CN111825824A - High-flame-retardant waterborne polyurethane and preparation method thereof - Google Patents
High-flame-retardant waterborne polyurethane and preparation method thereof Download PDFInfo
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- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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Abstract
The invention provides waterborne polyurethane and a preparation method thereof. The invention is to react non-phosphorus-containing polyol with specific phosphorus-containing polyol shown as a formula (1), phosphorus-containing stabilizer shown as a formula (2) and polyisocyanate to form prepolymer, emulsify the prepolymer and react the prepolymer with phosphorus-containing chain extender to form the waterborne polyurethane. Phosphorus-containing polyol in a formula (1) is adopted to introduce a phosphine-containing group into a soft segment of a polyurethane molecular chain to form a part of a water-based polyurethane structural unit, so that the water-based polyurethane has flame retardance without adding a flame retardant; the phosphorus-containing stabilizer shown in the formula (2) can promote the emulsification of the phosphine-containing waterborne polyurethane and solve the problem of unstable emulsion after chain extension, thereby solving the problems of difficult emulsification and difficult formation of aqueous dispersion when phosphine-containing groups are introduced into the molecular structure of the polyurethane. In addition, the soft segment, the stabilizer and the chain extender of the waterborne polyurethane are introduced with phosphine-containing groups, so that the flame retardant property is greatly improved, and the bonding force of the waterborne polyurethane is enhanced due to the introduction of a specific phosphorus-containing structure.
Description
Technical Field
The invention relates to the field of organic polymers, and particularly relates to high-flame-retardant waterborne polyurethane and a preparation method thereof.
Background
The waterborne polyurethane is a block type high molecular green environment-friendly material formed by alternately arranging flexible soft segments (polyester/polyether polyol) and rigid hard segments (isocyanate and micromolecular chain extender). The waterborne polyurethane not only has the special flexibility, friction resistance, low temperature resistance and good film forming capability of polyurethane, but also has extremely low VOC emission and reduces environmental pollution by taking water as a dispersing agent, and is widely applied to the fields of adhesives, coatings, fabric finishing agents, leather finishing agents, paper and fiber surface treating agents, water-based ink, paper making and the like. Waterborne polyurethanes have received considerable attention over the past decades and have been subject to considerable research.
However, the Limit Oxygen Index (LOI) of the polymer material, namely, the waterborne polyurethane, is generally low, i.e., the flame retardance is poor, and a fire hazard is inevitably generated in the using process. In order to reduce fire hazard and better protect life and property safety of people, the flame retardant property of the waterborne polyurethane is an important content of the functionalization of the waterborne polyurethane.
In the prior art, flame retardant modification of waterborne polyurethane exists in various ways: the flame retardant is added into the waterborne polyurethane and is subjected to flame retardant modification, so that the waterborne polyurethane with certain flame retardant property can be obtained. The flame retardant is inorganic flame retardant such as antimony oxide, aluminum hydroxide, magnesium hydroxide, montmorillonite, and expanded graphite, and organic flame retardant containing flame retardant elements such as bromine, boron, nitrogen, silicon, and phosphorus. The added flame-retardant waterborne polyurethane has simple process, but the flame-retardant components are added in blending, so that the stability of the waterborne polyurethane emulsion is extremely easy to reduce, even demulsification is caused, and meanwhile, the flame retardants are difficult to stably disperse in the waterborne polyurethane and are easy to form precipitates. Although the liquid flame retardant does not generate precipitation, the liquid flame retardant can affect the film forming property of the waterborne polyurethane and the performance of a formed adhesive film after film forming, such as stickiness, insufficient adhesive property and the like of the adhesive film, and the liquid flame retardant is easy to migrate out. The inorganic substances (such as magnesium hydroxide, aluminum hydroxide and the like) are generally added in a large amount to achieve the flame retardant effect, but the addition of a large amount of inorganic substances affects other properties of the polyurethane. The added flame-retardant waterborne polyurethane for flame-retardant finishing of the fabric in the market at present has the defects of opaque coating, large addition amount of flame retardant, poor water washing resistance and easy migration, so that the appearance of the fabric is influenced. Further, although flame retardant properties can be improved by introducing a flame retardant component into the molecular structure of the polyurethane, when the flame retardant component is increased, the polyurethane is difficult to emulsify, and the resulting aqueous dispersion is unstable, i.e., cannot form an aqueous polyurethane or is poor in stability, which causes problems in construction and application, and affects the performance of the use properties (e.g., flame retardancy, adhesiveness, etc.).
Disclosure of Invention
In view of the above, the present invention aims to provide a waterborne polyurethane and a preparation method thereof. The waterborne polyurethane provided by the invention can improve the flame retardance and the adhesive force, is easy to emulsify in the preparation process, and has good stability of the formed polyurethane dispersion liquid.
The invention provides a preparation method of high flame-retardant waterborne polyurethane, which comprises the following steps:
a) carrying out prepolymerization reaction on polyol, a stabilizer and polyisocyanate to obtain a prepolymer;
b) emulsifying the prepolymer to obtain emulsion;
c) mixing the emulsion with a phosphorus-containing chain extender for reaction to form waterborne polyurethane;
the polyol comprises a polymeric polyol;
the polyester polyol is phosphorus-free polyol and polyphosphate polyol;
the polyphosphate polyol has a structure represented by formula (1):
in formula (1): r is substituted or unsubstituted alkyl, substituted or unsubstituted phenyl; the polymerization degree n is 1-20;
the stabilizer comprises a phosphonate based stabilizer; the phosphonate based stabilizer has a structure represented by formula (2):
in formula (2): r is-COOH or-SO3Na; the polymerization degree n is 1 to 10.
Preferably, the phosphorus-containing chain extender has a structure represented by formula (3):
in formula (3): r is substituted or unsubstituted alkyl, substituted or unsubstituted phenyl.
Preferably, in the formula (1), the number of carbon atoms of the alkyl group is less than 5;
the phosphorus-free polyol is selected from one or more of polyether polyol and polyester polyol.
Preferably, in the formula (1), R is methyl or phenyl.
Preferably, in the formula (3), the number of carbon atoms of the alkyl group is less than 5.
Preferably, in the formula (3), R is methyl or phenyl.
Preferably, in the step a), the mass ratio of the polymeric polyol to the stabilizer to the polyisocyanate is 100: 1-20: 10-40;
the mass ratio of the phosphorus-free polyol to the polymeric polyol is 10-60%.
Preferably, the step a) includes:
a1) mixing polyalcohol and stabilizer, and drying to obtain dried substance;
a2) carrying out prepolymerization reaction on the dried product and polyisocyanate to obtain a prepolymer;
the drying temperature is 70-100 ℃;
the temperature of the prepolymerization reaction is 50-100 ℃.
Preferably, after step a) and before step b), the method further comprises:
dissolving the prepolymer in a solvent to obtain a prepolymer solution;
mixing the prepolymer solution with an alkaline neutralizing agent to obtain a neutralized prepolymer solution;
the step b) is as follows:
dispersing the neutralized prepolymer solution in water to form an emulsion;
in the step c):
the mass ratio of the phosphorus-containing chain extender to the polyhydric alcohol in the step a) is (7-10) to 200.
The invention also provides the high-flame-retardant waterborne polyurethane prepared by the preparation method in the technical scheme.
The invention is to react non-phosphorus-containing polyol with specific phosphorus-containing polyol shown as a formula (1), phosphorus-containing stabilizer shown as a formula (2) and polyisocyanate to form prepolymer, emulsify the prepolymer and react the prepolymer with phosphorus-containing chain extender to form the waterborne polyurethane. Phosphorus-containing polyol in a formula (1) is adopted to introduce a phosphine-containing group into a soft segment of a polyurethane molecular chain to form a part of a water-based polyurethane structural unit, so that the water-based polyurethane has flame retardance without adding a flame retardant and reaches a certain flame retardance level; the phosphorus-containing stabilizer shown in the formula (2) can promote the emulsification of the phosphine-containing waterborne polyurethane and solve the problem of unstable emulsion after chain extension, thereby solving the problems of difficult emulsification and difficult formation of aqueous dispersion when phosphine-containing groups are introduced into the molecular structure of the polyurethane. In addition, the soft segment, the stabilizer and the chain extender of the waterborne polyurethane are introduced with phosphine-containing groups, so that the proportion of the flame retardant in the waterborne polyurethane is obviously improved, the flame retardant property is greatly improved, and the bonding force of the waterborne polyurethane is also enhanced by introducing a specific phosphorus-containing structure.
Test results show that the limit oxygen index of the aqueous polyurethane dispersion prepared by the invention is more than 34%, and the peel strength is more than 11N/cm.
Detailed Description
The invention provides a preparation method of high flame-retardant waterborne polyurethane, which comprises the following steps:
a) carrying out prepolymerization reaction on polyol, a stabilizer and polyisocyanate to obtain a prepolymer;
b) emulsifying the prepolymer to obtain emulsion;
c) mixing the emulsion with a phosphorus-containing chain extender for reaction to form waterborne polyurethane;
the polyol comprises a polymeric polyol;
the polyester polyol is phosphorus-free polyol and polyphosphate polyol;
the polyphosphate polyol has a structure represented by formula (1):
in formula (1): r is substituted or unsubstituted alkyl, substituted or unsubstituted phenyl; the polymerization degree n is 1-20;
the stabilizer comprises a phosphonate based stabilizer; the phosphonate based stabilizer has a structure represented by formula (2):
in formula (2): r is-COOH or-SO3Na; the polymerization degree n is 1 to 10.
The invention is to react non-phosphorus-containing polyol with specific phosphorus-containing polyol shown as a formula (1), phosphorus-containing stabilizer shown as a formula (2) and polyisocyanate to form prepolymer, emulsify the prepolymer and react the prepolymer with phosphorus-containing chain extender to form the waterborne polyurethane. Phosphorus-containing polyol in a formula (1) is adopted to introduce a phosphine-containing group into a soft segment of a polyurethane molecular chain to form a part of a water-based polyurethane structural unit, so that the water-based polyurethane has flame retardance without adding a flame retardant and reaches a certain flame retardance level; the phosphorus-containing stabilizer shown in the formula (2) can promote the emulsification of the phosphine-containing waterborne polyurethane and solve the problem of unstable emulsion after chain extension, thereby solving the problems of difficult emulsification and difficult formation of aqueous dispersion when phosphine-containing groups are introduced into the molecular structure of the polyurethane. In addition, the soft segment, the stabilizer and the chain extender of the waterborne polyurethane are introduced with phosphine-containing groups, so that the proportion of the flame retardant in the waterborne polyurethane is obviously improved, the flame retardant property is greatly improved, and the bonding force of the waterborne polyurethane is also enhanced by introducing a specific phosphorus-containing structure.
With respect to step a):
in the present invention, the polyol includes a polymeric polyol. The polyester polyol is phosphorus-free polyol and polyphosphate polyol.
Wherein, the phosphorus-free polyol is preferably one or more of polyether polyol and polyester polyol. The polyester polyol is preferably one or more of a conventional polyester polyol and a polycarbonate polyol. The number average molecular weight of the phosphorus-free polyol is preferably 400 to 10000g/mol, more preferably 500 to 4000g/mol, and further preferably 1000 to 3000 g/mol. The source of the phosphorus-free polyol is not particularly limited in the present invention, and it may be a general commercial product or may be prepared in a conventional manner well known to those skilled in the art.
Wherein the polyphosphate polyol has a structure represented by formula (1):
in formula (1): r is substituted or unsubstituted alkyl, substituted or unsubstituted phenyl; the alkyl group is preferably an alkyl group having less than 5 carbon atoms. More preferably, R is methyl or phenyl. The polyphosphate ester polyol is polyphosphate ester polyol, and the polymerization degree n is 1-20, preferably 1-10. The invention adopts specific polyphosphate ester polyol shown in the formula (1) as one of the polyol raw materials, is matched with other polyols to polymerize to form polyurethane, and can introduce a specific phosphine-containing structure into a soft segment of a polyurethane molecular chain, so that the polyurethane has flame retardance without adding a flame retardant and reaches a certain flame retardance level.
In the present invention, the polyphosphate polyol represented by the formula (1) may be prepared by the following method: carrying out polycondensation reaction on diacid phosphate or dimethyl phosphate and ethylene glycol to form hydroxyl-terminated oligomeric phosphate polyol shown in a formula (1). The temperature of the polycondensation reaction is preferably 0-60 ℃, and the time is preferably 0.5-10 h.
In the present invention, the mass ratio of the phosphorus-free polyol to the polymeric polyol is preferably 10% to 60%, and more preferably 20% to 60%.
In the invention, the polyol can also comprise monomer diol, and the proportion of the hard segment of the aqueous polyurethane is increased according to the requirement. The monomer diol is preferably one or more of butanediol, propylene glycol, neopentyl glycol and dibromo neopentyl glycol. In the present invention, the mass ratio of the monomeric diol to the polymeric polyol is preferably (0.5 to 10) to 100.
In the present invention, the stabilizer includes a phosphonate-based stabilizer. The phosphonate based stabilizer has a structure represented by formula (2):
in formula (2): r is-COOH or-SO3Na; the polymerization degree n is 1 to 10, preferably 1 to 5. The stabilizer with a specific phosphonate structure shown in the formula (2) is adopted, and has a functional group carboxyl or sulfonic group capable of forming negative electricity, so that the emulsification of the phosphorus-containing polyurethane can be promoted, the problem that the phosphorus-containing polyurethane is difficult to emulsify due to the introduction of a flame-retardant component into the molecular structure of the polyurethane is solved, the phosphorus-containing polyurethane spontaneously forms a stable oil-in-water dispersion in water, and the strong emulsion stability can be presented without an external emulsifier.
The stabilizer containing phosphate ester structure in the formula (2) can be prepared by the following method: carrying out polycondensation reaction on phosphorus oxychloride, ethylene glycol and hydroxypropionic acid or sodium hydroxyethanesulfonate to form the stabilizer shown in the formula (2). The temperature of the polycondensation reaction is preferably 0-60 ℃, and the time is preferably 0.5-10 h.
In the present invention, the stabilizer may further include a non-phosphorus stabilizer (i.e., a stabilizer not containing phosphorus). The non-phosphorus stabilizer includes at least two hydroxyl groups and a negatively charged functional group. The negatively charged functional group is preferably a carboxyl group, a carboxylate group, a sulfonic acid group or a sulfonate group. The non-phosphorus stabilizer is preferably one or more of 2, 2-bis (hydroxymethyl) alkane monocarboxylic acid and sulfonated polyglycol. The 2, 2-bis (hydroxymethyl) alkane monocarboxylic acid is preferably 2, 2-bis (hydroxymethyl) propionic acid. The sulfonated polyglycol preferably has a number average molecular weight of 1000g/mol or less. More preferably, the sulfonated polyglycol is propoxylated 1-methyl-2-hydroxymethyl-3-hydroxy-1-propanesulfonate.
In the invention, the mass ratio of the stabilizer to the polyhydric alcohol is preferably (1-20) to 100, and more preferably (2-10) to 100. When the stabilizer comprises a non-phosphorus stabilizer, the mass ratio of the phosphonate-based stabilizer to the total stabilizer is preferably 50 to 100%.
In the present invention, the polyisocyanate preferably includes one or more of aliphatic diisocyanate and aliphatic triisocyanate. The aliphatic diisocyanate preferably comprises one or more of hexamethylene diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, 1, 4-cyclohexane diisocyanate, norbornane diisocyanate and cyclohexane dimethylene diisocyanate. The polyisocyanate may also include aromatic polyisocyanates. The aromatic polyisocyanate preferably comprises one or more of diphenylmethane diisocyanate, toluene-2, 4-diisocyanate and polymeric diphenylmethane diisocyanate.
In the present invention, the mass ratio of the polyisocyanate to the polyol is preferably (10 to 40) to 100, and more preferably (10 to 30) to 100.
In the invention, the temperature of the prepolymerization reaction is preferably 50-100 ℃, and more preferably 50-90 ℃. The time of the prepolymerization reaction is preferably 1-24 h.
In the present invention, the step a) preferably specifically comprises the following steps:
a1) mixing polyalcohol and stabilizer, and drying to obtain dried substance;
a2) and carrying out prepolymerization reaction on the dried product and polyisocyanate to obtain a prepolymer.
The types, the amounts and the like of the polyol, the stabilizer and the polyisocyanate are consistent with those in the technical scheme, and are not described again.
With respect to step a 1): the specific operation is to mix the materials, heat them, and stir them under vacuum condition to remove water and dry the mixture. The heating temperature is preferably 70-100 ℃. After mixing and drying, the resulting mixture is preferably cooled. The cooling is preferably to a temperature below 60 ℃.
With respect to step a 2): the temperature of the prepolymerization reaction is preferably 50-100 ℃, and more preferably 50-90 ℃. The time of the prepolymerization reaction is preferably 1-24 h.
In the present invention, the prepolymerization reaction is preferably carried out under the action of a catalyst. The catalyst is preferably one or more of an organic tin catalyst and an organic bismuth catalyst; more preferably one or more of dibutyl tin dilaurate and stannous octoate. The amount of the catalyst is preferably 0.1 to 5 percent of the mass of the polyisocyanate. In the course of prepolymerization reaction, the content of free isocyanate is used as the judgement index for stopping reaction, when the content of free isocyanate in the formed prepolymer is 0.2% -6%, preferably 1% -5%, the stopping reaction is implemented. The method for determining the free isocyanate content in the system is not particularly limited in the present invention, and may be a method well known to those skilled in the art, such as di-n-butylamine titration. In the invention, the operation of the termination reaction is specifically to cool the system, preferably to below 50 ℃. After the reaction was stopped, a prepolymer was obtained.
In the present invention, it is preferable to further perform dissolution and neutralization after obtaining the prepolymer and before emulsification, specifically as follows: dissolving the prepolymer in a solvent to obtain a prepolymer solution; and mixing the prepolymer solution with an alkaline neutralizing agent to obtain a neutralized prepolymer solution. In the present invention, the solvent is preferably a water-miscible solvent, and more preferably one or more of acetone and butanone. The mass ratio of the solvent to the prepolymer is preferably 70% or less, more preferably 60% or less. In the present invention, the alkaline neutralizing agent is preferably an organic base, and more preferably one or more of triethylamine, tri-n-butylamine, diethanolamine and triethanolamine. In the present invention, the amount of the alkaline neutralizing agent is preferably 2 to 10% based on the mass of the prepolymer. After neutralization, a neutralized prepolymer solution is obtained.
With respect to step b):
the specific operation of the emulsification is as follows: dispersing the neutralized prepolymer solution in water to form an emulsion. In the present invention, the amount of water is preferably 50 to 150% by mass based on the mass of the prepolymer. The dispersion is preferably an agitated dispersion. The rotation speed of the stirring is preferably 500-2000 rpm, and the stirring time is preferably 10-180 min. Under the action of the phosphonate stabilizer of the formula (2) added in the previous step, the phosphorus-containing polyurethane prepolymer is emulsified after the dispersion treatment. The diameter of the stable liquid drop of the emulsion prepared by the invention is 100-400 nm.
With respect to step c):
in the present invention, the phosphorus-containing chain extender preferably has a structure represented by formula (3):
in formula (3): r is substituted or unsubstituted alkyl, substituted or unsubstituted phenyl. The alkyl group is preferably an alkyl group having less than 5 carbon atoms. More preferably, R is methyl or phenyl. According to the invention, the specific phosphorus-containing chain extender is adopted for post chain extension reaction, P, N elements are introduced, the synergistic effect with the added polyphosphate ester polyol and phosphonate ester stabilizer can be generated, the synergistic flame-retardant effect is better than that generated by physically mixing multiple flame retardants, and the bonding force of the waterborne polyurethane can be enhanced. In the invention, the mass ratio of the phosphorus-containing chain extender to the prepolymer is preferably (2-10) to 100. In the present invention, the source of the phosphine-containing chain extender represented by the formula (3) is not particularly limited, and may be any commercially available product.
In the invention, the temperature for chain extension reaction after adding the chain extender is not particularly limited, and is room temperature, and specifically can be 10-40 ℃. In the post-chain extension process, the isocyanate end group NCO-of the prepolymer and the chain extender are subjected to chain extension until NCO-is not detected, and the post-treatment is carried out after the reaction is finished. The post-treatment is solvent removal. The solvent removal means of the present invention is not particularly limited, and may be any conventional removal means known to those skilled in the art, such as distillation. After the post-treatment, the aqueous polyurethane dispersion is obtained, and the stable phosphorus-containing aqueous polyurethane dispersion can be formed by the preparation method.
The invention also provides the high-flame-retardant waterborne polyurethane prepared by the preparation method in the technical scheme.
The high-flame-retardant waterborne polyurethane prepared by the invention has the following beneficial effects:
(1) the intrinsic flame-retardant waterborne polyurethane prepared by the invention adopts phosphorus-containing polyol shown in formula (1) to introduce phosphine-containing groups into a soft segment of a polyurethane molecular chain to form a part of a waterborne polyurethane structural unit, so that the waterborne polyurethane has flame retardance without adding a flame retardant and reaches a certain flame-retardant level; the method is to modify polyurethane on a molecular level, fundamentally overcomes the interface problem related to an additional flame retardant, directly introduces a flame retardant element/structure into polyurethane molecules, greatly reduces the using amount of flame retardant components, avoids the problems of easy volatilization, dissolution, migration, exudation and the like of the flame retardant, and has higher and more lasting flame retardant efficiency of the intrinsic flame retardant waterborne polyurethane under the condition of the same content of the flame retardant element. Meanwhile, the phosphorus-containing stabilizer shown in the formula (2) can promote the emulsification of the phosphine-containing waterborne polyurethane, and solves the problem of unstable emulsion after chain extension, thereby solving the problems of difficult emulsification and difficult formation of aqueous dispersion when phosphine-containing groups are introduced into the molecular structure of the polyurethane.
(2) The soft segment, the stabilizer and the chain extender of the waterborne polyurethane are all introduced with phosphine-containing groups, so that the proportion of the flame retardant in the waterborne polyurethane is obviously improved, and the flame retardant property is greatly improved; and the three types of phosphorus-containing substances have better adaptability, and the introduction of a specific phosphorus-containing structure enhances the binding power of the waterborne polyurethane.
(3) The water-based polyurethane of the invention simultaneously introduces a plurality of elements such as phosphorus, nitrogen and the like to generate a synergistic flame-retardant effect, and the synergistic flame-retardant effect is better than that generated by physically mixing a plurality of flame retardants.
The aqueous polyurethane dispersion provided by the invention can be mixed with a nonpolar adhesion promoter to prepare an aqueous polyurethane adhesive. The non-polar adhesion promoter is selected from one or more of polyolefin, polyacrylic acid-based resin and rosin-based resin. The aqueous polyurethane dispersion provided by the invention can be used in paint.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In the following examples, polyphosphate polyol of formula (1) was prepared according to the preparation method described above. The phosphonate-based stabilizer of formula (2) is prepared according to the preparation method described hereinbefore. The method for testing the NCO content of the system is a di-n-butylamine titration method.
Example 1
S1, preparing 100g polyester polyol (PCL1000, molecular weight 1000), 100g polyphosphate polyol (R is phenyl, hydroxyl value is 60mgKOH/g) shown in formula 1, and phosphonate stabilizer (R is-SO) shown in formula 23Na, hydroxyl value 210mgKOH/g)4.9g, mixing and adding into a reaction kettle provided with a condenser and a mechanical stirrer; the mixture was dried by heating to 85 ℃ while stirring under vacuum for 2.5h to remove water.
S2, cooling the mixture to below 50 ℃, adding 6.3g of isophorone diisocyanate, 8.7g of hexamethylene diisocyanate and 5.5mg of dibutyltin dilaurate, heating to 80 ℃, stirring for reacting for 4 hours, cooling to 60 ℃, continuing the reaction, measuring the NCO content until the NCO content reaches a target value range, cooling and stopping the reaction to obtain the prepolymer.
S3, adding 120g of acetone to dissolve the prepolymer to form a homogeneous solution, adding 0.5g of triethylamine, and uniformly mixing to form a neutralized prepolymer solution.
S4, mixing the neutralized prepolymer solution with 150g of deionized water, and mechanically stirring at 800rpm for 30min to form an emulsion.
S5, 8.0g of a phosphorus-containing diamine of formula 3 (R is methyl) is added to the emulsion and the reaction is continued at room temperature until no residual NCO is detected. And distilling under reduced pressure to remove acetone to obtain the aqueous polyurethane dispersion.
Example 2
S1, mixing polyether polyol (type 2000LM, molecular weight 2000)80g, polyphosphate polyol (R is methyl, hydroxyl value 55mgKOH/g) of formula 1 120g, and phosphonate stabilizer (R is-SO) of formula 23Na with a hydroxyl value of 205mgKOH/g)6.3g, and mixing and adding into a reaction kettle provided with a condenser and a mechanical stirrer; the mixture was dried by heating to 85 ℃ while stirring under vacuum for 2.5h to remove water.
And S2, cooling the mixture to below 50 ℃, adding 13.4g of isophorone diisocyanate and 5.5mg of dibutyltin dilaurate, heating to 80 ℃, stirring for reaction for 4 hours, cooling to 60 ℃, continuing the reaction, measuring the NCO content until the NCO content reaches a target value range, cooling and stopping the reaction to obtain the prepolymer.
S3, adding 120g of acetone to dissolve the prepolymer to form a homogeneous solution, adding 0.5g of triethylamine, and uniformly mixing to form a neutralized prepolymer solution.
S4, mixing the neutralized prepolymer solution with 150g of deionized water, and mechanically stirring at 800rpm for 30min to form an emulsion.
S5, 9.0g of a phosphorus-containing diamine of formula 3 (R is phenyl) is added to the emulsion and the reaction is continued at room temperature until no residual NCO is detected. And distilling under reduced pressure to remove acetone to obtain the aqueous polyurethane dispersion.
Example 3
S1, mixing and adding 50g of polyester polyol (type PEA2000, molecular weight 2000), 80g of polyphosphate polyol (R is methyl, hydroxyl value is 65mgKOH/g) shown in formula 1 and 5.9g of phosphonate stabilizer (R is-COOH, hydroxyl value is 225mgKOH/g) shown in formula 2 into a reaction kettle provided with a condenser and a mechanical stirrer; the mixture was dried by heating to 85 ℃ while stirring under vacuum for 2.5h to remove water.
S2, cooling the mixture to below 50 ℃, adding 4.6g of isophorone diisocyanate, 9.7g of hexamethylene diisocyanate and 5.5mg of dibutyltin dilaurate, heating to 80 ℃, stirring for reacting for 4 hours, cooling to 60 ℃, continuing the reaction, measuring the NCO content until the NCO content reaches a target value range, cooling and stopping the reaction to obtain the prepolymer.
S3, adding 120g of acetone to dissolve the prepolymer to form a homogeneous solution, adding 1.6g of triethylamine, and uniformly mixing to form a neutralized prepolymer solution.
S4, mixing the neutralized prepolymer solution with 150g of deionized water, and mechanically stirring at 800rpm for 30min to form an emulsion.
S5, 10.0g of a phosphorus-containing diamine of formula 3 (R is phenyl) is added to the emulsion and the reaction is continued at room temperature until no residual NCO is detected. And distilling under reduced pressure to remove acetone to obtain the aqueous polyurethane dispersion.
Example 4
S1, mixing 50g polyester polyol (type PHA3000, molecular weight 3000), 120g polyphosphate polyol (R is phenyl, hydroxyl value is 70mgKOH/g) of formula 1, and phosphonate stabilizer (R is-SO) of formula 23Na with a hydroxyl value of 215mgKOH/g) of 5.9g, and mixing and adding the mixture into a reaction kettle provided with a condenser and a mechanical stirrer; the mixture was dried by heating to 85 ℃ while stirring under vacuum for 2.5h to remove water.
S2, cooling the mixture to below 50 ℃, adding 6.2g of 1, 4-cyclohexane diisocyanate, 9.3g of hexamethylene diisocyanate and 5.5mg of stannous octoate, heating to 80 ℃, stirring for reaction for 4 hours, cooling to 60 ℃ for continuous reaction, measuring the NCO content until the NCO content reaches a target value range, and cooling to stop the reaction to obtain the prepolymer.
S3, adding 120g of acetone to dissolve the prepolymer to form a homogeneous solution, adding 1.6g of triethylamine, and uniformly mixing to form a neutralized prepolymer solution.
S4, mixing the neutralized prepolymer solution with 150g of deionized water, and mechanically stirring at 800rpm for 30min to form an emulsion.
S5, 7.0g of a phosphorus-containing diamine of formula 3 (R is methyl) is added to the emulsion and the reaction is continued at room temperature until no residual NCO is detected. And distilling under reduced pressure to remove acetone to obtain the aqueous polyurethane dispersion.
Example 5
S1, mixing 50g polyester polyol (type PHCD1000, molecular weight 1000), 140g polyphosphate polyol (R is phenyl, hydroxyl value 70mgKOH/g) of formula 1, and phosphonate stabilizer (R is-SO) of formula 23Na with a hydroxyl value of 220mgKOH/g)6.7g, and mixing and adding into a reaction kettle provided with a condenser and a mechanical stirrer; the mixture was dried by heating to 85 ℃ while stirring under vacuum for 3h to remove water.
S2, cooling the mixture to below 50 ℃, adding 5.9g of 4, 4' -dicyclohexylmethane diisocyanate, 9.5g of hexamethylene diisocyanate and 5.5mg of dibutyltin dilaurate, heating to 80 ℃, stirring for reaction for 4 hours, cooling to 60 ℃, continuing the reaction, measuring the NCO content until the NCO content reaches a target value range, cooling and stopping the reaction to obtain the prepolymer.
S3, adding 120g of acetone to dissolve the prepolymer to form a homogeneous solution, adding 1.6g of triethylamine, and uniformly mixing to form a neutralized prepolymer solution.
S4, mixing the neutralized prepolymer solution with 150g of deionized water, and mechanically stirring at 800rpm for 30min to form an emulsion.
S5, 10.0g of a phosphorus-containing diamine of formula 3 (R is phenyl) is added to the emulsion and the reaction is continued at room temperature until no residual NCO is detected. And distilling under reduced pressure to remove acetone to obtain the aqueous polyurethane dispersion.
Comparative example 1
The procedure is as for example 1 except that the phosphonate based stabilizer of formula 2 is replaced with the non-phosphorous stabilizer dimethylolpropionic acid.
Comparative example 2
The procedure of example 1 was followed except that the phosphorus-containing chain extender of formula 3 was replaced with non-phosphorus chain extender ethylenediamine.
Comparative example 3
The procedure of example 1 was followed except that the polyphosphate polyol of formula 1 was replaced with other non-phosphorus polyol-polyester polyol (type PCL1000, molecular weight 1000).
Example 6
After the aqueous polyurethane dispersions obtained in examples 1 to 5 and comparative examples 1 to 3 were prepared into polyurethane resin films, the properties were tested, and the results are shown in Table 1.
Wherein, the process of membrane preparation is: pouring a certain amount of the aqueous polyurethane dispersion into a polytetrafluoroethylene mold, leveling, standing at room temperature for 24 hours to dry the surface of the adhesive film, and drying at 80 ℃ for 2 hours to obtain the aqueous polyurethane adhesive film with the thickness of about 1 mm.
The following test items were tested as follows:
particle size testing of the emulsion: the following pairs of Zetasizer Nano SZ laser particle sizer manufactured by Markov instruments, England were used as 1: the 1000 diluted blue clear emulsion was subjected to a particle size test at a test temperature of 25 ℃.
Testing of peel strength: the measurement was carried out using PVC leather and a stainless steel plate as the base materials. Coating the aqueous polyurethane dispersion on the surface of PVC leather, placing the PVC leather into a blast oven for heat treatment at 60 ℃ for 30min, covering the PVC leather on the surface of a stainless steel plate, then hot-pressing the PVC leather for 0.5h under the pressure of 1MPa by using a press (the temperature of the press is set to be 60 ℃), then cooling the PVC leather to room temperature, symmetrically clamping two ends of the PVC leather in an upper clamp and a lower clamp separately, starting a GOTECHAI-7000S type tensile testing machine, separating the upper clamp and the lower clamp at the speed of 100mm/min, reading the peel strength, measuring 5 data of each group of samples, and taking the.
Limiting oxygen index test: the test was carried out using an impact KS-653B intelligent oxygen index apparatus. Making the flame-retardant waterborne polyurethane film into sample strips with the size of 150mm multiplied by 50mm, wherein 10 samples are obtained in each group, and taking an average value.
TABLE 1 Performance test results of examples 1 to 5 and comparative examples 1 to 3
As can be seen from the test results in Table 1, the flame retardant property and the adhesive property of the examples 1 to 5 of the present invention are significantly improved as compared with those of the comparative examples 1 to 3. Comparison with comparative examples 1-3 proves that the specific phosphonate ester stabilizer shown in formula 2, the phosphorus-containing chain extender shown in formula 3 and the specific polyphosphate ester polyol shown in formula 1 can be better matched, so that the flame retardant property is effectively improved, and the caking property is improved.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of high flame-retardant waterborne polyurethane is characterized by comprising the following steps:
a) carrying out prepolymerization reaction on polyol, a stabilizer and polyisocyanate to obtain a prepolymer;
b) emulsifying the prepolymer to obtain emulsion;
c) mixing the emulsion with a phosphorus-containing chain extender for reaction to form waterborne polyurethane;
the polyol comprises a polymeric polyol;
the polyester polyol is phosphorus-free polyol and polyphosphate polyol;
the polyphosphate polyol has a structure represented by formula (1):
in formula (1): r is substituted or unsubstituted alkyl, substituted or unsubstituted phenyl; the polymerization degree n is 1-20;
the stabilizer comprises a phosphonate based stabilizer; the phosphonate based stabilizer has a structure represented by formula (2):
in formula (2): r is-COOH or-SO3Na; the polymerization degree n is 1 to 10.
2. The preparation method according to claim 1, wherein the phosphorus-containing chain extender has a structure represented by formula (3):
in formula (3): r is substituted or unsubstituted alkyl, substituted or unsubstituted phenyl.
3. The production method according to claim 1, wherein in the formula (1), the number of carbon atoms of the alkyl group is less than 5;
the phosphorus-free polyol is selected from one or more of polyether polyol and polyester polyol.
4. The production method according to claim 1 or 3, wherein R in the formula (1) is a methyl group or a phenyl group.
5. The production method according to claim 2, wherein the number of carbon atoms of the alkyl group in the formula (3) is less than 5.
6. The production method according to claim 1 or 5, wherein R in the formula (3) is a methyl group or a phenyl group.
7. The preparation method of claim 1, wherein in the step a), the mass ratio of the polymeric polyol to the stabilizer to the polyisocyanate is 100: 1-20: 10-40;
the mass ratio of the phosphorus-free polyol to the polymeric polyol is 10-60%.
8. The method for preparing according to claim 1, wherein the step a) comprises:
a1) mixing polyalcohol and stabilizer, and drying to obtain dried substance;
a2) carrying out prepolymerization reaction on the dried product and polyisocyanate to obtain a prepolymer;
the drying temperature is 70-100 ℃;
the temperature of the prepolymerization reaction is 50-100 ℃.
9. The method of claim 1 or 8, further comprising, after step a) and before step b):
dissolving the prepolymer in a solvent to obtain a prepolymer solution;
mixing the prepolymer solution with an alkaline neutralizing agent to obtain a neutralized prepolymer solution;
the step b) is as follows:
dispersing the neutralized prepolymer solution in water to form an emulsion;
in the step c):
the mass ratio of the phosphorus-containing chain extender to the polyhydric alcohol in the step a) is (7-10) to 200.
10. The high-flame-retardant waterborne polyurethane prepared by the preparation method of any one of claims 1 to 9.
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