CN100528920C - Process for preparing high solid single component polyurethane elastor and its use - Google Patents
Process for preparing high solid single component polyurethane elastor and its use Download PDFInfo
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- CN100528920C CN100528920C CNB2004100534522A CN200410053452A CN100528920C CN 100528920 C CN100528920 C CN 100528920C CN B2004100534522 A CNB2004100534522 A CN B2004100534522A CN 200410053452 A CN200410053452 A CN 200410053452A CN 100528920 C CN100528920 C CN 100528920C
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- siloxanes
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Abstract
The polyurethane is prepared through the reaction between polyol and isocyanate and siloxane modification. The preparation process includes first synthesis of polyurethane prepolymer with end isocyanic radical and the subsequent modification with siloxane, or includes first synthesis of polyurethane prepolymer containing end isocyanic radical with siloxane containing isocyanate and the subsequent modification with siloxane containing active hydrogen. The modified polymer may be produced into paint film of 2-3 mm thickness, shore A hardness not lower than 60, elongation at rupture not smaller than 300 %, stretching strength not lower than 3 MPa and stable storage period of 3-6 months. The present invention is applied in making elastic polyurethane coating.
Description
Technical field
The present invention relates to chemical field, is a kind of high-solid level monocomponent polyurethane method for producing elastomers and application thereof.
Background technology
At present, generally adopt vulcabond and polyester or polyether glycol to react and makes end isocyano (hereinafter to be referred as NCO) wet-solidifying single-component polyurethane (hereinafter to be referred as PU) resin, the end NCO base and the airborne moisture reaction formation urea key that contain by polyurethane prepolymer reach the solidified purpose.Usually the urethane resin of high-solid level is mainly used in the less demanding tackiness agent of working viscosity and foaming, cast elastomeric material field, and for varnish and paint field working viscosity and performance demands, the solid content of wet-solidifying single-component polyurethane that is used for this field at present is generally below 70%.Because the CO2 gas that reaction produces during moisture curing remains in the coating easily, thereby influence the decorate properties and the mechanical property of coating, particularly for thick coating layer, especially obvious to Effect on Performance, reduce hardness, tensile strength and the unit elongation of coating greatly, so that the end application of NCO mono component wet solidifying PU resin on elastomer material is restricted.In addition, for reach environmental protection to the discharging of VOC (organic volatile branch) limit the quantity of and for the limit index of free tolylene diisocyanate (hereinafter to be referred as m-TDI) in the polyurethane coating, usually adopt direct synthetic method to reduce m-TDI and have certain limitation, and too big with the film evaporation method investment, the application of solvent-borne type end NCO base wet-solidifying single-component polyurethane is restricted.
Summary of the invention
The purpose of this invention is to provide a kind of excellent performance, high-solid level monocomponent polyurethane method for producing elastomers and application thereof.
A kind of high-solid level monocomponent polyurethane method for producing elastomers that the present invention proposes, elder generation is with isocyanic ester or contain the siloxanes of isocyano and the polyurethane prepolymer of polyol reaction preparation end isocyano, again through containing the silicone-modified of reactive hydrogen, used polyvalent alcohol is a polyether glycol, or polyester polyol, or epoxy polyol; Used isocyanic ester is an aromatic diisocyanate, or aliphatic diisocyanate; Used siloxanes is the siloxanes that contains reactive hydrogen, and used catalyzer is tin class or amines catalyst, and used solvent is not for containing the solvent of reactive hydrogen; Above-mentioned by weight percentage each raw material consumption is as follows:
Polyvalent alcohol 30-80%
Isocyanate-monomer 10-30%
The siloxanes 0.1-10% that contains reactive hydrogen
Catalyzer 0-0.2%
Solvent 0-10%,
Concrete preparation process is as follows: having the agitator that is equipped with of vacuum dewatering plant; thermometer; in the reactor of prolong; add the isocyanates monomer; solvent; catalyzer; polyvalent alcohol and the evenly slow permanent dropping in back of solvent with vacuum-drying; under nitrogen protection, slowly be warming up to 70-90 ℃ of reaction 3-4 hour; till the end isocyano-content remains unchanged substantially; cooling; dropping contains the siloxanes of reactive hydrogen; 60-80 ℃ of reaction 1-2 hour; cooling; discharging also packs; be performed polymer, use preceding under humidity environment, curing promptly to be elastomerics.
A kind of high-solid level monocomponent polyurethane method for producing elastomers that the present invention proposes, elder generation is with isocyanic ester or contain the siloxanes of isocyano and the polyurethane prepolymer of polyol reaction preparation end isocyano, again through containing the silicone-modified of reactive hydrogen, used polyvalent alcohol is a polyether glycol, or polyester polyol, or epoxy polyol; Used isocyanic ester is an aromatic diisocyanate, or aliphatic diisocyanate; Used siloxanes is the siloxanes that contains reactive hydrogen, and used catalyzer is tin class or amines catalyst, and used solvent is not for containing the solvent of reactive hydrogen; Above-mentioned by weight percentage each raw material consumption is as follows:
Polyvalent alcohol 30-80%
Isocyanate-monomer 10-30%
The siloxanes 0-10% that contains isocyano
The siloxanes 0.1-10% that contains reactive hydrogen
Catalyzer 0-0.2%
Solvent 0-10%,
Concrete preparation process is as follows: siloxanes, solvent, the catalyzer that will contain isocyano, add earlier in the reactor with polyol reaction 0.5-1.5 hour after, add the isocyanates monomer again and continue reaction 3-4 hour, till the end isocyano-content remained unchanged substantially, cooling dripped the siloxanes that contains reactive hydrogen, 60-80 ℃ of reaction 1-2 hour, cooling, discharging also pack, and are performed polymer, solidify before using promptly to be elastomerics under humidity environment.
Among the present invention, polyvalent alcohol adopts vacuum hydro-extraction, vacuum tightness 0.06-0.09MPa, temperature 80-110 ℃; Perhaps dewater with refluxing toluene.
Among the present invention, used polyvalent alcohol molecular weight is 50-10000, hydroxyl value is at 25～300mgKOH/g, polyvalent alcohol can be 1,4 butyleneglycols, neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, polyether Glycols, polyether-tribasic alcohol, polyester diol, polyester trivalent alcohol, epoxy dibasic alcohol, amido polyethers, PTMG etc. adopt one or more mixing wherein to use.
Among the present invention, used isocyanic ester is tolylene diisocyanate, diphenylmethanediisocyanate, naphthalene-1,5 vulcabond, many phenyl polymethine polyisocyanates, one or more in aliphatics hexamethylene diisocyanate, the isophorone diisocyanate mix use.
Among the present invention, the used siloxanes that contains isocyano is isocyanic ester methoxy silane, isocyanic ester Ethoxysilane, isocyanate-containing alkyl methoxy silane, isocyanate-containing alkyl Ethoxysilane, adopts wherein one or two or more kinds mixing to use.
Among the present invention, the used siloxanes that contains reactive hydrogen is sulfydryl, urea groups, primary amino, secondary amino group siloxanes, and adopting wherein, one or more mix use.
Among the present invention, used catalyzer is dibutyl tin laurate, stannous acetate, triethylenediamine, adopts wherein one or two or more kinds mixing to use.
Among the present invention, used solvent is toluene, dimethylbenzene, N-BUTYL ACETATE, vinyl acetic monomer, 4-methyl-2 pentanone, methylethylketone, solvent 100, solvent 150, uses wherein one or two or more kinds mixing to use.
Among the present invention, high-solid level monocomponent polyurethane elastomerics prepolymer solids constituent 〉=90% that makes at 25 ℃, solidifies thick-layer elastic coating shore A hardness 〉=60 of making after 7 days, elongation at break 〉=300%, tensile strength 〉=3Mpa during humidity 50%RH.
Among the present invention, the high-solid level monocomponent polyurethane elastomerics that makes is as the application of coating.Monocomponent polyurethane elastomerics solids constituent 〉=90% that the present invention obtains, free NCO≤0.4%, and reach the viscosity requirement of construction.(1) at 25 ℃, during humidity 50%RH, solidify the thick-layer elastic coating of making after 7 days, coating is bright and clean still, shoreA hardness 〉=60, elongation at break 〉=300%, tensile strength 〉=3Mpa.Can be applicable to the thick elastic coating that is coated with of PU, PU pavement material such as floor varnish, sports field are decorated varnish etc.(2) the polyurethane elastomer prepolymer that makes of the present invention has the wetting and dispersing property with pigment, filler excellence, can be mixed with elastic polyurethane coating with pigment, filler.High solid, the nontoxic thick elastic coating that is coated with; Coat-thickness can reach 2-3mm.Therefore, but adopt the elastomerics widespread use of preparation method's gained of the present invention.
Embodiment
1, the elastomeric preparation of monocomponent polyurethane
Example 1:
Having the agitator that is equipped with of vacuum dewatering plant; thermometer; in the 500ml round-bottomed flask of prolong; the adding hydroxyl value is 80KOH/g; molecular weight is 3000 polyether-tribasic alcohol 80 grams; hydroxyl value is 100KOH/g; molecular weight is 2000 polyester diol 160 grams; be warming up to 100 ℃; stir vacuum hydro-extraction down 1 hour; be cooled to 50 ℃; add tolylene diisocyanate 50 grams; dimethylbenzene 15 grams; catalyzer 0.06 gram; be warming up under the 80-90 ℃ of logical nitrogen protection and reacted 3-4 hour; with Di-n-Butyl Amine titration measuring NCO content; when NCO content remains unchanged substantially, be cooled to 40 ℃, drip aminopropyl trimethoxysilane coupling agent 8 grams; 60 ℃ of reactions were measured the discharging of NCO content after 2 hours.
Example 2:
Having the agitator that is equipped with of vacuum dewatering plant; thermometer; in the 500ml round-bottomed flask of prolong; the adding hydroxyl value is 60KOH/g; molecular weight is 1000 epoxy dibasic alcohol 60 grams; hydroxyl value is 200KOH/g; molecular weight is 2000 polyester diol 120 grams; be warming up to 100 ℃; stir vacuum hydro-extraction down 1 hour; be cooled to 50 ℃; add isocyanic ester propyl group Ethoxysilane 4.35 grams; toluene and N-BUTYL ACETATE solvent 10 grams are warming up to 70-90 ℃; nitrogen protection was reacted 1 hour down; add diphenylmethanediisocyanate 30 grams and continue reaction 3-4 hour; with Di-n-Butyl Amine titration measuring NCO content; when NCO content remains unchanged substantially, be cooled to 50 ℃, drip mercaptopropyl trimethoxysilane 1.99 grams; NCO content, discharging are measured in 100 ℃ of reactions after 2 hours.
Example 3
Having the agitator that is equipped with of vacuum dewatering plant; thermometer; in the 500ml round-bottomed flask of prolong; add neopentyl glycol 40 grams; hydroxyl value is 100KOH/g; molecular weight is 1000 PTMG 120 grams; be warming up to 100 ℃; stir vacuum hydro-extraction down 1 hour; be cooled to 50 ℃; add 1; 6-second vulcabond 30 grams; N-BUTYL ACETATE and methylpentanone 5 grams; catalyzer 0.08 gram; be warming up under the 80-90 ℃ of logical nitrogen protection and reacted 3-4 hour; with Di-n-Butyl Amine titration measuring NCO content; when NCO content remains unchanged substantially, be cooled to 40 ℃, drip cyclohexyl-aminopropyl methyl dimethoxysilane 0.2 gram; NCO content, discharging are measured in 80 ℃ of reactions after 2 hours.
Performance:
Example 1-3 makes colourless to little yellow transparent viscous liquid, and solid content 〉=90% is at 25 ℃, during humidity 50%RH, did solid work in 24 hours, solidify the thick-layer elastic coating of making after 7 days, coating is bright and clean still, hardness 〉=60shore A, elongation at break 〉=300%, tensile strength 〉=3Mpa.
2, the application of mono component wet solidifying siloxane modified polyurethane elastomer
Get any elastomerics prepolymer among the example 1-3, press following recipe ratio and pigment, filler blending dispersion under agitation:
Silicone-modified prepolymer 12-15
N-BUTYL ACETATE 2-3
Lime carbonate (10um) 20-25
Titanium dioxide (whitening agent) 0.5-1
T-12 0.02-0.03％
The coating normal temperature of making 2-3mm solidifies down, does solid work 7 days mensuration coating shoreA hardness 〉=70, elongation at break 〉=100%, tensile strength 〉=1.6Mpa after 24 hours.
Claims (11)
1, a kind of high-solid level monocomponent polyurethane method for producing elastomers, it is characterized in that earlier holding the polyurethane prepolymer of isocyano with isocyanic ester or the siloxanes that contains isocyano and polyol reaction preparation, again through containing the silicone-modified of reactive hydrogen, used polyvalent alcohol is a polyether glycol, or polyester polyol, or epoxy polyol; Used isocyanic ester is an aromatic diisocyanate, or aliphatic diisocyanate; Used siloxanes is the siloxanes that contains reactive hydrogen, and used catalyzer is tin class or amines catalyst, and used solvent is not for containing the solvent of reactive hydrogen; Above-mentioned by weight percentage each raw material consumption is as follows:
Polyvalent alcohol 30-80%
Isocyanate-monomer 10-30%
The siloxanes 0.1-10% that contains reactive hydrogen
Catalyzer 0-0.2%
Solvent 0-10%,
Concrete preparation process is as follows: having the agitator that is equipped with of vacuum dewatering plant; thermometer; in the reactor of prolong; add the isocyanates monomer; solvent; catalyzer; polyvalent alcohol and the evenly slow permanent dropping in back of solvent with vacuum-drying; under nitrogen protection, slowly be warming up to 70-90 ℃ of reaction 3-4 hour; till the end isocyano-content remains unchanged substantially; cooling; dropping contains the siloxanes of reactive hydrogen; 60-80 ℃ of reaction 1-2 hour; cooling; discharging also packs; be performed polymer, use preceding under humidity environment, curing promptly to be elastomerics.
2, a kind of high-solid level monocomponent polyurethane method for producing elastomers, it is characterized in that earlier holding the polyurethane prepolymer of isocyano with isocyanic ester or the siloxanes that contains isocyano and polyol reaction preparation, again through containing the silicone-modified of reactive hydrogen, used polyvalent alcohol is a polyether glycol, or polyester polyol, or epoxy polyol; Used isocyanic ester is an aromatic diisocyanate, or aliphatic diisocyanate; Used siloxanes is the siloxanes that contains reactive hydrogen, and used catalyzer is tin class or amines catalyst, and used solvent is not for containing the solvent of reactive hydrogen; Above-mentioned by weight percentage each raw material consumption is as follows:
Polyvalent alcohol 30-80%
Isocyanate-monomer 10-30%
The siloxanes 0-10% that contains isocyano
The siloxanes 0.1-10% that contains reactive hydrogen
Catalyzer 0-0.2%
Solvent 0-10%,
Concrete preparation process is as follows: siloxanes, solvent, the catalyzer that will contain isocyano, add earlier in the reactor with polyol reaction 0.5-1.5 hour after, add the isocyanates monomer again and continue reaction 3-4 hour, till the end isocyano-content remained unchanged substantially, cooling dripped the siloxanes that contains reactive hydrogen, 60-80 ℃ of reaction 1-2 hour, cooling, discharging also pack, and are performed polymer, solidify before using promptly to be elastomerics under humidity environment.
3, high-solid level monocomponent polyurethane method for producing elastomers according to claim 1 and 2 is characterized in that polyvalent alcohol adopts vacuum hydro-extraction, vacuum tightness 0.06-0.09MPa, temperature 80-110 ℃; Perhaps dewater with refluxing toluene.
4, high-solid level monocomponent polyurethane method for producing elastomers according to claim 1 and 2 is characterized in that used polyvalent alcohol molecular weight is 50-10000, and hydroxyl value is at 25～300mgKOH/g.
5, high-solid level monocomponent polyurethane method for producing elastomers according to claim 1 and 2, it is characterized in that used isocyanic ester is tolylene diisocyanate, diphenylmethanediisocyanate, naphthalene-1,5 vulcabond, many phenyl polymethine polyisocyanates, in aliphatics hexamethylene diisocyanate, the isophorone diisocyanate one or more mix use.
6, high-solid level monocomponent polyurethane method for producing elastomers according to claim 1 and 2, it is characterized in that the used siloxanes that contains isocyano is isocyanic ester methoxy silane, isocyanic ester Ethoxysilane, isocyanate-containing alkyl methoxy silane, isocyanate-containing alkyl Ethoxysilane, adopt wherein one or two or more kinds mixing to use.
7, high-solid level monocomponent polyurethane method for producing elastomers according to claim 1 and 2, it is characterized in that the used siloxanes that contains reactive hydrogen is sulfydryl, urea groups, primary amino, secondary amino group siloxanes, adopting wherein, one or more mix use.
8, according to claim 1 or 2 described high-solid level monocomponent polyurethane method for producing elastomers, it is characterized in that used catalyzer is dibutyl tin laurate, stannous acetate, triethylenediamine, adopt wherein one or two or more kinds mixing to use.
9, high-solid level monocomponent polyurethane method for producing elastomers according to claim 1 and 2, it is characterized in that: used solvent is toluene, dimethylbenzene, N-BUTYL ACETATE, vinyl acetic monomer, 4-methyl-2 pentanone, methylethylketone, solvent 100, solvent 150, uses wherein one or two or more kinds mixing to use.
10, according to the arbitrary described method of claim 1-9, it is characterized in that high-solid level monocomponent polyurethane elastomerics prepolymer solids constituent 〉=90% that makes, at 25 ℃, solidify the thick-layer elastic coating of making after 7 days during humidity 50%RH, coating shoreA hardness 〉=60, elongation at break 〉=300%, tensile strength 〉=3Mpa.
11, the high-solid level monocomponent polyurethane elastomerics that makes according to the arbitrary described method of claim 1-9 is as the application of coating.
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| CNB2004100534522A CN100528920C (en) | 2004-08-05 | 2004-08-05 | Process for preparing high solid single component polyurethane elastor and its use |
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| CNB2004100534522A CN100528920C (en) | 2004-08-05 | 2004-08-05 | Process for preparing high solid single component polyurethane elastor and its use |
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| CN100528920C true CN100528920C (en) | 2009-08-19 |
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