CN110540743B - Zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material and preparation method thereof - Google Patents
Zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material and preparation method thereof Download PDFInfo
- Publication number
- CN110540743B CN110540743B CN201910693822.5A CN201910693822A CN110540743B CN 110540743 B CN110540743 B CN 110540743B CN 201910693822 A CN201910693822 A CN 201910693822A CN 110540743 B CN110540743 B CN 110540743B
- Authority
- CN
- China
- Prior art keywords
- benzotriazole
- zinc oxide
- dopo
- melamine
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明提供了一种氧化锌‑DOPO功能化苯并三唑复合改性聚氨酯材料的制备方法，以苯并三唑，三聚氰胺和9，10‑二氢‑9‑氧杂‑10‑磷杂菲‑10‑氧化物(DOPO)作为原料依次反应，制备得到有机紫外吸收剂，该有机紫外吸收剂结构中同时含有苯并三唑和P‑H键部分，P‑H键片段能够捕获自由基，且与苯并三唑之间存在互相保护，能提高紫外线吸收片段和高分子材料的耐光性和耐黄变性，同时能提高聚氨酯材料的阻燃性能；通过复配纳米氧化锌，利用其广泛的紫外光吸收性及与有机紫外吸收剂的协同作用，进一步提高聚氨酯材料的紫外光吸收有效性和材料稳定性。The invention provides a preparation method of a zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material, comprising benzotriazole, melamine and 9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide (DOPO) is reacted as a raw material in turn to prepare an organic ultraviolet absorber, and the organic ultraviolet absorber structure contains both benzotriazole and P-H bond parts, and the P-H bond fragments can capture free radicals, And there is mutual protection with benzotriazole, which can improve the light resistance and yellowing resistance of ultraviolet absorbing fragments and polymer materials, and at the same time can improve the flame retardant performance of polyurethane materials; Ultraviolet light absorption and synergistic effect with organic ultraviolet absorbers further improve the ultraviolet light absorption effectiveness and material stability of polyurethane materials.
Description
Technical Field
The invention relates to the technical field of composite materials, and particularly relates to a zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material and a preparation method thereof.
Background
Polyurethane (PU) materials have been widely used as coating materials since the 80 s of the 20 th century, and are particularly important for building applications. The polyurethane material has good physical mechanical property, excellent acid and alkali resistance, good comprehensive performance, high strength, large elongation, good elasticity and bonding sealing performance, simple construction process and less restriction on construction and curing environment, and is suitable for various parts of buildings. Polyurethanes are classified into aliphatic, alicyclic and aromatic PU's according to the kind of isocyanate. Wherein, the aromatic polyurethane structure contains-NHCOO-and aromatic ring conjugated structural unit, which has strong adhesive force, good wear resistance, chemical resistance and other excellent performances, and the lower price has obvious competitive advantage and can be widely applied. However, the molecular chain structure stability of the aromatic PU under the conditions of ultraviolet radiation and the like is poor, and under the irradiation of ultraviolet light, aromatic rings and carbamate functional groups in the polyurethane are easy to oxidize or break bonds, so that the obvious aging phenomenon occurs, and the irreversible changes such as degradation and discoloration of the polyurethane material, great reduction of mechanical strength and the like are caused; and the polyurethane has low density, the limited oxygen index is only 16-18%, the polyurethane belongs to a flammable material, and simultaneously, the polyurethane can generate a large amount of toxic gases such as CO, HCN and the like during combustion, so that the popularization and the use of the polyurethane material are greatly limited.
At present, a direct and effective way to improve the UV aging resistance of aromatic PU is to add UV absorbers to the PU substrate. The ultraviolet absorbent added in the material is required to be safe and nontoxic, has good ultraviolet absorption effect, is stable to heat, light and chemicals, and has good performances of acid and alkali resistance, solvent resistance and the like. Currently, common ultraviolet absorbers include light-shielding agents such as ZnO; and organic ultraviolet absorbers such as benzotriazoles. The nano ZnO has high chemical stability, thermal stability, non-migration, tastelessness, no toxicity, no irritation, high refractive index, strong ultraviolet scattering capability, capability of providing broad-spectrum ultraviolet protection (UVA and UVB), low price and is the most inorganic ultraviolet shielding agent used at present. The benzotriazole ultraviolet absorbent has a wide range of absorption wavelength, has a higher light absorption index within 300-385nm, is close to the requirement of an ideal absorbent, has the advantages of oil resistance, discoloration resistance, low volatility, low toxicity and good compatibility with polymers, is suitable for various light-colored products, is the ultraviolet absorbent with the maximum yield at present, and is widely used in various high-molecular synthetic materials and products.
However, the high photocatalytic activity of the nano ZnO can accelerate the breaking of carbon-carbon bonds of organic matters in the surrounding environment, accelerate the aging and oxidative degradation of the matters and shorten the service life of the material; in the application of the benzotriazole ultraviolet absorbent, the benzotriazole ultraviolet absorbent is relatively small in molecular weight and is easy to migrate and diffuse in a high polymer material to cause loss, so that the ultraviolet absorption efficiency is reduced, and the use of the benzotriazole ultraviolet absorbent is limited.
The polyurethane materials in the market all need to be added with flame retardant to achieve the purpose of flame retardance. Common flame retardants are mainly classified into reactive type and additive type. The additive flame retardant is physically dispersed in the polyurethane matrix, does not react with the polyurethane matrix and reaction raw materials thereof, does not need to change greatly in the manufacturing process, has obvious flame retardant effect, is most widely applied in the current industry and accounts for about 90 percent of the total yield. The additive flame retardant is selected from halogen series, phosphorus series, nitrogen series, silicon series, antimony series, aluminum series, magnesium series, etc. The phosphorus flame retardant is mainly divided into an inorganic phosphorus flame retardant and an organic phosphorus flame retardant, and ammonium phosphate, ammonium polyphosphate and corresponding products are the more active research fields of the current phosphorus flame retardants and have very wide prospects as non-halogen flame retardants. However, these flame retardants have a problem of insufficient thermal stability, water resistance, blooming properties, processability, and the like.
With the development of industry, it is an urgent need to solve the problem of providing a polyurethane material with good light resistance, yellowing resistance and flame retardant property, which does not contain an additional flame retardant.
Disclosure of Invention
The invention aims to provide a zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material and a preparation method thereof. The zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material prepared by the preparation method provided by the invention does not contain an external flame retardant, and has good light resistance, yellowing resistance and flame retardant property.
The invention provides a preparation method of a zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material, which comprises the following steps:
(1) mixing melamine, benzaldehyde and an organic solvent, and carrying out condensation reaction to obtain modified melamine;
(2) mixing the modified melamine obtained in the step (1) with benzotriazole and formaldehyde substances, and carrying out condensation reaction to obtain modified melamine functionalized benzotriazole; the formaldehyde substances comprise paraformaldehyde and/or formaldehyde;
(3) mixing the modified melamine functionalized benzotriazole obtained in the step (2) with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a catalyst and an organic solvent, and carrying out addition reaction to obtain an organic ultraviolet absorbent;
(4) and (4) mixing the organic ultraviolet absorbent obtained in the step (3), nano zinc oxide and polyurethane to obtain the zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material.
Preferably, the temperature of the condensation reaction in the step (1) is 50-120 ℃, and the time of the condensation reaction is 1-5 h.
Preferably, the mass ratio of the melamine to the benzaldehyde in the step (1) is 1 (0.1-2).
Preferably, the temperature of the condensation reaction in the step (2) is 60-140 ℃, and the time of the condensation reaction is 1-5 h.
Preferably, the ratio of the modified melamine, the benzotriazole and the formaldehyde in the step (2) is (0.1-2) to 1 (0.1-2).
Preferably, the temperature of the addition reaction in the step (3) is 60-140 ℃, and the time of the addition reaction is 1-5 h.
Preferably, the ratio of the amount of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in the step (3) to the amount of the benzotriazole in the step (2) is (0.1-2): 1.
Preferably, the mixing temperature in the step (4) is 20-200 ℃, and the mixing time is 0.1-5 h.
Preferably, the ratio of the organic ultraviolet absorbent, the nano zinc oxide and the polyurethane in the step (4) is (0.5-5) to 1 (1-300).
The invention also provides a zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material prepared by the preparation method in the technical scheme, which comprises a polyurethane matrix and nano zinc oxide and DOPO functionalized benzotriazole distributed in the polyurethane matrix.
The invention provides a preparation method of a zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material, which comprises the following steps: mixing melamine, benzaldehyde and an organic solvent, and carrying out condensation reaction to obtain modified melamine; mixing the modified melamine with benzotriazole and formaldehyde substances, and carrying out condensation reaction to obtain modified melamine functionalized benzotriazole; the formaldehyde substances comprise paraformaldehyde and/or formaldehyde; mixing the modified melamine functionalized benzotriazole with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a catalyst and an organic solvent, and carrying out addition reaction to obtain an organic ultraviolet absorbent; and mixing the organic ultraviolet absorbent, nano zinc oxide and polyurethane to obtain the zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material. According to the invention, benzotriazole, melamine and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) are used as raw materials to react in sequence to prepare the organic ultraviolet absorbent, the structure of the organic ultraviolet absorbent simultaneously contains benzotriazole and a P-H bond part, the P-H bond segment can capture free radicals, mutual protection exists between the P-H bond segment and benzotriazole, the light resistance and yellowing resistance of the ultraviolet absorption segment and a high polymer material can be improved, and the flame retardant property of a polyurethane material can be improved; by compounding nano zinc oxide, the ultraviolet absorption effectiveness and the material stability of the polyurethane material are further improved by utilizing the wide ultraviolet absorptivity and the synergistic effect of the nano zinc oxide and the organic ultraviolet absorbent. Experimental results show that the zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material prepared by the preparation method provided by the invention has an ultraviolet shielding effect of 95%, a yellow index of less than or equal to 32 and a flame retardant property of grade B.
Detailed Description
The invention provides a preparation method of a zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material, which comprises the following steps:
(1) mixing melamine, benzaldehyde and an organic solvent, and carrying out condensation reaction to obtain modified melamine;
(2) mixing the modified melamine obtained in the step (1) with benzotriazole and formaldehyde substances, and carrying out condensation reaction to obtain modified melamine functionalized benzotriazole; the formaldehyde substances comprise paraformaldehyde and/or formaldehyde;
(3) mixing the modified melamine functionalized benzotriazole obtained in the step (2) with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a catalyst and an organic solvent, and carrying out addition reaction to obtain an organic ultraviolet absorbent;
(4) and (4) mixing the organic ultraviolet absorbent obtained in the step (3), nano zinc oxide and polyurethane to obtain the zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material.
The modified melamine is obtained by mixing melamine, benzaldehyde and an organic solvent and carrying out condensation reaction. In the present invention, the ratio of the amounts of the melamine and the benzaldehyde is preferably 1 (0.1 to 2), more preferably 1 (0.3 to 1.5). The source of the melamine and benzaldehyde is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used. In the invention, the purity of the melamine is preferably 99-99.9%; the purity of the benzaldehyde is preferably 99.5-99.9%.
In the present invention, the organic solvent preferably includes one or more of methanol, ethanol, isopropanol, n-butanol, n-hexanol, toluene, dimethyl sulfoxide, dimethylformamide, dichloromethane, ethyl acetate, trichloromethane, tetrachloromethane, alkanes, halogenated hydrocarbons. The amount of the organic solvent used is not particularly limited, and is subject to the conditions that the raw materials can be dissolved and the reaction is ensured. In the present invention, the ratio of the volume of the organic solvent to the amount of the melamine is preferably (10 to 100) mL (0.1 to 10) mol.
The mixing manner of the melamine, the benzaldehyde and the organic solvent is not particularly limited in the present invention, and the raw materials can be mixed in a manner well known to those skilled in the art. In the present invention, the mixing of the melamine, the benzaldehyde and the organic solvent is preferably performed under stirring.
In the invention, the condensation reaction temperature is preferably 50-120 ℃, more preferably 80-100 ℃, and most preferably 90 ℃; the time of the condensation reaction is preferably 1-5 h, and more preferably 2-3 h. In the invention, in the condensation reaction process, melamine and benzaldehyde are subjected to dehydration condensation to obtain Schiff base modified melamine.
After the condensation reaction of melamine and benzaldehyde is completed, the product of the condensation reaction is preferably filtered to obtain modified melamine. The operation of the filtration is not particularly limited in the present invention, and the filtration operation known to those skilled in the art may be employed.
After the modified melamine is obtained, the modified melamine is mixed with benzotriazole and formaldehyde substances, and the modified melamine functionalized benzotriazole is obtained through condensation reaction. In the present invention, the ratio of the amounts of the modified melamine, benzotriazole and formaldehyde is preferably (0.1 to 2):1, (0.1 to 2), and more preferably (0.5 to 1.5):1, (0.5 to 1.5). In the present invention, the formaldehyde-based substance includes paraformaldehyde and/or formaldehyde. The sources of the benzotriazole, paraformaldehyde and formaldehyde are not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used. In the invention, the purity of the benzotriazole is preferably 95-99%; the purity of the paraformaldehyde is preferably 99-99.5%; the purity of the formaldehyde is preferably 36% or more.
In the invention, the condensation reaction temperature is preferably 60-140 ℃, more preferably 80-120 ℃, and finally 90-100 ℃; the time of the condensation reaction is preferably 1-5 h, and more preferably 2-3 h. In the invention, the modified melamine is condensed with benzotriazole and formaldehyde by carbonylation to obtain an intermediate product.
After the condensation reaction of the modified melamine, the benzotriazole and the formaldehyde substance is completed, the invention preferentially divides the product of the condensation reaction to obtain the modified melamine functionalized benzotriazole. The operation of the water diversion is not particularly limited, and the technical scheme of water diversion well known by the technical personnel in the field can be adopted.
After the modified melamine functionalized benzotriazole is obtained, the modified melamine functionalized benzotriazole, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a catalyst and an organic solvent are mixed and subjected to addition reaction to obtain the organic ultraviolet absorbent. In the present invention, the ratio of the amounts of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and benzotriazole is preferably (0.1 to 2):1, and more preferably (0.6 to 1.5): 1. The source of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, DOPO for short, is not particularly limited, and commercially available products well known to those skilled in the art can be used. In the invention, the purity of the DOPO is preferably 95-99%.
In the present invention, the catalyst preferably includes one of hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, benzoic acid, and p-toluenesulfonic acid. In the present invention, the amount of the catalyst is preferably (0.01 to 0.1):1, and more preferably (0.02 to 0.05): 1. In the present invention, the catalyst functions to accelerate the reaction progress.
In the present invention, the organic solvent preferably includes one or more of methanol, ethanol, isopropanol, n-butanol, n-hexanol, toluene, dimethyl sulfoxide, dimethylformamide, dichloromethane, ethyl acetate, trichloromethane, tetrachloromethane, alkanes, halogenated hydrocarbons. The amount of the organic solvent used is not particularly limited, and is subject to the conditions that the raw materials can be dissolved and the reaction is ensured. In the present invention, the ratio of the volume of the organic solvent to the amount of DOPO is preferably (10 to 500) mL:1 mol.
The operation of mixing the modified melamine functionalized benzotriazole, the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, the catalyst and the organic solvent is not particularly limited, and the technical scheme of mixing raw materials, which is well known to a person skilled in the art, is adopted. In the present invention, the mixing of the modified melamine-functionalized benzotriazole with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, the catalyst and the organic solvent is preferably performed under stirring.
In the invention, the temperature of the addition reaction is preferably 60-140 ℃, and more preferably 80-130 ℃; the time of the addition reaction is preferably 1-5 h, and more preferably 1-3 h. In the invention, the modified melamine functionalized benzotriazole and DOPO are subjected to DOPO and imine bond addition reaction under the catalytic action of a catalyst to obtain the DOPO functionalized benzotriazole.
After the addition reaction is finished, the invention preferably performs reduced pressure distillation on the product of the addition reaction to obtain the organic ultraviolet absorbent. The operation of the reduced pressure distillation is not particularly limited in the present invention, and a technical scheme of reduced pressure distillation known to those skilled in the art may be adopted.
In the invention, when the reaction raw material is paraformaldehyde, the preparation principle of the organic ultraviolet absorbent is shown as formula I:
after the organic ultraviolet absorbent is obtained, the organic ultraviolet absorbent, the nano zinc oxide and the polyurethane are mixed to obtain the zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material. In the invention, the ratio of the organic ultraviolet absorbent, the nano zinc oxide and the polyurethane is preferably (0.5-5) to 1 (1-300), more preferably (1-4) to 1 (150-250), and most preferably (2-3) to 1: 200.
In the present invention, the nano zinc oxide is preferably a modified nano zinc oxide. In the invention, the particle size of the nano zinc oxide is preferably 1-500 nm, and more preferably 20-100 nm. The source of the nano zinc oxide is not particularly limited in the present invention, and the nano zinc oxide can be prepared by using a commercially available product known to those skilled in the art or by using a method for preparing nano zinc oxide known to those skilled in the art.
In the invention, the nano zinc oxide is preferably obtained by surface modification of common nano zinc oxide; the surface modification is specifically that common nano zinc oxide is added into an ethanol water solution, a silane coupling agent is added after ultrasonic dispersion is carried out for 30min, reaction is carried out at 80 ℃, and then vacuum drying is carried out, so as to obtain the modified nano zinc oxide. In the invention, the surface modification can further improve the dispersibility of the nano zinc oxide in the polyurethane material.
In the invention, the mixing temperature of the organic ultraviolet absorbent, the nano zinc oxide and the polyurethane is preferably 20-200 ℃, and more preferably 160 ℃; the mixing time is preferably 0.1-5 h, and more preferably 1-3 h.
The preparation method provided by the invention takes benzotriazole, melamine and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) as raw materials to react in sequence to prepare the organic ultraviolet absorbent, the structure of the organic ultraviolet absorbent simultaneously contains benzotriazole and P-H bond parts, the P-H bond segment can capture free radicals, and mutual protection exists between the P-H bond segment and benzotriazole, so that the light resistance and yellowing resistance of the ultraviolet absorption segment and a high polymer material can be improved, and the flame retardant property of a polyurethane material can be improved; by compounding nano zinc oxide, the ultraviolet absorption effectiveness and the material stability of the polyurethane material are further improved by utilizing the wide ultraviolet absorptivity and the synergistic effect of the nano zinc oxide and the organic ultraviolet absorbent.
In addition, the preparation method provided by the invention has the advantages of cheap raw materials and capability of reducing the production cost.
The invention also provides a zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material prepared by the preparation method in the technical scheme, which comprises a polyurethane matrix and nano zinc oxide and DOPO functionalized benzotriazole distributed in the polyurethane matrix.
In order to further illustrate the invention, the zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material and the preparation method thereof provided by the invention are described in detail below with reference to the examples, but the materials are not to be construed as limiting the scope of the invention.
Example 1:
adding 12.6g of melamine and 10.6g of benzaldehyde into a 500mL three-necked bottle, adding 50mL of dimethyl sulfoxide, stirring and dissolving, and reacting at 90 ℃ for 2 hours; after filtering, adding 22.5g of benzotriazole and 8.5g of formaldehyde, raising the temperature to 120 ℃, and carrying out reaction for 2 hours and then dividing water; adding 21.6g of DOPO, 0.2 g of acetic acid and 20ml of dimethyl sulfoxide, stirring until the DOPO is completely dissolved, keeping the temperature at 120 ℃ for reaction for 1.5 hours until the color disappears, and carrying out reduced pressure distillation to obtain a product with the yield of 90.7%.
Adding 1g of nano zinc oxide into a solvent, performing ultrasonic dispersion for 30min, adding a silane coupling agent, reacting at 80 ℃, performing vacuum drying, adding 2g of an organic ultraviolet absorbent and 200g of polyurethane, and stirring at 160 ℃ for 0.5h to uniformly mix to obtain the zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material. The ultraviolet absorption range is 208-386nm, the yellowing resistance delta E is 0.26, and the limiting oxygen index is 29.2 percent.
Example 2:
adding 12.6g of melamine and 9.6g of benzaldehyde into a 500mL three-necked bottle, adding 60mL of dimethyl sulfoxide, stirring and dissolving, and reacting at 95 ℃ for 1.5 hours; after filtering, adding 22.5g of benzotriazole and 3g of paraformaldehyde, raising the temperature to 110 ℃, and carrying out reaction for 2 hours and then carrying out water separation; adding 21.6g of DOPO, 0.2 g of acetic acid and 20ml of dimethyl sulfoxide, stirring until the DOPO is completely dissolved, keeping the temperature at 110 ℃ for reaction for 2 hours until the color disappears, and carrying out reduced pressure distillation to obtain a product with the yield of 87.4%.
Adding 1g of nano zinc oxide into a solvent, performing ultrasonic dispersion for 30min, adding a silane coupling agent, reacting at 80 ℃, performing vacuum drying, adding 2g of an organic ultraviolet absorbent and 200g of polyurethane, and stirring at 160 ℃ for 0.5h to uniformly mix to obtain the zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material. The ultraviolet absorption range is 212-382nm, the yellowing resistance delta E is 0.35, and the limiting oxygen index is 28.8 percent.
Example 3:
adding 12.6g of melamine and 12g of benzaldehyde into a 500mL three-necked bottle, adding 60mL of isopropanol, stirring and dissolving, and reacting at 80 ℃ for 2 hours; after filtering, adding 20.5g of benzotriazole and 8.5g of formaldehyde, raising the temperature to 110 ℃, and carrying out reaction for 2 hours and then dividing water; adding 1mol of DOPO, 0.2 g of acetic acid and 20ml of ethanol, stirring until the DOPO, the acetic acid and the ethanol are completely dissolved, keeping the temperature at 110 ℃ for reaction for 2 hours until the color disappears, and carrying out reduced pressure distillation to obtain a product with the yield of 85.2%.
Adding 1g of nano zinc oxide into a solvent, performing ultrasonic dispersion for 30min, adding a silane coupling agent, reacting at 80 ℃, performing vacuum drying, adding 2g of an organic ultraviolet absorbent and 200g of polyurethane, and uniformly mixing at 180 ℃ for 0.5h to obtain the zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material. The ultraviolet absorption range is 215-378nm, the yellowing resistance delta E is 0.33, and the limiting oxygen index is 28.6 percent.
Comparative example 1:
adding 1g of nano zinc oxide into a solvent, performing ultrasonic dispersion for 30min, adding a silane coupling agent, reacting at 80 ℃, performing vacuum drying, then adding 200g of polyurethane, stirring at 160 ℃ for 0.5h, and uniformly mixing to obtain the zinc oxide modified polyurethane material. The ultraviolet absorption range is 260-320nm, the yellowing resistance delta E is 0.74, and the limiting oxygen index is 19.7 percent.
Comparative example 2:
adding 1g of benzotriazole and 100g of polyurethane, and stirring and uniformly mixing at 160 ℃ for 0.5h to obtain the DOPO functionalized benzotriazole modified polyurethane material. The ultraviolet absorption range is 212-252nm and 286-386nm, the yellowing resistance delta E is 0.42, and the limiting oxygen index is 28.2 percent.
As can be seen from the above examples and comparative examples, the preparation method provided by the invention makes full use of the synergistic effect between DOPO functionalized benzotriazole and nano zinc oxide, so that the polyurethane material has good ultraviolet absorption performance and flame retardant performance.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. A preparation method of a zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material comprises the following steps:
(1) mixing melamine, benzaldehyde and an organic solvent, and carrying out condensation reaction to obtain modified melamine;
(2) mixing the modified melamine obtained in the step (1) with benzotriazole and formaldehyde substances, and carrying out condensation reaction to obtain modified melamine functionalized benzotriazole; the formaldehyde substances comprise paraformaldehyde and/or formaldehyde; the chemical formula of the benzotriazole is as follows:
(3) mixing the modified melamine functionalized benzotriazole obtained in the step (2) with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a catalyst and an organic solvent, and carrying out addition reaction to obtain an organic ultraviolet absorbent;
(4) and (4) mixing the organic ultraviolet absorbent obtained in the step (3), nano zinc oxide and polyurethane to obtain the zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material.
2. The preparation method according to claim 1, wherein the temperature of the condensation reaction in the step (1) is 50-120 ℃, and the time of the condensation reaction is 1-5 h.
3. The method according to claim 1 or 2, wherein the ratio of the amounts of the melamine and benzaldehyde substances in step (1) is 1 (0.1-2).
4. The preparation method according to claim 1, wherein the temperature of the condensation reaction in the step (2) is 60-140 ℃ and the time of the condensation reaction is 1-5 h.
5. The method according to claim 1 or 4, wherein the ratio of the amounts of the modified melamine, benzotriazole and formaldehyde in step (2) is (0.1-2) to 1 (0.1-2).
6. The preparation method according to claim 1, wherein the temperature of the addition reaction in the step (3) is 60 to 140 ℃ and the time of the addition reaction is 1 to 5 hours.
7. The method according to claim 1 or 6, wherein the ratio of the amount of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in the step (3) to the amount of the benzotriazole in the step (2) is (0.1-2): 1.
8. The method according to claim 1, wherein the mixing in step (4) is carried out at a temperature of 20 to 200 ℃ for 0.1 to 5 hours.
9. The preparation method according to claim 1 or 8, wherein the ratio of the amounts of the organic ultraviolet absorber, the nano zinc oxide and the polyurethane in the step (4) is (0.5-5) to 1 (1-300).
10. The zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material prepared by the preparation method of any one of claims 1 to 9 comprises a polyurethane matrix and nano zinc oxide and DOPO functionalized benzotriazole distributed in the polyurethane matrix.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910693822.5A CN110540743B (en) | 2019-07-30 | 2019-07-30 | Zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910693822.5A CN110540743B (en) | 2019-07-30 | 2019-07-30 | Zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110540743A CN110540743A (en) | 2019-12-06 |
| CN110540743B true CN110540743B (en) | 2021-09-28 |
Family
ID=68709892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910693822.5A Active CN110540743B (en) | 2019-07-30 | 2019-07-30 | Zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110540743B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117659390B (en) * | 2024-02-01 | 2024-04-09 | 深圳东创技术股份有限公司 | Thermoplastic polyurethane material and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08113704A (en) * | 1994-10-17 | 1996-05-07 | Asahi Denka Kogyo Kk | Production of aqueous polyurethane composition having discoloration resistance |
| CN1702137A (en) * | 2005-06-25 | 2005-11-30 | 西南科技大学 | Process for preparing epoxy adhesive capable of curing at room temperature for special assembly |
| CN102924862A (en) * | 2012-11-29 | 2013-02-13 | 开滦（集团）有限责任公司 | Polyformaldehyde modified material and preparation method thereof |
| CN103012765A (en) * | 2012-12-08 | 2013-04-03 | 北京服装学院 | Preparation method for moisture-absorbing and flame-retardant polyester fiber |
| WO2013174791A1 (en) * | 2012-05-22 | 2013-11-28 | Basf Se | Phosphinyliminophosphoranes as flame retardants |
| CN104364305A (en) * | 2011-12-05 | 2015-02-18 | 科莱恩金融(Bvi)有限公司 | Mixtures of flame protection means containing flame protection means and aluminium phosphites, method for production and use thereof |
| CN104892886A (en) * | 2015-06-29 | 2015-09-09 | 杨秀莲 | Hard flame-retardant polyurethane foam low in smoke release |
| CN105566240A (en) * | 2016-03-10 | 2016-05-11 | 济南正骐生物科技有限公司 | Melamine condensed benzaldehyde mono-Schiff base and preparation method thereof |
| CN109679270A (en) * | 2018-11-21 | 2019-04-26 | 苏州市同发塑业有限公司 | A kind of ABS composite material and preparation method thereof of fire-retardant dumb light |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010003771A1 (en) * | 1999-03-03 | 2001-06-14 | Chun-Shan Wang | Phosphorus-containing flame-retardant cured epoxy resins |
-
2019
- 2019-07-30 CN CN201910693822.5A patent/CN110540743B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08113704A (en) * | 1994-10-17 | 1996-05-07 | Asahi Denka Kogyo Kk | Production of aqueous polyurethane composition having discoloration resistance |
| CN1702137A (en) * | 2005-06-25 | 2005-11-30 | 西南科技大学 | Process for preparing epoxy adhesive capable of curing at room temperature for special assembly |
| CN104364305A (en) * | 2011-12-05 | 2015-02-18 | 科莱恩金融(Bvi)有限公司 | Mixtures of flame protection means containing flame protection means and aluminium phosphites, method for production and use thereof |
| WO2013174791A1 (en) * | 2012-05-22 | 2013-11-28 | Basf Se | Phosphinyliminophosphoranes as flame retardants |
| CN102924862A (en) * | 2012-11-29 | 2013-02-13 | 开滦（集团）有限责任公司 | Polyformaldehyde modified material and preparation method thereof |
| CN103012765A (en) * | 2012-12-08 | 2013-04-03 | 北京服装学院 | Preparation method for moisture-absorbing and flame-retardant polyester fiber |
| CN104892886A (en) * | 2015-06-29 | 2015-09-09 | 杨秀莲 | Hard flame-retardant polyurethane foam low in smoke release |
| CN105566240A (en) * | 2016-03-10 | 2016-05-11 | 济南正骐生物科技有限公司 | Melamine condensed benzaldehyde mono-Schiff base and preparation method thereof |
| CN109679270A (en) * | 2018-11-21 | 2019-04-26 | 苏州市同发塑业有限公司 | A kind of ABS composite material and preparation method thereof of fire-retardant dumb light |
Non-Patent Citations (4)
| Title |
|---|
| "Fabrication and Characterization of Flame-Retardant Nanoencapsulated n-Octadecane with Melamine-Formaldehyde Shell for Thermal Energy Storage";Du, Xiaosheng，等;《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》;20181105;第6卷(第11期);第15541-15549页 * |
| "Flame retardant and thermal decomposition mechanism of poly(butylene terephthalate)/DOPO-HQ composites";He min，等;《POLYMER COMPOSITES》;20190331;第40卷(第3期);第974-985页 * |
| "Mechanical and drilling properties of graphene oxide modified urea-melamine-phenol formaldehyde composites reinforced by glass fiber";Cao Wu，等;《COMPOSITES PART B-ENGINEERING》;20181221;第162卷;第378-387页 * |
| "新型磷-氮-硅复合阻燃材料的制备及性能研究";张小博;《山东化工》;20200831;第49卷(第15期);第3-4,7页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110540743A (en) | 2019-12-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110655652B (en) | A kind of metal hybrid POSS flame retardant, preparation method and application | |
| CN101724226A (en) | Modified hot setting resin and preparation method thereof | |
| CN103073725B (en) | A kind of expanding fire retardant and preparation method thereof | |
| CN100513411C (en) | Double-ring cage shape substituted silsesquioxane and its preparation method and uses | |
| CN100558716C (en) | Benzoxazine resin intermediate and its preparation method and use | |
| CN103289125B (en) | Phosphorus-nitrogen-silicon containing organic and inorganic hybrid fire retardant and preparation method thereof and formed polymer | |
| CN107400197A (en) | A kind of reaction-type flame-retarding epoxy curing agent and preparation method thereof | |
| CN110540743B (en) | Zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material and preparation method thereof | |
| CN108456314A (en) | A kind of broad spectrum type lignin macromolecule ultra-violet protecting agent and preparation method thereof | |
| CN106565926A (en) | Anti-ultraviolet aging chain extender for polyurethane and preparation method thereof | |
| CN109369958B (en) | A kind of preparation method of organic modified zirconium phosphate and its application | |
| Selvaraj et al. | Development of high-performance hybrid sustainable bio-composites from biobased carbon reinforcement and cardanol-benzoxazine matrix | |
| CN110563944B (en) | A kind of polyphosphazene covalent triazine polymer and its preparation method and application | |
| CN115433405A (en) | Anti-aging light conversion material, anti-aging light conversion film and preparation method thereof | |
| CN108178835B (en) | A kind of hindered amine modified lignin and its preparation method and application | |
| CN107098937A (en) | Fire retardant and preparation method thereof | |
| CN116478065B (en) | Preparation of biomass epoxy resin with degradable and flame-retardant characteristics | |
| CN110483331B (en) | Benzophenone Schiff base ultraviolet absorber and preparation method thereof | |
| CN106810720A (en) | A kind of network structure carbon forming agent and its preparation method and application | |
| CN103073585B (en) | Phosphor silicon nitrogen ternary coordination fire retardant, preparation method and application | |
| CN117304505A (en) | Preparation method and application of a lignin-based light stabilizer | |
| CN103074698B (en) | Multifunctional polyester fiber and preparation method thereof | |
| TWI802109B (en) | Composite material, film, and light-emitting device | |
| CN105688850B (en) | A kind of preparation method of nanometer of sulfydryl polysilsesquioxane para-aramid fiber compound adsorbent | |
| CN112920160B (en) | Degradable monomer based on cyclic acetal structure, and synthesis method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |