CN109265648A - A kind of Diamond Search aqueous polyurethane dispersion and preparation method - Google Patents
A kind of Diamond Search aqueous polyurethane dispersion and preparation method Download PDFInfo
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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- 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
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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Abstract
The invention discloses a kind of Diamond Search aqueous polyurethane dispersion, belong to adhesive field, its effective component is a kind of aqueous polyurethane emulsion of anionic, and the Diamond Search aqueous polyurethane dispersion includes double hydroxy polymers, polyisocyanates, hydrophilic agent, urea and chain extender；The present invention discloses the preparation methods of the Diamond Search aqueous polyurethane dispersion.A kind of Diamond Search aqueous polyurethane dispersion provided by the invention, aqueous polyurethane dispersion is prepared using the chain extender containing epoxy group and aldehyde radical, the formalin chain extender used in dispersion method will be melted and be substituted for other N- alkylating reagents, preparation method is simple, without containing volatile organic matters such as acetone, formaldehyde, the aqueous polyurethane dispersion that Diamond Search can be synthesized achievees the purpose that really environmentally protective human body and environmental-friendly.
Description
Technical field
The invention belongs to adhesive fields, and in particular to a kind of Diamond Search aqueous polyurethane dispersion and preparation method.
Background technique
The continuous phase of aqueous polyurethane is water, has many advantages, such as safety, easily keeping stores, is easy to use, at low cost, wide
It is general to be applied to coating, adhesive, fabric coating and finishing agent, leather finishing agent, sheet surface treating agent and Fiber strength
Agent.But with the gradually reinforcement of people's environmental consciousness, and control of the country to energy-saving and emission-reduction, low VOC (volatile organic compound
Object) even Diamond Search aqueous polyurethane new diseases research cause more extensive concern.Currently, aqueous polyurethane
Preparation generally use acetone method, prepolymer blend method and melting dispersion method, basic principle is by base polyurethane prepolymer for use as point
Hydrophilic radical appropriate is introduced in subchain, dispersion forms stable lotion in water.
Acetone method belongs to solwution method, is that isocyanate group performed polymer will be held to be dissolved in (third in the solvent that low boiling point can be miscible with water
Ketone is the most frequently used, therefore also known as acetone method), it is reacted with the compound of hydrophilic functional group, generates polyurethane ionomers, add water and stir
It realizes phase transfer, then recycles acetone with the way of distillation, obtain aqueous polyurethane emulsion.Such as application No. is the China of 201810285866.X
Patent, discloses a kind of preparation method of graphene-carbon nano tube/Waterborne PU Composite, and this method addition is suitable
Acetone adjusts viscosity, and the linear polyester performed polymer of acquisition-NCO sealing end, finally vacuum distillation removes acetone, and graphene-is made
Carbon nanotube/Waterborne PU Composite, this method technical maturity, obtained aqueous polyurethane dispersion stability are excellent
It is good, but organic solvent need to be recycled, the complexity of production technology is increased, and due to that can not steam completely organic solvent, gained
Aqueous polyurethane dispersion generally have certain smell, environmental-protecting performance and usage experience are poor.
Prepolymer blend method, for Mr. this method at the lower performed polymer of molecular weight, being diluted with solvent reduces viscosity, then chain extension
Mode reacted.Compared with acetone method, prepolymer blend method can substantially reduce the usage amount of solvent, develop in recent years fast
Speed, but the performed polymer molecular weight that prepolymer blend method generates is lower, and even across subsequent reaction, mechanical property still be will receive
It influences, the application for certain fields, the aqueous polyurethane dispersion performance of prepolymer blend method production is not as good as obtained by acetone method
Aqueous polyurethane dispersion.
Melting dispersion condensation method, this method are that first synthesis end group is the prepolymer of the low viscosity of isocyanate group, are added
Urea or NH3It is reacted in the body, generates the double biurets of polyurethane or the end urea groups oligomer containing ionic group.By
In such end urea groups oligomer without containing active-NCO group, it is easy to it is dispersed in water without any organic solvent,
Aqueous polyurethane without solvent dispersion can theoretically be prepared using this kind melting dispersion copolymerization method.But existing technique side
Method is usually to carry out chain extending reaction to it using certain density formalin on the basis of obtained biuret oligomers,
The polyurethane-urea polymers of higher molecular weight are obtained, but carry out chain extending reaction using formalin during the preparation process, not
Can really it achieve the purpose that environmentally protective.
Summary of the invention
In order to overcome the defects of the prior art described above, the technical problems to be solved by the present invention are: providing a kind of Diamond Search water
Property dispersions of polyurethanes, and prepare without using formaldehyde, acetone and other organic solvent the Diamond Search aqueous polyurethane point of higher molecular weight
The method of granular media.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention are as follows: a kind of Diamond Search aqueous polyurethane point is provided
Granular media, general structure are as follows:
Wherein, M is chain extender, contains epoxy group and aldehyde radical, the structural formula of R5 in the structure of M are as follows:
Wherein, R1 and R3 is the straight chain fatty alkyl being made of 2-10 methylene；
The structural formula of R2 is
X is carboxyl or sulfonic group.
The preparation method of above-mentioned Diamond Search aqueous polyurethane dispersion, includes the following steps:
(1) base polyurethane prepolymer for use as containing hydrophilic group is prepared:
Under the protective condition of drying nitrogen, double hydroxy polymers and hydrophilic agent are mixed under conditions of 100 DEG C -120 DEG C
It closes, vacuumizes 0.5h, until moisture is lower than 0.1%, be cooled to 50 DEG C hereinafter, polyisocyanates is added, in 65 DEG C -75 DEG C stir
Under the conditions of mixing, 3h-4h is reacted, is cooled to 30 DEG C -50 DEG C, obtains the poly- ammonia that the end group in structure containing hydrophilic group is isocyanate group
Ester performed polymer；
(2) polyurethane-biuret oligomers are prepared:
Under agitation, aqueous solution of urea is warming up to 100 DEG C, the end group containing hydrophilic group for taking step (1) to obtain is
The base polyurethane prepolymer for use as of isocyanate group is added in 100 DEG C of aqueous solution of urea, is warming up to 130-135 DEG C, at such a temperature
Continue insulation reaction 2.5-3h, the polyether polyols that end group is urea groups can be obtained；
(3) chain extending reaction:
At 60 DEG C -120 DEG C, chain extender is added, continues insulation reaction 1h-2h, 40 DEG C -50 DEG C is cooled to, in high-speed stirring
It mixes in machine, adds water, resulting aqueous polyurethane dispersion solid content is diluted between 40%-60%, high-speed stirred dispersion
After 30min, aqueous polyurethane-allophanamide dispersion can be obtained.
The beneficial effects of the present invention are: the present invention prepares aqueous polyurethane using the chain extender containing epoxy group and aldehyde radical
Dispersion is avoided using organic solvent, is not also used formalin, is really achieved the purpose of Diamond Search, safe and non-toxic, right
Human body and environmental-friendly achievees the purpose that really environmentally protective, and simple process, high production efficiency.
Specific embodiment
To explain the technical content, the achieved purpose and the effect of the present invention in detail, it is explained below in conjunction with embodiment.
The most critical design of the present invention is: being substituted for other for the formalin chain extender used in dispersion method is melted
N- alkylating reagent, avoid the environmental issue that may cause with formalin.
The present invention provides a kind of Diamond Search aqueous polyurethane dispersion, general structure are as follows:
Wherein, M is chain extender, contains epoxy group and aldehyde radical, the structural formula of R5 in the structure of M are as follows:
Wherein, R1 and R3 is the straight chain fatty alkyl being made of 2-10 methylene；
The structural formula of R2 is
X is carboxyl or sulfonic group.
The preparation method of above-mentioned Diamond Search aqueous polyurethane dispersion, includes the following steps:
(1) base polyurethane prepolymer for use as containing hydrophilic group is prepared:
Under the protective condition of drying nitrogen, double hydroxy polymers and hydrophilic agent are mixed under conditions of 100 DEG C -120 DEG C
It closes, vacuumizes 0.5h, until moisture is lower than 0.1%, be cooled to 50 DEG C hereinafter, polyisocyanates is added, in 65 DEG C -75 DEG C stir
Under the conditions of mixing, 3h-4h is reacted, is cooled to 30 DEG C -50 DEG C, obtains the poly- ammonia that the end group in structure containing hydrophilic group is isocyanate group
Ester performed polymer；
(2) polyurethane-biuret oligomers are prepared:
Under agitation, aqueous solution of urea is warming up to 100 DEG C, the end group containing hydrophilic group for taking step (1) to obtain is
The base polyurethane prepolymer for use as of isocyanate group is added in 100 DEG C of aqueous solution of urea, is warming up to 130-135 DEG C, at such a temperature
Continue insulation reaction 2.5-3h, the polyether polyols that end group is urea groups can be obtained；
(3) chain extending reaction:
At 60 DEG C -120 DEG C, chain extender is added, continues insulation reaction 1h-2h, 40 DEG C -50 DEG C is cooled to, in high-speed stirring
It mixes in machine, adds water, resulting aqueous polyurethane dispersion solid content is diluted between 40%-60%, high-speed stirred dispersion
After 30min to get arrive the aqueous poly- ammonia dispersion of Diamond Search.
The synthesis equation of the preparation method of above-mentioned Diamond Search aqueous polyurethane dispersion is described as follows:
As can be seen from the above description, the beneficial effects of the present invention are: by using the chain extender containing epoxy group and aldehyde radical
Aqueous polyurethane dispersion is prepared, i.e., will melt the formalin chain extender used in dispersion method and be substituted for other N- alkyl
Change reagent, preparation method is simple, and cost is relatively low, without containing volatile organic matters such as acetone, formaldehyde, can synthesize the water of Diamond Search
Property dispersions of polyurethanes, it is safe and non-toxic, to human body and environmental-friendly, achieve the purpose that really environmentally protective, while preparation process
In introduce hydrophilic radical, itself there is emulsification, the subsequent collocation with other compositions is not necessarily to additional emulsifier when using, together
When be less prone to unstable phenomenon when using.
Further, the molar ratio of double hydroxy polymer A, polyisocyanates B, hydrophilic agent C, urea D and chain extender M
For 1:1.5-3:0.2-1:0.6-2:0.2-2；Wherein: D=2 × (B-A-C), 0.3≤B-A-C≤1, M < D.
Further, double hydroxy polymers be polyoxypropyleneglycol, polyethylene glycol, polytetrahydrofuran ether glycol,
The average molecular weight range of one or more of polycaprolactone glycol and polybutadiene diol, double hydroxy polymers exists
1000-3000Da。
Seen from the above description, above-mentioned double hydroxy polymers, it is nontoxic, nonirritant, there is excellent mechanical property, have
Good water solubility, suitable for preparing aqueous polyurethane dispersion, the aqueous polyurethane dispersion favorable dispersibility of acquisition.
Further, the polyisocyanates is isophorone diisocyanate, toluene di-isocyanate(TDI), diphenyl methane
Diisocyanate, hexamethylene diisocyanate and 4, one or more of 4'- dicyclohexyl methyl hydride diisocyanate.
Seen from the above description, polyisocyanates is to prepare one of primary raw material of dispersions of polyurethanes, above-mentioned raw materials valence
Lattice are different, and volatility and irritation are also different, select raw material according to actual production demand and production capacity.
Further, the hydrophilic agent be dihydromethyl propionic acid, dimethylolpropionic acid, N- (2- aminoethyl)-alanine,
N- (2- aminoethyl)-tarine sodium or 2,4- diamino benzene sulfonic acid.
Seen from the above description, hydrophilic agent being added can be such that surface tension declines rapidly, allow aqueous polyurethane in water
In stable dispersion, the water dispersible and automatic emulsifying performance of the aqueous polyurethane of above-mentioned hydrophilic agent preparation be preferable.
Further, the chain extender is N- alkylating reagent, and the N- alkylating reagent is 3,4- epoxycyclohexyl
Methyl -3,4- epoxycyclohexyl formic acid esters, terephthalaldehyde, o-phthalaldehyde or m-terephthal aldehyde.
Seen from the above description, chain extender can be such that strand extends with the functional group reactions on linear polymer chain,
Short chain molecule becomes long-chain macromolecule, increases molecular weight, and then improve the mechanical property of product, heatproof, wear-resisting property.
Embodiment 1:
(1) base polyurethane prepolymer for use as containing hydrophilic group is prepared:
Under the protective condition of drying nitrogen, the polyoxypropyleneglycol of 1mol and the hydrophilic agent dihydroxy first of 0.5mol is added
Base propionic acid vacuumizes 0.5h under conditions of 100 DEG C, until the mixture moisture of polyoxypropyleneglycol and hydrophilic agent is
0.09%, it is cooled to 50 DEG C, 2.1mol isophorone diisocyanate is added, under the conditions of 65 DEG C of temperature, the reaction was continued 3h,
It can obtain the base polyurethane prepolymer for use as of the base containing carboxylated hydrophilic in structure；
(2) polyurethane-biuret oligomers are prepared:
Under agitation, the aqueous solution of urea of 1.2mol is warming up to 100 DEG C, take that step (1) obtains containing hydrophilic group
Base polyurethane prepolymer for use as is added in 100 DEG C of aqueous solution of urea, is warming up to 135 DEG C, continues insulation reaction 3h at such a temperature, i.e.,
The polyether polyols that end group is urea groups can be obtained；
(3) chain extending reaction:
Under 120 DEG C of stirring condition, in step (2) in obtained urethane oligomer be added 1.1mol to benzene
Dicarbaldehyde chain extender continues insulation reaction 2h, is cooled to 45 DEG C, and in high-speed mixer, suitable quantity of water is added, and gained is aqueous poly-
The solid content of urethane dispersion is diluted to 50% or so；High-speed stirred disperses after 30min to divide to get to aqueous polyurethane-allophanamide
Granular media.
Embodiment 2:
(1) base polyurethane prepolymer for use as containing hydrophilic group is prepared:
Under the protective condition of drying nitrogen, the polytetrahydrofuran ether glycol and 0.6mol hydrophilic agent N- (2- of 1mol is added
Aminoethyl)-tarine sodium vacuumizes 0.5h under conditions of 110 DEG C, until polytetrahydrofuran ether glycol and hydrophily
Mixture moisture be 0.08%, be cooled to 50 DEG C, 2mol toluene di-isocyanate(TDI) be added, under the conditions of 70 DEG C of temperature, reaction
4h, it can obtain the base polyurethane prepolymer for use as of the hydrophilic group containing sulfonic group in structure；
(2) polyurethane-biuret oligomers are prepared:
Under agitation, the aqueous solution of urea of 0.8mol is warming up to 100 DEG C, then contains parent for what step (1) obtained
Water-based polyurethane performed polymer is added in 100 DEG C of aqueous solution of urea, is warming up to 130 DEG C, is continued insulation reaction at such a temperature
The polyether polyols that end group is urea groups can be obtained in 2.5h；
(3) chain extending reaction:
Under 60 DEG C of stirring condition, 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexyl formic acid of 0.2mol is added
Ester chain extender continues insulation reaction 2h, is cooled to 50 DEG C, in high-speed mixer, suitable quantity of water is added, aqueous polyurethane is dispersed
The solid content of body is diluted to 50%；High-speed stirred disperse 30min after to get arrive aqueous polyurethane-allophanamide dispersion.
Embodiment 3:
(1) base polyurethane prepolymer for use as containing hydrophilic group is prepared:
Under the protective condition of drying nitrogen, the polybutadiene diol of 1mol and the hydrophilic agent 2 of 0.2mol, 4- diamino is added
Base benzene sulfonic acid vacuumizes 0.5h under conditions of 100 DEG C, until the moisture of substance is lower than 0.1% in system, is cooled to 45 DEG C,
2.2mol hexamethylene diisocyanate, under the conditions of 65 DEG C of temperature, the reaction was continued 4h is added, it can obtain containing in structure
The base polyurethane prepolymer for use as of carboxylated hydrophilic base；
(2) polyurethane-biuret oligomers are prepared:
Under agitation, the aqueous solution of urea of 2.0mol is warming up to 100 DEG C, then contains parent for what step (1) obtained
Water-based polyurethane performed polymer is added in 100 DEG C of aqueous solution of urea, is warming up to 133 DEG C, is continued insulation reaction at such a temperature
The polyether polyols that end group is urea groups can be obtained in 3h；
(3) chain extending reaction:
Under 90 DEG C of stirring condition, the isophthalic of 1.1mol is added in obtained urethane oligomer in step (2)
Dicarbaldehyde chain extender continues insulation reaction 2h, is cooled to 40 DEG C, and in high-speed mixer, suitable quantity of water is added, and gained is aqueous poly-
The solid content of urethane dispersion is diluted to 45%；After high-speed stirred disperses 30min, aqueous polyurethane-allophanamide dispersion can be obtained
Body.
Embodiment 4:
(1) base polyurethane prepolymer for use as containing hydrophilic group is prepared:
Under the protective condition of drying nitrogen, the hydrophilic agent dimethylolpropionic acid of polyethylene glycol and 1mol that 1mol is added exists
Under conditions of 100 DEG C, 0.5h is vacuumized, until the mixture moisture of polyethylene glycol and hydrophilic agent is 0.07%, is cooled to 50 DEG C,
3mol methyl diphenylene diisocyanate, under the conditions of 75 DEG C of temperature, the reaction was continued 3h is added, it can obtain containing in structure
The base polyurethane prepolymer for use as of carboxylated hydrophilic base；
(2) polyurethane-biuret oligomers are prepared:
Under agitation, the aqueous solution of urea of 2.0mol is warming up to 100 DEG C, then contains parent for what step (1) obtained
Water-based polyurethane performed polymer is added in 100 DEG C of aqueous solution of urea, is warming up to 135 DEG C, is continued insulation reaction at such a temperature
The polyether polyols that end group is urea groups can be obtained in 2.7h；
(3) chain extending reaction:
Under 100 DEG C of stirring condition, the adjacent benzene of 1.9mol is added in obtained urethane oligomer in step (2)
Dicarbaldehyde chain extender continues insulation reaction 1h, is cooled to 40 DEG C, and in high-speed mixer, suitable quantity of water is added, and gained is aqueous poly-
The solid content of urethane dispersion is diluted to 40%；High-speed stirred disperse 30min after to get arrive aqueous polyurethane-allophanamide dispersion.
Embodiment 5:
(1) base polyurethane prepolymer for use as containing hydrophilic group is prepared:
Under the protective condition of drying nitrogen, the polycaprolactone glycol of 1mol and hydrophilic agent N- (the 2- ammonia of 0.2mol is added
Ethyl)-alanine under conditions of 120 DEG C, vacuumizes 0.5h, until the mixture moisture of polycaprolactone glycol and hydrophilic agent
It is 0.09%, is cooled to 40 DEG C, 4, the 4'- dicyclohexyl methyl hydride diisocyanate of 1.5mol is added, in 72 DEG C of temperature condition
Under, the reaction was continued 3.5h, it can obtain the base polyurethane prepolymer for use as of the base containing carboxylated hydrophilic in structure；
(2) polyurethane-biuret oligomers are prepared:
Under agitation, the aqueous solution of urea of 0.6mol is warming up to 100 DEG C, then take that step (1) obtains containing parent
Water base end group is that the base polyurethane prepolymer for use as of isocyanate group is added in 100 DEG C of aqueous solution of urea, is warming up to 135 DEG C,
Continue insulation reaction 3h at this temperature, the polyether polyols that end group is urea groups can be obtained；
(3) chain extending reaction:
Under 120 DEG C of stirring condition, the adjacent benzene of 0.2mol is added in obtained urethane oligomer in step (2)
Dicarbaldehyde chain extender continues insulation reaction 1.5h, is cooled to 50 DEG C, and in high-speed mixer, suitable quantity of water is added, and gained is aqueous
The solid content of dispersions of polyurethanes is diluted to 60%；High-speed stirred disperses after 30min to disperse to get to aqueous polyurethane-allophanamide
Body.
Aqueous polyurethane dispersion obtained in above-described embodiment 1-5 and common commercially available aqueous polyurethane dispersion are produced
Product compare test, referring to the method in " limits of harmful substances in GB18583-2008 indoor decorating and refurnishing materials adhesive "
VOC detection is carried out, every group setting three are averaged in parallel, and test result is as shown in table 1:
Table 1
| Sample ID | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Commercial product 1 | Commercial product 2 |
| VOC(mg/kg) | 13 | 8 | 19 | 22 | 18 | 850 | 672 |
Wherein the VOC of embodiment 1-5 is the complete monomer of polymer unreacted, and content is few；Commercial product 1
VOC is mainly acetone, contains the complete monomer of about 30mg/kg unreacted；The VOC of commercial product 2 is mainly butanone and cyclohexanone
Mixture, contain the complete monomer of about 20mg/kg unreacted.
By above-mentioned test result it is found that the VOC content of aqueous polyurethane dispersion is far below common city in embodiment 1-5
Sell aqueous polyurethane dispersion product.Using the aqueous polyurethane dispersion preparation method referred in the present invention, zero can be obtained
VOC aqueous polyurethane product.
In conclusion the aqueous polyurethane dispersion of Diamond Search provided by the invention, by using containing epoxy group and aldehyde radical
Chain extender prepare aqueous polyurethane dispersion, i.e., will melt the formalin chain extender used in dispersion method and be substituted for other
N- alkylating reagent, preparation method is simple, and used material is easy to get, cost is relatively low, and without containing the volatilization such as acetone, formaldehyde
Property organic matter, the aqueous polyurethane dispersion of Diamond Search can be synthesized, it is safe and non-toxic, to human body and environmental-friendly, reach really green
The purpose that colour circle is protected, while hydrophilic radical is introduced in preparation process, itself there is emulsification, it is subsequent to be taken with other compositions
With being not necessarily to additional emulsifier when using, while while using, is less prone to unstable phenomenon.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalents made by bright description are applied directly or indirectly in relevant technical field, are similarly included in this hair
In bright scope of patent protection.
Claims (7)
1. a kind of Diamond Search aqueous polyurethane dispersion, which is characterized in that its general structure are as follows:
Wherein, M is chain extender, contains epoxy group and aldehyde radical, the structural formula of R5 in the structure of M are as follows:
Wherein, R1 and R3 is the straight chain fatty alkyl being made of 2-10 methylene；
The structural formula of R2 is-CH2CH2CH2CH2Or
X is carboxyl or sulfonic group.
2. the preparation method of Diamond Search aqueous polyurethane dispersion according to claim 1, which is characterized in that including as follows
Step:
(1) base polyurethane prepolymer for use as containing hydrophilic group is prepared:
Under the protective condition of drying nitrogen, double hydroxy polymers and hydrophilic agent are mixed under conditions of 100 DEG C -120 DEG C, is taken out
Vacuum 0.5h is cooled to 50 DEG C hereinafter, polyisocyanates is added, in 65 DEG C -75 DEG C of stirring bar until moisture is lower than 0.1%
Under part, 3h-4h is reacted, is cooled to 30 DEG C -50 DEG C, it is pre- to obtain the polyurethane that the end group in structure containing hydrophilic group is isocyanate group
Aggressiveness；
(2) polyurethane-biuret oligomers are prepared:
Under agitation, aqueous solution of urea is warming up to 100 DEG C, the end group containing hydrophilic group that step (1) is obtained is isocyanide
The base polyurethane prepolymer for use as of perester radical is added in 100 DEG C of aqueous solution of urea, is warming up to 130-135 DEG C, is continued at such a temperature
The polyether polyols that end group is urea groups can be obtained in insulation reaction 2.5-3h；
(3) chain extending reaction:
At 60 DEG C -120 DEG C, chain extender is added, continues insulation reaction 1h-2h, 40 DEG C -50 DEG C is cooled to, in high-speed mixer
In, add water, resulting aqueous polyurethane dispersion solid content is diluted between 40%-60%, high-speed stirred disperses 30min
Afterwards to get arrive the aqueous poly- ammonia dispersion of Diamond Search.
3. the preparation method of Diamond Search aqueous polyurethane dispersion according to claim 2, which is characterized in that double hydroxyls
Based polyalcohol A, polyisocyanates B, hydrophilic agent C, urea D and chain extender M molar ratio be 1:1.5-3:0.2-1:0.6-2:
0.2-2；Wherein: D=2 × (B-A-C), 0.1≤B-A-C≤1, M < D.
4. the preparation method of Diamond Search aqueous polyurethane dispersion according to claim 2, which is characterized in that double hydroxyls
Based polyalcohol is polyoxypropyleneglycol, polyethylene glycol, polytetrahydrofuran ether glycol, polycaprolactone glycol and polybutadiene diol
One or more of, the average molecular weight range of double hydroxy polymers is in 1000-3000Da.
5. the preparation method of Diamond Search aqueous polyurethane dispersion according to claim 2, which is characterized in that the polyisocyanate
Cyanate is isophorone diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, two isocyanide of hexa-methylene
Acid esters and 4, one or more of 4'- dicyclohexyl methyl hydride diisocyanate.
6. the preparation method of Diamond Search aqueous polyurethane dispersion according to claim 2, which is characterized in that described hydrophilic
Agent be dihydromethyl propionic acid, dimethylolpropionic acid, N- (2- aminoethyl)-alanine,
N- (2- aminoethyl)-tarine sodium or 2,4- diamino benzene sulfonic acid.
7. the preparation method of Diamond Search aqueous polyurethane dispersion according to claim 2, which is characterized in that the chain extension
Agent is N- alkylating reagent, and the N- alkylating reagent is 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexyl formic acid esters, right
Phthalaldehyde, o-phthalaldehyde or m-terephthal aldehyde.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110606929A (en) * | 2019-09-18 | 2019-12-24 | 牡丹江师范学院 | Epoxy modified waterborne polyurethane emulsion convenient to store and transport, preparation method and storage method |
| CN117550993A (en) * | 2023-11-01 | 2024-02-13 | 深圳泊瑞科技有限公司 | Asymmetric-activity chain extender, preparation method and application thereof, and preparation method of waterborne polyurethane |
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| CN102432872A (en) * | 2010-06-16 | 2012-05-02 | 陶氏环球技术公司 | Ambient temperature curable isocyanate-free compositions for preparing crosslinked polyurethanes |
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| CN102432872A (en) * | 2010-06-16 | 2012-05-02 | 陶氏环球技术公司 | Ambient temperature curable isocyanate-free compositions for preparing crosslinked polyurethanes |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110606929A (en) * | 2019-09-18 | 2019-12-24 | 牡丹江师范学院 | Epoxy modified waterborne polyurethane emulsion convenient to store and transport, preparation method and storage method |
| CN117550993A (en) * | 2023-11-01 | 2024-02-13 | 深圳泊瑞科技有限公司 | Asymmetric-activity chain extender, preparation method and application thereof, and preparation method of waterborne polyurethane |
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