% o'clock, adds raw material (F) defoamer, flow agent and cooling raw material 2/3rds dehydrations (B) ester class and benzene class mixed solvent afterwards immediately, cools to below 60 ℃, filter discharging.
12, the manufacture method of a kind of low free toluene diisocyanate polyurethane curing agent according to claim 10 is characterized in that described reactor is the four-hole boiling flask that agitator, thermometer and temperature detection instrument are housed.
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| CN101955575A (en) * | 2010-03-04 | 2011-01-26 | 广东嘉宝莉化工（集团）有限公司 | Polyurethane curing agent compounded by diphenylmethane diisocyanate and hydroxyl compound |
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