CN105732952B - A kind of high-modulus non-ionic water polyurethane and preparation method thereof - Google Patents
A kind of high-modulus non-ionic water polyurethane and preparation method thereof Download PDFInfo
- Publication number
- CN105732952B CN105732952B CN201610168222.3A CN201610168222A CN105732952B CN 105732952 B CN105732952 B CN 105732952B CN 201610168222 A CN201610168222 A CN 201610168222A CN 105732952 B CN105732952 B CN 105732952B
- Authority
- CN
- China
- Prior art keywords
- preparation
- ionic water
- modulus
- polymer
- modulus non
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to Material Field, in particular to a kind of high-modulus non-ionic water polyurethane and preparation method thereof.The preparation method of high-modulus non-ionic water polyurethane generates hydrophilic isocyanate monomer the following steps are included: isocyanates polymer is reacted with polyglycol ether；Hydrophilic isocyanate monomer, polyester and/or polyether polyol, small molecular alcohol reaction synthesis combed base polyurethane prepolymer for use as, are then added amine chain extender and water carry out dispersion and emulsion up to high-modulus non-ionic water polyurethane.The hydrophilic chain of the combed base polyurethane prepolymer for use as of preparation method synthesis is on side chain, and when amine chain extender and water being added to carry out dispersion and emulsion, for phase reversal viscosity in 20000-50000cps, emulsification is simple；Lotion contains raising admittedly, does not need other cosolvents, modulus is in 25-100N/m；Partial size is evenly distributed in 10-20nm, and equipment investment is low in industrial production, easy to operate, energy-saving and emission-reduction.
Description
Technical field
The present invention relates to Material Fields, in particular to a kind of high-modulus non-ionic water polyurethane and its preparation side
Method.
Background technique
Aqueous polyurethane is for ionic mostly, and pH is affected to it.Non-ion aqueous polyurethane is usually to use
The method of additional emulsifier, or reference polyethylene glycol is as hydrophilic radical；Former approach stability is bad, and the latter is synthesizing
In the process, viscosity is excessive, and hydrophilic segment is on main chain, and emulsification is difficult when Water-borne modification, and operability is too poor, and lotion contains low admittedly
Deng.
Synthetic method is to introduce hydrophilic radical in polyol hydroxyls part mostly at present, mainly reference polyethylene glycol conduct
Hydrophilic monomer, or pass through hydrophilic modifying in polyol moiety, synthesize aqueous polyurethane.Major defect is, synthesis it is aqueous
Viscoelastic polyurethane is spent greatly, and hydrophilic segment is on main chain, and emulsification is difficult when Water-borne modification, and operability is too poor, and lotion contains low admittedly, is helped
Solvent is more, and the aqueous polyurethane modulus of synthesis is small.
It is such as disclosed application No. is 201410838491.7 patent of invention and a kind of solvent-free prepare non-ion aqueous gather
The method of urethane, first Y-shaped side-chain non-ion hydrophilic chain extender of the synthesis containing 2 terminal hydroxy groups, then with poly-dihydric alcohol and
After isocyanates reaction, the side chain performed polymer of Y-shaped side-chain non-ion hydrophilic chain extender chain extension generation-NCO end group is added, so
Small molecule dihydric alcohol, oligomer polyol one or two mixture are added afterwards, it is water-soluble that deionization is added immediately after mixing evenly
Liquid high speed dispersion, last temperature reaction obtain stable solvent-free non-ionic aqueous polyurethane emulsion.This method passes through a step
Synthetic method, carboxyl are evenly distributed in molecule segment.
In short, the aqueous polyurethane hydrophilic segment of existing technology synthesis is on main chain, viscosity is big, the bad control of modulus size
System.When adding water dispersion, hydrophilic segment and oleophylic segmented structure fuzzy add water to be easy swelling, and particle diameter distribution is wider, phase reversal
It is difficult.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of high-modulus non-ionic water polyurethane, passes through isocyanide
Acid esters is hydrophilically modified, synthesis hydrophilic isocyanate-monomer, and the base polyurethane prepolymer for use as of synthesis is comb-type structure, and viscosity is small, no
Cosolvent is needed, Water-borne modification is convenient, it is easy to be water dispersible, solid content and modulus are high, and equipment investment is low in industrial production, behaviour
Make simple, energy-saving and emission-reduction.
The second object of the present invention is to provide the preparation method system of high-modulus non-ionic water polyurethane described in one kind
At high-modulus non-ionic water polyurethane, the nonionic functional segments of the non-ionic water polyurethane are easy to control on side chain
Hard segment content processed, controllable range are 20%-80%, modulus 25-100N/m, and partial size is evenly distributed in 10-20nm, easily
In phase reversal.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of preparation method of high-modulus non-ionic water polyurethane, comprising the following steps:
(a), isocyanates polymer is reacted under conditions of organic tin catalyst with polyglycol ether, is generated hydrophilic
Property isocyanate-monomer；
(b), the hydrophilic isocyanate monomer, polyester and/or polyether polyol, small molecular alcohol reaction synthesis combed are poly-
Urethane performed polymer, is then added amine chain extender and water carries out dispersion and emulsion up to high-modulus non-ionic water polyurethane.
A kind of preparation method of high-modulus non-ionic water polyurethane provided by the invention, first by isocyanates polymer with
Polyglycol ether graft reaction under conditions of catalyst obtains hydrophilic isocyanate monomer, the hydrophilic isocyanate monomer
Synthesis combed base polyurethane prepolymer for use as, the combed polyurethane prepolymer of synthesis are reacted with polyester and/or polyether polyol, small molecular alcohol again
The hydrophilic chain of body is on side chain, and when amine chain extender and water being added to carry out dispersion and emulsion, hydrophilic segment can be very good package oleophylic
Segment, phase reversal viscosity have very big drop in 20000-50000cps, compared to the 100000cps that is greater than in traditional method
Low, allowing for emulsification in this way becomes more simple, easily operated；Lotion contains raising admittedly, does not need other cosolvents, synthesis it is non-
Ion aqueous polyurethane modulus has for 15-30N/m than traditional modulus and is substantially improved in 25-100N/m；The nonionic of synthesis
Aqueous polyurethane partial size is evenly distributed in 10-20nm, and equipment investment is low in industrial production, and easy to operate, energy conservation subtracts
Row.
Further, in step (a), the isocyanates polymer is HDI polymer, MDI polymer, IPDI poly
Body, H12MDI polymer, TDI polymer are any one or more of.If these isocyanates polymers can be tripolymer, four
Aggressiveness, pentamer etc.；Each polymer may be the mixture of different polymers, if HDI polymer can be HDI trimerization
The mixture of body, the HDI tetramer and HDI pentamer.
Preferably, the polyglycol ether is any one of poly glycol monomethyl ether, polyethylene glycol monobutyl ether or two kinds.
The molecular weight of poly glycol monomethyl ether and polyethylene glycol monobutyl ether is not less than 100, is suitable for the present invention.Such as polyethyleneglycol first
The molecular weight of ether can be 100,200,500,800 etc., the molecular weight of polyethylene glycol monobutyl ether can for 100,200,500,
520,800 etc..
Verified, the isocyanates polymer and polyglycol ether of the above type are grafted under conditions of catalyst
Reaction, obtains hydrophilic isocyanate monomer.
Through testing, it is preferable that in step (a), the molar ratio of the isocyanates polymer and the polyglycol ether
For 1:0.9-1.1.Wherein, isocyanates polymer and the molar ratio of polyglycol ether be 1:1 more preferably.The two cooperation, it is completely anti-
Hydrophilic isocyanate monomer should be generated.
Further, in step (a), the organic tin catalyst is selected from dibutyl tin dilaurate, stannous octoate
Any one of or two kinds；
The additive amount of the organic tin catalyst is the isocyanates polymer and the polyglycol ether total weight
1 ‰ -5 ‰.
Further, in step (a), the temperature of reaction is 75-85 DEG C, reaction time 2-3h.
After above-mentioned condition is reacted, hydrophilic isocyanate monomer is obtained.
Further, in step (b), by weight, 60-80 parts of hydrophilic isocyanate monomer, polyester and/or poly-
20-40 parts of ether, 0.5-1 parts of small molecular alcohol, 2-3 parts of amine chain extender.Wherein, polyester can be 1,4-butanediol adipic acid binary
Alcohol polyester (PBA), neopentyl glycol adipic acid glycol polyesters (PAN) and other polyester.The molecular weight of polyester can generally make
Range is 400-6000, more preferable 1000-4000, most preferably 1000-3000.
Polyethers can be polypropylene glycol ether (PPG) etc., and the generally workable range of the molecular weight of polyethers is 400-6000, more
It is preferred that 1000-4000, most preferably 1000-3000.
In step (b), the additive amount of the water is 80% of each raw material gross weight in step (b), the high-modulus made
The solid content of non-ionic water polyurethane is 20%, to meet requirement of the existing market to the product.
Further, the specific steps of step (b) are as follows:
Hydrophilic isocyanate monomer, polyester and/or polyether polyol is first added, in 80-90 DEG C of heat preservation 2.5-3.5h；
Then small molecular alcohol is added, continues to keep the temperature 1.5-2.5h, obtains combed base polyurethane prepolymer for use as；
38-42 DEG C, under stirring is cooled to, amine chain extender and water, mixing is added.
Dispersion and emulsion is carried out by the way that chain extender and water is added, finally obtains high-modulus non-ionic water polyurethane.
In the present invention, polyester and/or polyether polyol are added to finally obtained high-modulus non-ionic water polyurethane shape
At the soft segment of the structure, other raw materials are hard section.Content of soft segmer is higher, and hydrophily is stronger, and obtained performed polymer is more readily dispersible
Emulsification, correspondingly, modulus values are relatively smaller.
In order to which sticky liquid is quickly carried out dispersion and emulsion, further, in step (b), the stirring
Revolving speed is 800-1500r/min.
The small molecular alcohol be any one of 1,4-butanediol, neopentyl glycol, 1,6- hexylene glycol, Isosorbide-5-Nitrae-cyclohexanediol or
It is a variety of.
Further, in step (b), the amine chain extender is ethylenediamine, isophorone diamine, hexamethylene diamine, hydration
Hydrazine, diethylenetriamine, triethylene tetramine are any one or more of.
Compared with prior art, the invention has the benefit that
(1) preparation method of a kind of high-modulus non-ionic water polyurethane provided by the invention, by nonionic functional segments
It is arranged on the side chain of non-ionic water polyurethane, easily controllable hard segment content, controllable range is 20%-80%, modulus
For 25-100N/m, partial size is evenly distributed in 10-20nm, is easy to phase reversal.
(2) preparation method of a kind of high-modulus non-ionic water polyurethane provided by the invention, the polyurethane prepolymer of synthesis
Body is comb-type structure, and viscosity is small, does not need cosolvent, and Water-borne modification is convenient, it is easy to is water dispersible, solid content and modulus are high.
(3) present invention also defines the reaction conditions and reactant in preparation process, to reach expected purpose, and
In industrial production, equipment investment is low, easy to operate, energy-saving and emission-reduction.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products of commercially available acquisition can be passed through.
Embodiment 1
A kind of preparation method of high-modulus non-ionic water polyurethane, comprising the following steps:
(1) in the four-hole boiling flask with tetrafluoro stirring, HDI trimer is put into, is heated to 85 DEG C, molecular weight, which is added, is
520 polyethylene glycol monobutyl ether, wherein the molar ratio of HDI trimer and polyethylene glycol monobutyl ether is 1:1；In catalysts conditions
Under, 3h is kept the temperature, synthesizes and hydrophilic isocyanate monomer is made；
(2) the 1,4-butanediol adipic acid that 40 gram-molecular weights are 2000 is added into 120 grams of hydrophilic isocyanate monomers
The polypropylene glycol ether (PPG) that glycol polyesters (PBA) and 40 gram-molecular weights are 2000,90 DEG C of heat preservation 3h are inside added 1.6 grams
1,4-butanediol continues to keep the temperature 2h；40 DEG C are cooled to, under high velocity agitation, 167.28 grams of water and 4.5 grams of isophorones is added
Mixed liquor is detected using rotational viscometer, obtain phase reversal viscosity be 25000cps, finally obtain solvent-free high-modulus it is non-from
Sub- aqueous polyurethane, is measured using measure apparatus of youngs modulus, and modulus 35N/m, partial size is evenly distributed in 10-20nm.
Embodiment 2
A kind of preparation method of high-modulus non-ionic water polyurethane, comprising the following steps:
(1) in the four-hole boiling flask with tetrafluoro stirring, TDI tripolymer is put into, is heated to 75 DEG C, molecular weight, which is added, is
500 polyethylene glycol monobutyl ether, wherein the molar ratio of TDI tripolymer and polyethylene glycol monobutyl ether is 1:1；In catalysts conditions
Under, 2h is kept the temperature, synthesizes and hydrophilic isocyanate monomer is made；
(2) into 140 grams of hydrophilic isocyanate monomers, the polypropylene glycol ether (PPG) that 60 gram-molecular weights are 1000,80 DEG C
3h is kept the temperature, 2 grams of 1,4-butanediol are inside added, continues to keep the temperature 2h；40 DEG C are cooled to, under high velocity agitation, is added 165.6 grams
The mixed liquor of water and 5 grams of hydrazine hydrates, is detected using rotational viscometer, and obtaining phase reversal viscosity is 36000cps, finally obtains nothing
The high-modulus non-ionic water polyurethane of solvent, is measured using measure apparatus of youngs modulus, and modulus 69N/m, partial size is in 10-
20nm is evenly distributed.
Embodiment 3
(1) in the four-hole boiling flask with tetrafluoro stirring, IPDI tripolymer is put into, is heated to 85 DEG C, molecular weight, which is added, is
500 poly glycol monomethyl ether, wherein the molar ratio of IPDI tripolymer and poly glycol monomethyl ether is 1:1, in catalysts conditions
Under, 3h is kept the temperature, synthesizes and hydrophilic isocyanate monomer is made；
(2) into 400 grams of hydrophilic isocyanate monomers, be added 150 gram-molecular weights be 2000 1,4-butanediol oneself two
2.8 grams of 1,4-butanediol are inside added in sour glycol polyesters (PBA), 90 DEG C of heat preservation 3h, continue to keep the temperature 2h；40 DEG C are cooled to,
Under high velocity agitation, the mixed liquor of 452.8 grams of water and 6.8 grams of diethylenetriamines and 6.4 grams of hydrazine hydrates is added, it is viscous using rotation
Degree meter detection, obtaining phase reversal viscosity is 40000cps, finally obtains solvent-free high-modulus non-ionic water polyurethane, is used
Measure apparatus of youngs modulus measurement, modulus 78N/m, partial size are evenly distributed in 10-20nm.
Embodiment 4
A kind of preparation method of high-modulus non-ionic water polyurethane, comprising the following steps:
(1) in the four-hole boiling flask with tetrafluoro stirring, H12MDI polymer is put into, is heated to 80 DEG C, molecular weight is added
For 100 poly glycol monomethyl ether, wherein the molar ratio of H12MDI polymer and poly glycol monomethyl ether is 1:0.9；
Catalyst dibutyltin dilaurylate is added, the additive amount of catalyst is H12MDI polymer and polyethyleneglycol first
The 1 ‰ of ether total weight keep the temperature 3h under catalysts conditions, synthesize and hydrophilic isocyanate monomer is made；
(2) in 120 grams of hydrophilic isocyanate monomers for generating reaction, poly- the third two that 40 gram-molecular weights are 2000 are added
The 1,4-butanediol adipic acid glycol polyesters (PBA) that alcohol ether (PPG) and 50 gram-molecular weights are 2000,80 DEG C of heat preservation 3.5h,
1 gram of neopentyl glycol is added in the inside, continues to keep the temperature 1.5h；Cool to 38 DEG C, stirring revolving speed be 1000r/min stirring under,
The mixed liquor of 172 grams of water and 4 grams of ethylenediamines is added, is detected using rotational viscometer, obtaining phase reversal viscosity is 20000cps, most
Solvent-free high-modulus non-ionic water polyurethane is obtained eventually, is measured using measure apparatus of youngs modulus, modulus 25N/m, grain
Diameter is evenly distributed in 10-20nm.
Embodiment 5
A kind of preparation method of high-modulus non-ionic water polyurethane, comprising the following steps:
(1) in the four-hole boiling flask with tetrafluoro stirring, HDI polymer and MDI polymer is put into, 75 DEG C is heated to, adds
Enter poly glycol monomethyl ether and polyethylene glycol monobutyl ether that molecular weight is 200, wherein HDI polymer and MDI polymer and poly- second
The molar ratio of glycol monomethyl ether and polyethylene glycol monobutyl ether is 1:1；
Catalyst dibutyltin dilaurylate and stannous octoate is added, the additive amount of catalyst is H12MDI polymer and gathers
The 3 ‰ of ethylene glycol monobutyl ether total weight keep the temperature 2.5h under catalysts conditions, synthesize and hydrophilic isocyanate monomer is made；
(2) in 160 grams of hydrophilic isocyanate monomers for generating reaction, poly- the third two that 80 gram-molecular weights are 2000 are added
2 grams of Isosorbide-5-Nitrae-cyclohexanediols are inside added in alcohol ether (PPG), 90 DEG C of heat preservation 2.5h, continue to keep the temperature 1.5h；42 DEG C are cooled to, is being stirred
The revolving speed mixed is that the mixed liquor of 198.4 grams of water, 2 grams of ethylenediamines and 4 grams of isophorone diamine is added under the stirring of 1500r/min,
It is detected using rotational viscometer, obtaining phase reversal viscosity is 33000cps, finally obtains solvent-free high-modulus non-ionic water
Polyurethane is measured using measure apparatus of youngs modulus, and modulus 52N/m, partial size is evenly distributed in 10-20nm.
Embodiment 6
A kind of preparation method of high-modulus non-ionic water polyurethane, comprising the following steps:
(1) in the four-hole boiling flask with tetrafluoro stirring, investment IPDI polymer, H12MDI polymer and TDI polymer,
85 DEG C are heated to, the polyethylene glycol monobutyl ether that molecular weight is 500 is added, wherein IPDI polymer, H12MDI polymer and TDI
The molar ratio of polymer and polyethylene glycol monobutyl ether is 1:1.1；
Octoate catalyst stannous is added, the additive amount of catalyst is IPDI polymer, H12MDI polymer and TDI polymer
With the 5 ‰ of polyethylene glycol monobutyl ether total weight, under catalysts conditions, 2h is kept the temperature, synthesizes and hydrophilic isocyanate monomer is made；
(2) in 140 grams of hydrophilic isocyanate monomers for generating reaction, poly- the third two that 60 gram-molecular weights are 3000 are added
0.5 gram of 1,4-butanediol, 0.5 gram of 1,6- hexylene glycol, 0.5 gram of Isosorbide-5-Nitrae-hexamethylene is inside added in alcohol ether (PPG), 85 DEG C of heat preservation 3h
Glycol continues to keep the temperature 2.5h；Cool to 40 DEG C, stirring revolving speed be 1000r/min stirring under, 166 grams of water and 2 grams are added
The mixed liquor that diamines, 1 gram of diethylenetriamine, 1 gram of triethylene tetramine are restrained oneself in ethylenediamine, 1 gram of isophorone diamine, 1, using rotation
Viscosimeter detection, obtaining phase reversal viscosity is 37000cps, finally obtains solvent-free high-modulus non-ionic water polyurethane, adopts
It is measured with measure apparatus of youngs modulus, modulus 65N/m, partial size is evenly distributed in 10-20nm.
Embodiment 7
A kind of preparation method of high-modulus non-ionic water polyurethane, comprising the following steps:
(1) with tetrafluoro stirring four-hole boiling flask in, put into TDI polymer, TDI polymer be commercially available TDI tripolymer,
The mixture of the TDI tetramer and TDI pentamer is heated to 85 DEG C, and the poly glycol monomethyl ether that molecular weight is 600 is added, wherein
The molar ratio of TDI polymer and poly glycol monomethyl ether is 1:0.9；
Catalyst dibutyltin dilaurylate is added, the additive amount of catalyst is TDI polymer and poly glycol monomethyl ether
The 3 ‰ of total weight keep the temperature 2h under catalysts conditions, synthesize and hydrophilic isocyanate monomer is made；
(2) in 120 grams of hydrophilic isocyanate monomers for generating reaction, Isosorbide-5-Nitrae-fourth that 45 gram-molecular weights are 1000 is added
Glycol adipic acid glycol polyesters (PBA), 80 DEG C of heat preservation 3.5h, be inside added 1 gram of 1,4-butanediol and 0.5 gram of 1,6- oneself two
Alcohol continues to keep the temperature 2h；Cool to 38 DEG C, stirring revolving speed be 800r/min stirring under, 136.8 grams of water and 1 gram of second are added
The mixed liquor that diamines, 1.5 grams of hydrazine hydrates are restrained oneself in diamines, 1 gram of isophorone diamine, 1, is detected using rotational viscometer, obtains phase
Reversion viscosity is 39000cps, solvent-free high-modulus non-ionic water polyurethane is finally obtained, using measure apparatus of youngs modulus
Measurement, modulus 75N/m, partial size are evenly distributed in 10-20nm.
Embodiment 8
A kind of preparation method of high-modulus non-ionic water polyurethane, comprising the following steps:
(1) in the four-hole boiling flask with tetrafluoro stirring, MDI polymer is put into, is heated to 80 DEG C, molecular weight, which is added, is
500 poly glycol monomethyl ether and polyethylene glycol monobutyl ether, wherein MDI polymer and poly glycol monomethyl ether and polyethylene glycol
The molar ratio of monobutyl ether is 1:1；
Catalyst dibutyltin dilaurylate and stannous octoate is added, the additive amount of catalyst is MDI polymer and poly- second
The 2 ‰ of glycol monomethyl ether and polyethylene glycol monobutyl ether total weight keep the temperature 2.5h under catalysts conditions, synthesize and hydrophily is made
Isocyanate-monomer；
(2) into 140 grams of hydrophilic isocyanate monomers, the polypropylene glycol ether (PPG) that 60 gram-molecular weights are 1000 is added,
1 gram of 1,4-butanediol, 0.5 gram of Isosorbide-5-Nitrae-cyclohexanediol is inside added in 85 DEG C of heat preservation 3h, continues to keep the temperature 2h；40 DEG C are cooled to,
The revolving speed of stirring is that 166 grams of water and 1 gram of ethylenediamine is added, 1 gram of isophorone diamine, 1 restrains oneself two under the stirring of 1200r/min
Amine, 1 gram of hydrazine hydrate, 1 gram of diethylenetriamine, 1 gram of triethylene tetramine mixed liquor, detected, obtained opposite using rotational viscometer
Turning viscosity is 36000cps, finally obtains solvent-free high-modulus non-ionic water polyurethane, is surveyed using measure apparatus of youngs modulus
Fixed, modulus 68N/m, partial size is evenly distributed in 10-20nm.
Embodiment 9
A kind of preparation method of high-modulus non-ionic water polyurethane, comprising the following steps:
(1) in the four-hole boiling flask with tetrafluoro stirring, MDI polymer is put into, is heated to 80 DEG C, molecular weight, which is added, is
500 poly glycol monomethyl ether and polyethylene glycol monobutyl ether, wherein MDI polymer and poly glycol monomethyl ether and polyethylene glycol
The molar ratio of monobutyl ether is 1:1；
Catalyst dibutyltin dilaurylate and stannous octoate is added, the additive amount of catalyst is MDI polymer and poly- second
The 2 ‰ of glycol monomethyl ether and polyethylene glycol monobutyl ether total weight keep the temperature 2.5h under catalysts conditions, synthesize and hydrophily is made
Isocyanate-monomer；
(2) into 160 grams of hydrophilic isocyanate monomers, the polypropylene glycol ether (PPG) that 40 gram-molecular weights are 1000 is added,
1 gram of 1,4-butanediol, 0.5 gram of Isosorbide-5-Nitrae-cyclohexanediol is inside added in 85 DEG C of heat preservation 3h, continues to keep the temperature 2h；40 DEG C are cooled to,
The revolving speed of stirring is that 166 grams of water and 1 gram of ethylenediamine is added, 1 gram of isophorone diamine, 1 restrains oneself two under the stirring of 1200r/min
Amine, 1 gram of hydrazine hydrate, 1 gram of diethylenetriamine, 1 gram of triethylene tetramine mixed liquor, detected, obtained opposite using rotational viscometer
Turning viscosity is 50000cps, finally obtains solvent-free high-modulus non-ionic water polyurethane, is surveyed using measure apparatus of youngs modulus
Fixed, modulus 100N/m, partial size is evenly distributed in 10-20nm.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (12)
1. a kind of preparation method of high-modulus non-ionic water polyurethane, which comprises the following steps:
(a), isocyanates polymer is reacted under conditions of organic tin catalyst with polyglycol ether, it is different generates hydrophily
Cyanate ester monomer；
(b), the hydrophilic isocyanate monomer, polyester and/or polyether polyol, small molecular alcohol reaction synthesis combed polyurethane
Performed polymer, is then added amine chain extender and water carries out dispersion and emulsion up to high-modulus non-ionic water polyurethane；
In step (b), by weight, 60-80 parts of hydrophilic isocyanate monomer, polyester and/or 20-40 parts of polyethers are small
0.5-1 parts of molecule alcohol, 2-3 parts of amine chain extender；
The specific steps of step (b) are as follows:
Hydrophilic isocyanate monomer, polyester and/or polyether polyol is first added, in 80-90 DEG C of heat preservation 2.5-3.5h；
Then small molecular alcohol is added, continues to keep the temperature 1.5-2.5h；
38-42 DEG C, under stirring is cooled to, amine chain extender and water, mixing is added.
2. the preparation method of high-modulus non-ionic water polyurethane according to claim 1, which is characterized in that in step
(a) in, the isocyanates polymer is HDI polymer, MDI polymer, IPDI polymer, H12MDI polymer, TDI poly
Body is any one or more of；
The polyglycol ether is any one of poly glycol monomethyl ether, polyethylene glycol monobutyl ether or two kinds.
3. the preparation method of high-modulus non-ionic water polyurethane according to claim 2, which is characterized in that in step
(a) in, the molar ratio of the isocyanates polymer and the polyglycol ether is 1:0.9-1.1.
4. the preparation method of high-modulus non-ionic water polyurethane according to claim 3, which is characterized in that the isocyanide
The molar ratio of acid esters polymer and the polyglycol ether is 1:1.
5. the preparation method of high-modulus non-ionic water polyurethane according to claim 1, which is characterized in that in step
(a) in, the organic tin catalyst is selected from any one of dibutyl tin dilaurate, stannous octoate or two kinds；
The additive amount of the organic tin catalyst is the isocyanates polymer and the polyglycol ether total weight
1‰-5‰。
6. the preparation method of high-modulus non-ionic water polyurethane according to claim 1-5, which is characterized in that
In step (a), the temperature of reaction is 75-85 DEG C, reaction time 2-3h.
7. the preparation method of high-modulus non-ionic water polyurethane according to claim 1, which is characterized in that in step
(b) in,
The additive amount of the water is 80% of each raw material gross weight in step (b).
8. the preparation method of high-modulus non-ionic water polyurethane according to claim 7, which is characterized in that in step
(b) in, the revolving speed of the stirring is 800-1500r/min；
The molecular weight of the polyester and the polyethers is 400-6000；
The small molecular alcohol is any one of 1,4-butanediol, neopentyl glycol, 1,6- hexylene glycol, Isosorbide-5-Nitrae-cyclohexanediol or more
Kind.
9. the preparation method of high-modulus non-ionic water polyurethane according to claim 8, which is characterized in that the polyester
Molecular weight with the polyethers is 1000-4000.
10. the preparation method of high-modulus non-ionic water polyurethane according to claim 9, which is characterized in that described poly-
The molecular weight of ester and the polyethers is 1000-3000.
11. the preparation method of the described in any item high-modulus non-ionic water polyurethanes of -5 or 7-10 according to claim 1, special
Sign is, in step (b), the amine chain extender is ethylenediamine, isophorone diamine, hexamethylene diamine, hydrazine hydrate, divinyl three
Amine, triethylene tetramine are any one or more of.
12. high-modulus made from the preparation method of the described in any item high-modulus non-ionic water polyurethanes of claim 1-11 is non-
Ion aqueous polyurethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610168222.3A CN105732952B (en) | 2016-03-21 | 2016-03-21 | A kind of high-modulus non-ionic water polyurethane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610168222.3A CN105732952B (en) | 2016-03-21 | 2016-03-21 | A kind of high-modulus non-ionic water polyurethane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105732952A CN105732952A (en) | 2016-07-06 |
| CN105732952B true CN105732952B (en) | 2019-03-08 |
Family
ID=56251088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610168222.3A Active CN105732952B (en) | 2016-03-21 | 2016-03-21 | A kind of high-modulus non-ionic water polyurethane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105732952B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651922B (en) * | 2018-12-01 | 2022-04-26 | 烟台大学 | Waterborne polyurethane toughened waterborne epoxy resin anticorrosive paint and preparation method thereof |
| CN111019082B (en) * | 2019-12-16 | 2021-07-27 | 东南大学 | Nonionic photo-curing polyurethane aqueous dispersion resin composition with excellent compatibility and preparation method and application thereof |
| CN112126041A (en) * | 2020-08-13 | 2020-12-25 | 嘉兴元朔高分子科技有限公司 | Solvent-free hydrophilic modification method for oil-based polyurethane high polymer |
| CN113817133A (en) * | 2021-09-18 | 2021-12-21 | 湖南松井新材料股份有限公司 | Room-temperature self-crosslinking water-based nonionic polyurethane dispersion and preparation method and application thereof |
| CN113881011A (en) * | 2021-09-30 | 2022-01-04 | 明新孟诺卡(江苏)新材料有限公司 | Preparation method of nonionic solvent-free waterborne polyurethane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5367017A (en) * | 1992-05-01 | 1994-11-22 | Miles Inc. | Aqueous polyurea dispersions prepared by an emulsion polymerization process |
| CN101885829A (en) * | 2010-07-12 | 2010-11-17 | 中科院广州化学有限公司 | Alcohol end capping nonionic polyurethane cross-linking agent and preparation method and application thereof |
| CN102690404A (en) * | 2011-02-18 | 2012-09-26 | 中国石油化工股份有限公司 | Nonionic waterborne polyurethane dispersoid and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001354847A (en) * | 2000-06-14 | 2001-12-25 | Asahi Denka Kogyo Kk | Nonionic water-dispersible type polyurethane composition |
-
2016
- 2016-03-21 CN CN201610168222.3A patent/CN105732952B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5367017A (en) * | 1992-05-01 | 1994-11-22 | Miles Inc. | Aqueous polyurea dispersions prepared by an emulsion polymerization process |
| CN101885829A (en) * | 2010-07-12 | 2010-11-17 | 中科院广州化学有限公司 | Alcohol end capping nonionic polyurethane cross-linking agent and preparation method and application thereof |
| CN102690404A (en) * | 2011-02-18 | 2012-09-26 | 中国石油化工股份有限公司 | Nonionic waterborne polyurethane dispersoid and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105732952A (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105732952B (en) | A kind of high-modulus non-ionic water polyurethane and preparation method thereof | |
| Honarkar | Waterborne polyurethanes: A review | |
| Nanda et al. | The influence of the ionic concentration, concentration of the polymer, degree of neutralization and chain extension on aqueous polyurethane dispersions prepared by the acetone process | |
| CN103709363B (en) | A kind of sulfonate type high solid content polyurethane emulsion and its preparation method and application | |
| CN107082860B (en) | Self-emulsifying waterborne polyurethane curing agent and preparation method thereof | |
| CN101516943B (en) | Aqueous polyurethane/polyurea dispersions | |
| CN101307130B (en) | Anion water-soluble polyurethane disperse system for finishing leather and method for preparing same | |
| CN100404576C (en) | Prepn process of nanometer starch crystal modified water-base polyurethane | |
| CN102702471A (en) | Method for preparing solvent-free aqueous polyurethane dispersion | |
| CN102405243B (en) | Aqueous polyurethane resin dispersion | |
| CN101495530A (en) | Polytrimethylene ether-based polyurethane ionomers | |
| TW201016740A (en) | Polyurethane urea solutions | |
| Harjunalanen et al. | The effects of altered reaction conditions on the properties of anionic poly (urethane-urea) dispersions and films cast from the dispersions | |
| Daemi et al. | Molecular engineering of manipulated alginate-based polyurethanes | |
| CN106543402B (en) | A kind of preparation method of cross-linking block-graft type high molecular polymer | |
| Travinskaya et al. | Waterborne polyurethane based starch containing materials: preparation, properties and study of degradability | |
| CN110099965A (en) | The preparation method of carboxylic aqueous resin composition, formed body and polycarbodiimide compound | |
| CN105440240B (en) | Prepare the continuous production method of aqueous polyurethane ionomer and its dispersion | |
| CN102352010B (en) | Preparation method for aqueous polyurethane-polyurea dispersion | |
| CN107674173A (en) | Aqueous polyurethane crosslinking agent and preparation method thereof | |
| CN108546323A (en) | Cation is from matting resin and its preparation method and application | |
| CN109575228A (en) | A kind of polyurethane resin and its preparation method and application | |
| Guo et al. | Synthesis and properties of high-functionality hydroxyl-terminated polyurethane dispersions | |
| CN107964104B (en) | Solvent-free aqueous polyurethane dispersion, and preparation method and application thereof | |
| Durrieu et al. | Preparation of aqueous anionic poly‐(urethane‐urea) dispersions: Influence of the nature and proportion of the urethane groups on the dispersion and polymer properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A high modulus non-ionic waterborne polyurethane and its preparation method Effective date of registration: 20230203 Granted publication date: 20190308 Pledgee: China Postal Savings Bank Limited by Share Ltd. Shexian branch Pledgor: HUANGSHAN LIANGU NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2023980032041 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |