CN114560992B - Preparation method of UV-cured flame-retardant transparent polyurethane - Google Patents

Preparation method of UV-cured flame-retardant transparent polyurethane Download PDF

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CN114560992B
CN114560992B CN202210059686.6A CN202210059686A CN114560992B CN 114560992 B CN114560992 B CN 114560992B CN 202210059686 A CN202210059686 A CN 202210059686A CN 114560992 B CN114560992 B CN 114560992B
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polyurethane
flame
phosphoric acid
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curing
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CN114560992A (en
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黄传霞
王自安
席日勇
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Hangzhou Yichuan New Material Co ltd
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Abstract

The invention relates to the field of organic polymer materials, and provides a preparation method of UV (ultraviolet) curing flame-retardant transparent polyurethane, which aims to solve the problems that a flame retardant is separated out from a material system or the light transmittance of the material is influenced, and the like.

Description

Preparation method of UV-cured flame-retardant transparent polyurethane
Technical Field
The invention relates to the field of organic high polymer materials, in particular to a preparation method of UV curing flame-retardant transparent polyurethane modified by copolymerization of annular tetrasilyl alcohol and alkyl phosphoric acid.
Background
The ultraviolet curing material has low energy consumption and no pollution in the preparation process, and is widely applied to a plurality of fields. The high-transparency ultraviolet light cured polyurethane has the advantages of good mechanical property, flexibility, good adhesion with a base material and the like, and is widely applied to coating, adhesive and sealing materials of electronic devices. However, polyurethane is inflammable, and its limiting oxygen index is only about 18, and when the temperature is higher than 160 deg.c, it is easy to decompose and self-ignite to release toxic gas, such as HCN, CO, etc. The flammability of polyurethane also forms a potential threat to our life and property safety, and thus, there is a need to develop transparent photocurable polyurethane materials with flame retardant properties.
The organic silicon material has the advantages of temperature resistance, weather resistance, ultraviolet radiation resistance and the like, and meanwhile, the organic silicon is a halogen-free flame retardant and is also a char-forming smoke suppressant. When the polysiloxane compound is used for flame retarding the high molecular material, most of polysiloxane can migrate to the surface of the material to form the high molecular shaving material with the surface being a polysiloxane enrichment layer. When the polyurethane copolymer containing silicon oxygen group is subjected to strong heat, an inorganic oxygen-insulating heat-insulating protective layer containing-Si-O-bond and-Si-C-bond can be formed, so that the thermal decomposition product is prevented from escaping, the thermal decomposition of the matrix material is inhibited, and the purposes of flame retardance, low smoke and low toxicity are achieved. At present, most of research is linear polysiloxane with active functional groups and POSS-containing flame retardants, and the two types can provide more silicon elements, are favorable for forming a good protective carbon layer in the combustion process, and play roles in coacervate phase flame retardance. However, the linear polysiloxane segments reach a certain length and the polyurethane modified therewith will be opaque. The hydroxyl-free polysilsesquioxane cannot participate in polyurethane synthesis reaction, and has poor solubility, if the hydroxyl-free polysilsesquioxane is directly added into a polyurethane system, the hydroxyl-free polysilsesquioxane can be separated out from the system, so that the transparency is affected, and the mechanical properties of the material are reduced. Although cage polysilsesquioxane with hydroxyl can participate in polyurethane synthesis reaction, the hydroxyl number is too large and concentrated, and the addition of a small amount of the cage polysilsesquioxane with hydroxyl can easily cause the cross-linking of a polymerization reaction system, thereby influencing the quality and the production safety of products.
The phosphorus flame retardant such as phosphate compound, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof is also an important halogen-free flame retardant, and has the advantages of high efficiency and low toxicity. It is typically used with silicone flame retardants to achieve phosphorus-silicon synergistic flame retardance. In the phosphorus-silicon synergistic flame-retardant system, organic silicon is degraded firstly when in combustion, and the organic silicon is migrated to the surface of a material due to small surface tension, so that the organic phosphorus is catalyzed to degrade into acid, the macromolecule is dehydrated to form carbon, the formed carbon layer is polymerized with silicon oxide with lower viscosity, the viscosity, strength and compactness of the carbon layer are increased, fragments or gas and the like generated by the macromolecule degradation are coated, a compact heat-insulating layer for insulating heat, air and the like is formed, and the combustion of the macromolecule material is stopped or slowed down, so that the flame retardance of the macromolecule material is improved. Similarly, the direct addition of phosphorus flame retardants to uv-curable polyurethanes also affects the light transmittance and mechanical properties of the cured product.
Disclosure of Invention
In order to solve the problems of precipitation of the flame retardant from a material system or influence on the light transmittance of the material, the invention provides a preparation method of the UV-cured flame-retardant transparent polyurethane, and the prepared material has excellent mechanical properties, good transparency and excellent flame retardant property and can be used for flame-retardant coating and flame-retardant sealant of optical devices.
The invention is realized by the following technical scheme: the preparation method of the UV curing flame-retardant transparent polyurethane comprises the following steps:
(1) Adding annular tetrasilicon alcohol, dialkyl phosphoric acid, polyether glycol, a catalyst and a solvent into a reaction container, and dropwise adding diisocyanate at 40-80 ℃ to react for 2-8 hours to obtain isocyanate-terminated polyurethane;
the annular tetrasilicon alcohol is one or more selected from tetramethyl tetrasilicon alcohol, tetraphenyl tetrasilicon alcohol and tetravinyl tetrasilicon alcohol. Prepared according to a conventional method, the reaction structural formula is shown as follows:
wherein R is selected from CH 3 -、C 6 H 5 -、CH 2 CH-, and one of CH-.
The annular silicon tetraol can generate an inorganic oxygen-isolating heat-insulating protective layer containing Si-O bonds and/or Si-C bonds in the combustion process, so that the overflow of combustion decomposition products is prevented, the thermal decomposition is inhibited, and the flame retardance of the material is improved.
The dibasic alkyl phosphoric acid is selected from one or more of methyl phosphoric acid, phenyl phosphoric acid, propyl phosphonic acid and butyl phosphonic acid, and the structural formula is shown as follows:
the polyether glycol is one or more of PEG-200, PEG-400, PEG-600, PEG-800, PPG-1000 and PPG-2000 which are sold in the market; preferably, the polyether glycol is one or more selected from PEG-400, PEG-600, PPG-1000 and PPG-2000;
the mole numbers of the hydroxyl groups of the annular silicon tetraol, the dialkyl phosphoric acid and the polyether glycol are the total hydroxyl groups, wherein the hydroxyl groups of the annular silicon tetraol account for 1-25% of the total amount, the hydroxyl groups of the dialkyl phosphoric acid account for 1-25% of the total amount, and the hydroxyl groups of the polyether glycol account for the rest of the total hydroxyl groups.
The diisocyanate is selected from one or more of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate isomer mixture (TDI), diphenylmethane diisocyanate (MDI), 1, 6-Hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI); preferably, the diisocyanate is selected from one or more of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate isomer mixture (TDI), 1, 6-Hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI). The amount of diisocyanate to be used is such that the molar ratio of the amount of hydroxyl groups in the diisocyanate groups to the total amount of hydroxyl groups is 1.4:1 to 2.0:1, and more preferably, the diisocyanate groups are added dropwise under nitrogen protection.
The catalyst is diisobutyl tin dilaurate, the use amount of the catalyst is 0.1-1 wt% of the total mass of the annular tetra-silanol, the dialkyl phosphoric acid and the polyether glycol, and preferably, the use amount of the catalyst diisobutyl tin dilaurate is 0.4-0.8 wt% of the total mass of the annular tetra-silanol, the dialkyl phosphoric acid and the polyether glycol.
The solvent is selected from one or more of acetone, tetrahydrofuran, dichloroethane and dichloromethane, the use amount is the amount for dissolving the solute, preferably 0.5-1.5 times of the total mass of the annular tetrasilicon alcohol, the dialkyl phosphoric acid and the polyether glycol, and the solvent is used for uniform reaction materials and full reaction.
By adopting a method of copolymerization modification of annular tetrasilicon alcohol, alkyl phosphoric acid, polyether glycol and diisocyanate, phosphorus is introduced into polyurethane molecular chains, and phosphorus-containing chain segments are partially decomposed in the initial stage of fire, so that polyurethane dehydration and carbonization can be promoted, the amount of combustible gas generated by thermal decomposition of polyurethane is reduced, and the generated carbon film can isolate external air and heat.
(2) Reacting isocyanate-terminated polyurethane with methacrylate with hydroxyl at 40-80 ℃ for 2-4 h, decompressing at 80-100 ℃/130mmHg until no fraction is generated in 5min, and evaporating the solvent to obtain acrylate-terminated polyurethane;
the methacrylate with hydroxyl is at least one of hydroxyethyl methacrylate and hydroxypropyl methacrylate.
The molar ratio of hydroxyl in the methacrylate with hydroxyl to isocyanate groups in the isocyanate-terminated polyurethane is 1:1, and the hydroxyl-based hydroxypropyl methacrylate is not reacted completely, and the hydroxyl-based hydroxypropyl methacrylate exists in small molecules, so that the performance is affected; the isocyanate is excessive, and the isocyanate is easy to foam and is unstable in storage. (3) And (3) carrying out UV irradiation reaction and curing on the polyurethane blocked by acrylic ester under the initiation of an initiator for 30-120 s to obtain the UV curing flame-retardant transparent polyurethane.
The initiator is an ultraviolet initiator and is selected from one of commercially available initiators 1173 and 184, and the use amount of the initiator is 1-9% of the total mass of the polyurethane blocked by acrylic ester; preferably, the initiator is used in an amount of 3 to 6% of the total mass of the acrylate-terminated polyurethane.
The UV irradiation reaction curing conditions are as follows: the power of the light source is 100W-1000W, the main peak wavelength is 365nm or 405nm, the distance from the light source is 20cm, the hardness of the pencil is increased along with the longer curing time, the crosslinking density of the curing reaction is gradually increased, but the crosslinking density is kept unchanged after the curing reaction is increased to a certain time. Generally, the pencil hardness is first increased, then unchanged, and then slightly decreased (because of degradation caused by long irradiation time). The curing time is preferably 40 to 90s.
The invention adopts a method of copolymerization modification of annular tetra-silanol with four hydroxyl groups and alkyl phosphoric acid with two hydroxyl groups, polyether glycol and diisocyanate to prepare the phosphorus-silicon synergistic flame-retardant ultraviolet light-cured transparent polyurethane material, and overcomes the problems of poor compatibility of a flame retardant and polyurethane, easy precipitation, poor mechanical property of a condensate and the like in the existing organic silicon modified transparent polyurethane flame-retardant modification, thus obtaining the ultraviolet light-cured transparent polyurethane with high transparency, excellent mechanical property and excellent flame retardant property. The prepared UV cured flame-retardant transparent polyurethane has the tensile strength of 1.0-5.5 MPa, the limiting oxygen index of 24-32, the pencil hardness of H-6H and the light transmittance of 80-95 percent, and can be applied to flame-retardant coating and flame-retardant sealant of optical devices.
Compared with the prior art, the invention has the beneficial effects that: the obtained material has excellent mechanical property, good transparency and excellent flame retardant property.
Detailed Description
The technical scheme of the present invention is further described by the following specific examples, but the examples are not intended to limit the scope of the present invention. Unless otherwise indicated, all materials used in the examples of the present invention are those commonly used in the art, and all methods used in the examples are those commonly used in the art.
In this embodiment, the analytical test method is as follows:
limiting Oxygen Index (LOI) test: sample sizes of 130mm by 6mm by 3mm were performed according to ASTM D2683;
tensile strength test: according to GB/T528-2009/ISO 37:2005, 5 averages were tested on an A1-7000M-GD tensile tester;
light transmittance test: the ultraviolet-visible spectrophotometer type 300 Evolution of Thermo Fisher company in the United states of America is used for testing the light transmittance of the polymer, the testing wavelength range is 400-800 nm, and the thickness of the sample is 10mm;
pencil hardness: the hardness of the paint film is measured according to GB/T6739-2006 "measurement of paint film hardness by the method of paint and varnish pencil".
Example 1
(1) 30.40g of tetramethyl tetrahydroxy cyclotetrasilanol, 19.20g of methyl phosphoric acid, 320.0g of PEG-800, 1.478g of diisobutyl tin dilaurate and 184.80g of acetone are added into a clean 2L four-neck flask with a thermometer, the mixture is stirred for 5min under the protection of nitrogen, 355.71g of IPDI is added dropwise, and then the temperature is raised to 80 ℃ for reaction for 3h, so that isocyanate-terminated polyurethane is obtained;
(2) Adding 208.29g of hydroxyethyl methacrylate into the isocyanate-terminated polyurethane obtained in the step (1), continuing to react for 3 hours at 80 ℃, decompressing at 80 ℃/130mmHg until no fraction exists for 5min, and evaporating the solvent to obtain transparent liquid, namely the polyurethane which is modified by copolymerization of acrylic ester-terminated, annular tetra-silanol and alkyl phosphoric acid;
(3) Adding an ultraviolet initiator 1173 into the acrylate-terminated polyurethane obtained in the step (2), wherein the use amount of the ultraviolet initiator is 5wt% of the acrylate-terminated polyurethane, and the ultraviolet initiator is used for initiating and curing, the power of a light source is 1000W, the wavelength of a main peak is 365nm, and the distance from the light source is 20cm; the properties of the obtained UV-cured transparent flame retardant material were changed with curing time as shown in Table 1.
TABLE 1 Material Properties prepared at different UV curing times
Example 2
The preparation method of example 1 was followed except that the amount of the ultraviolet initiator 1173 used in step (3) was such that the initiation curing time was 90s, to obtain a UV-cured transparent flame retardant material, the properties of which are shown in table 2.
TABLE 2 Material Properties prepared with different initiator amounts
Example 3
(1) 30.40g of tetramethyl tetrahydroxy cyclotetrasilanol, 19.20g of methyl phosphoric acid, 80.0g of PEG-200, 1.296g of diisobutyl tin dilaurate and 129.6g of acetone are added into a clean 2L four-neck flask with a thermometer inserted, the mixture is stirred for 5min under the protection of nitrogen, 355.71g of IPDI is added dropwise, and then the temperature is raised to 80 ℃ for reaction for 3h, so that isocyanate-terminated polyurethane is obtained;
(2) Adding 208.29g of hydroxyethyl methacrylate into the obtained isocyanate-terminated polyurethane, continuing to react for 3 hours at 80 ℃, decompressing at 80 ℃/130mmHg until no fraction exists for 5 minutes, and evaporating the solvent to obtain transparent liquid, namely the polyurethane which is modified by copolymerization of acrylic ester-terminated, annular tetra-silanol and alkyl phosphoric acid;
(3) To 20g of the resulting acrylate-terminated polyurethane was added 0.2g of an ultraviolet initiator 184, and the curing conditions of the UV irradiation reaction were: the power of the light source is 1000W, the main peak wavelength is 405nm, the distance from the light source is 20cm, and the ultraviolet light initiates curing for 90s to obtain UV curing flame-retardant transparent polyurethane;
the gel rate of the prepared UV curing flame-retardant transparent polyurethane is 99.0%, the pencil hardness is 6H, the light transmittance is 88.4%, the tensile strength is 5.5MPa, and the limiting oxygen index is 32.0.
Example 4
(1) 55.20g of tetraphenyl tetrahydroxy-cyclotetrasilanol, 31.618g of phenylphosphoric acid, 160.0g of PEG-400, 0.247g of diisobutyl tin dilaurate and 370.7g of dichloroethane are added into a clean 2L four-neck flask which is inserted with a thermometer, stirred for 5min under the protection of nitrogen, then 269.11g of HDI is added dropwise, and then the temperature is raised to 40 ℃ for reaction for 8h, so that isocyanate-terminated polyurethane is obtained;
(2) Adding 208.23g of hydroxyethyl methacrylate into the obtained isocyanate-terminated polyurethane, continuing to react for 4 hours at 40 ℃, decompressing at 80 ℃/130mmHg until no fraction exists for 5 minutes, and evaporating the solvent to obtain transparent liquid, namely the polyurethane which is modified by copolymerization of acrylic ester-terminated, annular tetra-silanol and alkyl phosphoric acid;
(3) To 20g of the resulting acrylate-terminated polyurethane was added 0.3g of an ultraviolet initiator 1173 under the following UV irradiation reaction curing conditions: the power of the light source is 800W, the main peak wavelength is 405nm, the distance from the light source is 20cm, and the ultraviolet light is cured for 70 seconds to obtain UV curing flame-retardant transparent polyurethane;
the gel rate of the obtained UV curing flame-retardant transparent polyurethane is 99.5%, the pencil hardness is 6H, the light transmittance is 90.0%, the tensile strength is 5.1MPa, and the limiting oxygen index is 31.0.
Example 5
(1) 35.20g of tetravinyl tetrahydroxy-cyclotetrasilanol, 24.816g of propylphosphoric acid, 240.0g of PEG-600, 1.201g of diisobutyl tin dilaurate and 300.3g of tetrahydrofuran are added into a clean 2L four-neck flask which is inserted with a thermometer, stirred for 5min under the protection of nitrogen, 400.4g of MDI is added dropwise, and then the temperature is raised to 80 ℃ for reaction for 2h, so that isocyanate-terminated polyurethane is obtained;
(2) Adding 208.23g of hydroxyethyl methacrylate into the obtained isocyanate-terminated polyurethane, continuing to react for 2 hours at 80 ℃, decompressing at 100 ℃/130mmHg until no fraction exists for 5 minutes, and evaporating the solvent to obtain transparent liquid, namely the polyurethane which is modified by copolymerization of acrylic ester-terminated, annular tetra-silanol and alkyl phosphoric acid;
(3) To 20g of the resulting acrylate-terminated polyurethane was added 0.4g of an ultraviolet initiator 1173 under the following UV irradiation reaction curing conditions: the power of the light source is 500W, the main peak wavelength is 365nm, the distance from the light source is 20cm, and the ultraviolet light initiates curing for 70s to obtain UV curing flame-retardant transparent polyurethane;
the gel rate of the obtained UV curing flame-retardant transparent polyurethane is 99.0%, the pencil hardness is 5H, the light transmittance is 92.5%, the tensile strength is 5.3MPa, and the limiting oxygen index is 30.5.
Example 6
(1) 55.20g of tetraphenyl tetrahydroxy-cyclotetrasilanol, 31.618g of phenylphosphoric acid, 400.0g of PPG-1000, 2.923g of diisobutyl tin dilaurate and 243.6g of methylene dichloride are added into a clean 2L four-neck flask which is inserted with a thermometer, after stirring for 5min under the protection of nitrogen, 278.65g of TDI is added dropwise, and then the temperature is raised to 40 ℃ for reaction for 8h, so that isocyanate-terminated polyurethane is obtained;
(2) Adding 208.23g of hydroxyethyl methacrylate into the obtained isocyanate-terminated polyurethane, continuing to react for 4 hours at 40 ℃, decompressing at 90 ℃/130mmHg until no fraction exists for 5 minutes, and evaporating the solvent to obtain transparent liquid, namely the polyurethane which is modified by copolymerization of acrylic ester-terminated, annular tetra-silanol and alkyl phosphoric acid;
(3) To 20g of the resulting acrylate-terminated polyurethane was added 0.5g of an ultraviolet initiator 1173 under the following UV irradiation reaction curing conditions: the power of the light source is 400W, the main peak wavelength is 365nm, the distance from the light source is 20cm, and the ultraviolet light initiates curing for 80 seconds to obtain UV curing flame-retardant transparent polyurethane;
the gel rate of the obtained UV curing flame-retardant transparent polyurethane is 99.5%, the pencil hardness is 4H, the light transmittance is 95.0%, the tensile strength is 4.2MPa, and the limiting oxygen index is 30.0.
Example 7
(1) 55.20g of tetraphenyl tetrahydroxy-cyclotetrasilanol, 31.618g of phenylphosphoric acid, 800.0g of PPG-2000, 2.923g of diisobutyl tin dilaurate and 643.6g of methylene dichloride are added into a clean 2L four-neck flask which is inserted with a thermometer, after stirring for 5min under the protection of nitrogen, 278.65g of TDI is added dropwise, and then the temperature is raised to 40 ℃ for reaction for 8h, so that isocyanate-terminated polyurethane is obtained;
(2) Adding 208.23g of hydroxyethyl methacrylate into the obtained isocyanate-terminated polyurethane, continuing to react for 4 hours at 40 ℃, decompressing at 90 ℃/130mmHg until no fraction exists for 5 minutes, and evaporating the solvent to obtain transparent liquid, namely the polyurethane which is modified by copolymerization of acrylic ester-terminated, annular tetra-silanol and alkyl phosphoric acid;
(3) To 20g of the resulting acrylate-terminated polyurethane was added 0.6g of an ultraviolet initiator 1173 under the following UV irradiation reaction curing conditions: the power of the light source is 400W, the main peak wavelength is 405nm, the distance from the light source is 20cm, and the ultraviolet light initiates curing for 80 seconds to obtain UV curing flame-retardant transparent polyurethane;
the gel rate of the obtained UV curing flame-retardant transparent polyurethane is 99.5%, the pencil hardness is 3H, the light transmittance is 95.0%, the tensile strength is 3.0MPa, and the limiting oxygen index is 29.5.
Example 8
(1) 27.60g of tetraphenyl tetrahydroxy-cyclotetrasilanol, 13.81g of butyl phosphoric acid, 360.0g of PEG-600, 3.212g of diisobutyl tin dilaurate and 300.3g of tetrahydrofuran are added into a clean 2L four-neck flask which is inserted with a thermometer, stirred for 5min under the protection of nitrogen, 390.95g of MDI is added dropwise, and then the temperature is raised to 80 ℃ for reaction for 2h to obtain isocyanate-terminated polyurethane;
(2) Adding 203.31g of hydroxyethyl methacrylate into the obtained isocyanate-terminated polyurethane, continuing to react for 2 hours at 80 ℃, decompressing at 100 ℃/130mmHg until no fraction exists for 5 minutes, and evaporating the solvent to obtain transparent liquid, namely the polyurethane which is modified by copolymerization of acrylic ester-terminated, annular tetra-silanol and alkyl phosphoric acid;
(3) To 20g of the resulting acrylate-terminated polyurethane was added 0.7g of an ultraviolet initiator 1173 under the following UV irradiation reaction curing conditions: the power of the light source is 800W, the main peak wavelength is 365nm, the distance from the light source is 20cm, and the ultraviolet light initiates curing for 80 seconds to obtain UV curing flame-retardant transparent polyurethane;
the gel fraction of the obtained UV cured flame-retardant transparent polyurethane is 99.8%, the pencil hardness is 5H, the light transmittance is 92.5%, the tensile strength is 5.0MPa, and the limiting oxygen index is 28.0.
Example 9
(1) 13.875g of tetraphenyl tetrahydroxy-cyclotetrasilanol, 6.905g of butyl phosphoric acid, 420.0g of PEG-600, 3.212g of diisobutyl tin dilaurate and 300.3g of tetrahydrofuran are added into a clean 2L four-neck flask with a thermometer inserted, stirred for 5min under the protection of nitrogen, then 400.54g of MDI is added dropwise, and then the temperature is raised to 80 ℃ for reaction for 2h to obtain isocyanate-terminated polyurethane;
(2) Adding 208.29g of hydroxyethyl methacrylate into the obtained isocyanate-terminated polyurethane, continuing to react for 3 hours at 70 ℃, decompressing at 100 ℃/130mmHg until no fraction exists for 5 minutes, and evaporating the solvent to obtain transparent liquid, namely the polyurethane which is modified by copolymerization of acrylic ester-terminated, annular tetra-silanol and alkyl phosphoric acid;
(3) To 20g of the resulting acrylate-terminated polyurethane was added 0.8g of an ultraviolet initiator 1173 under the following UV irradiation reaction curing conditions: the power of the light source is 300W, the main peak wavelength is 405nm, the distance from the light source is 20cm, and the ultraviolet light initiates curing for 90s to obtain UV curing flame-retardant transparent polyurethane;
the gel rate of the obtained UV curing flame-retardant transparent polyurethane is 99.8%, the pencil hardness is 4H, the light transmittance is 95.0%, the tensile strength is 4.0MPa, and the limiting oxygen index is 26.5.
Example 10
(1) 6.938g of tetraphenyl tetrahydroxy-cyclotetrasilanol, 3.453g of butyl phosphoric acid, 450.0g of PEG-600, 3.212g of diisobutyl tin dilaurate and 300.3g of tetrahydrofuran are added into a clean 2L four-neck flask with a thermometer inserted, stirred for 5min under the protection of nitrogen, then 400.47g of MDI is added dropwise, and the temperature is raised to 50 ℃ for 7h of reaction, so that isocyanate-terminated polyurethane is obtained;
(2) Adding 208.26g of hydroxyethyl methacrylate into the obtained isocyanate-terminated polyurethane, continuing to react for 3 hours at 60 ℃, decompressing at 100 ℃/130mmHg until no fraction exists for 5 minutes, and evaporating the solvent to obtain transparent liquid, namely the polyurethane which is modified by copolymerization of acrylic ester-terminated, annular tetra-silanol and alkyl phosphoric acid;
(3) To 20g of the resulting acrylate-terminated polyurethane was added 0.9g of an ultraviolet initiator 1173 under the following UV irradiation reaction curing conditions: the power of the light source is 200W, the main peak wavelength is 405nm, the distance from the light source is 20cm, and the ultraviolet light initiates curing for 90s to obtain UV curing flame-retardant transparent polyurethane;
the gel rate of the obtained UV curing flame-retardant transparent polyurethane is 99.8%, the pencil hardness is 2H, the light transmittance is 95.0%, the tensile strength is 2.8MPa, and the limiting oxygen index is 25.5.
Example 11
(1) 2.220g of tetraphenyl tetrahydroxy-cyclotetrasilanol, 1.105g of butyl phosphoric acid, 470.4g of PEG-600, 3.212g of diisobutyl tin dilaurate and 300.3g of tetrahydrofuran are added into a clean 2L four-neck flask with a thermometer inserted, stirred for 5min under the protection of nitrogen, then 400.43g of MDI is added dropwise, and then the temperature is raised to 50 ℃ for reaction for 7h, so that isocyanate-terminated polyurethane is obtained;
(2) Adding 230.68g of hydroxypropyl methacrylate into the obtained isocyanate-terminated polyurethane, continuing to react for 4 hours at 50 ℃, decompressing at 100 ℃/130mmHg until no fraction exists for 5 minutes, and evaporating the solvent to obtain transparent liquid, namely the polyurethane which is modified by copolymerization of acrylic ester-terminated, annular tetra-silanol and alkyl phosphoric acid;
(3) To 20g of the resulting acrylate-terminated polyurethane was added 1g of an ultraviolet initiator 1173 under the following UV irradiation reaction curing conditions: the power of the light source is 200W, the main peak wavelength is 405nm, the distance from the light source is 20cm, and the ultraviolet light initiates curing for 90s to obtain UV curing flame-retardant transparent polyurethane;
the gel rate of the obtained UV curing flame-retardant transparent polyurethane is 99.8%, the pencil hardness is 2H, the light transmittance is 95.0%, the tensile strength is 2.0MPa, and the limiting oxygen index is 24.0.
Example 12
(1) 27.60g of tetraphenyl tetrahydroxy-cyclotetrasilanol, 13.81g of butyl phosphoric acid, 360.0g of PEG-600, 3.212g of diisobutyl tin dilaurate and 300.3g of tetrahydrofuran are added into a clean 2L four-neck flask which is inserted with a thermometer, stirred for 5min under the protection of nitrogen, 400.40g of MDI is added dropwise, and then the temperature is raised to 70 ℃ for reaction for 4h to obtain isocyanate-terminated polyurethane;
(2) Adding 208.22g of hydroxyethyl methacrylate into the obtained isocyanate-terminated polyurethane, continuing to react for 4 hours at 40 ℃, decompressing at 100 ℃/130mmHg until no fraction exists for 5 minutes, and evaporating the solvent to obtain transparent liquid, namely the polyurethane which is modified by copolymerization of acrylic ester-terminated, annular tetra-silanol and alkyl phosphoric acid;
(3) To 20g of the resulting acrylate-terminated polyurethane was added 1.1g of an ultraviolet initiator 1173 under the following UV irradiation reaction curing conditions: the power of the light source is 1000W, the main peak wavelength is 365nm, the distance from the light source is 20cm, and the ultraviolet light initiates curing for 90s to obtain the UV curing flame-retardant transparent polyurethane;
the gel rate of the obtained UV curing flame-retardant transparent polyurethane is 99.0%, the pencil hardness is 6H, the light transmittance is 94.2%, the tensile strength is 5.5MPa, and the limiting oxygen index is 27.5.
Example 13
(1) 27.60g of tetraphenyl tetrahydroxy-cyclotetrasilanol, 13.81g of butyl phosphoric acid, 360.0g of PEG-600, 3.212g of diisobutyl tin dilaurate and 300.3g of tetrahydrofuran are added into a clean 2L four-neck flask which is inserted with a thermometer, stirred for 5min under the protection of nitrogen, 300.30g of MDI is added dropwise, and then the temperature is raised to 70 ℃ for reaction for 3h to obtain isocyanate-terminated polyurethane;
(2) Adding 104.11g of hydroxyethyl methacrylate into the obtained isocyanate-terminated polyurethane, continuing to react for 2 hours at 80 ℃, decompressing at 100 ℃/130mmHg until no fraction exists for 5min, and evaporating the solvent to obtain transparent liquid, namely the polyurethane which is modified by copolymerization of acrylic ester-terminated, annular tetra-silanol and alkyl phosphoric acid;
(3) To 20g of the resulting acrylate-terminated polyurethane was added 1.2g of an ultraviolet initiator 1173 under the following UV irradiation reaction curing conditions: the power of the light source is 1000W, the main peak wavelength is 365nm, the distance from the light source is 20cm, and the ultraviolet light initiates curing for 90s to obtain the UV curing flame-retardant transparent polyurethane;
the gel rate of the obtained UV curing flame-retardant transparent polyurethane is 90.2%, the pencil hardness is 3H, the light transmittance is 90.0%, the tensile strength is 3.0MPa, and the limiting oxygen index is 28.5.
Example 14
(1) 27.60g of tetraphenyl tetrahydroxy-cyclotetrasilanol, 13.81g of butyl phosphoric acid, 360.0g of PEG-600, 3.212g of diisobutyl tin dilaurate and 300.3g of tetrahydrofuran are added into a clean 2L four-neck flask which is inserted with a thermometer, stirred for 5min under the protection of nitrogen, 360.36g of MDI is added dropwise, and then the temperature is raised to 60 ℃ for reaction for 5h, so that isocyanate-terminated polyurethane is obtained;
(2) Adding 166.58g of hydroxyethyl methacrylate into the obtained isocyanate-terminated polyurethane, continuing to react for 2 hours at 80 ℃, decompressing at 100 ℃/130mmHg until no fraction exists for 5 minutes, and evaporating the solvent to obtain transparent liquid, namely the polyurethane which is modified by copolymerization of acrylic ester-terminated, annular tetra-silanol and alkyl phosphoric acid;
(3) To 20g of the resulting acrylate-terminated polyurethane was added 1.4g of an ultraviolet initiator 1173 under the following UV irradiation reaction curing conditions: the power of the light source is 1000W, the main peak wavelength is 365nm, the distance from the light source is 20cm, and the ultraviolet light initiates curing for 90s to obtain the UV curing flame-retardant transparent polyurethane;
the gel fraction of the obtained UV cured flame-retardant transparent polyurethane is 92.5%, the pencil hardness is 5H, the light transmittance is 91.5%, the tensile strength is 3.4MPa, and the limiting oxygen index is 28.5.

Claims (7)

1. The preparation method of the UV curing flame-retardant transparent polyurethane is characterized by comprising the following steps of:
(1) Adding annular tetrasilicon alcohol, dialkyl phosphoric acid, polyether glycol, a catalyst and a solvent into a reaction container, and dropwise adding diisocyanate at 40-80 ℃ to react for 2-8 hours to obtain isocyanate-terminated polyurethane;
the annular tetrasilicon alcohol is one or more selected from tetramethyl tetrasilicon alcohol, tetraphenyl tetrasilicon alcohol and tetravinyl tetrasilicon alcohol, and the structural formula is as follows:
wherein R is selected from CH 3 -、C 6 H 5 -、CH 2 One of CH-;
the dibasic alkyl phosphoric acid is selected from one or more of methyl phosphoric acid, phenyl phosphonic acid, propyl phosphonic acid and butyl phosphonic acid, and the structural formula is shown as follows;
；
the molar numbers of the hydroxyl groups of the annular silicon tetraol, the dialkyl phosphoric acid and the polyether glycol are the total hydroxyl groups, wherein the hydroxyl groups of the annular silicon tetraol account for 1-25% of the total amount, the hydroxyl groups of the dialkyl phosphoric acid account for 1-25% of the total amount, and the hydroxyl groups of the polyether glycol account for the rest of the total hydroxyl groups;
(2) Reacting isocyanate-terminated polyurethane with methacrylate with hydroxyl at 40-80 ℃ for 2-4 hours, and evaporating the solvent at 80-100 ℃/130mmHg under reduced pressure to obtain acrylate-terminated polyurethane;
(3) And curing the acrylate-terminated polyurethane for 30-120 s under the initiation of an initiator to obtain the UV-cured flame-retardant transparent polyurethane.
2. The method for preparing the UV-curable flame-retardant transparent polyurethane according to claim 1, wherein the diisocyanate is used in a molar ratio of the amount of isocyanate groups in the diisocyanate groups to the total amount of hydroxyl groups of 1.4:1-2.0:1.
3. The method for preparing the UV-cured flame-retardant transparent polyurethane according to claim 1, wherein the catalyst in the step (1) is diisobutyl tin dilaurate, and the use amount is 0.1-1wt% of the total mass of the annular tetrasilyl alcohol, the dialkyl phosphoric acid and the polyether glycol.
4. The method for producing a UV-curable flame-retardant transparent polyurethane according to claim 1, wherein the molar ratio of hydroxyl groups in the hydroxyl-group-containing methacrylate to isocyanate groups in the isocyanate-terminated polyurethane in the step (2) is 1:1.
5. The method for preparing the UV-curable flame-retardant transparent polyurethane according to claim 1, wherein the initiator in the step (3) is used in an amount of 1-9% of the total mass of the acrylate-terminated polyurethane.
6. The method for producing a UV-curable flame-retardant transparent polyurethane according to claim 1 or 5, wherein the UV-irradiation reaction curing conditions are: the power of the light source is 100W-1000W, the main peak wavelength is 365nm or 405nm, and the distance from the light source is 20cm.
7. The method for preparing the UV-cured flame-retardant transparent polyurethane according to claim 1, wherein the tensile strength of the UV-cured flame-retardant transparent polyurethane is 1.0-5.5 MPa, the limiting oxygen index is 24-32, the pencil hardness is H-6H, and the light transmittance is 80-95%.
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Citations (2)

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Publication number Priority date Publication date Assignee Title
US3245922A (en) * 1961-06-01 1966-04-12 Hooker Chemical Corp Phosphorus-containing urethane compositions
CN108456483A (en) * 2018-02-08 2018-08-28 湖州科博信息科技有限公司 A kind of one pack system water proof fire retardant polyurethane coating

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3245922A (en) * 1961-06-01 1966-04-12 Hooker Chemical Corp Phosphorus-containing urethane compositions
CN108456483A (en) * 2018-02-08 2018-08-28 湖州科博信息科技有限公司 A kind of one pack system water proof fire retardant polyurethane coating

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