CN109280162A - A kind of preparation method of flame retardant polyether polyol and preparation method thereof and halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles - Google Patents
A kind of preparation method of flame retardant polyether polyol and preparation method thereof and halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles Download PDFInfo
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- CN109280162A CN109280162A CN201810929111.9A CN201810929111A CN109280162A CN 109280162 A CN109280162 A CN 109280162A CN 201810929111 A CN201810929111 A CN 201810929111A CN 109280162 A CN109280162 A CN 109280162A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2203/00—Macromolecular materials of the coating layers
- D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06N2203/068—Polyurethanes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
- D06N2209/067—Flame resistant, fire resistant
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- Dispersion Chemistry (AREA)
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Abstract
The invention belongs to fire proofing technical field, the preparation method of a kind of flame retardant polyether polyol and preparation method thereof and halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles is provided.The preparation method of flame retardant polyether polyol includes: to react PPG with isocyanates to obtain the first performed polymer；The preparation method design science, it is easy to operate, it is suitable for large-scale industrial production；Flame retardant effect and the excellent flame retardant polyether polyol of modified effect can be prepared.The preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles includes: using polyether polyol provided by the invention, flame-retardant modified to Aqueous Polyurethane Coating Agent progress soft segment in the form of partially substituting soft segment polyethers, the extinguishing waterborn polyurethane coating agent enable overcomes the inherent shortcoming of blended extinguishing waterborn polyurethane；And small using additive amount, flame retardant effect is excellent.
Description
Technical field
The invention belongs to fire proofing technical fields, specifically, being related to a kind of flame retardant polyether polyol and its preparation side
The preparation method of method and halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles.
Background technique
With the raising of living standards of the people and the enhancing of awareness of safety, the flame retardant property of textile is more by people's
Pay attention to.Various countries are proposed the household textiles of the states such as stringent flame-retardancy requirements, especially America and Europe to textile raw material and product, must
Must have flame retarding function just can enter market.
Two kinds are broadly divided into the processing method of Fire-proof Finishing Agents for Textile at present, one is uses to prepare fire-retardant polyester fibre, main
It to be obtained using the method for co-blended copolymerization, fire retardant or ignition-proof element is introduced in polyester fiber preparation process, realizes fiber
It is fire-retardant, for preparing flame retardant textiles；However, the polyester fiber obtained using this kind of method that there are application surfaces is narrow, at
The disadvantages of this is high.Another method is to use flame-proof treatment, including pad the method for baking, dipping drying method, coating, organic solvent
Method, the method for spraying treatment, wherein coating has wider application because of the features such as its is easy to operate, flame retarding efficiency is high.
Top finish is to keep fabric positive and negative in one layer of (or multilayer) film high-molecular compound in fabric surface even application
Face has the surface dressing technology of different function.Common coating agent has organosilicon, natural rubber, synthetic rubber, polyacrylic acid
Ester, polyurethane, polytetrafluoroethylene (PTFE) and polyvinyl chloride etc., respectively have its own advantage and disadvantage.Wherein, Waterborne Polyurethane Fabric Coatings are not only
Appearance of fabrics and feel can be improved, make fabric functional, have the specific functions such as waterproof, moisture-inhibiting, also as using water as dispersion
Agent makes it have the advantages that environmental protection, safe, easy to use and be concerned.
At present for there are two types of the fire-retardant researchs of Aqueous Polyurethane Coating Agent, one kind be utilized in polyurethane coating agent plus
Enter that common fire retardant is fire-retardant to achieve the purpose that, such as document " application of the expansion type flame retardant in dacron coating
Can " in Zeng Jun et al. expansion type flame retardant (being compounded by ammonium polyphosphate, pentaerythrite, melamine) is added in coating agent
Flame-proof treatment for fabric；Document " the preparation of pressurization closed graphene oxide/waterborne polyurethane nanometer composite material and fire-retardant
Performance " it is middle that wait people quietly uses in-situ polymerization and autonomous dress method respectively recklessly, it is compound to be prepared for graphene oxide/aqueous polyurethane nano
Material.Another method be will with ignition-proof element and have can reactive group compound, in the form of chemical bond introduce water
Property polyurethane molecular in, obtain in reactive extinguishing waterborn polyurethane, such as document Chen He et al. with dibromoneopentyl glycol to expand
Ignition-proof element is introduced into aqueous polyurethane by chain agent with the flame-retardant modified mode of hard section.
The studies above has the following problems: (1) fire retardant is volatile, molten in the fire-retardant Aqueous Polyurethane Coating Agent of blending type
Out, migration etc., so that flame-retardant textile be made to lose flame retardant effect；(2) existing response type Aqueous Polyurethane Coating Agent is using introducing
Halide-containing realizes that coating is fire-retardant, is unfavorable for environmental protection.
Summary of the invention
For deficiency above-mentioned in the prior art, it is polynary that the first object of the present invention is the provision of a kind of flame retarding polyether
Alcohol；The flame retardant polyether polyol has flame retardant effect excellent, can substitute the form of soft segment polyethers to Aqueous Polyurethane Coating Agent
It is flame-retardant modified to carry out soft segment, thus the features such as enhancing its anti-flammability, overcome the inherent shortcoming of blending type extinguishing waterborn polyurethane.
For deficiency above-mentioned in the prior art, the second object of the present invention is the provision of a kind of flame retardant polyether polyol
Preparation method；The preparation method design science, it is easy to operate, it is suitable for large-scale industrial production.
For deficiency above-mentioned in the prior art, the third object of the present invention is the provision of a kind of Halogen resistance used for textiles
Fire the preparation method of Aqueous Polyurethane Coating Agent；The preparation method uses polyether polyol provided by the invention, partially to substitute
It is flame-retardant modified that the form of soft segment polyethers carries out soft segment to Aqueous Polyurethane Coating Agent；Obtained extinguishing waterborn polyurethane coating agent energy
Enough overcome the inherent shortcoming of blended extinguishing waterborn polyurethane；And small using additive amount, flame retardant effect is excellent.
In order to achieve the above object, the solution that the present invention uses is:
A kind of preparation method of flame retardant polyether polyol, comprising the following steps: by polyphosphoric acids and pentaerythrite in 50-80
DEG C, 0.1MPa hybrid reaction, flow back 2-4h, obtain the first mixture；By the first mixture, polyalcohol and potassium hydroxide in vacuum
Water-less environment mixing, after being warming up to 80-100 DEG C, control pressure is 0.1-0.5MPa, and epoxide is added；Then it is warming up to
100-120 DEG C, control pressure is 0.05-0.1MPa, reacts 1-3h, obtains crude flame retarding polyether；It is more to be refining to obtain polyethers again
First alcohol.
A kind of flame retardant polyether polyol that the preparation method using above-mentioned flame retardant polyether polyol is prepared.
A kind of preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles, comprising the following steps: by polyoxygenated
Propylene glycol (PPG) reacts to obtain the first performed polymer with isocyanates；After being diluted using acetone to the first performed polymer, then plus
Enter above-mentioned polyether polyol, reaction obtains the second performed polymer；When second performed polymer is cooled to 50 DEG C, is obtained with chain extender reaction
Three performed polymers；Third performed polymer reacts to obtain the 4th performed polymer with triethylamine；4th performed polymer and deionized water are stirred, decompression
Extinguishing waterborn polyurethane coating agent is obtained after distillation removal solvent.
A kind of flame retardant polyether polyol provided by the invention and preparation method thereof and halogen-free flameproof used for textiles are aqueous poly-
The beneficial effect of the preparation method of urethane coating agent is:
The preparation method of flame retardant polyether polyol provided by the invention, using polyphosphoric acid and pentaerythrite in certain reaction
Under the conditions of carry out reacting obtained polyether polyol, pass through parameters in the scientific design and preparation process to experimental procedure
Reasonable control, it is polynary that the fire-retardant and excellent flame retarding polyether of modified effect can be prepared in coordinated between parameters
Alcohol.
Flame retardant polyether polyol provided by the invention, the preparation method preparation of flame retardant polyether polyol provided by the present invention
It obtains；The flame retardant polyether polyol has flame retardant effect excellent, can substitute the form of soft segment polyethers to aqueous polyurethane coating
Agent progress soft segment is flame-retardant modified, thus the features such as enhancing its anti-flammability, overcome the inherent shortcoming of blending type extinguishing waterborn polyurethane.
The preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles provided by the invention, the preparation method use
Polyether polyol provided by the invention, it is fire-retardant to Aqueous Polyurethane Coating Agent progress soft segment in the form of partially substituting soft segment polyethers
It is modified；And in the scientific design and preparation process for passing through preparation step parameters Reasonable Regulation And Control, the flame-retardant water made
Property polyurethane coating agent can overcome the inherent shortcoming of blended extinguishing waterborn polyurethane；And, fire-retardant effect small using additive amount
Fruit is excellent.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to a kind of flame retardant polyether polyol provided in an embodiment of the present invention and preparation method thereof and nothing used for textiles
The preparation method of halogen extinguishing waterborn polyurethane coating agent is specifically described.
A kind of preparation method of flame retardant polyether polyol, comprising the following steps:
By polyphosphoric acids and pentaerythrite in 50-80 DEG C, 0.1MPa hybrid reaction, flow back 2-4h, obtains the first mixture；
Wherein, inventor creatively has found, controls when by the mass ratio of polyphosphoric acids and pentaerythrite as 0.8:1, and reaction more adds
Entirely.
Then the first mixture, polyalcohol and potassium hydroxide are mixed in vacuum water-less environment, after being warming up to 80-100 DEG C,
Control pressure is 0.1-0.5MPa, and epoxide is added.
Then it is warming up to 100-120 DEG C, control pressure is 0.05-0.1MPa, reacts 1-3h, obtains crude flame retarding polyether；
Again through being refining to obtain polyether polyol.
It should be noted that in the present embodiment, polyether polyol here is the mixture of a variety of polyether polyol, warp
Conventional substances detection is mainly the substance of following three kinds of molecular formula:
It should be noted that in the present embodiment, purification uses conventional process, specific method is described as follows: prepared
1 part of crude flame retarding polyether in be added 1.2-2.5% phosphoric acid (85%), then thereto be added 0.5-1.2% diatomite
Adsorbent is adsorbed, filter, dry after obtain substantially without the remaining purification polyether polyol of catalyst.
Inventor creatively has found, each by being related in the scientific design and each step of above-mentioned preparation step
The polyether polyols with excellent fire-retardancy and modified performance are prepared in mutual coordinated between item parameter, common synergy
Alcohol.
A kind of preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles, comprising the following steps: by PPG with it is different
Polyisocyanate reactant obtains the first performed polymer.It should be noted that in the present embodiment, specifically, PPG and isocyanates are pressed 1:
1, the mass ratio of the material of 1:2 or 2:1 is added in the four-hole boiling flask equipped with reflux condensing tube, mechanical stirring and thermometer, and heating is anti-
It should obtain the first performed polymer.
Then, after being diluted using acetone to the first performed polymer, above-mentioned polyether polyol is added, reaction obtains second
Performed polymer.Further, in the present embodiment, specifically, it is added into the first performed polymer and is with the mass ratio of the first performed polymer
The acetone of 3-8:92-97 is diluted, and it is more that polyethers provided by the invention then is added according to the 6-15% of the first prepolymer mass
First alcohol reacts 1h, obtains the second performed polymer.
Then, when the second performed polymer is cooled to 50 DEG C, third performed polymer is obtained with chain extender reaction.In the present embodiment
In, specifically, when the temperature of the second performed polymer is down to 50 DEG C, the chain extender reaction 2h of the second prepolymer mass 5-8% is added；
It should be noted that in the present embodiment, chain extender includes 2,2- dihydromethyl propionic acid (DMPA), third performed polymer is obtained.It needs
It is noted that n-butylamine, which can be used, in third performed polymer surveys whether its NCO% content reaches theoretical value.
Then in third performed polymer and triethylamine and salt-forming reaction obtains the 4th performed polymer.
Then the 4th performed polymer and deionized water are subjected to high-speed stirred dispersion；In the present embodiment, further, go from
The additive amount of sub- water and the additive amount of acetone are consistent；Then it carries out obtaining the poly- ammonia of extinguishing waterborn after removing solvent after vacuum distillation 3h
Ester coating agent.
Inventor creatively has found that the preparation method uses polyether polyol provided by the invention, soft partially to substitute
It is flame-retardant modified that the form of section polyethers carries out soft segment to Aqueous Polyurethane Coating Agent；And by the scientific design of preparation step, and
The Reasonable Regulation And Control of parameters in preparation process, the extinguishing waterborn polyurethane coating agent enable overcome blended flame-retardant water
The inherent shortcoming of property polyurethane；And small using additive amount, flame retardant effect is excellent.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles is present embodiments provided, including following
Step:
PPG and isocyanates are added by the mass ratio of the material of 2:1 equipped with reflux condensing tube, mechanical stirring and thermometer
In four-hole boiling flask, temperature reaction obtains the first performed polymer；Being added into the first performed polymer with the mass ratio of the first performed polymer is 3:
97 acetone is diluted, and polyether polyol provided by the invention, reaction then is added according to the 15% of the first prepolymer mass
1h obtains the second performed polymer；When the temperature of the second performed polymer is down to 50 DEG C, the DMPA that the second prepolymer mass 6% is added is anti-
Answer 2h；Then in third performed polymer and triethylamine and salt-forming reaction obtains the 4th performed polymer；Then by the 4th performed polymer and go from
Sub- water carries out high-speed stirred dispersion, and deionized water is consistent with the additive amount of acetone；Then solvent is removed after carrying out vacuum distillation 3h
After obtain extinguishing waterborn polyurethane coating agent.
Embodiment 2
A kind of preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles is present embodiments provided, including following
Step:
PPG and isocyanates are added by the mass ratio of the material of 1:2 equipped with reflux condensing tube, mechanical stirring and thermometer
In four-hole boiling flask, temperature reaction obtains the first performed polymer；Being added into the first performed polymer with the mass ratio of the first performed polymer is 8:
92 acetone is diluted, and polyether polyol provided by the invention, reaction then is added according to the 15% of the first prepolymer mass
1h obtains the second performed polymer；When the temperature of the second performed polymer is down to 50 DEG C, the DMPA that the second prepolymer mass 6% is added is anti-
Answer 2h；Then in third performed polymer and triethylamine and salt-forming reaction obtains the 4th performed polymer；Then by the 4th performed polymer and go from
Sub- water carries out high-speed stirred dispersion, and deionized water is consistent with the additive amount of acetone；Then solvent is removed after carrying out vacuum distillation 3h
After obtain extinguishing waterborn polyurethane coating agent.
Embodiment 3
A kind of preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles is present embodiments provided, including following
Step:
PPG and isocyanates are added by the mass ratio of the material of 1:1 equipped with reflux condensing tube, mechanical stirring and thermometer
In four-hole boiling flask, temperature reaction obtains the first performed polymer；Being added into the first performed polymer with the mass ratio of the first performed polymer is 5:
95 acetone is diluted, and polyether polyol provided by the invention, reaction then is added according to the 15% of the first prepolymer mass
1h obtains the second performed polymer；When the temperature of the second performed polymer is down to 50 DEG C, the DMPA that the second prepolymer mass 6% is added is anti-
Answer 2h；Then in third performed polymer and triethylamine and salt-forming reaction obtains the 4th performed polymer；Then by the 4th performed polymer and go from
Sub- water carries out high-speed stirred dispersion, and deionized water is consistent with the additive amount of acetone；Then solvent is removed after carrying out vacuum distillation 3h
After obtain extinguishing waterborn polyurethane coating agent.
Embodiment 4
A kind of preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles is present embodiments provided, including following
Step:
PPG and isocyanates are added by the mass ratio of the material of 1:1 equipped with reflux condensing tube, mechanical stirring and thermometer
In four-hole boiling flask, temperature reaction obtains the first performed polymer；Being added into the first performed polymer with the mass ratio of the first performed polymer is 5:
95 acetone is diluted, and polyether polyol provided by the invention, reaction then is added according to the 6% of the first prepolymer mass
1h obtains the second performed polymer；When the temperature of the second performed polymer is down to 50 DEG C, the DMPA that the second prepolymer mass 5% is added is anti-
Answer 2h；Then in third performed polymer and triethylamine and salt-forming reaction obtains the 4th performed polymer；Then by the 4th performed polymer and go from
Sub- water carries out high-speed stirred dispersion, and deionized water is consistent with the additive amount of acetone；Then solvent is removed after carrying out vacuum distillation 3h
After obtain extinguishing waterborn polyurethane coating agent.
Embodiment 5
A kind of preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles is present embodiments provided, including following
Step:
PPG and isocyanates are added by the mass ratio of the material of 1:1 equipped with reflux condensing tube, mechanical stirring and thermometer
In four-hole boiling flask, temperature reaction obtains the first performed polymer；Being added into the first performed polymer with the mass ratio of the first performed polymer is 5:
95 acetone is diluted, and polyether polyol provided by the invention, reaction then is added according to the 12% of the first prepolymer mass
1h obtains the second performed polymer；When the temperature of the second performed polymer is down to 50 DEG C, the DMPA that the second prepolymer mass 5% is added is anti-
Answer 2h；Then in third performed polymer and triethylamine and salt-forming reaction obtains the 4th performed polymer；Then by the 4th performed polymer and go from
Sub- water carries out high-speed stirred dispersion, and deionized water is consistent with the additive amount of acetone；Then solvent is removed after carrying out vacuum distillation 3h
After obtain extinguishing waterborn polyurethane coating agent.
Embodiment 6
A kind of preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles is present embodiments provided, including following
Step:
PPG and isocyanates are added by the mass ratio of the material of 1:2 equipped with reflux condensing tube, mechanical stirring and thermometer
In four-hole boiling flask, temperature reaction obtains the first performed polymer；Being added into the first performed polymer with the mass ratio of the first performed polymer is 8:
92 acetone is diluted, and polyether polyol provided by the invention, reaction then is added according to the 9% of the first prepolymer mass
1h obtains the second performed polymer；When the temperature of the second performed polymer is down to 50 DEG C, the DMPA that the second prepolymer mass 8% is added is anti-
Answer 2h；Then in third performed polymer and triethylamine and salt-forming reaction obtains the 4th performed polymer；Then by the 4th performed polymer and go from
Sub- water carries out high-speed stirred dispersion, and deionized water is consistent with the additive amount of acetone；Then solvent is removed after carrying out vacuum distillation 3h
After obtain extinguishing waterborn polyurethane coating agent.
Comparative example 1
This comparative example provides a kind of preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles, including following
Step:
PPG and isocyanates are added by the mass ratio of the material of 1:1 equipped with reflux condensing tube, mechanical stirring and thermometer
In four-hole boiling flask, temperature reaction obtains the first performed polymer；Being added into the first performed polymer with the mass ratio of the first performed polymer is 2:
98 acetone is diluted, and polyether polyol provided by the invention, reaction then is added according to the 5% of the first prepolymer mass
1h obtains the second performed polymer；When the temperature of the second performed polymer is down to 50 DEG C, the DMPA that the second prepolymer mass 4% is added is anti-
Answer 2h；Then in third performed polymer and triethylamine and salt-forming reaction obtains the 4th performed polymer；Then by the 4th performed polymer and go from
Sub- water carries out high-speed stirred dispersion, and deionized water is consistent with the additive amount of acetone；Then solvent is removed after carrying out vacuum distillation 3h
After obtain extinguishing waterborn polyurethane coating agent.
Comparative example 2
This comparative example provides a kind of preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles, including following
Step:
PPG and isocyanates are added by the mass ratio of the material of 1:1 equipped with reflux condensing tube, mechanical stirring and thermometer
In four-hole boiling flask, temperature reaction obtains the first performed polymer；Being added into the first performed polymer with the mass ratio of the first performed polymer is 9:
91 acetone is diluted, and polyether polyol provided by the invention, reaction then is added according to the 16% of the first prepolymer mass
1h obtains the second performed polymer；When the temperature of the second performed polymer is down to 50 DEG C, the DMPA that the second prepolymer mass 9% is added is anti-
Answer 2h；Then in third performed polymer and triethylamine and salt-forming reaction obtains the 4th performed polymer；Then by the 4th performed polymer and go from
Sub- water carries out high-speed stirred dispersion, and deionized water is consistent with the additive amount of acetone；Then solvent is removed after carrying out vacuum distillation 3h
After obtain extinguishing waterborn polyurethane coating agent.
Comparative example 3
This comparative example provides a kind of preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles, including following
Step:
PPG and isocyanates are added by the mass ratio of the material of 1:1 equipped with reflux condensing tube, mechanical stirring and thermometer
In four-hole boiling flask, temperature reaction obtains the first performed polymer；Being added into the first performed polymer with the mass ratio of the first performed polymer is 5:
95 acetone is diluted, and obtains the second performed polymer；When the temperature of the second performed polymer is down to 50 DEG C, the second pre-polymerization constitution is added
The DMPA of amount 5% reacts 2h；Then in third performed polymer and triethylamine and salt-forming reaction obtains the 4th performed polymer；Then by the 4th
Performed polymer and deionized water carry out high-speed stirred dispersion, and deionized water is consistent with the additive amount of acetone；Then it is evaporated under reduced pressure
Extinguishing waterborn polyurethane coating agent is obtained after removing solvent after 3h.
Experimental example 1
Experimental method: experimental group 1-9 is set by embodiment 1-6 and comparative example 1-3, test experiments group 1-9 is mentioned respectively
Emulsion particle diameter, stability of emulsion, the limit oxygen index LOL of glue film, the glue film of the extinguishing waterborn polyurethane coating agent of confession stretch strong
Degree and glue film elongation at break；Test method is as follows:
Emulsion particle diameter: using Dandong Bai Te BT-9300HT to lotion carry out laser particle size analysis, 25 DEG C of test temperature, surely
Fix time 1.5min；
Stability of emulsion: being added the lotion of 5mL in centrifuge tube, and revolving speed 2000r/min is centrifuged 10min, observes lotion
Delamination；If illustrating emulsion-stabilizing without precipitating；
The preparation of glue film: polyurethane aqueous coating agent is poured into Teflon mould, allows its natural casting film-forming, so
After be placed at room temperature for 4 days, after its substantially dry, be placed on being heat-treated 1 day in baking oven, temperature setting be 65 DEG C, then take
It is placed in out spare in desiccator；
The limit oxygen index of glue film measures: glue film is cut into 150 × 50mm2Batten, every group 10, using ZR-311
Limit oxygen index instrument is tested；
The Mechanics Performance Testing of glue film: glue film is cut into defined dumbbell shape sample, and (part of detecting is 4 × 16mm2),
Its tensile strength, rate of extension 20mm/min are measured using XLL100A type tensile testing machine, test temperature is 25 DEG C, every group
5 samples are tested, results are averaged；
The test for the extinguishing waterborn polyurethane coating agent that experimental group 1-9 is provided is shown in Table 1:
The performance test for the extinguishing waterborn polyurethane coating agent that 1 experimental group 1-9 of table is provided
From the data in table 1, it can be seen that compared to comparative example 9, using the nothing used for textiles of embodiment 1-6 and comparative example 1-2 offer
The performance for the Aqueous Polyurethane Coating Agent that the preparation method of halogen extinguishing waterborn polyurethane coating agent is prepared is more excellent；It compares
It is prepared in the preparation method for the halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles that comparative example 1-2, embodiment 1-6 are provided
Aqueous Polyurethane Coating Agent performance it is more excellent；It is above-mentioned the experimental results showed that, using experiment provided in an embodiment of the present invention
The extinguishing waterborn polyurethane coating agent that method is prepared can overcome the inherent shortcoming of blended extinguishing waterborn polyurethane；It uses
Additive amount is small, and flame retardant effect is more excellent.
In conclusion flame retardant polyether polyol provided by the invention has flame retardant effect excellent, soft segment polyethers can be substituted
Form to Aqueous Polyurethane Coating Agent carry out soft segment it is flame-retardant modified, to enhance its anti-flammability, overcome blending type extinguishing waterborn
The features such as inherent shortcoming of polyurethane.The preparation method design science of flame retardant polyether polyol provided by the invention, it is easy to operate,
Suitable for large-scale industrial production.The preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles provided by the invention is adopted
With polyether polyol provided by the invention, soft segment resistance is carried out to Aqueous Polyurethane Coating Agent in the form of partially substituting soft segment polyethers
Combustion is modified；Obtained extinguishing waterborn polyurethane coating agent can overcome the inherent shortcoming of blended extinguishing waterborn polyurethane；And
Small using additive amount, flame retardant effect is excellent.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of flame retardant polyether polyol, it is characterised in that: by polyphosphoric acids and pentaerythrite 50-80 DEG C,
0.1MPa hybrid reaction, flow back 2-4h, obtains the first mixture；By first mixture, polyalcohol and potassium hydroxide in true
Empty water-less environment mixing, after being warming up to 80-100 DEG C, control pressure is 0.1-0.5MPa, and epoxide is added；Then it heats up
To 100-120 DEG C, control pressure is 0.05-0.1MPa, reacts 1-3h, obtains crude flame retarding polyether；Again through being refining to obtain polyethers
Polyalcohol.
2. the preparation method of flame retardant polyether polyol according to claim 1, it is characterised in that: the polyphosphoric acids and institute
The mass ratio for stating pentaerythrite is 0.8:1.
3. a kind of flame retarding polyether that the preparation method using flame retardant polyether polyol as claimed in claim 2 is prepared is polynary
Alcohol.
4. a kind of preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles, it is characterised in that: the following steps are included:
Polyoxypropyleneglycol is reacted to obtain the first performed polymer with isocyanates；First performed polymer is carried out using acetone
After dilution, polyether polyol as claimed in claim 3 is added, reaction obtains the second performed polymer；The second performed polymer cooling
When to 50 DEG C, third performed polymer is obtained with chain extender reaction；The third performed polymer reacts to obtain the 4th performed polymer with triethylamine；
4th performed polymer and deionized water are stirred, obtain extinguishing waterborn polyurethane lotion after vacuum distillation removal solvent.
5. the preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles according to claim 4, feature exist
In: the ratio of the amount of the substance of the polyoxypropyleneglycol and the isocyanates is 1:1,1:2 or 2:1.
6. the preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles according to claim 4, feature exist
In: the mass ratio of the acetone and first performed polymer is 3-8:92-97.
7. the preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles according to claim 4, feature exist
In: the mass ratio of the polyether polyol and first performed polymer is 6-15:100.
8. the preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles according to claim 4, feature exist
In: the mass ratio of the chain extender and second performed polymer is 5-8:100.
9. the preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles according to claim 8, feature exist
In: the chain extender includes 2,2- dihydromethyl propionic acid.
10. the preparation method of halogen-free flameproof Aqueous Polyurethane Coating Agent used for textiles according to claim 4, feature exist
In: the mass ratio of the deionized water and the acetone is 1:1.
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| CN103073692A (en) * | 2013-01-31 | 2013-05-01 | 烟台前进化工有限公司 | Producing method of water-base polyurethane |
| CN107057032A (en) * | 2017-04-26 | 2017-08-18 | 合肥科天水性科技有限责任公司 | A kind of high-performance water-based polyurethane resin and preparation method for spinning coating |
| CN107383359A (en) * | 2017-08-21 | 2017-11-24 | 什邡市太丰新型阻燃剂有限责任公司 | A kind of anti-inflaming polyurethane hard foam PPG and preparation method thereof |
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|---|---|---|---|---|
| CN1749291A (en) * | 2005-09-29 | 2006-03-22 | 上海申真企业发展有限公司 | Flame-retardant polyurethane water dispersion and its preparing method |
| CN101831168A (en) * | 2010-05-14 | 2010-09-15 | 上海克络蒂材料科技发展有限公司 | Polyurethane rigid foam exterior wall thermal insulation material with high flame retardancy and preparation method thereof |
| CN103073692A (en) * | 2013-01-31 | 2013-05-01 | 烟台前进化工有限公司 | Producing method of water-base polyurethane |
| CN107057032A (en) * | 2017-04-26 | 2017-08-18 | 合肥科天水性科技有限责任公司 | A kind of high-performance water-based polyurethane resin and preparation method for spinning coating |
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Application publication date: 20190129 |