CN114773565A - Flame-retardant thermoplastic polyurethane resin, preparation method and application thereof, and protective clothing - Google Patents
Flame-retardant thermoplastic polyurethane resin, preparation method and application thereof, and protective clothing Download PDFInfo
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- CN114773565A CN114773565A CN202210222930.6A CN202210222930A CN114773565A CN 114773565 A CN114773565 A CN 114773565A CN 202210222930 A CN202210222930 A CN 202210222930A CN 114773565 A CN114773565 A CN 114773565A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/08—Heat resistant; Fire retardant
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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
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
- C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- A—HUMAN NECESSITIES
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Abstract
The inventionProvided is a flame retardant thermoplastic polyurethane resin, wherein the polyurethane resin comprises at least the following structural units:
wherein R is1Is a polyol, R2Is isocyanate. The polyurethane resin provided by the invention contains a large amount of isocyanurate structures with flame retardant property, the flame retardant grade of the isocyanurate structures is greater than or equal to UL-94VTM-1, and the transparent polyurethane resin has good transparency; no halogen is contained, and the environment is protected; the flame retardant does not contain phosphorus element, and after long-term storage, the flame retardant grade is not reduced because of easy water absorption, and the performance of the material is not obviously attenuated. Firstly, adding aliphatic diisocyanate and phthalic anhydride polyester polyol to form a carbamate structure; then adding a catalyst, carrying out trimerization reaction on an excessive isocyanate structure under the protection of nitrogen to form an isocyanurate structure, and finally carrying out chain extension under the action of a chain extender to form macromolecular polyurethane resin. In this method, a plasticizer acts as a solvent for the reaction while adjusting the softness of the polyurethane resin.
Description
Technical Field
The invention relates to a flame-retardant thermoplastic polyurethane resin, a preparation method of the flame-retardant thermoplastic polyurethane resin, application of the flame-retardant thermoplastic polyurethane resin in preparation of positive pressure protective clothing, and the positive pressure protective clothing.
Background
The existing nuclear power disposable positive pressure protective clothing product adopts a PVC material as a flame-retardant fabric, the PVC material contains halogen, great environmental pollution is generated during waste treatment (deep burying and burning), and particularly chlorine-containing acidic substances and dioxin released during burning have strong corrosiveness and carcinogenicity, so that the problems of environmental pollution, equipment destruction and human safety are caused. At present, halogen-free flame retardant polyurethane (TPU) in the market mostly adopts phosphorus-containing flame retardant to be blended with TPU resin particles and then is calendered to form a film. The addition proportion of the flame retardant is required to exceed 20 percent in order to reach the grade UL-94VTM-0 required by the flame retardant grade of the product, and the calendered film has poor transparency or the transparency is reduced after being placed at the addition proportion reaching the flame retardant grade. In addition, the phosphorus-containing flame retardant has hygroscopicity, the flame retardant grade is reduced after long-term storage, and the material performance is obviously attenuated.
SUMMARY OF THE PATENT FOR INVENTION
The invention provides a polyurethane resin with flame retardant property, which is used for overcoming the defects of the prior art, and the flame retardant thermoplastic polyurethane resin does not contain phosphorus element and has basically unchanged transparency after being placed for a long time.
In one aspect, the present invention provides a flame retardant thermoplastic polyurethane resin characterized in that the transparent flame retardant thermoplastic polyurethane resin comprises at least the following structural units:
In another aspect, the present invention also provides a method for preparing a flame retardant thermoplastic polyurethane resin, characterized in that the method comprises the steps of:
a. under the conditions of stirring and nitrogen protection, mixing aliphatic diisocyanate, phthalic anhydride polyester polyol and a plasticizer to obtain a mixture 1; wherein the mole number of the aliphatic diisocyanate is larger than that of the phthalic anhydride polyester polyol; heating the mixture 1 to 60-100 ℃, and reacting for 10-60 minutes at the temperature to obtain a reaction mixture 1;
b. adding a catalyst into the reaction mixture 1 under the conditions of stirring and nitrogen protection to obtain a mixture 2, heating the mixture 2 to 100-140 ℃, and reacting for 10-60 minutes at the temperature to obtain a mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure;
c. under the conditions of stirring and nitrogen protection, adding a chain extender into the mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure at the temperature of 100-140 ℃, obtaining a mixture 3, and reacting at the temperature of 100-140 ℃ for 40-80 minutes to obtain the flame-retardant thermoplastic polyurethane resin.
The flame-retardant thermoplastic polyurethane resin provided by the invention contains a large amount of isocyanurate structures with flame-retardant performance, the flame-retardant grade of the flame-retardant thermoplastic polyurethane resin is greater than or equal to UL-94VTM-1, and the flame-retardant thermoplastic polyurethane resin has good transparency; no halogen is contained, and the environment is protected; the flame retardant does not contain phosphorus, and after the flame retardant is placed for a long time, the flame retardant grade cannot be reduced due to easy water absorption, and the performance of the material cannot be obviously attenuated.
The polyurethane resin prepared by the method for preparing the flame-retardant thermoplastic polyurethane resin provided by the invention has good flame-retardant performance, and the performance is kept stable and is not attenuated in the quality guarantee period of the product. Firstly, adding aliphatic diisocyanate and phthalic anhydride polyester polyol to form a carbamate structure, namely a polyurethane resin main body structure; then adding a catalyst, carrying out trimerization reaction on an excessive isocyanate structure under the protection of nitrogen and at the temperature to form an isocyanurate structure, and finally carrying out chain extension under the action of a chain extender to form macromolecular polyurethane resin. In addition, in the preparation method, the plasticizer is used as a reaction solvent, so that the preparation process is simplified, the toughness of the prepared polyurethane resin is adjusted, and the preparation method is environment-friendly.
Drawings
FIG. 1 is an infrared spectrum of a flame retardant thermoplastic polyurethane resin prepared in example 1 of the present application; wherein, is 1635--1The absorption peak between the three is the absorption peak of the isocyanurate structure, the peak strength is different along with the deviation of the high and low positions of the content, 3310-3500cm-1The broad peak at which the stretching vibration of the amino (or ureido) formate N-H occurs is 1550cm-1Is subjected to N-H bending vibration, 1742.24cm-1The three absorption peaks are the characteristic peaks of the amino (or ureido) formate bond, and show that the synthetic product is actually of a polyurethane structure, wherein the peak of the stretching vibration of the C ═ O bond appears at 1742.24cm-1Instead of 1716cm-1It is shown that the polyurethane is a polyester polyurethane rather than a polyether polyurethane.
Detailed Description
The invention provides a flame-retardant thermoplastic polyurethane resin, which is characterized by at least comprising the following structural units:
In a preferred embodiment, R1Is polyethylene glycol phthalate glycol, 1, 6-hexanediol phthalate glycol and polyphthalateAnd (3) one or more of neopentyl glycol acid ester diol.
In order to obtain better flame retardant properties, in a preferred embodiment, the isocyanurate constitutes 15 to 35%, preferably 20 to 30%, of the molar mass of the flame retardant thermoplastic polyurethane resin.
In order to obtain a flame retardant thermoplastic polyurethane resin having excellent toughness, in a preferred embodiment, the flame retardant thermoplastic polyurethane resin further contains a plasticizer.
In order to obtain better toughness, in a preferred embodiment, the plasticizer constitutes 20 to 50%, preferably 30 to 40%, of the mass of the flame retardant thermoplastic polyurethane resin.
In a preferred embodiment, the flame retardant thermoplastic polyurethane resin is prepared by the following process:
a. mixing aliphatic diisocyanate, phthalic anhydride polyester polyol and a plasticizer under stirring and in a nitrogen atmosphere to obtain a mixture 1; wherein the molar ratio of the aliphatic diisocyanate to the phthalic anhydride polyester polyol is 3-6: 1, the amount of the plasticizer is 20 to 50 percent by weight, preferably 30 to 40 percent by weight of the total amount of the aliphatic diisocyanate and the phthalic anhydride polyester polyol; heating the mixture 1 to 70-90 ℃, and reacting for 20-40 minutes at the temperature to obtain a reaction mixture 1;
b. adding a catalyst into the reaction mixture 1 under the stirring condition and in the nitrogen atmosphere to obtain a mixture 2, heating the mixture 2 to 110-130 ℃, and reacting for 20-40 minutes at the temperature to obtain a mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure;
c. adding a chain extender into the mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure under stirring and in a nitrogen atmosphere at 110-130 ℃, wherein the molar ratio of the added amount of the chain extender to the mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure is 1: 0.5-1, obtaining a mixture 3, and reacting at 110-130 ℃ for 50-70 minutes to obtain the flame-retardant thermoplastic polyurethane resin.
Preferably, in step a, the molar ratio of the aliphatic diisocyanate to the phthalic anhydride polyester polyol is 4-5: 1;
preferably, in step a, the plasticizer is used in an amount of 30 to 40% by weight based on the total amount of the aliphatic diisocyanate and the phthalic anhydride polyester polyol.
The phthalic anhydride polyester polyol may be a phthalic anhydride polyester polyol commonly used in the art; in a preferred embodiment, the phthalic anhydride polyester polyol is selected from one or more of polyethylene terephthalate glycol, 1, 6-hexanediol poly phthalate, and neopentyl glycol phthalate glycol.
In a preferred embodiment, the phthalic anhydride polyester polyol has a molecular weight of 1000-.
The aliphatic diisocyanate may be an aliphatic diisocyanate commonly used in the art; in a preferred embodiment, the isocyanate is one or more selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and 1,4 cyclohexane diisocyanate.
In the present application, the plasticizer is used on the one hand to adjust the toughness of the polyurethane resin and on the other hand to act as a solvent for the reaction of the aliphatic diisocyanate and the phthalic anhydride polyester polyol.
The plasticizer may be a plasticizer commonly used in the art, and in a preferred embodiment, the plasticizer is selected from one or more of dioctyl terephthalate, dimethoxyethylene terephthalate, tricresyl phosphate, dipropylene terephthalate, and triethylene glycol nonanoate.
The chain extender may be a chain extender commonly used in the art, and is preferably a diol or a diamine.
The diol may be one commonly used in the art, and in a preferred embodiment, the diol is one or more selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, and hexylene glycol.
The diamine may be one or more diamines commonly used in the art, and in a preferred embodiment, the diamine is selected from ethylenediamine, propylenediamine, hexamethylenediamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, and benzidine.
In a preferred embodiment, in step a, the stirring speed is 700-900 rpm; in the step b, the stirring speed is 1100-1300 rpm; in step c, the stirring speed is 1900-.
The present application also provides a method for preparing a flame retardant thermoplastic polyurethane resin, characterized in that the method comprises the steps of:
a. mixing aliphatic diisocyanate, phthalic anhydride polyester polyol and a plasticizer under stirring and in a nitrogen atmosphere to obtain a mixture 1; wherein the mole number of the aliphatic diisocyanate is larger than that of the phthalic anhydride polyester polyol; heating the mixture 1 to 60-100 ℃, and reacting for 10-60 minutes at the temperature to obtain a reaction mixture 1;
b. adding a catalyst into the reaction mixture 1 under the stirring condition and in the nitrogen atmosphere to obtain a mixture 2, heating the mixture 2 to 100-140 ℃, and reacting for 10-60 minutes at the temperature to obtain a mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure;
c. adding a chain extender into the mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure under stirring and in a nitrogen atmosphere at the temperature of 100-140 ℃ to obtain a mixture 3, and reacting at the temperature of 100-140 ℃ for 40-80 minutes to obtain the flame-retardant thermoplastic polyurethane resin.
In step a, the mole number of the aliphatic diisocyanate is larger than that of the phthalic anhydride polyester polyol, and the molar ratio thereof is preferably larger than 2, and more preferably larger than 3.
In the step a, an isocyanurate structure with flame retardant property is formed by a method without adding a catalyst firstly and controlling the mole number of the aliphatic diisocyanate to be larger than that of the phthalic anhydride polyester polyol, wherein the structure of the isocyanate and the structure of the isocyanurate are respectively shown as the following I and II:
in a preferred embodiment, the method comprises the steps of:
a. under stirring and nitrogen atmosphere, aliphatic diisocyanate, phthalic anhydride polyester polyol and plasticizer are mixed according to a molar ratio of 1: 3-1: 6 mixing to obtain a mixture 1, heating the mixture 1 to 70-90 ℃, and reacting for 20-40 minutes at the temperature to obtain a reaction mixture 1;
b. adding a catalyst into the reaction mixture 1 under the stirring condition and in the nitrogen atmosphere to obtain a mixture 2, heating the mixture 2 to 110-130 ℃, and reacting for 20-40 minutes at the temperature to obtain a mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure;
c. adding a chain extender into the mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure under stirring and in a nitrogen atmosphere at 110-130 ℃, wherein the molar ratio of the added amount of the chain extender to the mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure is 1: 0.5-1, obtaining a mixture 3, and reacting at 110-130 ℃ for 50-70 minutes to obtain the flame-retardant thermoplastic polyurethane resin.
Preferably, in step a, the molar ratio of the aliphatic diisocyanate to the phthalic anhydride polyester polyol is 4-5: 1;
preferably, in step a, the plasticizer is used in an amount of 30 to 40% by weight based on the total amount of the aliphatic diisocyanate and the phthalic anhydride polyester polyol.
The catalyst may be a catalyst commonly used in the art, preferably dibutyltin dilaurate, tri-n-butyl methoxy tin or stannous octoate.
Preferably, the mass ratio of the catalyst to the aliphatic diisocyanate is 0.005-0.01:1, preferably 0.008: 1.
the phthalic anhydride polyester polyol may be a phthalic anhydride polyester polyol commonly used in the art; in a preferred embodiment, the phthalic anhydride polyester polyol is selected from one or more of polyethylene terephthalate glycol, 1, 6-hexanediol poly phthalate, and neopentyl glycol phthalate glycol.
In a preferred embodiment, the phthalic anhydride polyester polyol has a molecular weight of 1000-.
The aliphatic diisocyanate may be an aliphatic diisocyanate commonly used in the art; in a preferred embodiment, the isocyanate is one or more selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and 1,4 cyclohexane diisocyanate.
In the present application, the plasticizer is used on the one hand to adjust the toughness of the polyurethane resin and on the other hand to serve as a solvent for the reaction of the aliphatic diisocyanate and the phthalic anhydride polyester polyol.
The plasticizer may be a plasticizer commonly used in the art, and in a preferred embodiment, the plasticizer is selected from one or more of dioctyl terephthalate, dimethoxyethylene terephthalate, tricresyl phosphate, dipropylene terephthalate, and triethylene glycol nonanoate.
The chain extender may be a chain extender commonly used in the art, and is preferably a diol or a diamine.
The diol may be a diol commonly used in the art, and in a preferred embodiment, the diol is one or more selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, and hexylene glycol.
The diamine may be one or more diamines commonly used in the art, and in a preferred embodiment, the diamine is selected from ethylenediamine, propylenediamine, hexamethylenediamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, and benzidine.
In a preferred embodiment, in step a, the stirring speed is 700 and 900 revolutions per minute.
In a preferred embodiment, in step b, the stirring speed is 1100-1300 rpm.
In a preferred embodiment, in step c, the stirring speed is 1900-2100 rpm.
The invention also relates to application of the flame-retardant thermoplastic polyurethane resin in preparation of positive pressure protective clothing.
The invention also relates to positive pressure protective clothing, the main body of which is prepared from the flame-retardant thermoplastic polyurethane resin provided by the invention; the main body of the positive pressure protective clothing comprises a front part, a back, sleeves, trouser legs, a helmet and the like.
Example 1
4,4' -dicyclohexylmethane diisocyanate (HMDI, CAS:822-06-0) was added dropwise to a mixture of phthalic anhydride polyester polyol (DGPA, CAS:32472-85-8) (molecular weight 3000 daltons) and dioctyl terephthalate (DOTP) under nitrogen atmosphere at a stirring speed of 800 rpm; wherein the mol ratio of the 4,4 '-dicyclohexyl methane diisocyanate to the phthalic anhydride polyester polyol is 3:1, and the using amount of the dioctyl terephthalate is 30 percent of the total weight of the 4,4' -dicyclohexyl methane diisocyanate and the phthalic anhydride polyester polyol. Keeping the rotating speed at 800 revolutions per minute, heating to 80 ℃ and reacting for 30 minutes to obtain a reaction mixture 1;
then adding a catalyst dibutyltin dilaurate (CAS:77-58-7, the using amount of dibutyltin dilaurate is 0.01 mass of 4,4' -dicyclohexylmethane diisocyanate) to form a mixture 2, heating the mixture 2 to 120 ℃ under the protection condition of N2, and continuously reacting for 30 minutes at the stirring speed of 1200 r/min to obtain an isocyanurate structure polyurethane prepolymer with NCO end capping;
at 2000 rpm, the chain extender 1.4 butanediol (BD, CAS:110-63-4) was added in such an amount that the molar ratio of the chain extender to the mixture of polyurethane prepolymers with an NCO-terminated isocyanurate structure was 1: 0.5; reacting at 120 ℃ for 60 minutes to obtain TPU resin, and cooling and granulating to obtain the flame-retardant TPU master batch 1.
Example 2
Under the nitrogen atmosphere, under the stirring speed of 700 r/min, isophorone diisocyanate is added into the mixed solution of polydiethylene glycol phthalate (molecular weight 2000 daltons) and dimethoxy ethylene glycol phthalate in a dropwise manner; wherein the molar ratio of the isophorone diisocyanate to the phthalic anhydride polyester polyol is 6:1, and the using amount of the dimethoxy ethylene glycol phthalate is 50 percent of the total weight of the isophorone diisocyanate and the polyethylene glycol phthalate. Keeping the rotating speed at 700 revolutions per minute, heating to 70 ℃ and reacting for 40 minutes to obtain a reaction mixture 1;
then adding a catalyst tri-N-butylmethoxy tin, wherein the using amount of the tri-N-butylmethoxy tin is 0.008 mass of isophorone diisocyanate, forming a mixture 2, heating the mixture 2 to 110 ℃ under the protection of N2, and continuously reacting for 40 minutes at the stirring speed of 1100 r/min to obtain an isocyanurate structure polyurethane prepolymer with NCO end capping;
at the rotating speed of 1900 r/min, adding a chain extender ethylenediamine, wherein the addition amount of the chain extender is such that the molar ratio of the chain extender to the mixture of polyurethane prepolymers with an NCO-terminated isocyanurate structure is 1: 1. reacting at 110 ℃ for 70 minutes to obtain TPU resin, and cooling and granulating to obtain the flame-retardant TPU master batch 2.
Example 3
Under the nitrogen atmosphere, at the stirring speed of 900 rpm, hexamethylene diisocyanate is dropwise added into a mixed solution of dipropylene glycol phthalate and neopentyl glycol phthalate glycol (molecular weight of 2500 daltons); wherein the mole ratio of hexamethylene diisocyanate to poly neopentyl glycol phthalate glycol is 4:1, and the amount of dipropylene glycol phthalate is 40% of the total weight of hexamethylene diisocyanate and poly neopentyl glycol phthalate glycol. Keeping the rotating speed at 900 revolutions per minute, heating to 80 ℃ and reacting for 20 minutes to obtain a reaction mixture 1;
then adding a catalyst stannous octoate, wherein the using amount of the stannous octoate is 0.005 of the mass of hexamethylene diisocyanate, forming a mixture 2, heating the mixture 2 to 130 ℃ under the protection of N2, and continuously reacting for 20 minutes at the stirring speed of 1300 r/min to obtain an isocyanurate structure polyurethane prepolymer with NCO end capping;
at the rotating speed of 2100 revolutions per minute, adding a chain extender glycol, wherein the adding amount of the chain extender is that the molar ratio of the chain extender to the mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure is 1: 0.8; reacting for 50 minutes at 130 ℃ to obtain TPU resin, and granulating after cooling to obtain the flame-retardant TPU master batch 3.
And (4) performance testing:
the flame-retardant TPU master batches 1, 2 and 3 prepared in the embodiments 1 to 3 are respectively melted, casted and calendered into flame-retardant films TPU-1, TPU-2 and TPU-3 with the thickness of 0.3 mm. Respectively detecting the flame retardance and the transparency of the prepared flame retardant films TPU-1, TPU-2 and TPU-3 and the flame retardant films 1 and 2 of the commercially available phosphorus-containing polyurethane according to a UL-94 standard method; and flame retardancy and transparency measured after 3 months at 60 ℃, 60% relative humidity, the results of which are shown in the following table:
as can be seen from the above table, the polyurethane resin film provided by the present invention has excellent flame retardant property and transparency, and after being left in an environment of higher temperature and humidity for 3 months, the change of the flame retardant property thereof cannot be detected, and the transparency thereof is slightly reduced; the phosphorus-containing polyurethane flame-retardant film sold in the market has poor transparency, and after the flame-retardant film is placed in the same environment for the same time, the flame-retardant property of the flame-retardant film is obviously reduced, and the transparency is further deteriorated.
Claims (25)
1. A flame retardant thermoplastic polyurethane resin, characterized in that the transparent flame retardant thermoplastic polyurethane resin comprises at least the following structural units:
2. The flame retardant thermoplastic polyurethane resin according to claim 1, wherein R is R1Is polyethylene glycol terephthalate di-phthalateOne or more of alcohol, poly-1, 6-hexanediol phthalate glycol and poly-neopentyl glycol phthalate glycol.
3. The flame retardant thermoplastic polyurethane resin of claim 1 wherein said isocyanurate structure comprises from 15 to 35 percent of the molar mass of said flame retardant thermoplastic polyurethane resin.
4. The flame retardant thermoplastic polyurethane resin according to claim 1, wherein the flame retardant thermoplastic polyurethane resin contains a plasticizer.
5. The flame retardant thermoplastic polyurethane resin according to claim 1, wherein the plasticizer accounts for 20 to 50% by mass of the flame retardant thermoplastic polyurethane resin.
6. The flame retardant thermoplastic polyurethane resin according to claim 1, wherein the flame retardant thermoplastic polyurethane resin is prepared by the following process:
a. under the conditions of stirring and nitrogen protection, mixing aliphatic diisocyanate, phthalic anhydride polyester polyol and a plasticizer to obtain a mixture 1; wherein the molar ratio of the aliphatic diisocyanate to the phthalic anhydride polyester polyol is 3-6: 1, the dosage of the plasticizer is 20-50 wt% of the total amount of the aliphatic diisocyanate and the phthalic anhydride polyester polyol; heating the mixture 1 to 70-90 ℃, and reacting for 20-40 minutes at the temperature to obtain a reaction mixture 1;
b. adding a catalyst into the reaction mixture 1 under the conditions of stirring and nitrogen protection to obtain a mixture 2, heating the mixture 2 to 110-;
c. under the conditions of stirring and nitrogen protection, adding a chain extender into a mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure at the temperature of 110-130 ℃, wherein the molar ratio of the added amount of the chain extender to the mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure is 1: 0.5-1, obtaining a mixture 3, and reacting at 110-130 ℃ for 50-70 minutes to obtain the flame-retardant thermoplastic polyurethane resin.
7. The flame retardant thermoplastic polyurethane resin according to claim 6, wherein the phthalic anhydride polyester polyol is one or more selected from the group consisting of polyethylene terephthalate glycol, 1, 6-hexanediol poly-phthalate glycol, and neopentyl glycol phthalate glycol; the aliphatic diisocyanate is selected from one or more of isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and 1,4 cyclohexane diisocyanate; the plasticizer is selected from one or more of dioctyl terephthalate, dimethoxy ethylene glycol phthalate, tricresyl phosphate, dipropylene glycol phthalate and triethylene glycol nonanoate; the chain extender is dihydric alcohol or diamine.
8. The flame retardant thermoplastic polyurethane resin as claimed in claim 6, wherein the molecular weight of said phthalic anhydride polyester polyol is 1000-3000 daltons.
9. The flame retardant thermoplastic polyurethane resin according to claim 6, wherein the diol is one or more selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, and hexylene glycol.
10. The flame retardant thermoplastic polyurethane resin according to claim 6, wherein the diamine is one or more selected from the group consisting of ethylenediamine, propylenediamine, hexamethylenediamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine and benzidine.
11. The flame retardant thermoplastic polyurethane resin according to any one of claims 6 to 10, wherein in step a, the stirring speed is 700-900 rpm; in the step b, the stirring speed is 1100-1300 rpm; in step c, the stirring speed is 1900-.
12. A method for preparing a flame retardant thermoplastic polyurethane resin, characterized in that the method comprises the steps of:
a. under the conditions of stirring and nitrogen protection, mixing aliphatic diisocyanate, phthalic anhydride polyester polyol and a plasticizer to obtain a mixture 1; wherein the mole number of the aliphatic diisocyanate is more than that of the phthalic anhydride polyester polyol; heating the mixture 1 to 60-100 ℃, and reacting for 10-60 minutes at the temperature to obtain a reaction mixture 1;
b. adding a catalyst into the reaction mixture 1 under the conditions of stirring and nitrogen protection to obtain a mixture 2, heating the mixture 2 to 100-140 ℃, and reacting for 10-60 minutes at the temperature to obtain a mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure;
c. under the conditions of stirring and nitrogen protection, adding a chain extender into the mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure at the temperature of 100-140 ℃ to obtain a mixture 3, and reacting at the temperature of 100-140 ℃ for 40-80 minutes to obtain the flame-retardant thermoplastic polyurethane resin.
13. Method according to claim 12, characterized in that it comprises the following steps:
a. under the conditions of stirring and nitrogen protection, mixing aliphatic diisocyanate, phthalic anhydride polyester polyol and a plasticizer to obtain a mixture 1; wherein the molar ratio of the aliphatic diisocyanate to the phthalic anhydride polyester polyol is 3-6: 1, the amount of the plasticizer is 20-50 wt% of the total amount of the aliphatic diisocyanate and the phthalic anhydride polyester polyol; heating the mixture 1 to 70-90 ℃, and reacting for 20-40 minutes at the temperature to obtain a reaction mixture 1;
b. adding a catalyst into the reaction mixture 1 under the conditions of stirring and nitrogen protection to obtain a mixture 2, heating the mixture 2 to 110-130 ℃, and reacting for 20-40 minutes at the temperature to obtain a mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure;
c. under the conditions of stirring and nitrogen protection, adding a chain extender into the mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure at the temperature of 110-130 ℃, wherein the molar ratio of the adding amount of the chain extender to the mixture of the polyurethane prepolymer with the NCO-terminated isocyanurate structure is 1: 0.5-1, obtaining a mixture 3, and reacting at 110-130 ℃ for 50-70 minutes to obtain the flame-retardant thermoplastic polyurethane resin.
14. The method according to claim 13, wherein the phthalic anhydride polyester polyol is selected from one or more of the group consisting of polyethylene terephthalate glycol, 1, 6-hexanediol phthalate glycol, and neopentyl glycol phthalate glycol.
15. The method as set forth in claim 13, wherein the phthalic anhydride polyester polyol has a molecular weight of 1000-3000 daltons.
16. The method according to claim 12, wherein the aliphatic diisocyanate is selected from one or more of isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and 1,4 cyclohexane diisocyanate.
17. The method according to claim 12, wherein the plasticizer is one or more selected from the group consisting of dioctyl terephthalate, dimethoxyethylene terephthalate, tricresyl phosphate, dipropylene terephthalate and triethylene glycol pelargonate.
18. The method of claim 12, wherein the chain extender is a diol or a diamine.
19. The method according to claim 12, wherein the diol is one or more selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, and hexylene glycol.
20. The method according to claim 12, wherein the diamine is selected from one or more of ethylenediamine, propylenediamine, hexamethylenediamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, and benzidine.
21. The method as claimed in claim 12, wherein in step a, the stirring speed is 700-900 rpm.
22. The method as claimed in claim 12, wherein in step b, the stirring speed is 1100-1300 rpm.
23. The method as claimed in any one of claims 12 to 22, wherein in step c, the stirring speed is 1900-.
24. Use of the flame retardant thermoplastic polyurethane resin according to any one of claims 1 to 11 for the preparation of protective clothing of positive pressure type.
25. A positive pressure protective garment, characterized in that a main body of the positive pressure protective garment is made of the flame retardant thermoplastic polyurethane resin according to any one of claims 1 to 11.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1802395A (en) * | 2003-06-12 | 2006-07-12 | 亨茨曼国际有限公司 | Process for preparing a polyisocyanurate polyurethane material |
| CN103665305A (en) * | 2013-12-06 | 2014-03-26 | 上海华峰新材料研发科技有限公司 | High-flame-retardance polyisocyanurate hard foam and preparation method thereof |
| CN104093759A (en) * | 2012-02-08 | 2014-10-08 | 拜耳知识产权有限责任公司 | Method for producing a hard polyurethane-polyisocyanurate foamed material |
| CN108623771A (en) * | 2017-03-15 | 2018-10-09 | 科思创德国股份有限公司 | Hydroxy-end capped base polyurethane prepolymer for use as and preparation method thereof |
-
2022
- 2022-03-09 CN CN202210222930.6A patent/CN114773565A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1802395A (en) * | 2003-06-12 | 2006-07-12 | 亨茨曼国际有限公司 | Process for preparing a polyisocyanurate polyurethane material |
| CN104093759A (en) * | 2012-02-08 | 2014-10-08 | 拜耳知识产权有限责任公司 | Method for producing a hard polyurethane-polyisocyanurate foamed material |
| CN103665305A (en) * | 2013-12-06 | 2014-03-26 | 上海华峰新材料研发科技有限公司 | High-flame-retardance polyisocyanurate hard foam and preparation method thereof |
| CN108623771A (en) * | 2017-03-15 | 2018-10-09 | 科思创德国股份有限公司 | Hydroxy-end capped base polyurethane prepolymer for use as and preparation method thereof |
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