Fluorescent polyurethane rigid foam as well as preparation method and application thereof

Abstract

The invention discloses fluorescent polyurethane rigid foam as well as a preparation method and application thereof.The fluorescent polyurethane rigid foam comprises a component A and a component B. The component A comprises the following components in parts by weight: 5-20 parts of polyether polyol; 10 to 30 parts of polyether polyol with a fluorescent effect; 10 to 40 parts of aromatic polyester polyol; 10 to 40 parts of a flame retardant; 2-5 parts of a foam stabilizer; 0.1 to 2 parts of an amine catalyst; 1-8 parts of a trimerization catalyst; 10-20 parts of a foaming agent; and the component B is isocyanate. The fluorescent polyurethane rigid foam prepared by the invention can be used in the anti-counterfeiting field of high-end polyurethane rigid foam, inorganic pigments are not required to be added, and production equipment cannot be colored, so that the production efficiency is improved, and the equipment investment is reduced; foaming equipment is not damaged; the field detection is fast and efficient and is not easy to imitate.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of polyurethane rigid foam, in particular to a fluorescent polyurethane rigid foam, and a preparation method and use thereof. BACKGROUND

[0002] Polyurethane rigid foam is an important synthetic polymer material, which has excellent physical and mechanical properties, chemical resistance, and unique excellent thermal insulation performance. Generally, polyurethane rigid foam can be prepared from isocyanate and combined polyether two components, and the combined polyether is generally composed of polyether polyol, polyester polyol, blowing agent, catalyst and other components. Fluorescence is a photoluminescence phenomenon. When a certain substance is excited by a specific wavelength of incident light, it absorbs light energy and enters an excited state, and emits light of a specific color to return to the ground state.

[0003] In view of the different performance requirements of polyurethane in the market, such as low thermal conductivity, high strength, high flame retardance, etc., various companies have developed differentiated products to meet market demand. In order to show the uniqueness of the product, special colors are often used to improve the recognition. At present, there are two methods to change the color of polyurethane: adding inorganic pigment particles and organic pigments. Common inorganic pigments include metal oxides, sulfides and sulfates, chromates, molybdates, etc. Inorganic pigment particles have strong thermal stability and light stability, but the tinting strength is poor. Common organic pigments include azo pigments, lake pigments, heterocyclic pigments, condensed ring ketone pigments, etc. Organic pigments have strong tinting strength, but they are prone to oxidation in the later stage. The above two color changing methods give polyurethane different colors and improve the recognition, but they are easy to be imitated by competitors and it is difficult to establish a real technical barrier. In the production process, pigments are also easy to adhere to the production pipeline or reaction kettle, causing pollution to other products, so a special production line needs to be established, increasing the cost. In addition, the addition of inorganic pigment particles will also affect the foaming equipment, which is easy to cause wear of the injection pump and blockage of the foaming gun head.

[0004] In summary, there is an urgent need for a high-performance polyurethane rigid foam combination material that can solve the problems of easy imitation, high cost, and damaged equipment, while maintaining the excellent physical properties of polyurethane. SUMMARY

[0005] In view of the above problems, the purpose of the present application is to provide a fluorescent polyurethane rigid foam and a preparation method and use thereof. In the synthesis of polyether, a naphthalimide group with a helical conformation is introduced. This group has an aggregation-induced emission effect. When the molecule is aggregated in the polyurethane rigid foam, it emits light of a specific color under the excitation of a specific wavelength of ultraviolet light, giving the polyurethane anti-counterfeiting function. This method does not require additional production equipment and does not require additional costs; the molecule has no difference from conventional polyether and will not cause damage to the foaming equipment; the naphthalene ring structure in the molecule also gives the polyurethane rigid foam higher strength, providing customers with high-value products.

[0006] To achieve the above-mentioned object, the technical scheme adopted by the present application is as follows:

[0007] A fluorescent polyurethane rigid foam, raw materials including A component and B component, the mass ratio of the A component and the B component is 100:130-250;

[0008] Among the A component, the following components are included by weight parts:

[0009]

[0010] The B component is isocyanate.

[0011] The polyether polyol functionality is 2-5, the hydroxyl value is 80-450 mgKOH / g, the viscosity is 100-30000 mPa.s, and the water content is less than 0.1%.

[0012] In a preferred example of the present application, the polyether polyol is a product obtained by reacting a trifunctional glycerol and / or a difunctional diethylene glycol as a starter.

[0013] The hydroxyl value of the fluorescent polyether polyol is 80-230 mgKOH / g, and its structural formula is as follows:

[0014]

[0015] Wherein 2≤X≤4, 1≤Y≤3.

[0016] The fluorescent polyether polyol is formed by using a diethylene glycol and other active monomers as a starter, and initiating the formation of a hydroxyl-terminated polyether by using an epoxy propane and an oxidized naphthalimide fluorescent monomer under the action of a catalyst. In an embodiment, the molar ratio of the epoxy propane and the oxidized naphthalimide fluorescent monomer is 1:1.1-1:1.3, the catalyst is one or more of di-n-butylamine, zinc oxide, dibutyltin dilaurate, and titanium acid tetraisopropyl ester, the reaction temperature is 140-180℃, and the reaction time is 8-10 hours.

[0017]

[0018] A synthesis process of the oxidized naphthalimide fluorescent monomer is as follows: 4-bromo-1,8-naphthalic anhydride reacts with allylamine in an ethanol solution at 80-100℃ to generate a naphthalic anhydride with a double bond; then a nucleophilic substitution is carried out in a DMSO solution at 80-100℃ with potassium carbonate as a catalyst to generate 4-phenoxy-N-allyl-1,8-naphthalimide, and the reaction time is 4-6 hours.

[0019]

[0020] The double bond in the fluorescent monomer with the naphthalimide structure is epoxidized: the monomer undergoes double bond epoxidation under peracetic acid catalysis, with chloroform as solvent, reaction temperature 70-85℃, and reaction time 10-12 hours.

[0021]

[0022] In a preferred embodiment of the present invention, the aromatic polyester polyol has a functionality of 2-6, a hydroxyl value of 150-380 mgKOH / g, and a viscosity of 8000-30000 mPa.s, preferably Stepan PS2452.

[0023] In a preferred embodiment of the present invention, the foaming agent is a mixture of water and alkane, wherein the alkane includes n-pentane (NP), isopentane (IP), and cyclopentane (CP), and preferably, the mass ratio of water to alkane is 1:4 to 1:6.

[0024] In a preferred embodiment of the present invention, the flame retardant is one or more of the following: tris(2-chloroethyl) phosphate, tris(1-chloro-2-propyl) phosphate, triethyl phosphate, tetra(2-chloroethyl) ethylidene diphosphate, dimethyl methylphosphonate, and pentabromodiphenyl ether.

[0025] The foam stabilizer is a polysiloxane-polyoxyolefin ether block copolymer, such as Maihao S-8996, S-8770, S-8905, Momentive L-6100NT, L5388, Air Products DC198, BYK Silbyk 9000, Silbyk9201, Silbyk 9400 or one or more.

[0026] In a preferred embodiment of the present invention, the amine catalyst is one or more of the following: triethylenediamine, N-methyldicyclohexylamine, dimethylcyclohexylamine, pentamethyldiethylenetriamine, tetramethylethylenediamine, tetramethylpropylenediamine, N,N-bis(dimethylaminopropyl)isopropanolamine, N-methylimidazole, stannous octoate, and dibutyltin dilaurate.

[0027] The trimerizing catalyst is a potassium metal salt catalyst.

[0028] In a preferred embodiment of the present invention, the B component is selected from one or more of polymeric MDI and liquefied modified MDI, preferably one or more of Wanhua Chemical's PM400, Bayer's 44V20 and BASF's M50S.

[0029] On the other hand, the present invention also provides a method for preparing fluorescent rigid polyurethane foam, comprising the following steps:

[0030] S1: Component A is prepared by uniformly mixing polyether polyol, fluorescent polyether polyol, aromatic polyester polyol, flame retardant, foam stabilizer, amine catalyst, trimer catalyst and foaming agent.

[0031] S2: Mix component A obtained in S1 with component B polyisocyanate, and then foam under high pressure to obtain the polyurethane rigid foam.

[0032] Preferably, the conditions for the high-pressure foaming process are: material temperature 25-35℃, gauge pressure 110-160 bar, mold temperature 50-70℃, and demolding time 5-15 min.

[0033] In a preferred embodiment of the present invention, the density of the fluorescent polyurethane rigid foam is 32 kg / m³. 3 -100kg / m 3 It emits blue fluorescence when excited by 365nm ultraviolet light.

[0034] Finally, the present invention also provides the application of the fluorescent polyurethane rigid foam material in high-end insulation materials such as cold storage panels, external wall insulation panels, and intermittent panels.

[0035] The beneficial effects of this invention are as follows:

[0036] First, the fluorescent polyurethane rigid foam provided by this invention introduces monomers with fluorescent effects into the synthesis process of polyether polyols without requiring additional production equipment or incurring additional costs; it does not require the introduction of inorganic pigment particles and will not damage the foaming equipment; the fluorescent color only appears at a specific wavelength, has low visual recognition, and is not easy to imitate.

[0037] Secondly, the naphthalene ring structure in this molecule also gives rigid polyurethane foam higher strength, bringing high-value products to customers. Detailed Implementation

[0038] To better understand the present invention, the following examples further illustrate the content of the present invention, but the content of the present invention is not limited to the following embodiments.

[0039] Sources of some raw materials:

[0040] PM400: Wanhua Chemical Group Co., Ltd.

[0041] The starting polyether polyol is a mixture of sucrose and diethylene glycol: R4110B (viscosity 3500 mPa·s at 25℃, functionality 4, hydroxyl value 440 mg KOH / g), Wanhua Chemical (Yantai) Rongwei Polyurethane Co., Ltd.

[0042] Glyceryl-based polyether polyol: A303 (viscosity 640 mPa·s at 25℃, functionality 3, hydroxyl value 560 mg KOH / g), Wanhua Chemical (Yantai) Rongwei Polyurethane Co., Ltd.

[0043] A fluorescent polyether polyol (functionality 2, hydroxyl value 120 mg KOH / g, viscosity 18000 mPa·s) was synthesized by the following method:

[0044] After purging the reactor with nitrogen, 30 g of 4-bromo-1,8-naphthalene anhydride and 6 g of allylamine were added and reacted in ethanol solution at 90 °C to generate naphthalene anhydride with double bonds. Then, 10 g of phenol was added, and nucleophilic substitution was carried out in DMSO solution at 90 °C using potassium carbonate as a catalyst to generate a pale yellow powder of 4-phenoxy-N-allyl-1,8-naphthalimide. The reaction time was 5 hours. NMR characterization data: 1H NMR (300 MHz, Chloroform-d) δ 5.19 (s, 1H), 5.22 (s, 1H), 5.87 (s, 1H), 4.93 (s, 12H), 8.44 (d, 1H), 7.85 (t, 1H), 8.26 (d, 1H), 6.89 (d, 1H), 7.14 (q, 5H).

[0045] The double bond in the fluorescent monomer with the naphthalimide structure was epoxidized: after purging the reactor with nitrogen, 30 g of 4-phenoxy-N-allyl-1,8-naphthalimide was added, using chloroform as solvent, at a reaction temperature of 75 °C for 11 hours, to obtain the oxidized fluorescent monomer. NMR characterization data: 1H NMR (300 MHz, Chloroform-d) δ 2.48 (d, 2H), 3.16 (q, 1H), 3.33 (d, 2H), 8.44 (d, 1H), 7.85 (t, 1H), 8.26 (d, 1H), 6.89 (d, 1H), 7.14 (q, 5H).

[0046] Under nitrogen protection, 2g of dibutyltin dilaurate and 70g of diethylene glycol were added, and the mixture was kept at 100℃ for 1 hour. Then, 100g of propylene oxide and 360g of oxidized naphthalimide fluorescent monomer were added sequentially, and the mixture was reacted at 160℃ for 9 hours to form a polyether with hydroxyl-terminated ends. NMR characterization data, 1H NMR (300 MHz, Chloroform-d): δ 3.65 (t, 1H), 3.44 (q, 2H), 3.56 (q, 2H), 3.54 (t, 4H), 3.38 (d, 4H), 3.34 (t, 2H), 1.37 (d, 6H), 3.51 (d, 2H), 4.17 (q, 1H), 3.58 (d, 1H), 3.35 (d, 2H), 8.43 (d, 3H), 8.26 (d, 1H), 6.89 (d, 1H), 7.41 (q, 5H). Where X = 2, Y = 1.

[0047] Polyester polyol: WRP244 (viscosity 6000mPa·s at 25℃, functionality 2, hydroxyl value 440mgKOH / g), Wanhua Chemical (Yantai) Rongwei Polyurethane Co., Ltd.

[0048] Flame retardant: TCPP, or tri(1-chloro-2-propyl) phosphate.

[0049] Foaming agent: L6100NT, Momentive.

[0050] Gel catalyst: Pentamethyldiethylenetriamine, Evonik Specialty Chemicals (Shanghai) Co., Ltd.

[0051] Trimerization catalyst: DabcoPT304, Air Product.

[0052] Foaming agent: CP, Shanghai Hongpu Chemical Technology Co., Ltd.

[0053] Examples 1-4, Comparative Example 1

[0054] The amounts (parts by weight) of each component in the examples and comparative examples are shown in Table 1.

[0055] A method for preparing rigid polyurethane foam material includes the following steps:

[0056] S1: Component A is prepared by uniformly mixing polyols, flame retardants, foam stabilizers, catalysts, and foaming agents;

[0057] S2: Mix component A and component B polyisocyanate, and then foam under high pressure to obtain rigid polyurethane foam;

[0058] The conditions for the high-pressure foaming process are: material temperature 30℃, gauge pressure 100 bar, mold temperature 60℃, and demolding time 12 min.

[0059] Table 1

[0060]

[0061]

[0062] The rigid polyurethane foams obtained in the above examples and comparative examples were excited and tested for fluorescence under 365 nm and 254 nm ultraviolet light. Intensity data were tested according to GB / T 21558-2008, and the measured performance is shown in Table 2.

[0063] Table 2

[0064] Example 1 Example 2 Example 3 Example 4 Comparative Example 365 nm Light blue fluorescence Dark blue fluorescence Dark blue fluorescence Light blue fluorescence No fluorescence 254 nm No fluorescence No fluorescence No fluorescence No fluorescence No fluorescence Intensity (KPa) 132 138 147 128 121

[0065] As can be seen from the table above, the polyurethane rigid foams containing different amounts of fluorescent polyether polyols in the examples exhibit different degrees of blue fluorescence under 365nm ultraviolet light excitation; however, they show no fluorescence behavior under 254nm ultraviolet light excitation.

[0066] Currently, the commonly used method of dyeing polyurethane rigid foam is costly and can easily damage equipment. The fluorescent polyurethane rigid foam of this invention has the characteristics of low cost, equipment friendliness, low visual recognition and difficulty in imitation, and can be used as a substitute.

[0067] The content mentioned in the above embodiments is not intended to limit the present invention. Any obvious substitutions are within the protection scope of the present invention without departing from the inventive concept of the present invention.

Claims

1. A fluorescent polyurethane rigid foam, raw materials comprising A component and B component, mass ratio of the A component and the B component being 100:130-250; wherein The A component comprises the following components by weight: The B component is isocyanate.

2. The fluorescent polyurethane rigid foam according to claim 1, wherein, The polyether polyol has a functionality of 2-5, a hydroxyl value of 80-450 mgKOH / g, a viscosity of 100-30000 mPa.s, and a water content of less than 0.1%; and / or the aromatic polyester polyol has a functionality of 2-6, a hydroxyl value of 150-380 mgKOH / g, a viscosity of 8000-30000 mPa.s, and is preferably Stepan PS2452.

3. The fluorescent polyurethane rigid foam according to claim 1 or 2, characterized in that, The fluorescent polyether polyol has a hydroxyl value of 80-230 mgKOH / g, and a structure as follows: 2≤X≤4, 1≤Y≤3.

4. The fluorescent polyurethane rigid foam according to any one of claims 1 to 3, wherein The blowing agent is a mixture of water and alkanes, and the alkanes include n-pentane (NP), isopentane (IP), and cyclopentane (CP). Preferably, the mass ratio of water to alkanes is 1:4 to 1:

6.

5. The fluorescent polyurethane rigid foam according to any one of claims 1 to 4, wherein The flame retardant is one or more of tris (2-chloroethyl) phosphate, tris (1-chloro-2-propyl) phosphate, triethyl phosphate, tetra (2-chloroethyl) ethylene diphosphate, dimethyl methylphosphonate, and pentabromodiphenyl ether.

6. The fluorescent polyurethane rigid foam according to any one of claims 1 to 5, wherein The cell regularizer is one or more of polysiloxane-polyoxyalkylene ether block copolymers such as Momentive L-6100NT, L5388, Air Products DC198, BYK Silbyk 9000, Silbyk 9201, and Silbyk 9400.

7. The fluorescent polyurethane rigid foam according to any one of claims 1 to 6, wherein The amine catalyst is one or more of triethylenediamine, N-methyl dicyclohexylamine, dimethylcyclohexylamine, pentamethyldiethylene triamine, tetramethylethylenediamine, tetramethylpropylenediamine, N,N-bis (dimethylaminopropyl) isopropanolamine, N-methyl imidazole, stannous octoate, and dibutyl tin dilaurate; and / or the trimerization catalyst is a metal potassium salt catalyst.

8. The fluorescent polyurethane rigid foam according to any one of claims 1 to 7, wherein, The B component is selected from one or more of polymeric MDI and liquefied modified MDI, and is preferably one or more of PM400 from Wanhua Chemical, 44V20 from Bayer, and M50S from BASF. 9.A method for preparing the fluorescent polyurethane rigid foam according to any one of claims 1-8, comprising the following steps: S1: uniformly mixing polyether polyol, fluorescent polyether polyol, aromatic polyester polyol, flame retardant, cell regularizer, amine catalyst, trimerization catalyst, and blowing agent to obtain the A component; S2: mixing the A component obtained in S1 with the B component polyisocyanate, and foaming under high pressure to obtain the polyurethane rigid foam; Preferably, the conditions of the high-pressure foaming process are as follows: material temperature 25-35℃, gauge pressure 110-160 bar, mold temperature 50-70℃, and demolding time 5-15 min.

10. Use of the fluorescent polyurethane rigid foam according to any one of claims 1 to 8 or the fluorescent polyurethane rigid foam prepared according to the preparation method of claim 9 in high-end thermal insulation materials such as cold storage board, external wall insulation board, intermittent board, etc.

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