CN106977681A - A kind of hyperbranched blending modified chain extension extinguishing waterborn polyurethane of hard section - Google Patents

Abstract

The present invention relates to the hyperbranched blending modified chain extension extinguishing waterborn polyurethane of hard section of one kind, belong to fire proofing field.The aqueous polyurethane is comprised the following steps：Hydrophilic chain extender and diisocyanate are added after macromolecular polyol is dehydrated, reacts constant to NCO content, phosphorus-containing polyol small molecule is added, it is constant to NCO content, add salt forming agent A and obtain performed polymer；Added water to performed polymer, add acetone/butanone/N methylpyrrolidone solutions of water plus phosphorous diamine chain stretching agent, obtain emulsion；The AWHBPU aqueous solution neutralized with salt forming agent B is added into emulsion emulsifiers, revolving removes solvent, obtains the aqueous polyurethane.The aqueous polyurethane improves fire resistance and halogen-free environmental by the way that hard section is flame-retardant modified；Fire resistance and improve mechanical property, stability and improve by rear chain extension Modified lift；It is blended by AWHBPU and rear chain extension extinguishing waterborn polyurethane, further improves mechanical property and stability.

Description

A kind of hyperbranched blended hard segment modified and extended chain flame retardant waterborne polyurethane

technical field

The invention relates to a hyperbranched blended hard segment modified chain-extended flame-retardant water-based polyurethane, which belongs to the field of flame-retardant materials.

technical background

Water-based polyurethane is non-toxic, non-polluting, and has strong designability, but it also has disadvantages such as poor flame retardancy, insufficient mechanical properties, and poor emulsion stability.

For the modification of the flame retardant performance of waterborne polyurethane, there are mainly two methods: physical blending modification and intrinsic flame retardant modification. It is divided into soft segment flame retardant modification, hard segment flame retardant modification and soft and hard segment co-modification. The flame retardant modification of the hard segment is realized by introducing small molecules of phosphorus-containing polyols with flame retardant properties into the polyurethane hard segment, which has the advantages of good flame retardant effect and little impact on the properties of the film.

Aiming at the shortcomings of waterborne polyurethane such as insufficient flame retardancy and poor mechanical properties, it can be improved by post-chain extension technology. Post-chain extension refers to the chain extension after polyurethane emulsification or during the emulsification process, which is simple to operate and easy to produce on a large scale. Patent application CN105316949A discloses a kind of hard-segment-modified chain-extended flame-retardant waterborne polyurethane and its preparation method, which increases the content of flame-retardant components and improves the flame-retardant performance by introducing small molecules of organic phosphorus polyols as hard segments; and in The use of phosphorus-containing diamine flame retardants for post-chain extension during emulsification further improves the flame retardant performance, but the stability of the emulsion and the mechanical properties of the film are still insufficient.

Hyperbranched waterborne polyurethane is a class of macromolecules with a highly branched structure. Its unique structure and properties enable it to improve the emulsion stability and mechanical properties of waterborne polyurethane. Patent CN104047176A discloses a preparation method of hyperbranched waterborne polyurethane/compounded flame retardant waterborne polyurethane blend emulsion. By blending hyperbranched waterborne polyurethane with terminal hydroxyl blocked and flame retardant waterborne polyurethane, the mechanical properties of waterborne polyurethane coating are improved ; But when the content of hyperbranched water-based polyurethane is high, its flame retardant performance drops significantly, which limits the practical application of this product.

Contents of the invention

Aiming at the defects in the prior art, the object of the present invention is to provide a chain-extended flame-retardant waterborne polyurethane after modification of the hyperbranched blended hard segments.

The purpose of the present invention is achieved through the following technical means.

A kind of hyperbranched blending hard segment modified chain extension flame retardant water-based polyurethane, the water-based polyurethane is prepared by the following method:

Dehydrate the macromolecular polyol at 110°C-140°C for 1h-3h, add a hydrophilic chain extender at 40°C-80°C, then add diisocyanate, raise the temperature to 80°C-85°C, and react until the -NCO content is no longer Change, add phosphorus-containing polyol small molecules to continue the reaction until the -NCO content no longer changes, cool down to 20°C ~ 40°C, add salt-forming agent A for neutralization reaction for 10min ~ 30min, to obtain a prepolymer; to the prepolymer Add water at 0°C to 10°C for emulsification. Immediately after adding water, add the acetone/butanone/N-methylpyrrolidone solution containing phosphorus diamine chain extender, carry out post-chain extension while emulsifying, and emulsify for 10min to 15min Obtain an emulsion; add the acetyl-blocked hyperbranched water-based polyurethane (AWHBPU) aqueous solution neutralized with salt-forming agent B into the emulsion, continue to emulsify for 5 minutes to 10 minutes to mix evenly, and finally remove acetone/butanone/N-formazol by rotary evaporation base pyrrolidone to obtain an emulsion, which is a kind of hyperbranched blended hard segment modified and chain-extended flame-retardant waterborne polyurethane according to the present invention.

Wherein, the macromolecular polyol is a polyether or polyester polyol with a molecular weight greater than 500, including polypropylene glycol (PPG), polyglycerol, polytetrahydrofuran ether glycol (PTMG) and polycaprolactone glycol (PCL) more than one of them.

The hydrophilic chain extender includes more than one of dimethylolpropionic acid (DMPA), 2,2-dimethylolbutyric acid and 2,3-dihydroxysuccinic acid.

Described diisocyanate is isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), 1,6-hexyl diisocyanate (HDI), dicyclohexylmethane diisocyanate (H ₁₂ MDI) and tetramethylcyclohexyl One or more types of diisocyanates (TMXDI).

The phosphorus-containing polyol small molecule is N,N-bis(2-hydroxyethyl)aminomethylphosphonate (Fyrol-6), bis(2-hydroxyethyl)methylphosphate, bis(2- Hydroxyethyl)phenylphosphate, bis(3-hydroxyphenyl)methylphosphate or bis(3-hydroxyphenyl)phenylphosphate.

The salt-forming agent A and the salt-forming agent B each independently include triethylamine (TEA) or tri-n-butylamine.

The phosphorus-containing diamine chain extender includes bis(aminophenyl)phenylphosphine oxide (BPPO), 2,4,8,10-tetraoxa-3,9-diphosphaspiro-3,9- One or more of dioxy-3,9-bis(3-aminophenyl) (BPPA), bis(3-aminophenyl)phenylphosphorous oxide (BAPPO) and aminophenylphosphorous oxide (BAPO).

The acetyl-blocked hyperbranched waterborne polyurethane (AWHBPU) is the hyperbranched waterborne polyurethane (AWHBPU) using acetic anhydride as an end-capping agent described in the patent application CN 102851987 A.

The AWHBPU aqueous solution neutralized with the salt-forming agent B is obtained by preparing the AWHBPU with water into an aqueous solution with a mass concentration of 10% to 40%, adding the salt-forming agent B, and mixing uniformly.

Taking the mass sum of the macromolecular polyol, hydrophilic chain extender, diisocyanate, phosphorus-containing polyol small molecule, salt-forming agent A, salt-forming agent B, phosphorus-containing diamine chain extender and AWHBPU as the total mass, Based on the total mass as 100%, wherein, the mass fraction of the hydrophilic chain extender is 3% to 10%, the mass fraction of the phosphorus-containing polyol small molecule is 5% to 20%, and the phosphorus-containing diamine chain extension The mass fraction of the agent is 5% to 20%, and the mass fraction of AWHBPU is 3% to 15%; r is defined as a macromolecular polyol, a hydrophilic chain extender, a diisocyanate, a small molecule of a phosphorus-containing polyol, and a salt-forming agent A , the ratio of the molar weight of isocyanate (-NCO) to the molar weight of hydroxyl (-OH) in salt-forming agent B and phosphorus-containing diamine chain extender, and 2>r>1; the molar weight of salt-forming agent A and The content of carboxyl group (-COOH) in the hydrophilic chain extender is the same, and the molar amount of salt-forming agent B is the same as that of carboxyl group in AWHBPU; the molar amount of amine group in the phosphorus-containing diamine chain extender needs to be less than that of the prepolymer The molar amount of isocyanate participating in post-chain extension.

When adding phosphorus-containing polyol small molecules, the solvent butanone can be added to adjust the viscosity, so that the reaction system can be stirred.

Preferably, the purity of the water is higher than that of deionized water.

The chain-extended flame-retardant water-based polyurethane of a hyperbranched blended hard segment modified by the present invention can be an emulsion or an adhesive film; the adhesive film is obtained by modifying the hyperbranched blended hard segment and then extended The flame-retardant water-based polyurethane emulsion is naturally dried to form a film, and then vacuum-dried until the weight does not change.

Beneficial effect

1. The present invention provides a kind of hyperbranched blended hard segment modification and chain extension flame retardant waterborne polyurethane, which improves the flame retardant performance of waterborne polyurethane through hard segment flame retardant modification, as an intrinsic flame retardant waterborne polyurethane flame retardant component It is not easy to move out, and the flame retardant effect is stable. And halogen-free, non-toxic and environmentally friendly;

2. The present invention provides a kind of hyperbranched blended hard segment modified post-chain extension flame retardant water-based polyurethane, which further improves the flame-retardant performance through post-chain extension modification and also improves the mechanical properties of the water-based polyurethane, and makes the water-based polyurethane The stability of the emulsion is improved, and the operation is simple;

3. The present invention provides a hyperbranched blended hard segment modified chain-extended flame-retardant water-based polyurethane, which further improves the flame-retardant water-based polyurethane by blending the hydroxyl-terminated hyperbranched water-based polyurethane with post-chain extended flame-retardant water-based polyurethane The mechanical properties of polyurethane and the stability of the emulsion are further improved, making it possible to prepare flame-retardant waterborne polyurethane with high solid content, which has the advantages of excellent performance and good economic benefits.

detailed description

In the following examples, the preparation method of the hyperbranched blended hard segment modified chain-extended flame-retardant water-based polyurethane film is as follows:

Take 50 g of the hyperbranched blended hard segment modified chain-extended flame-retardant water-based polyurethane emulsion prepared in the embodiment and spread it on a polytetrafluoroethylene plate, dry it naturally at room temperature to form a film, and place the film in a vacuum at 70 ° C. Baking in a drying oven until the weight does not change any more, to obtain a film of hyperbranched blended hard segment modified and chain-extended flame-retardant waterborne polyurethane.

Mechanical property test of hyperbranched blended hard segment modified chain extended flame retardant waterborne polyurethane film:

According to the national standard 1040-79, the adhesive film of the hyperbranched blended hard segment modified in the following examples is made into a sample, and the AGS-J type mechanical testing machine (Shimadzu Corporation of Japan) is used. The material testing machine tests each group of 5 samples, and the test temperature is kept at 25°C.

Oxygen index (LOI) test: According to GB/T2406, the film of the modified hyperbranched co-hard segment obtained in the following examples is made into a sample, and the LFY of the Shandong Textile Science Research Institute is used. -606B digital display oxygen index tester to test the LOI of the sample.

Acetyl-blocked hyperbranched water-based polyamine (AWHBPU) is prepared according to the method of patent CN102851987A in the following examples, and the specific preparation method is:

In a 1000mL four-necked flask with a stirring device, with nitrogen as a protective gas, 142.32g of isophorone diisocyanate (IPDI) was added, the system was heated to 65°C, and 42.912g of 2,2-dihydroxypropionic acid ( DMPA), dissolved in 240mL DMF, was slowly added dropwise into a four-neck flask through a constant pressure dropping funnel within 2h, and after reacting for about 6h, the temperature of the system was lowered to below -5°C using an ice-salt bath. Dissolve 33.84g of diethanolamine (DEOA) in 150mL of DMF, and drop it into a four-necked flask through a constant-pressure dropping funnel. The dropping process lasts for 1 hour. After the dropping, continue to react at this temperature for 2 hours. Raise the temperature of the system to 85°C, and add 0.1 mL of dibutyltin dilaurate (DBTDL) as a catalyst to continue the reaction for 2 h, and add 8 mL of end-capping agent diethylamine (DEA) for 0.5 h to obtain a colorless transparent liquid. The product was transferred to a pear-shaped bottle, and the rotary evaporation was performed at 70°C until the colorless viscous liquid was reached but no solid was precipitated. Using 4000 mL of anhydrous ether as a precipitant for reverse precipitation, slowly pour the product into a beaker filled with anhydrous ether, and stir rapidly with a stirring paddle while pouring to obtain a slightly viscous white precipitate. The precipitate was suction-filtered and rinsed several times with anhydrous ether, then transferred to a watch glass, and placed in a vacuum drying oven at 95°C for 24 hours in vacuum to obtain a large amount of hyperbranched waterborne polyurethane (WHBPU) in the form of white powder.

In a 250mL three-necked flask with a stirring device, add 100g WHBPU and 100mL acetic anhydride, add 10g 98% concentrated sulfuric acid as a catalyst, and react in 300mL pyridine at 80°C for 4h. After the reaction, the solution was rotary evaporated to a viscous liquid but no solid precipitated, and the viscous liquid was slowly poured into 4000 mL of anhydrous ether, and stirred rapidly with a stirring paddle while pouring to obtain a white precipitate. Vacuum drying at 90° C. for 12 hours gave white powdery acetyl-blocked hyperbranched waterborne polyurethane (AWHBPU).

Example 1

Add 33.45g of PPG1000 to a 250mL three-necked flask with a stirring device, vacuumize and stir at 110°C for 1 hour to remove moisture, cool down to 80°C, add 5.25g of DMPA, then add 24.82g of TDI, connect the condenser, and then Raise the temperature to 85°C for 2 hours until the -NCO content does not change, then add 7.50g of Fyrol-6 and 20g butanone to continue the reaction for 3h, until the -NCO content does not change, after cooling down to 40°C, add 3.98g of TEA Add 135 mL of deionized water at 0°C to the prepolymer under vigorous stirring with an emulsifier at a speed of 2400 rpm for emulsification, and add BPPO immediately after adding water The acetone solution, wherein, the quality of BPPO is 8.25g, post-chain extension is carried out while emulsifying, emulsifying for 15min to obtain an emulsion; then add the AWHBPU aqueous solution neutralized with salt-forming agent B into the emulsion, continue stirring for 5min to mix evenly, Then it was left standing for 12 hours to defoam, and finally the methyl ethyl ketone and acetone were removed by rotary evaporation to obtain a hyperbranched blended hard segment modified chain-extended flame-retardant aqueous polyurethane emulsion with a solid content of 30%.

The AWHBPU aqueous solution neutralized with the salt forming agent B is obtained by adding 1.20 g of TEA and mixing uniformly after 8.23 g of AWHBPU is prepared with 40 mL of deionized water.

The chain-extended flame-retardant water-based polyurethane emulsion and its film after modification of the hyperbranched blended hard segment prepared in this example were tested as follows:

(1) The emulsion does not delaminate or precipitate after being placed at room temperature for one year;

(2) Recording the tensile strength of the film is 37.2MPa;

(3) The limiting oxygen index of the film was measured to be 29.2.

Example 2

Add 44.6g of PPG1000 to a 250mL three-necked flask with a stirring device, vacuumize and stir at 110°C for 2h to remove moisture, cool down to 80°C, add 7.00g of DMPA, then add 33.01g of TDI, connect the condenser, and then Raise the temperature to 85°C for 2 hours until the -NCO content does not change, then add 10.0g of Fyrol-6 and 20g of butanone to continue the reaction for 3h, after cooling down to 40°C, add 5.31g of TEA into the three-necked flask for neutralization for 10 minutes , to obtain a prepolymer; add 135mL of deionized water at 10°C to the prepolymer under vigorous stirring with an emulsifier at a speed of 2400 rpm for emulsification, and immediately add the N-methylpyrrolidone solution of BPPA after adding water, Among them, the mass of BPPA is 13.91g, and post-chain extension is carried out while emulsifying, and the emulsion is obtained by emulsifying for 15 minutes; then the AWHBPU aqueous solution neutralized with salt-forming agent B is added to the emulsion, and the stirring is continued for 5 minutes to mix evenly, and then it is left to stand for 12 hours Defoaming, and finally rotary evaporation to remove butanone and N-methylpyrrolidone, to obtain a hyperbranched blended hard segment modified chain-extended flame-retardant aqueous polyurethane emulsion with a solid content of 30%.

The AWHBPU aqueous solution neutralized with the salt forming agent B is obtained by adding 1.03 g of TEA and mixing uniformly after 7.08 g of AWHBPU is prepared into an aqueous solution with 40 mL of deionized water.

The chain-extended flame-retardant water-based polyurethane emulsion and its film after modification of the hyperbranched blended hard segment prepared in this example were tested as follows:

(1) The emulsion does not delaminate or precipitate after being placed at room temperature for one year;

(2) Recording that the tensile strength of the film is 32.1MPa;

(3) The limiting oxygen index of the film was measured to be 30.0.

Example 3

Add 53.52g of PTMG2000 to a 250mL three-necked flask with a stirring device, vacuumize and stir at 110°C for 2h to remove moisture, cool down to 80°C, add 4.20g of DMPA and 19.86g of TDI, connect a condenser, and then raise the temperature to 85°C ℃ for 2 hours, until the -NCO content does not change, then add 6.00g of Fyrol-6 and 20g butanone to continue the reaction for 3 hours, until the -NCO content does not change, after cooling down to 40 ℃, add 3.18g of TEA into the three-necked flask Neutralize and react for 10 minutes to obtain a prepolymer; add 165mL of deionized water at 5°C to the prepolymer under vigorous stirring with an emulsifier at a speed of 2400 rpm for emulsification, and immediately add the acetone solution of BPPO after adding water , where the mass of BPPO is 6.6g, post-chain extension is carried out while emulsifying, emulsifying for 15min to obtain an emulsion; then add the AWHBPU aqueous solution neutralized with salt-forming agent B into the emulsion, continue stirring for 5min to mix evenly, and let it stand for 12h Defoaming, rotary evaporation to remove acetone and butanone, to obtain a hyperbranched blended hard segment modified chain-extended flame-retardant aqueous polyurethane emulsion with a solid content of 30%.

The AWHBPU aqueous solution neutralized with the salt forming agent B is obtained by adding 0.30 g of TEA and mixing uniformly after 2.06 g of AWHBPU is prepared into an aqueous solution with 10 mL of deionized water.

The chain-extended flame-retardant water-based polyurethane emulsion and its film after modification of the hyperbranched blended hard segment prepared in this example were tested as follows:

(1) The emulsion does not delaminate or precipitate after being placed at room temperature for one year;

(2) Recording the tensile strength of the film is 30.6MPa;

(3) The limiting oxygen index of the film was measured to be 30.2.

Claims (5)

1. a kind of hyperbranched blending hard segment modification rear chain extension flame retardant water-based polyurethane, it is characterized in that: described water-based polyurethane is prepared by following method: Dehydrate the macromolecular polyol at 110°C-140°C for 1h-3h, add a hydrophilic chain extender at 40°C-80°C, then add diisocyanate, raise the temperature to 80°C-85°C, and react until the -NCO content is no longer Change, add phosphorus-containing polyol small molecules to continue the reaction until the -NCO content no longer changes, cool down to 20 ° C ~ 40 ° C, add salt-forming agent A to react for 10 min ~ 30 min, to obtain a prepolymer; add 0 to the prepolymer ℃～10℃ water for emulsification, immediately after adding water, add acetone/butanone/N-methylpyrrolidone solution containing phosphorus diamine chain extender, emulsify for 10min～15min to obtain emulsion; neutralize with salt forming agent B Add the AWHBPU aqueous solution into the emulsion, continue to emulsify for 5 minutes to 10 minutes, and finally remove the acetone/butanone/N-methylpyrrolidone by rotary evaporation to obtain the emulsion, which is a kind of hyperbranched blended hard segment modified and chain extended flame retardant Waterborne polyurethane; The macromolecular polyol is a polyether or polyester polyol with a molecular weight greater than 500; The hydrophilic chain extender includes more than one of dimethylolpropionic acid, 2,2-dimethylolbutyric acid and 2,3-dihydroxysuccinic acid; The diisocyanate is more than one of isophorone diisocyanate, toluene diisocyanate, 1,6-hexyl diisocyanate, dicyclohexylmethane diisocyanate and tetramethylcyclohexyl diisocyanate; The phosphorus-containing polyol small molecules are N,N-bis(2-hydroxyethyl)aminomethyl phosphonate, bis(2-hydroxyethyl)methyl phosphate, bis(2-hydroxyethyl)benzene base phosphate, bis(3-hydroxyphenyl)methyl phosphate or bis(3-hydroxyphenyl)phenyl phosphate; The salt-forming agent A and the salt-forming agent B respectively independently comprise triethylamine or tri-n-butylamine; The phosphorus-containing diamine chain extender includes bis(aminophenyl)phenylphosphine oxide, 2,4,8,10-tetraoxa-3,9-diphosphaspiro-3,9-dioxo- More than one of 3,9-bis(3-aminophenyl), bis(3-aminophenyl)phenylphosphine oxide and aminophenylphosphine oxide; The AWHBPU is the hyperbranched water-based polyurethane using acetic anhydride as an end-capping agent described in the patent application CN 102851987A; The AWHBPU aqueous solution neutralized with the salt-forming agent B is obtained by configuring the AWHBPU water into an aqueous solution with a mass concentration of 10% to 40%, adding the salt-forming agent B, and mixing uniformly; Taking the mass sum of the macromolecular polyol, hydrophilic chain extender, diisocyanate, phosphorus-containing polyol small molecule, salt-forming agent A, salt-forming agent B, phosphorus-containing diamine chain extender and AWHBPU as the total mass, Based on the total mass as 100%, the mass fraction of the hydrophilic chain extender is 3% to 10%, the mass fraction of the phosphorus-containing polyol small molecule is 5% to 20%, and the mass fraction of the phosphorus-containing diamine chain extender is The mass fraction is 5% to 20%, and the mass fraction of AWHBPU is 1% to 15%; Define r as the molar weight of isocyanate and hydroxyl group in macromolecular polyol, hydrophilic chain extender, diisocyanate, phosphorus-containing polyol small molecule, salt-forming agent A, salt-forming agent B and phosphorus-containing diamine chain extender Molar ratio, 2>r>1; The molar weight of the salt-forming agent A is the same as the content of the carboxyl group in the hydrophilic chain extender, and the molar weight of the salt-forming agent B is the same as the content of the carboxyl group in the AWHBPU; The molar amount of amine groups in the phosphorus-containing diamine chain extender is less than the molar amount of isocyanate groups participating in post-chain extension in the prepolymer. 2. A kind of hyperbranched blending hard segment modification according to claim 1, chain extension flame retardant water-based polyurethane, is characterized in that: described macromolecular polyol comprises polypropylene glycol, polyglycerol, polytetrahydrofuran ether glycol and One or more kinds of polycaprolactone diols. 3. A hyperbranched blended hard segment modified chain-extended flame-retardant water-based polyurethane according to claim 1 or 2, characterized in that: when adding small molecules of phosphorus-containing polyols, methyl ethyl ketone is added to adjust the viscosity. 4. According to claim 1 or 2, a kind of hyperbranched blended hard segment modified chain-extended flame-retardant waterborne polyurethane is characterized in that: the purity of the water is above the purity of deionized water. 5. A hyperbranched blended hard segment modified chain-extended flame-retardant water-based polyurethane according to claim 3, characterized in that: the purity of the water is above the purity of deionized water.