CN102167793B - Method for preparing polyurethane prepolymer and trihydroxy copolyether intermediate - Google Patents
Method for preparing polyurethane prepolymer and trihydroxy copolyether intermediate Download PDFInfo
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- CN102167793B CN102167793B CN201110058576.XA CN201110058576A CN102167793B CN 102167793 B CN102167793 B CN 102167793B CN 201110058576 A CN201110058576 A CN 201110058576A CN 102167793 B CN102167793 B CN 102167793B
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Abstract
The invention relates to a method for preparing a polyurethane prepolymer, which is prepared by reacting copolyether intermediate, serving as a base, formed by copolymerizing special oxene and propylene oxide with trihydroxy groups with isocyanate with double functional groups or multiple functional groups; novel superior polyurethane with high water-proof property and high moisture permeability can be obtained by adding a chain extender into the prepolymer for reaction and can be made into a water-proof and moisture-permeable thin film; and the thin film can be compounded with a fabric to make a clothing fabric with high water pressure resistance and high moisture permeability.
Description
Technical field
The present invention relates to the preparation method of the high thoroughly wet base polyurethane prepolymer for use as of a kind of high water pressure resistant, the invention still further relates to the trihydroxy copolyether intermediate for the preparation of the high thoroughly wet urethane of high water pressure resistant.
Background technology
Just invented as elastomeric rubber at urethane during World War II, also be used for doing afterwards water-proof material, but as be coated on windproof and rain proof on the garment material, but general this urethane saturating moisture wears very vexed, and damp and hot, very uncomfortable.Not only waterproof but also thoroughly polyurethane material original of moisture, review in W. L. Gore ﹠ Associates, Inc. company at the first-elected Waterproof ﹠ Moisture Permeable Film garment material eighties, the patent US 4532316 of W. L. Gore ﹠ Associates, Inc. company in 1984 at first proposes the making concept of waterproof moisture-penetrating urethane, has from then on rolled the research and development tide of waterproof moisture-penetrating urethane.
The making method of US Patent No. 4532316 disclosed waterproof moisture-penetrating urethanes is to contain isocyanate-monomer and the polyoxyethylene glycol reaction of double-functional group, mol ratio is about between the 2:1 to 6:1, and then add a small amount of dihydroxyl chainextender, chainpropagation, at last by moisture reaction moulding, this type of urethane can be coated with processing under solvent-free condition, but it is not water-fastness, need to be attached on the polytetrafluoroethylmicroporous microporous membrane the requirement that this class urethane monofilm does not reach the high moisture permeable membrane of high water pressure resistant.
US Patent No. 5208313 discloses the manufacture method of improved waterproof moisture-penetrating urethane, it is that the isocyanate-monomer that will contain double-functional group not only reacts with polyoxyethylene glycol, also add and contain dihydric not hydrophilic intermediate such as organosilicon or polytetramethylene ether glycol (PTMEG) or pet reaction, water-wash resistance and water pressure resistance can improve like this, but sacrificed water vapour permeability, the requirement that this class urethane monofilm does not reach the high moisture permeable membrane of high water pressure resistant yet.US Patent No. 5461122 discloses the manufacture method of improved waterproof moisture-penetrating urethane, it is that the isocyanate-monomer that will contain double-functional group not only reacts with polyoxyethylene glycol, also add contain dihydric not hydrophilic intermediate mixture such as organosilicon and polytetramethylene ether glycol and poly-propylene oxide and or some special polyester and polyhutadiene or polyisobutene reaction, such water-wash resistance, tackiness and water pressure resistance can improve, but sacrificed water vapour permeability, the requirement that this class urethane monofilm does not still reach the high moisture permeable membrane of high water pressure resistant.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of preparation method of base polyurethane prepolymer for use as is provided, and the base polyurethane prepolymer for use as that adopts the method to obtain can be prepared the high thoroughly polyurethane material of moisture of high water pressure resistant.
The present invention also will provide a kind of trihydroxy copolyether intermediate simultaneously, and it is applicable to prepare urethane and membrane product or the tensio-active agent of Waterproof Breathable.
For solving above technical problem, a kind of technical scheme that the present invention takes is: a kind of preparation method of base polyurethane prepolymer for use as, it comprises the steps:
1., the copolyether intermediate of preparation trihydroxy-propylene oxide and oxyethylene: the ring-opening polymerization that the monomer of trifunctional first and propylene oxide in autoclave is carried out the fs makes and obtains the trifunctional polyether intermediate of number-average molecular weight between 1000-3000, then pass in the reactor ring-opening polymerization that oxyethylene carries out subordinate phase make reaction obtain number-average molecular weight between 2000-9000 the trifunctional propylene oxide and the copolyether intermediate of oxyethylene, wherein, participating in the propylene oxide of reaction and the weight ratio of oxyethylene is that 1:9 is between the 6:4, the monomer of described trifunctional is to have 3 functional groups that can participate in the epoxy addition polyreaction, at last, obtain the copolyether intermediate of trihydroxy-propylene oxide and oxyethylene from the copolyether intermediate of described trifunctional propylene oxide and oxyethylene, drying and dehydrating;
2., preparation base polyurethane prepolymer for use as: after dewatering first in the polyurethane reaction still, add bifunctional or many functional group isocyanates's monomer under the dry condition, then drip step 1. the copolyether intermediate of the trihydroxy-propylene oxide of gained and oxyethylene make reaction generate base polyurethane prepolymer for use as, the molar ratio of described isocyanate-monomer and described copolyether intermediate is 2-9:1, temperature of reaction is controlled between 30 ℃-150 ℃, reaction times 0.5-8 hour.
According to the present invention, step 1. described trihydroxy-polyether intermediate number-average molecular weight preferably between 3000 to 7000, the weight ratio scope of the propylene oxide that it is final and oxyethylene preferably at 2:8 between the 4:6.The monomer of described trifunctional is preferably the organism of hydroxyl or epoxy group(ing), molecular weight between 80-800, anhydrous glycerol for example, 1,2,3-trihydroxy methyl propane, 1,2,6-trihydroxy-hexane, the small organic molecules such as anhydrous trolamine, the preferably affixture of number-average molecular weight between 200-600 of above small organic molecule and propylene oxide or oxyethylene addition, for example affixture of three propylene oxides and glycerine.
The temperature range of the reaction of fs, subordinate phase is between 0 ℃-200 ℃, and reaction pressure can add suitable solvent or solubilizing agent not between 1-100 kilogram/square centimeter.Reaction is preferably carried out more preferably 40 ℃-120 ℃ under 30 ℃-150 ℃ of temperature.Above-mentioned ring-opening reaction can for example be carried out under the effect of alkali at the ring opening catalyst of routine.Yet among the application, the preferred use contains two complex compounds of planting transition metal ion and cyanamide (CN-) ion and organic solvent such as dioxan, transition metal ion comprises Zn(II), Fe(II), Fe(III), Co(II), Ni(II), Mo(IV), Al(III), V(V), Sr(II), W(IV), W(VI), Mn(II), Cr(III), Cu(II), Sn(II), and Pb(II) etc., it prepares content many places in american documentation literature in detail detailed description, for example U.S. Patent number US3427256, US3941849, US4055188, US4472560, US4477589, US4721818, US5627120.
Step is gained trihydroxy-polyether intermediate 1., and the analytical procedure of its feature available core mr is verified, comprises the mensuration of its molecular weight, and propylene oxide, the oxyethylene composition content in the mesosome hereinto.Product end group wherein〉all be hydroxyl more than 98%, unsaturated endgroup content＜2% is fit to be used as the described polyurethane of this patent.Other feature such as its range of viscosities are between 50-600 cps (the specimen temperature is measured with Brook Field viscosity tester at 60 degree).
Step 2. described isocyanic ester can be diphenylmethanediisocyanate (MDI) and derivative such as many functional group isocyanates, hydrogenated diphenyl methane diisocyanate (HMDI), methylenebis phenyl isocyanate (TDI), 1,6-hexane diisocyanate (HDI) etc.The poly-hydroxy chainextender is preferably the organism that contains 2 or a plurality of hydroxyls, molecular weight between 50-500, BDO for example, 1,4-hexanaphthene dimethyl alcohol, glycerine, 1,2,3-trihydroxy methyl propane, 1,2,6-trihydroxy-hexane, the organism such as anhydrous trolamine.Multi-functional linking agent is to go the auxiliary agent that reticulates molecular structure, for example trimeric cyanamide-Formalin resin (melamine formaldehyde resin) or Resins, epoxy.
The another technical scheme that the present invention takes is: the copolyether intermediate of a kind of trihydroxy-propylene oxide and oxyethylene, its number-average molecular weight between the 2000-9000, proportion between 1.0-1.25, propylene oxide wherein and the weight ratio of oxyethylene at 1:9 between the 6:4.
Preparation method according to the copolyether intermediate of trihydroxy-propylene oxide of the present invention and oxyethylene is as follows: with the monomer of trifunctional in autoclave first and the propylene oxide ring-opening polymerization of carrying out the fs make and obtain the trifunctional polyether intermediate of number-average molecular weight between 1000-3000, then pass in the reactor ring-opening polymerization that oxyethylene carries out subordinate phase make reaction obtain number-average molecular weight between 2000-9000 the trifunctional propylene oxide and the copolyether intermediate of oxyethylene, wherein, participating in the propylene oxide of reaction and the weight ratio of oxyethylene is that 1:9 is between the 6:4, the monomer of described trifunctional is to have 3 functional groups that can participate in the epoxy addition polyreaction, at last, obtain the copolyether intermediate of described trihydroxy-propylene oxide and oxyethylene from the copolyether intermediate of described trifunctional propylene oxide and oxyethylene.
Trihydroxy-polyether intermediate of the present invention, the analytical procedure of its feature available core mr is verified, comprises the mensuration of its molecular weight, and propylene oxide, the oxyethylene composition content in the mesosome hereinto.Product end group wherein〉all be hydroxyl more than 98%, unsaturated endgroup content＜2% is fit to be used as the described polyurethane of this patent.Other feature such as its range of viscosities are between 50-600 cps (the specimen temperature is measured with Brook Field viscosity tester at 60 degree).If when tensio-active agent usefulness, its hydrophilic and oleophilic value (calculating of HLB value) is between 7-18.Cloud and mist point (Cloud point) temperature is all〉50 degree.Surface tension is between 30-50 dyne/centimetre (dyne/cm).
Add in the prepared base polyurethane prepolymer for use as according to the present invention after chainextender carries out chain extension, can make polyurethane film by coating method.The thickness of polyurethane film can be the 20-180 micron, and weight can reach water pressure resistance more than or equal to 0.5 kilogram/square centimeter about 20-200 gram/square meter, and Water Vapour Permeability is more than or equal to 10000 gram water/square meter/skies; When weight during at 40-100 gram/square meter, can reach water pressure resistance more than or equal to 1 kilogram/square centimeter, Water Vapour Permeability is greater than 10000 gram water/square meter/skies; When weight during at 20-50 gram/square meter, can reach water pressure resistance more than or equal to 0.5 kilogram/square centimeter, Water Vapour Permeability is more than or equal to 10000 gram water/square meter/skies.
Add in the prepared urethane according to the present invention after chainextender carries out chain extension, also can by be coated on garment material or the macromolecule membrane or on the matrix material of the two to form the high pressure resistant anti-polyurethane high molecule material that wets; Perhaps at first urethane is made high pressure resistant anti-wet polyurethane film, be compounded to form the polyurethane high molecule material by will be high pressure resistant anti-polyurethane film and the garment material or macromolecule membrane or the volume matrix material of the two of wetting again.What described garment material can be artificial or natural fiber is made weaves cotton cloth or tNonwovens, such as nylon, and terylene, cotton etc., can be singly to spin or blended yarn weaved fabric.Macromolecule membrane can be the film of micropore or atresia, micropore polyester film for example, microvoid polyurethane film, microporous polyethylene film, expanded microporous polytetra fluoroethylene-EPTEE film etc.Adopt the polyurethane high molecule material of urethane of the present invention, its urethane spread can reach water pressure resistance more than or equal to 1 kilogram/square centimeter when 40-100 gram/square meter, and Water Vapour Permeability is more than or equal to 10000 gram water/square meter/skies; Spread can reach water pressure resistance greater than 0.5 kilogram/square centimeter when 20-50 gram/square meter, Water Vapour Permeability is greater than 12000 gram water/square meter/skies.
Among the present invention, watertight testing method adopts ISO 811; The testing method of Water Vapour Permeability adopts JIS L1099-B1 method.
Because the enforcement of above technical scheme, the present invention compared with prior art has following advantage:
The present invention is take the copolyether intermediate of specific trihydroxy-propylene oxide and oxyethylene as the basis, make it to obtain base polyurethane prepolymer for use as with isocyanate reaction, this base polyurethane prepolymer for use as can obtain the high thoroughly urethane of moisture of high water pressure resistant after reacting with chainextender, can make the high garment material that thoroughly wets of high water pressure resistant.
Embodiment
The present invention will be further described in detail below in conjunction with specific embodiment, but the invention is not restricted to following examples.
Embodiment 1
The present embodiment provides the preparation method of the copolyether intermediate (POEO-5000) of a kind of trihydroxy-propylene oxide and oxyethylene, and detailed process is as follows: (chemical structural formula of ring opening catalyst is Zn to add the ring opening catalyst of the made fresh can make propylene oxide and oxyethane open loop in autoclave
3
[Fe (CN)
6
]
2
* 2.5C
4
H
8
O
2
* 2.5H
2
O is C wherein
4
H
8
O
2
Refer to dioxan, the preparation method of catalyzer can be referring to US Patent No. 3941849, no longer describe in detail at this) and the trifunctional monomer (this monomer is the affixture of three propylene oxides and glycerine, number-average molecular weight 260, be the products C P-260 of Dow Chemical company), after the reactor sealing, after using first the nitrogen deoxygenation, then pass into propylene oxide, temperature of reaction is controlled at about 45 ℃, reacted about 24 hours, the propylene oxide ring-opening polymerization produces number-average molecular weight and is about 1700 polyether intermediate, and the consumption of catalyzer accounts for approximately 0.5% of product weight.Then, in above-mentioned reactor, add oxyethylene, temperature of reaction also is to be controlled at about 45 ℃, reacted about 24 hours, obtain the copolyether intermediate that reaction product is trihydroxy-propylene oxide and oxyethylene, its number-average molecular weight is about 5000, the molecular weight of this reaction product and form the checking of equal available core magnetic resonance analysis method, wherein the product end group all is hydroxyl more than 98%, unsaturated endgroup content is lower than 2%, and wherein propylene oxide and the oxyethylene weight ratio in product is about 7:17.The viscosity of product under temperature 60 C is about between the 300-400 cps, and product proportion is about between 1.0-1.1.
Embodiment 2
The present embodiment provides the preparation method of the copolyether intermediate (POEO-3000) of a kind of trihydroxy-propylene oxide and oxyethylene, and detailed process is as follows: (chemical structural formula of ring opening catalyst is Zn to add the ring opening catalyst of the made fresh can make propylene oxide and oxyethane open loop in autoclave
3
[Co (CN)
6
]
2
* 2.5C
4
H
8
O
2
* 2.5H
2
O is C wherein
4
H
8
O
2
Refer to dioxan, the preparation method of catalyzer can be referring to US Patent No. 3941849, no longer describe in detail at this) and the trifunctional monomer (this monomer is the affixture of three propylene oxides and glycerine, number-average molecular weight 260, be the products C P-260 of Dow Chemical company), after the reactor sealing, after using first the nitrogen deoxygenation, then pass into propylene oxide, temperature of reaction is controlled at about 45 ℃, reacted about 24 hours, the propylene oxide ring-opening polymerization produces number-average molecular weight and is about 1200 polyether intermediate, and the consumption of catalyzer accounts for approximately 0.7% of product weight.Then, in above-mentioned reactor, add oxyethylene, temperature of reaction also is to be controlled at about 45 ℃, reacted about 24 hours, obtain the copolyether intermediate that reaction product is trihydroxy-propylene oxide and oxyethylene, its number-average molecular weight is about 3000, the molecular weight of reaction product and form equal available core magnetic resonance analysis method and verify, wherein the product end group all is hydroxyl more than 98%, and unsaturated endgroup content is lower than 2%.Wherein propylene oxide and the oxyethylene weight ratio in product is about 1:2.The viscosity of product under temperature 60 C is about between the 200-300 cps, and product proportion is about between 1.0-1.1.
Embodiment 3
The present embodiment provides the preparation method of the copolyether intermediate (POEO-7500) of a kind of trihydroxy-propylene oxide and oxyethylene, detailed process is as follows: the ring opening catalyst (with embodiment 1) and the trifunctional monomer CP-260 that add the made fresh that can make propylene oxide and oxyethane open loop in autoclave, after the reactor sealing, after using first the nitrogen deoxygenation, then pass into propylene oxide, temperature of reaction is controlled at about 45 ℃, reacted about 24 hours, the propylene oxide ring-opening polymerization produces number-average molecular weight and is about 2500 polyether intermediate, and the consumption of catalyzer accounts for approximately 0.3% of product weight.Then, add oxyethylene in above-mentioned reactor, temperature of reaction also is to be controlled at about 45 ℃, reacts about 24 hours, obtains the copolyether intermediate of trihydroxy-propylene oxide and oxyethylene, and its number-average molecular weight is about 7500.The molecular weight of reaction product and form the checking of equal available core magnetic resonance analysis method, wherein the product end group all is hydroxyl more than 98%, and unsaturated endgroup content is lower than 2%, and wherein propylene oxide and the oxyethylene weight ratio in product is about 11:25.The viscosity of product under temperature 60 C is about between the 400-600 cps.Product proportion is about between 1.0-1.1.
Embodiment 4
In the reactor of urethane, the deoxygenation that dewaters of at first finding time, then add diphenylmethanediisocyanate (MDI), temperature is raised to 60 ℃, drip again from the trihydroxy-propylene oxide of embodiment 1 gained and the copolyether intermediate (POEO-5000) of oxyethylene, the two molar ratio is MDI:POEO-5000=3:1, and temperature of reaction is controlled between 70～80 ℃, reacts 2 hours.Then drop to room temperature and obtain base polyurethane prepolymer for use as.Before doing coating test, add again the BDO chainextender in the performed polymer and carry out chain extending reaction and obtain polyurethane adhesive, the charging capacity of BDO is approximately 1.9 times (mol ratio) of MDI, is coated on the nylon cloth that was beforehand with anti-water-sprinkling again, advance baking oven for heating to 120 ℃, maturation.When the about 70 gram/square meters of its spread, water pressure resistance〉1 kilogram/square centimeter, thoroughly wet 10000 gram/square meters/sky.When the about 40 gram/square meters of its spread, water pressure resistance〉0.5 kilogram/square centimeter, thoroughly wet 12000 gram/square meters/sky.Wash and see afterwards that to look into its fastness out of question for 5 times, hydraulic pressure and thoroughly in the wet scope that basically maintains before the washing.
Same polyurethane adhesive is coated on the separate-type paper, advances baking oven for heating to 120 ℃, maturation, and tearing it down obtains very smooth polyurethane film.When the about 80 gram/square meters of its spread, water pressure resistance〉1 kilogram/square centimeter, Water Vapour Permeability〉10000 gram/square meters/sky.When the about 40 gram/square meters of its spread, water pressure resistance〉0.5 kilogram/square centimeter, Water Vapour Permeability〉15000 gram/square meters/sky.
Embodiment 5
In the reactor of urethane, the deoxygenation that dewaters of at first finding time, then add first methylenebis phenyl isocyanate (TDI), temperature is raised to 80 ℃, drip again from the trihydroxy-propylene oxide of the gained of embodiment 2 and the copolyether intermediate (POEO-3000) of oxyethylene, mol ratio is TDI:POEO-3000=8:1, and temperature of reaction is controlled between 80～90 ℃, reacts 2 hours.Then drop to room temperature and obtain base polyurethane prepolymer for use as.Before doing the coating test, in performed polymer, add 1 again, the mixed chain extender of 4-butyleneglycol and trihydroxy methyl propane is carried out chain extending reaction and is obtained polyurethane adhesive, 1, the charging capacity of 4-butyleneglycol and trihydroxy methyl propane is respectively approximately 5 times and 0.9 times (mol ratio) of TDI, be coated on again on the nylon cloth that was beforehand with anti-water-sprinkling, advance baking oven for heating to 120 ℃, maturation.When the about 80 gram/square meters of its spread, water pressure resistance〉1 kilogram/square centimeter, Water Vapour Permeability〉10000 gram/square meters/sky.When the about 40 gram/square meters of its spread, water pressure resistance〉0.5 kilogram/square centimeter, Water Vapour Permeability〉12000 gram/square meters/sky.Wash and see afterwards that to look into its fastness out of question for three times, hydraulic pressure and thoroughly in the wet scope that basically maintains before the washing.
Same polyurethane adhesive is coated on the separate-type paper, advances baking oven for heating to 120 ℃, maturation, and tearing it down obtains very smooth polyurethane film.When the about 90 gram/square meters of its film weight, water pressure resistance〉1 kilogram/square centimeter, Water Vapour Permeability〉10000 gram/square meters/sky.When the about 45 gram/square meters of its spread, water pressure resistance〉0.5 kilogram/square centimeter, Water Vapour Permeability〉15000 gram/square meters/sky.
Comparative Examples 1(and embodiment 4 contrasts)
In the reactor of urethane, the deoxygenation that dewaters of at first finding time, then add first diphenylmethanediisocyanate (MDI), temperature is raised to 60 ℃, drip again the polyoxyethylene glycol (PEG-3000) of molecular weight 3000 and the poly-propylene oxide glycol (PPG-2000) of molecular weight 2000, mol ratio is MDI:PEG-3000:PPG-2000=3:1:1, and temperature of reaction is controlled between 70～80 ℃, reacts 2 hours.Then drop to room temperature.Before doing coating test, add again the approximately BDO chainextender of 0.9 mol ratio of relative MDI, be coated on again on the nylon cloth that was beforehand with anti-water-sprinkling, advance baking oven for heating to 120 ℃, maturation.When the about 70 gram/square meters of its spread, water pressure resistance＜1 kilogram/square centimeter, Water Vapour Permeability＜10000 gram/square meters/sky.When the about 40 gram/square meters of its spread, water pressure resistance＜0.5 kilogram/square centimeter, Water Vapour Permeability＜12000 gram/square meters/sky.Do not reach the garment material requirement of high-waterproof high-moisture-permeable, it is bad that its fastness is looked in the rear sight of washing.
Same polyurethane adhesive is coated on the separate-type paper, advances baking oven for heating to 120 ℃, maturation, and tearing it down obtains smooth polyurethane film.When the about 80 gram/square meters of its film weight, water pressure resistance＜1 kilogram/square centimeter, thoroughly wet＜10000 gram/square meters/sky.When the about 40 gram/square meters of its spread, water pressure resistance＜0.5 kilogram/square centimeter, thoroughly wet＜15000 gram/square meters/sky.Do not reach the garment film requirement of high-waterproof high-moisture-permeable.
Comparative example 2(and embodiment 5 contrasts)
In the reactor of urethane, the deoxygenation that dewaters of at first finding time, then add first methylenebis phenyl isocyanate (TDI), temperature is raised to 80 ℃, add again the polyoxyethylene glycol (PEG-2000) of molecular weight 2000 and the poly-propylene oxide glycol (PPG-1000) of molecular weight 1000, mol ratio is TDI:PEG-2000:PPG-1000=8:1:1, and temperature of reaction is controlled between 80～90 ℃, reacts 2 hours.Then drop to room temperature.Before doing coating test, add again the approximately mixed chain extender of the BDO of 5:0.9 mol ratio/trihydroxy methyl propane of relative TDI, be coated on again on the nylon cloth that was beforehand with anti-water-sprinkling, advance baking oven for heating to 120 ℃, maturation.When the about 80 gram/square meters of its spread, water pressure resistance＜1 kilogram/square centimeter, Water Vapour Permeability＜10000 gram/square meters/sky.When the about 40 gram/square meters of its spread, water pressure resistance＜0.5 kilogram/square centimeter, Water Vapour Permeability＜12000 gram/square meters/sky.Do not reach the garment material requirement of high-waterproof high-moisture-permeable, it is bad that its fastness is looked in the rear sight of washing.
Same polyurethane adhesive is coated on the separate-type paper, advances baking oven for heating to 120 ℃, maturation, and tearing it down obtains smooth polyurethane film, when the about 90 gram/square meters of its film weight, water pressure resistance＜1 kilogram/square centimeter, Water Vapour Permeability＜10000 gram/square meters/sky; When the about 45 gram/square meters of its spread, water pressure resistance＜0.5 kilogram/square centimeter, Water Vapour Permeability＜15000 gram/square meters/sky, the garment film requirement that does not reach high-waterproof high-moisture-permeable.
What above embodiment 4-5 adopted all is the copolyether intermediate of trihydroxy-propylene oxide provided by the present invention and oxyethylene, all can produce clothes polyurethane coating fabric and the polyurethane film of high-waterproof high-moisture-permeable.Opposite; Comparative Examples 1-2; do not adopt the copolyether intermediate of trihydroxy-propylene oxide provided by the present invention and oxyethylene; relative only alone their single polyether intermediate all can't be produced clothes polyurethane coating fabric and the polyurethane film of the high-waterproof high-moisture-permeable in the protection domain of the presently claimed invention.
Above-described embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all should fall within the scope of protection of the present invention
Claims (7)
1. the preparation method of a base polyurethane prepolymer for use as is characterized in that: comprise the steps:
1., the copolyether intermediate of preparation trihydroxy-propylene oxide and oxyethane: the ring-opening polymerization that the monomer of trifunctional first and propylene oxide in autoclave is carried out the fs makes and obtains the trifunctional polyether intermediate of number-average molecular weight between 1000-3000, then pass in the reactor ring-opening polymerization that oxyethane carries out subordinate phase make reaction obtain number-average molecular weight between 2000-9000 the trifunctional propylene oxide and the copolyether intermediate of oxyethane, wherein, participating in the propylene oxide of reaction and the weight ratio of oxyethane is that 1:9 is between the 6:4, the monomer of described trifunctional is to have 3 functional groups that can participate in the epoxy addition polyreaction, at last, obtain the copolyether intermediate of trihydroxy-propylene oxide and oxyethane from the copolyether intermediate of described trifunctional propylene oxide and oxyethane, drying and dehydrating;
2., preparation base polyurethane prepolymer for use as: after dewatering first in the polyurethane reaction still, add bifunctional or many functional group isocyanates's monomer under the dry condition, then drip step 1. the trihydroxy-propylene oxide of gained and the copolyether intermediate of oxyethane, the molar ratio of described isocyanate-monomer and described copolyether intermediate is 2-9:1, temperature of reaction is controlled between 30 ℃-150 ℃, reaction times 0.5-8 hour, obtain described base polyurethane prepolymer for use as.
2. the preparation method of base polyurethane prepolymer for use as according to claim 1 is characterized in that: step 1. in, the functional group of the monomer of described trifunctional is hydroxyl or epoxy group(ing), the molecular weight of the monomer of described trifunctional is between 80-600.
3. the preparation method of base polyurethane prepolymer for use as according to claim 2 is characterized in that: step 1. in, the monomer of described trifunctional is the organism and the organic affixture that contains epoxy group(ing) of hydroxyl, number-average molecular weight is between 200-600.
4. the preparation method of base polyurethane prepolymer for use as according to claim 1 is characterized in that: step 1. in, the temperature of the reaction of described fs, the reaction of subordinate phase is 30 ℃-150 ℃.
5. the preparation method of base polyurethane prepolymer for use as according to claim 1 is characterized in that: step 1. in, participating in the propylene oxide of reaction and the weight ratio of oxyethane is that 2:8 is between the 4:6.
6. the preparation method of base polyurethane prepolymer for use as according to claim 1 is characterized in that: step 1. in, control the number-average molecular weight of copolyether intermediate of described propylene oxide and oxyethane between 3000-7000.
7. the preparation method of base polyurethane prepolymer for use as according to claim 1 is characterized in that: also adding in the reaction process of step in 2. has with the polyester of 2 hydroxyls or with the organosilicon of 2 hydroxyls or the combination of the two.
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| CN101472969A (en) * | 2006-06-23 | 2009-07-01 | 拜尔材料科学有限公司 | Viscoelastic foams with slower recovery and improved tear |
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| WO2008079614A1 (en) * | 2006-12-21 | 2008-07-03 | Dow Global Technologies Inc. | Polyurethane catalysis based on the combination of autocatalytic polyol and urea |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101472969A (en) * | 2006-06-23 | 2009-07-01 | 拜尔材料科学有限公司 | Viscoelastic foams with slower recovery and improved tear |
Non-Patent Citations (2)
| Title |
|---|
| 张志勇等.高活性低不饱和度聚醚的合成研究.《云南化工》.2008,第35卷(第2期),12-14. |
| 高活性低不饱和度聚醚的合成研究;张志勇等;《云南化工》;20080430;第35卷(第2期);12-14 * |
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