CN100351297C - 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
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- CN100351297C CN100351297C CNB2004100151351A CN200410015135A CN100351297C CN 100351297 C CN100351297 C CN 100351297C CN B2004100151351 A CNB2004100151351 A CN B2004100151351A CN 200410015135 A CN200410015135 A CN 200410015135A CN 100351297 C CN100351297 C CN 100351297C
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- toluene diisocyanate
- curing agent
- free toluene
- solidifying agent
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 56
- 239000004814 polyurethane Substances 0.000 title claims abstract description 26
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract 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 46
- 239000000203 mixture Substances 0.000 claims abstract description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 229920000570 polyether Polymers 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000012046 mixed solvent Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000013530 defoamer Substances 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 10
- 150000001555 benzenes Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000001143 conditioned effect Effects 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
- -1 sec-n-octyl alcohol Chemical compound 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
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 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
- 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
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 8
- 239000003973 paint Substances 0.000 abstract description 5
- 229920005749 polyurethane resin Polymers 0.000 abstract description 4
- 239000011527 polyurethane coating Substances 0.000 abstract description 3
- 150000007824 aliphatic compounds Chemical class 0.000 abstract 2
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 abstract 1
- 239000002518 antifoaming agent Substances 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000013008 moisture curing Methods 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
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000003673 urethanes Chemical class 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 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
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- 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
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 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
- 238000001914 filtration Methods 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
- 238000004519 manufacturing process Methods 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
- 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
Landscapes
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a solidifying agent with low-free toluene diisocyanate for polyurethane, and a preparation method of the solidifying agent. The solidifying agent is prepared from the following components: (A) 18 to 25 wt% of toluene diisocyanate or mixture of two kinds of toluene diisocyanate, (B) 35 to 65 wt% of mixture of an ester solvent and a benzene solvent, (C) 2 to 4 wt% of trihydroxymethyl propane, (D) 3 to 5 wt% of aliphatic compound comprising at least two hydroxy groups, (E) 10 to 15 wt% of low-molecular polyether, (F) 0.2 to 0.5 wt% of defoaming agent and 0.1 to 0.3 wt% of leveling agent, wherein the molecular weight of the aliphatic compound is from 60 to 150. In the present invention, a direct synthesis method is adopted, the solidifying agent for polyurethane is synthesized under the condition that subsequent treatment devices for distillation, extraction, etc. do not need to be added, and the content of the free toluene diisocyanate completely conforms to that of the high level required by GB18581-2001 to the monomer content of free toluene diisocyanate in a polyurethane coating; in addition, the performances, such as wearability, surface hardness, pliability, glossiness of a paint film, etc. of a bi-component polyurethane resin coating prepared by mixing the solidifying agent with a hydroxy group component, are not affected.
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) boiling point is less than 200 ℃ ester class and benzene class mixed solvent 35～65%; (C) TriMethylolPropane(TMP) 2～4%; (D) contain 1～2 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, back adding (C) stirs, 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 weight percentage that detects the NCO group is to add raw material (F) and (B) of cooling raw material 2/3rds after dewatering at 3.7～4.5% o'clock immediately), cooling, filtration, discharging.
Making step of the present invention is: (D), (E) after will dewatering earlier, (B) with 1/3rd add 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 percentage composition that detects the NCO group is 3.7～4.5% o'clock, add immediately raw material (F) and the cooling raw material (2/3rds through the dehydration after (B), cool 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 60～150 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 less than sticking power, level is greater than opacifying power, 8/m is greater than water tolerance (24h) wear resistance, g is greater than abrasion resistance, inferior less than | Not | 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 (9)
1, a kind of low free toluene diisocyanate polyurethane curing agent is characterized in that:
Its raw material is formed and 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 1～2 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;
Contain 1～2 hydroxyl, molecular weight 1/3rd adding reactors after will dewater respectively earlier 35～65% parts of 60～150 10～15% parts of 3～5% parts of fatty compoundss, low molecular polyethers, ester class and benzene class mixed solvents, add 2～4% parts of TriMethylolPropane(TMP)s after stirring, be warming up to 50～70 ℃, stirred 10～20 minutes, dissolve the acidity that the back adds phosphoric acid conditioned reaction system fully Deng TriMethylolPropane(TMP), press formula ratio then and add 18～25% parts of tolylene diisocyanates, 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 3.7～4.5% o'clock, add 2/3rds of 35～65% parts of cooling starting ester class after 0.2～0.5% part of raw material defoamer, 0.1～0.3% part of flow agent and the dehydration and benzene class mixed solvents immediately, cool to below 60 ℃, filter discharging.
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-tolylene diisocyanate or 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 is characterized in that: wherein to account for the percentage composition of solidifying agent be 10-25% to esters solvent, and the percentage composition that benzene kind solvent accounts for solidifying agent is 25-40%.
5, low free toluene diisocyanate polyurethane curing agent according to claim 1, it is characterized in that: describedly contain 1～2 hydroxyl, molecular weight is the 1-propyl alcohol at the fatty compounds of 60-150, the 2-propyl alcohol, the 1-butanols, the 2-butanols, Pentyl alcohol, the 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, the 3-butyleneglycol, 1, the 4-butyleneglycol, diethyl ethylene glycol, 2, the 3-butyleneglycol, the dipropyl ethylene glycol one two different glycol that contract, dipropylene glycol, or tripropyl ethylene glycol.
6, described a kind of low free toluene diisocyanate polyurethane curing agent according to claim 1, it is characterized in that: described low molecular polyether is a dihydroxyl polyoxygenated propyl ether: one of N-204, N-201, N-215, N-210, N-220, N-235, or trihydroxy-oxidation propyl ether: N-303 or N-330.
7, 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.
8, a kind of low free toluene diisocyanate polyurethane curing agent according to claim 1, contain 1～2 hydroxyl after it is characterized in that to dewater earlier, molecular weight is at 60～150 fatty compounds 3～5%, / 3rd adding reactors that 10～15% parts of low molecular polyethers and ester class and benzene class mixed solvent are 35～65% parts, add 2～4% parts of TriMethylolPropane(TMP)s after stirring, be warming up to 60 ± 2 ℃, stirred 15 minutes, dissolve the acidity that the back adds phosphoric acid conditioned reaction system fully Deng TriMethylolPropane(TMP), press formula ratio then and add 18～25% parts of tolylene diisocyanates, 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, add 2/3rds of 35～65% parts of cooling starting ester class after 0.2～0.5% part of raw material defoamer, 0.1～0.3% part of flow agent and the dehydration and benzene class mixed solvents immediately, after the dehydration, cool to below 60 ℃, filter discharging.
9, a kind of low free toluene diisocyanate polyurethane curing agent according to claim 1 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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| CN101456940B (en) * | 2008-12-31 | 2011-04-20 | 广东华润涂料有限公司 | Dissolvant type polyurethane curing agent synthetic method for producing low free toluene diisocyanate content |
| CN101955575B (en) * | 2010-03-04 | 2012-12-26 | 嘉宝莉化工集团股份有限公司 | Polyurethane curing agent compounded by diphenylmethane diisocyanate and hydroxyl compound |
| CN103130980B (en) * | 2013-02-04 | 2015-07-01 | 华南理工大学 | Preparation method for low free toluene diisocyanate (TDI) polyurethane pre-polymer curing agent |
| CN103497662A (en) * | 2013-08-28 | 2014-01-08 | 广西梧州龙鱼漆业有限公司 | Polyether-modified polyurethane curing agent and preparation method thereof |
| CN104073146B (en) * | 2014-06-17 | 2016-07-20 | 江苏科技大学 | A kind of waterborne epoxy-polyurethane floor coatings and preparation method thereof |
| CN104592483B (en) * | 2015-01-14 | 2017-06-06 | 嘉宝莉化工集团股份有限公司 | Environment-protecting polyurethane curing agent and its preparation method and application |
| CN107880249A (en) * | 2017-11-24 | 2018-04-06 | 鹤山市信兴化工有限公司 | A kind of polyurethane curing agent and preparation method thereof |
| CN109824865B (en) * | 2018-12-26 | 2021-09-07 | 万华化学集团股份有限公司 | Preparation method of polyisocyanate curing agent with storage stability and curing agent |
| CN111019078B (en) * | 2019-12-31 | 2022-04-05 | 北京华腾新材料股份有限公司 | Waterborne polyurethane curing agent and preparation method and application thereof |
| CN112644225A (en) * | 2020-12-29 | 2021-04-13 | 永佳工业车辆(苏州)有限公司 | Cart caster with steering positioning brake mechanism and manufacturing method thereof |
| CN114195974B (en) * | 2021-12-06 | 2022-10-18 | 季华实验室 | Polyurethane prepolymer and preparation method thereof, and polyurethane product |
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