CN100528963C - Polyurethane resin composition and its preparing process - Google Patents
Polyurethane resin composition and its preparing process Download PDFInfo
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- CN100528963C CN100528963C CN 200710002553 CN200710002553A CN100528963C CN 100528963 C CN100528963 C CN 100528963C CN 200710002553 CN200710002553 CN 200710002553 CN 200710002553 A CN200710002553 A CN 200710002553A CN 100528963 C CN100528963 C CN 100528963C
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Abstract
The invention discloses a polyurethane resin composition, which comprises the following parts: macromole polyatomic alcohol, isocyanate, micromole diamin/micromole diatomic alcohol, activator, anti-oxidant, dissolvent, terminating agent, Wherein weight ratio of macromole polyatomic alcohol, isocyanate, micromole diamin/micromole diatomic alcohol, activator, anti-oxidant, terminating agent against total weight is 0.2-0.7:1; mole ratio of macromole polyatomic alcohol against mole ratio of micromole diamin or micromole diatomic alcohol is 1 : 0-12; mole ratio of micromole diamin or micromole diatomic alcohol against isocyanate is 1:0.80-1.10. This invention can be used to ink, spraying paint and polyurethane resin of leather surface additive, which possesses good property.
Description
Technical field
The present invention relates to the macromolecular organic field that learns a skill, be specifically related to a kind of polyurethane resin composition that can be used for printing ink/coating preparation, single component, self-drying type and preparation method thereof.
Background technology
In the prior art, urethane resin is because of having excellent abrasion resistance, scuff resistance, weather resistance, solvent resistance, adhesiveproperties and good low-temperature performance, elasticity, sticking power, insulativity, gloss, gloss retention, and its adjustability is good, can satisfy various application requiring, be widely used.At present, urethane resin is the important source material of preparation printing ink, leather surface treatment agent, coating, especially urethane resin is that the coating of filmogen is that polyurethane coating (also being polyurethane paint) at first begins suitability for industrialized production by Germany the forties in 20th century, put into production in succession in various countries after the sixties in 20th century, and developed the kind of a lot of polyurethane coatings.Polyurethane coating has been widely used in applications such as footwear material, leather, fabric, chemical industry equipment, marine ship, electromechanical equipment, timber, cement, plays important effect in modern society.
If divide from component, polyurethane coating then has the branch of single component and two-pack; Two-pack is meant that polyurethane coating is divided into first, second two components, the first component contains isocyanate group, second component hydroxyl, need before the use at the construction field (site) two components to be mixed with composition according to a certain percentage, just can cover with paint, lacquer, colour wash, etc. after the two reaction, being easy to influences construction quality because of the metering mistake, complicated operation, to be subjected to the time during use, restrictions such as envrionment conditions, for example China's invention 85104908, China's invention 86101515, China's invention 87105713, China invention 90105044.X, China's invention 92113828.8, China invention 95195489.X, China's invention 00116520.8, China's invention 02111494.3, China's invention 03140686, U.S.'s invention 5260358, U.S.'s invention 4341689, U.S.'s invention 4983671, U.S.'s invention 5154950, U.S.'s invention 5502148, U.S.'s invention 6160075, U.S.'s invention 6169141, U.S.'s invention 6423816,6458898 disclosed technical schemes are invented by the U.S., all are to prepare the bicomponent polyurethane coating aspect; And one-can urethane coating is easy to use, and not needing to resemble needs user's allotment voluntarily at the scene the two-pack, coatings formulated surplus, out of date phenomenon also can not occur.
In existing various one-can urethane coatings, can be divided into moisture-curable, dead front type, self-drying type etc. again according to different curing modes.The rate of drying of moisture-curable polyurethane coating is subjected to the influence of humidity in the air, need under the bigger environment of moisture, place for a long time, curing molding gradually, in the winter time under the situation that temperature and humidity is all low, be difficult to solidify, and storage time is short, be easy to when storage, just solidify automatically because of airborne moisture, lose the value of use, for example China's invention 200310119059.4, China invention 200310119058.X, China's invention 200310119060.7,5138017 disclosed technical schemes are invented all about preparation moisture-curable polyurethane coating aspect by the U.S.; Though and blocked polyurethane paint has good storage stability because sealed isocyanic ester temporarily, need to open the isocyanate reacting group that is closed by improving temperature, thereby further reaction realizes curing molding, the temperature of heating sometimes will reach 150 ℃ even higher, this just need use in special occasion, also need to consume a large amount of heat energy, for example China's invention 95100827.7, U.S.'s invention 4005041, U.S.'s invention 4474937, U.S.'s invention 4478894, U.S.'s invention 5202406, U.S.'s invention 5541279, U.S.'s invention 5646228, U.S.'s invention 5728795, disclosed technical scheme all are about the preparation blocked polyurethane paint; The self-drying type polyurethane coating does not promptly need long-time placement the under the bigger environment of moisture, need not realize solidifying at a large amount of heat energy of special occasion consumption yet, it can be at any environment following within a short period of time of free curing molding, the while storage-stable, and still find no the technical scheme that disclosed comparatively complete, safe preparation single component self-drying type polyurethane coating is correlated with urethane resin product and method both at home and abroad.
The polyurethane coating of single component self-drying type also contains more free isocyanate usually with resin; this have certain toxic free isocyanate; when its content is higher; not only paint film property there is negative influence; also can environmental pollution; influence the healthy of workmen; therefore when the preparation polyurethane coating; all require the free isocyanate in the finished product is reacted; do not influencing under the product quality premise; it is safe low-level that the content of free isocyanate in the product is dropped to; and China's invention 99119948.0; China's invention 02109937.5; China's invention 01817800.6; China's invention 02804593.9; in China's invention 03118882.6, all unexposed this kind treatment process.
Summary of the invention
At existing above-mentioned deficiency in currently available products and the technology of preparing, one of purpose of the present invention promptly is, the polyurethane coating polyurethane resin composition of a kind of single component that is applicable to printing ink, leather surface treatment agent and spraying paint, self-drying type, low free isocyanate is provided.
The present invention also aims to, a kind of efficient, safe preparation method of above-mentioned polyurethane resin composition is provided.
For achieving the above object, technical scheme provided by the invention is as follows:
A kind of polyurethane resin composition, it weight ratio that comprises following component and each component is: macromolecular polyol 10~30%, isocyanic ester 5~25%, small molecules diamine/small molecules dibasic alcohol 0~10%, terminator 0.05%~3%, catalyzer 0.001~1%, oxidation inhibitor 0~3%, all the other are solvent.
Described terminator is methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, Di-n-Butyl Amine equimolecular quantity less than one of single alcohol of 500, monoamine or its mixture.
Aforesaid polyurethane resin composition, the weight percent of its component is: the weight sum of wherein said macromolecular polyol, isocyanic ester, small molecules diamine/small molecules dibasic alcohol, catalyzer, oxidation inhibitor, terminator is 0.2~0.7: 1 with the ratio of gross weight.
Aforesaid polyurethane resin composition is characterized in that, described macromolecular polyol mole number is 1: 0~12 with the ratio of the mole number of small molecules diamine/small molecules dibasic alcohol; Described macromolecular polyol and the small molecules diamine/mole number of small molecules dibasic alcohol are 1: 0.80~1.10 with the ratio of the mole number of isocyanic ester.
Described macromolecular polyol functional group is between 2~3, and molecular weight is between 500~5000; Comprise polyethylene glycol adipate glycol, poly-hexanodioic acid-1,4 one butanediol ester glycol, polyneopentyl glycol adipate glycol, poly-own diester Diethylene Glycol esterdiol, poly-adipate glycol-1,4 one butanediol ester glycol, poly-own diester ethylene glycol-Diethylene Glycol esterdiol, poly-own diester ethylene glycol and 1,2-propylene glycol esterdiol, poly-hexanodioic acid neopentyl glycol-1,4-butanediol ester glycol, polypropylene glycol ether glycol, the poly-tetrahydrochysene ether glycol and composition thereof of muttering; Described small molecules diamine comprises quadrol, hexanediamine, 1,2-Pn, 1, and 3-Pn, isophorone diamine, tetramethylene-diamine, molecular weight is less than diamine of 500 and composition thereof; The small molecules dibasic alcohol comprises ethylene glycol, propylene glycol, and butyleneglycol, hexylene glycol, to Benzenediol, neopentyl glycol, Diethylene Glycol, molecular weight is less than dibasic alcohol of 500 and composition thereof; It also can be the mixture of aforementioned dibasic alcohol and/or diamine.
Described catalyzer is to comprise triethylene diamine, N, other organo-metallic catalyst such as tertiary amine catalyst such as N-dimethylcyclohexylamine, two-(2 methylethyl) ether and stannous octoate, dibutyl tin laurate, organotin, organo-bismuth and composition thereof; Described oxidation inhibitor is ester class, Hinered phenols or its mixture; Described solvent is ketone, benzene class, alcohols, ester class isopolarity and non-polar solvent and composition thereof, as pimelinketone, ethanol, Virahol, isopropylcarbinol, toluene, dimethylbenzene, gasoline, solvent oil, acetone, butanone, dimethyl formamide (DMF), ethyl acetate, butylacetate, isophorone.
Described isocyanic ester is aliphatics or aromatic polyisocyanate, as m-benzene diisocyanate, PPDI, polymethine polyphenyl polyisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, ditan 4,4 '-or 2,4-or 2,2 '-vulcabond (MDI), hexamethylene-diisocyanate (HDI) and composition thereof.
The preparation method of aforementioned polyurethane resin composition, it comprises the steps:
(1) described macromolecular polyol is transported in the reactor, stir, 0~-0.1MPa, 80~160 ℃ condition under vacuum hydro-extraction;
(2) described macromolecular polyol is after dehydration, treat that its temperature drops to normal temperature described small molecules diamine/small molecules dibasic alcohol, catalyzer, oxidation inhibitor, solvent are input in the reactor, in reactor, drop into 70%~99% the isocyanic ester account for the isocyanic ester total amount after stirring again, in temperature of reaction is under 40~100 ℃ of conditions, after the successive reaction 1~9 hour, add remaining 1%~30% isocyanic ester again, reacted 1~3 hour;
(3) detection composition viscosity after reaching 1000~50000MPaS (35 ℃), then adds terminator reaction 1~3 hour, obtains described polyurethane resin composition.
The preparation method of aforementioned polyurethane resin composition, described step (3) also comprises the steps:
(31) viscosity of detection composition does not reach 1000~50000MPaS (35 ℃) as it, then continue to add 0.1%~10% the extra isocyanic ester that accounts for the isocyanic ester total amount and continues reaction 1~3 hour;
(32) viscosity of detection composition again, as reaching 1000~50000MPaS (35 ℃) not yet, repeating step (31) is after the composition viscosity reaches 1000~50000MPaS (35 ℃), add terminator reaction 1~3 hour, obtain described polyurethane resin composition.
The invention has the advantages that: polyurethane resin composition provided by the present invention, the content of free isocyanate wherein is lower, and is safe in utilization; Its excellent performance is suitable for printing ink and leather surface treatment agent, and especially its spraying paint that mixes is specially adapted to rubber boots material, polyurethane shoe material and TPR footwear material; It is to the PU sole, rubber-sole, and leather, materials such as PU leather have excellent sticking power, and good luster, and good anti-tortuosity, scrath resistance and resistance to bond are arranged; The preparation method of said composition provided by the present invention, step is succinct, efficient is high, the constant product quality of preparation.
The present invention is further described below in conjunction with embodiment.
Embodiment
Concrete prescription of several polyurethane resin composition that adopt the invention technical scheme and preparation method thereof is provided below.
Embodiment 1: the molecular weight that adds 140 grams in 2000 milliliters four-hole boiling flask of agitator, reflux condensing tube and thermometer is housed is 2000 polyethylene glycol adipate glycol, heat to 110-130 ℃, keep 0~-the 0.1MPa vacuum under dehydration after 2 hours, treat that its temperature reduces to normal temperature, start then to stir and add ethylene glycol 38.1 grams, N-BUTYL ACETATE 312.9 grams, pimelinketone 126 grams, dimethylbenzene 72 grams, antioxidant 1010 4 grams, stannous octoate 0.2 gram; Stir after 0.5 hour, add MDI 155 grams, stirring reaction, system generation thermopositive reaction this moment, temperature rises naturally, heat with electric mantle after the homo(io)thermism, and constant temperature 70-80 ℃ react 2 hours after, the viscosity of detection composition; If viscosity reaches 4000-20000MPaS (35 ℃), add isopropylcarbinol 4 gram reactions 1 hour; It is 40 ± 2% polyurethane composition that blowing promptly obtains solid content; If do not reach 4000-20000MPaS (35 ℃), the MDI that then in batches adds 0.5 to 5 gram again is incubated 2 hours, detect viscosity again, after its viscosity reaches 4000-20000MPaS (35 ℃), add isopropylcarbinol 4 gram reactions 1 hour, it is 40 ± 2% polyurethane resin composition that blowing promptly obtains solid content.
Embodiment 2: the molecular weight that add 220 grams in 2000 milliliters four-hole boiling flask of agitator, reflux condensing tube and thermometer is housed are the 1000 poly-tetrahydrochysenes ether glycol (PTMG) of muttering, heat to 110-130 ℃ 0, keep 0~-0.1MPa vacuum hydro-extraction 2 hours, reduce to normal temperature; Start then to stir and add hexylene glycol 16.3 grams, pimelinketone 343 grams, butanone 122.5 grams, toluene 89 grams, dibutyl tin laurate 0.2 gram; Stir and add 2 after 0.5 hour, 4-tolylene diisocyanate and 2, the mixture of 6-tolylene diisocyanate (TDI) (the mixed weight ratio is 80: 20) 60 grams, stirring reaction, system generation thermopositive reaction this moment temperature so rises, after the homo(io)thermism with electric mantle heating and 80-85 ℃ of reaction after 2 hours, the viscosity of detection composition; If viscosity reaches 4000-20000MPaS (35 ℃), add propyl alcohol 4 gram reactions 1 hour.It is 35 ± 2% polyurethane composition that blowing promptly obtains solid content.If do not reach 4000-20000MPaS (35 ℃), the TDI that in batches adds 0.5 to 5 gram is incubated 2 hours, reaches 4000-20000MPaS (35 ℃) back up to viscosity and adds propyl alcohol 4 gram reactions 1 hour; It is 35 ± 2% polyurethane composition that blowing promptly obtains solid content.
Embodiment 3: the molecular weight that adds 85.3 grams in 1000 milliliters four-hole boiling flask of agitator, reflux condensing tube and thermometer is housed is 1500 poly-adipate glycols-1,4-butanediol ester glycol, heat to 120-150 ℃ of vacuum hydro-extraction 2 hours, reduce to normal temperature; Start then and stir adding butyleneglycol 26.1 grams, newly become glycol 26.1 grams, vinyl acetic monomer 120.4 grams, butanone 337.2 grams, toluene 24.1 restrains, triphenyl phosphite 7.8 grams, organic bismuth catalyst 1.5 grams; Stir after 0.5 hour and to add MDI 148 grams, stirring reaction, system generation thermopositive reaction this moment, temperature rises naturally, heat with electric mantle after the homo(io)thermism, and 80-90 ℃ react 2 hours after, the viscosity of detection composition; If viscosity reaches 4000-20000MPaS (35 ℃), add Di-n-Butyl Amine 0.5 gram reaction 1 hour.It is 38 ± 2% polyurethane composition that blowing promptly obtains solid content.If do not reach 4000-20000MPaS (35 ℃), the MDI that in batches adds 0.5 to 5 gram is incubated 2 hours, reaches 4000-20000MPaS (35 ℃) back up to viscosity and adds Di-n-Butyl Amine 0.5 gram reaction 1 hour; It is 38 ± 2% polyurethane composition that blowing promptly obtains solid content.
Embodiment 4: the molecular weight that adds 85.3 grams in 1000 milliliters four-hole boiling flask of agitator, reflux condensing tube and thermometer is housed is 2000 poly adipate succinic acid ester glycol, heats to 120-160 ℃ of vacuum hydro-extraction 2 hours, reduces to normal temperature; Start then to stir and add neopentyl glycol 46.9 grams, pimelinketone 293.3 grams, butanone 110.6 grams, dimethylbenzene 15 grams, antioxidant 1010 1.4 grams, triphenyl phosphite 1.4 grams, dibutyl tin laurate 0.2 gram; Stir after 0.5 hour and to add the MDI125 gram, stirring reaction, system generation thermopositive reaction this moment, temperature so rises, after the homo(io)thermism with the electric mantle heating, and 75-85 ℃ of reaction after 2 hours, the viscosity of detection composition; If viscosity reaches 4000-20000MPaS (35 ℃), add Virahol 4 gram reactions 1 hour.It is 38 ± 2% polyurethane composition that blowing promptly obtains solid content.If do not reach 4000-20000MPaS (35 ℃), the MDI that in batches adds 0.5 to 5 gram is incubated 2 hours, reaches 4000-20000MPaS (35 ℃) back up to viscosity and adds Virahol 4 gram reactions 1 hour.It is 38 ± 2% polyurethane composition that blowing promptly obtains solid content.
Embodiment 5: the molecular weight that adds 300 grams in 2000 milliliters four-hole boiling flask of agitator, reflux condensing tube and thermometer is housed is 1000 polypropylene glycol ether glycol (PPG), heat to 80-120 ℃ of vacuum hydro-extraction 2 hours, reduce to normal temperature and start stirring adding butyleneglycol 90 grams then, pimelinketone 371 grams, butanone 170 grams, toluene 50 grams, oxidation inhibitor 246 (BHT) 5 gram dibutyl tin laurates 0.2 gram; Stir and add 2 after 0.5 hour, 4-tolylene diisocyanate and 2, the mixture of 6-tolylene diisocyanate (TDI) (the mixed weight ratio is 80: 20) 198 grams, stirring reaction, system generation thermopositive reaction this moment, temperature so rises, and heats with electric mantle after the homo(io)thermism, and 80-85 ℃ the reaction 2 hours after, the viscosity of detection composition; If viscosity reaches 4000-20000MPaS (35 ℃), add propyl alcohol 2 gram reactions 1 hour.It is 50 ± 2% polyurethane composition that blowing promptly obtains solid content.If do not reach 4000-20000MPaS (35 ℃), the TDI that in batches adds 0.5 to 5 gram is incubated 2 hours, reaches 4000-20000MPaS (35 ℃) back up to viscosity and adds propyl alcohol 2 gram reactions 1 hour.It is 50 ± 2% polyurethane composition that blowing promptly obtains solid content.
Embodiment 6: the molecular weight that adds 248.5 grams in 1000 milliliters four-hole boiling flask of agitator, reflux condensing tube and thermometer is housed is 3000 poly adipate succinic acid ester glycol, heats to 110-130 ℃ of vacuum hydro-extraction 2 hours, reduces to normal temperature; Start then to stir and add hexylene glycol 38.9 grams, isophorone diamine 1.5 grams, pimelinketone 332.2 grams, butylacetate 110.4 grams, antioxidant 1010 7.8 grams, dibutyl tin laurate 0.5 gram; Stir after 0.5 hour and to add HDI 67 grams, stirring reaction, system generation thermopositive reaction this moment, temperature so rises, after the homo(io)thermism with the electric mantle heating and 80-85 ℃ of reaction after 2 hours, the viscosity of detection composition; If viscosity reaches 4000-20000MPaS (35 ℃), add butanols 5 gram reactions 1 hour.It is 45 ± 2% polyurethane composition that blowing promptly obtains solid content.If do not reach 4000-20000MPaS (35 ℃), the MDI that in batches adds 0.5 to 5 gram is incubated 2 hours, reaches 4000-20000MPaS (35 ℃) back up to viscosity and adds butanols 5 gram reactions 1 hour; It is 45 ± 2% polyurethane composition that blowing promptly obtains solid content.
Component and the proportioning thereof that is used for the polyurethane resin composition of products such as production spraying paint provided by the present invention, in other embodiments, the weight ratio of its component and each component can also be selected in following scope: macromolecular polyol 10~30%, isocyanic ester 5~25%, small molecules diamine/small molecules dibasic alcohol 0~10%, terminator 0.05%~3%, catalyzer 0.001~1%, oxidation inhibitor 0~3%, and all the other are solvent; Terminator wherein is methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, Di-n-Butyl Amine equimolecular quantity less than one of single alcohol of 500, monoamine or its mixture; Polyurethane resin composition wherein, the weight percent of its component is: the weight sum of wherein said macromolecular polyol, isocyanic ester, small molecules diamine/small molecules dibasic alcohol, catalyzer, oxidation inhibitor, terminator is 0.2~0.7: 1 with the ratio of gross weight; Polyurethane resin composition wherein is characterized in that, described macromolecular polyol mole number is 1: 0~12 with the ratio of the mole number of small molecules diamine/small molecules dibasic alcohol; Described macromolecular polyol and the small molecules diamine/mole number of small molecules dibasic alcohol are 1: 0.80~1.10 with the ratio of the mole number of isocyanic ester; Macromolecular polyol functional group wherein is between 2~3, and molecular weight is between 500~5000; Comprise polyethylene glycol adipate glycol, poly-hexanodioic acid-1,4 one butanediol ester glycol, polyneopentyl glycol adipate glycol, poly-own diester Diethylene Glycol esterdiol, poly-adipate glycol-1,4 one butanediol ester glycol, poly-own diester ethylene glycol-Diethylene Glycol esterdiol, poly-own diester ethylene glycol and 1,2-propylene glycol esterdiol, poly-hexanodioic acid neopentyl glycol-1,4-butanediol ester glycol, polypropylene glycol ether glycol, the poly-tetrahydrochysene ether glycol and composition thereof of muttering; Described small molecules diamine comprises quadrol, hexanediamine, 1,2-Pn, 1, and 3-Pn, isophorone diamine, tetramethylene-diamine, molecular weight is less than diamine of 500 and composition thereof; The small molecules dibasic alcohol comprises ethylene glycol, propylene glycol, and butyleneglycol, hexylene glycol, to Benzenediol, neopentyl glycol, Diethylene Glycol, molecular weight is less than dibasic alcohol of 500 and composition thereof; It also can be the mixture of aforementioned dibasic alcohol and/or diamine; Catalyzer wherein is to comprise triethylene diamine, N, other organo-metallic catalyst such as tertiary amine catalyst such as N-dimethylcyclohexylamine, two-(2 methylethyl) ether and stannous octoate, dibutyl tin laurate, organotin, organo-bismuth and composition thereof; Described oxidation inhibitor is ester class, Hinered phenols or its mixture; Described solvent is ketone, benzene class, alcohols, ester class isopolarity and non-polar solvent and composition thereof, as pimelinketone, ethanol, Virahol, isopropylcarbinol, toluene, dimethylbenzene, gasoline, solvent oil, acetone, butanone, dimethyl formamide (DMF), ethyl acetate, butylacetate, isophorone; Isocyanic ester wherein is aliphatics or aromatic polyisocyanate, as m-benzene diisocyanate, PPDI, polymethine polyphenyl polyisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, ditan 4,4 '-or 2,4-or 2,2 '-vulcabond (MDI), hexamethylene-diisocyanate (HDI) and composition thereof.
As the described identical or proximate component of the above embodiment of the present invention, and adopt the identical or proximate method of the present invention, resultant other polyurethane resin composition and preparation method thereof are all within protection domain of the present invention.
Claims (6)
1. the preparation method of a polyurethane resin composition, it is characterized in that, its raw material comprises that the weight ratio of following component and each component is: macromolecular polyol 10~30%, isocyanic ester 10~25%, small molecules diamine and/or small molecules dibasic alcohol 0~10%, terminator 0.05%~3%, catalyzer 0.001~1%, oxidation inhibitor 0~3%, and all the other are solvent;
Its preparation process is as follows:
(1) macromolecular polyol is transported in the reactor, stirs, 0~-0.1MPa, 80~160 ℃ condition under vacuum hydro-extraction;
(2) described macromolecular polyol is after dehydration, treat that its temperature drops to normal temperature, small molecules diamine and/or small molecules dibasic alcohol, catalyzer, oxidation inhibitor, solvent are input in the reactor, in reactor, drop into 70%~99% the isocyanic ester account for the isocyanic ester gross weight after stirring again, in temperature of reaction is under 40~100 ℃ of conditions, after the successive reaction 1~9 hour, add remaining 1%~30% isocyanic ester again, reacted 1~3 hour;
(3) detection composition viscosity, when 35 ℃ be issued to 1000~50000MPaS after, then added terminator reaction 1~3 hour, obtain described polyurethane resin composition;
Described macromolecular polyol functional group is between 2~3, and molecular weight is between 500~5000; Described small molecules diamine and/or small molecules dibasic alcohol are molecular weight less than 500 dibasic alcohol, diamine or its mixture, and described isocyanic ester is aliphatics or aromatic polyisocyanate or its mixture.
2. according to the preparation method of the described polyurethane resin composition of claim 1, it is characterized in that described step (3) is replaceable to be following steps:
(31) viscosity of detection composition does not reach 1000~50000MPaS as it under 35 ℃, then continue to add 0.1%~10% the extra isocyanic ester that accounts for the isocyanic ester gross weight and continue reaction 1~3 hour;
(32) viscosity of detection composition again, under 35 ℃, do not reach 1000~50000MPaS as it, repeating step (31), up to the composition viscosity 35 ℃ be issued to 1000~50000MPaS after, add terminator reaction 1~3 hour, obtain described polyurethane resin composition.
3. according to the preparation method of the described polyurethane resin composition of claim 2, it is characterized in that, described catalyzer is tertiary amine catalyst or organo-metallic catalyst or its mixture, described oxidation inhibitor is ester class, Hinered phenols or its mixture, and described solvent is polarity or non-polar solvent or its mixture.
4. according to the preparation method of the described polyurethane resin composition of claim 3, it is characterized in that described terminator is a molecular weight less than 500 single alcohol, monoamine or its mixture.
5. according to the preparation method of the described polyurethane resin composition of claim 3, it is characterized in that the weight sum of wherein said macromolecular polyol, isocyanic ester, small molecules diamine and/or small molecules dibasic alcohol, catalyzer, oxidation inhibitor, terminator is 0.2~0.7: 1 with the ratio of gross weight.
6. according to the preparation method of the described polyurethane resin composition of claim 3, it is characterized in that described macromolecular polyol mole number is 1: 0~12 with the ratio of the mole number of small molecules diamine and/or small molecules dibasic alcohol; The mole number of described macromolecular polyol and small molecules diamine and/or small molecules dibasic alcohol is 1: 0.80~1.10 with the ratio of the mole number of isocyanic ester.
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US3875086A (en) * | 1973-08-10 | 1975-04-01 | Jefferson Chem Co Inc | Urethane containing monohydric polyether chain stoppers |
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US3875086A (en) * | 1973-08-10 | 1975-04-01 | Jefferson Chem Co Inc | Urethane containing monohydric polyether chain stoppers |
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