CN116284669A - High mechanical strength flame-retardant waterborne polyurethane based on hydrogen bond synergistic effect - Google Patents
High mechanical strength flame-retardant waterborne polyurethane based on hydrogen bond synergistic effect Download PDFInfo
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- CN116284669A CN116284669A CN202310399006.XA CN202310399006A CN116284669A CN 116284669 A CN116284669 A CN 116284669A CN 202310399006 A CN202310399006 A CN 202310399006A CN 116284669 A CN116284669 A CN 116284669A
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Images
Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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Abstract
The invention belongs to the field of materials, and relates to a flame retardant material, in particular to anti-corrosion waterborne polyurethane and an anti-corrosion waterborne polyurethane modified flame retardant material. The flame-retardant waterborne polyurethane emulsion is prepared from Castor Oil (CO), polycaprolactone diol (PCL), OP550, 1, 4-bis (2-hydroxyethoxy) benzene (HQEE) and 2, 2-dimethylolbutyric acid (DMBA), wherein the molar ratio of CO, PCL, OP, HQEE, DMBA and IPDI is controlled at 48:12: (3-20): (186-352): (55-97): (328-553). The prepared WPU has excellent flame retardant effect.
Description
Technical Field
The invention belongs to the field of materials, and relates to a flame retardant material, in particular to anti-corrosion waterborne polyurethane and an anti-corrosion waterborne polyurethane modified flame retardant material.
Background
More than 1 million fires occur every day worldwide, causing hundreds of deaths. In recent years, about 4 tens of thousands of fires occur in China each year, more than 2000 people die, 3000 to 4000 people are disabled, and billions of yuan are directly lost by the fires each year. It was reported that the 2019 co-report fire was 23.3 ten thousand, the 1335 people were killed, the 837 people were injured, and the direct property loss was 36.12 hundred million yuan.
The flame-retardant material is a material capable of inhibiting or delaying combustion and is not inflammable and combustible, and is widely applied to the fields of clothing, petroleum, chemical industry, metallurgy, shipbuilding, fire protection, national defense and the like. The following organic halides are used as the common species. As the main bromide, decabromodiphenyl acid (DBDPO), tetrabromobisphenol A (TBBPA), brominated Polystyrene (BPS) and the like are commonly used. The chloride is only used for chlorinated paraffin and chlorinated polyethylene. The halides are often used in conjunction with antimony trioxide or phosphide. (2) An organic phosphorus compound. Inorganic phosphorus and halogenated phosphorus can be classified into two types. The halogen-free phosphorus is mainly phosphoric acid such as Triphenyl (TPP) and the like. The halogen-free phosphorus needs to be added in conjunction with the phosphorus halide. The halogenated phosphorus contains two elements of phosphorus and halogen in the molecule and has intramolecular synergistic effect, so that the halogenated phosphorus can be singly used, and common varieties such as Trichloroethylene (TECP) and the like can be used. (3) Nitrogen system. The main varieties include melamine and the like, are commonly used in PA and PU, and are used cooperatively with phosphorus flame retardants.
The key to the green-keeping of flame retardant materials is the choice of flame retardant. Polymeric or macromolecular flame retardants are a hot spot development direction for green environmental-friendly flame retardants due to their inherently low toxicity and non-bioaccumulation in structure
In the flame retardation of high polymers (various plastics including engineering plastics), the main principle of the flame retardant is the addition type brominated flame retardant which has the advantages of small consumption, high flame retardation efficiency and wide adaptability. The polybrominated diphenyl ethers (PBDPOs) in the brominated species produce toxic carcinogenic Polybrominated Benzoalkanes (PBDD) and Polybrominated Benzofurans (PBDF) upon combustion. And the halogen flame retardant generates a large amount of smoke and toxic and corrosive gas during combustion, which can cause the serious defect that the corrosion of a circuit system switch and other metal objects and the damage to human respiratory tracts and other organs cannot be caused by fire alone.
CN115141596a discloses a high-strength high-toughness polyurethane heat-conducting structural adhesive and a preparation method thereof. The strength and toughness of the material can be improved simultaneously by utilizing the combined action of the polyfunctional polyester polyol, the polyether polyol modified isocyanate-terminated polyurethane prepolymer and the low molecular weight isocyanate.
CN202011153945.9 provides a high-insulation low-temperature-resistant intumescent flame-retardant polyurethane material, and a preparation method and application thereof, wherein the high-insulation low-temperature-resistant intumescent flame-retardant polyurethane material comprises the following components in percentage by mass: 20 to 60 percent of low molecular weight polyol, 0 to 30 percent of chain extender, 0.1 to 4 percent of catalyst, 0.1 to 2.5 percent of antioxidant, 0.1 to 2.5 percent of defoamer, 0.1 to 2.5 percent of wetting dispersant, 5 to 70 percent of flame retardant, 5 to 40 percent of plasticizer, 0 to 30 percent of filler and 1 to 30 percent of curing agent.
CN201410130856.0 discloses a phosphorized lignin-based flame-retardant reinforced polyurethane hard foam and a preparation method thereof, wherein the polyurethane foam is prepared by mixing, pouring and foaming 50-90 parts of bio-based polyol, 10-50 parts of phosphorized lignin, 1-3 parts of amine catalyst, 0.05-0.2 part of tin catalyst, 0.5-2 parts of foam stabilizer, 100-140 parts of isocyanate and 4-7 parts of water.
However, there are still many difficulties in synthesizing aqueous polyurethanes that satisfy both mechanical properties and flame retardant properties.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a polyurethane material, in particular high-strength degradable flame-retardant waterborne polyurethane, and a preparation method and application thereof. The degradable flame-retardant waterborne polyurethane with excellent mechanical properties is prepared. In order to achieve all these functions with each other in one design, we carefully designed the molecular structure of the soft and hard segments of the aqueous polyurethane. Degradable Castor Oil (CO) and polycaprolactone diol (PCL) are used as soft segments. The flame retardant properties of Exolit OP550 and trimethylol phosphorus oxide (THPO) are described. The multiple inter-hydrogen/inter-hydrogen interactions in the system are responsible for the high mechanical strength (fig. 1). The tensile strength is 23-39 MPa, and the flame-retardant Limiting Oxygen Index (LOI) is up to 28.34%. Importantly, our WPU was degradable with a mass loss rate of 37% after 3 months of natural burial in the soil. This work will provide a new way to make environmentally friendly high performance waterborne polyurethane.
The invention adopts the following technical scheme:
the invention provides a flame-retardant waterborne polyurethane emulsion which is prepared from Castor Oil (CO), polycaprolactone diol (PCL), OP550, 1, 4-bis (2-hydroxyethoxy) benzene (HQEE) and 2, 2-dimethylolbutyric acid (DMBA), wherein the molar ratio of CO, PCL, OP, HQEE, DMBA and IPDI is controlled at 48:12: (3-20): (186-352): (55-97): (328-553).
The invention also provides a flame-retardant waterborne polyurethane modified flame-retardant material, which comprises a substrate and a film cured by the flame-retardant waterborne polyurethane emulsion coated on the surface of the substrate. The substrate includes cardboard, wood, cotton, and the like.
The film thickness of the polyurethane cured film is 0.5-2 mm.
The preparation method of the flame-retardant waterborne polyurethane modified flame-retardant material comprises the steps of dropwise adding and spraying the WPU emulsion onto a substrate, or dipping the substrate into the WPU emulsion. The WPU emulsion is the flame-retardant Waterborne Polyurethane (WPU) emulsion.
The Fire Performance Index (FPI) and the Fire Growth Index (FGI) values of the flame-retardant waterborne polyurethane modified cardboard were 0.033 and 12.96 respectively.
The invention provides a synthetic method of a flame-retardant Waterborne Polyurethane (WPU) emulsion, which comprises the following steps:
1) Placing Castor Oil (CO), polycaprolactone diol (PCL), OP550, 1, 4-bis (2-hydroxyethoxy) benzene (HQEE) and 2, 2-dimethylolbutyric acid (DMBA) in a vacuum oven, and drying;
2) Placing the dried CO, PCL, OP550,550 into a reaction vessel, adding a solvent, placing in an oil bath environment at 25-40 ℃, slowly dripping IPDI into a three-neck flask with CO, PCL, OP550,550, and then dripping a catalyst;
3) Raising the temperature of the oil bath to 70-90 ℃ and reacting for 1-3 hours.
4) HQEE and DMBA dissolved with acetone were added, followed by catalyst. The reaction is carried out for 3 to 5 hours.
5) Firstly, the temperature of the oil bath pot is reduced to 30-50 ℃, and then triethylamine is added in the environment of 30-50 ℃ and stirred for 20-40 min.
6) Adding a predetermined amount of distilled water containing 3wt% THPO, stirring at a speed of 1100-1300 rpm for 0.5-2 hours. Obtaining the flame-retardant Waterborne Polyurethane (WPU) emulsion.
Preferably, the drying in step 1) is carried out at 100-120℃for 1-3h. More preferably, the mixture is dried in a vacuum oven at 110℃for 2h.
Preferably, the vacuum in the step 1) is 125 to 140Pa. Preferably, the vacuum in step 1) is a vacuum of 133Pa.
Preferably, in step 2), the solvent is Tetrahydrofuran (THF), preferably in an amount to solubilize the reactants of step 1). The catalyst is dibutyl tin dilaurate (DBTDL), and the catalyst (DBTDL) is preferably used in an amount capable of initiating polymerization. The full name of IPDI is isophorone diisocyanate (Isophorone Diisocyanate).
Preferably, in step 2), it is placed in an oil bath environment at 30 ℃.
Preferably, in step 2), a condensing reflux device is assembled, nitrogen is introduced into the system to exhaust the air inside, and then IPDI is slowly dropped into a three-necked flask having CO, PCL, OP and 52550 by a constant pressure funnel, followed by dropping a catalyst (DBTDL).
Preferably, in step 2), the molar ratio of CO, PCL, OP 550:550 and IPDI is controlled at 48:12:3:328, 48:12:7:386, 48:12:14:473 or 48:12:20:553.
Preferably, in step 4), the molar ratio of CO, PCL, OP, HQEE, DMBA and IPDI is controlled at 48:12: (3-20): (186-352): (55-97): (328-553); the OP550 content in the WPU is 5-20wt%. More preferably, the molar ratio of CO, PCL, OP, HQEE, DMBA and IPDI is controlled to be 48:12:3:186:55:328, 48:12:7:230:65:386, 48:12:14:294:81:473, or 48:12:20:352:97:553.
Preferably, in step 5), the molar ratio of triethylamine to DMBA is (0.8 to 1.5): 1. More preferably, in step 5), the molar ratio of triethylamine to DMBA is 1:1.
Preferably, the predetermined amount of distilled water of 3wt% thpo in step 6) means: the addition amount of THPO is 3% of the total mass of all monomers in the reaction process, namely the total mass of the monomers is PCL+CO+IPDI+HQEE+DMBA+triethylamine, and the total mass is marked as M. At this time, 0.03M THPO was weighed out and added to 2M distilled water to prepare 3wt% of distilled water of THPO. The solids content of the emulsion thus finally prepared was regarded as 33%.
THPO is trimethylol phosphorus oxide, and THPO is a phosphorus-containing flame retardant, which is equivalent to blending into a polyurethane system to improve the flame retardant property of the polyurethane material.
The obtained flame-retardant WPU has high tensile stress of 35MPa, elongation of 156% and toughness of 48.69 MJ.m -3 . The limiting oxygen index is 27.55% or more, preferably 27.55 to 28.34%.
The invention provides application of the flame-retardant Waterborne Polyurethane (WPU) emulsion, which is used for electric insulation packaging materials, electrical component pouring sealants, waterproof coatings, anti-corrosion coatings, cold-resistant coatings, fireproof expansion sealing elements, adhesives and the like.
The invention has the following beneficial effects:
the prepared WPU has excellent flame retardant effect. WPU has the highest "V0" class flame retardant performance, meeting UL-94 test standards, and as the proportion of OP550 increases from 10wt% to 20wt%, the Limiting Oxygen Index (LOI) of WPU increases from 27.55 to 28.34. The peak value of heat release rate (PHRR) of the modified cardboard is reduced by 32.15 percent compared with that of the cardboard before modification. Average Heat Release Rate (HRR) from 221.02 kW.m before modification -2 Reduced to modification41.07 kW.m after -2 Reduced by 81.4% (fig. 6 b). As shown in fig. 6c, the ignition time (Tig) of the cardboard increased from 13s before modification to 21s after modification by 61.5%.
The Fire Performance Index (FPI) and Fire Growth Index (FGI) values of the cardboard before and after modification varied from 0.03 and 14.41 to 0.033 and 12.96, respectively, indicating that flame retardant WPU has great potential in flame retardant applications.
Drawings
FIG. 1 is a schematic diagram of the molecular structure of the preparation of aqueous polyurethane and the internal hydrogen bond network.
XRD analysis of flame retardant WPU of figure 2.
Figure 3 a) DSC profile of degradable WPU. b) DMA curves of degradable WPUs.
Figure 4 adhesion strength and physical picture of degradable WPU on different substrates.
Figure 5 is a digital photograph of a degradable WPU at different ignition times.
Fig. 6 a) Heat Release Rate (HRR) of the base paper and the modified paper. b) Average HRR of the base paper and the modified paper. c) Ignition time (Tig) of the base paper and the modified paper. d) The heat flow is 35 kW.m -2 When in use, the flame retardant WPU has a Fireproof Performance Index (FPI) and a Fireproof Growth Index (FGI).
FIG. 7 is a polyurethane flame retardant property test apparatus. The top surface temperature is determined by an infrared camera. A piece of paper with the thickness of 0.55mm is selected, the two sides of the paper are coated with the coating with the thickness of 0.1mm, the infrared thermal imager is arranged at 45 degrees, and the position 30cm above the sample is photographed every 3 seconds until the paper is burnt.
Fig. 8a shows the maximum surface temperature of the base paper determined by the infrared camera. b. The maximum surface temperature of the modified paper as determined by the infrared camera.
Detailed Description
Raw materials and reagents
Polycaprolactone diol (PCL), castor Oil (CO), isophorone diisocyanate (IPDI), 2-dimethylolbutanoic acid (DMBA), triethylamine (TEA), phosphate Buffered Saline (PBS), all analytically pure, all available from Shanghai Meilin Biochemical technologies Co. Acetone (acetone), analytically pure, shandong Jinan Kochia Corp. 1, 4-bis (2-hydroxyethoxy) benzene (HQEE), dibutyl tin dilaurate (DBTDL), analytically pure, shanghai Ala Biochemical technologies Co., ltd. Tetrahydrofuran (THF), analytically pure, national pharmaceutical products chemical agents limited. Phosphoric acid acyl Trimethates (THPOs), analytically pure, wuhans michael biotechnology limited. The wild lipase, analytically pure, is available from Shanghai, inc. Sylgard 184 (PDMS), analytically pure, shanghai en libao trade limited. Exolit OP550, analytically pure, clariant chemical company, inc.
Experimental instrument
Analytical balance, model ZB603C, meltrele-tolidor instruments inc. Microcomputer controlled electronic universal tester, model WDW-02, jinan Hengsi Sheng Dai instruments. Vacuum drying oven, DZF-6020 type, consolidates Yingyu of city to Hua instrument factory. The circulating water vacuum pump, SHZ-D (III), consolidates Yingyu of city and gives it to Hua instrument factory. Drawing adhesive force tester, XH-M type, beijing Tiandi star fire instrument and meter company. Electrothermal constant temperature blast drying oven, DHG-9070A type, consolidates the Limited liability company of the national instruments in the city. Rotary evaporator, RE-1002 type, shanghai asia biochemical instrumentation factory. Digital display constant-speed powerful electric stirrer, JB90-SH model, and on sea standard model factory. A precise salt fog tester, LS-UT-6, china LESTEST company. Heat collection type constant temperature heating magnetic stirrer, DF-101S type, shanghai Mei Yingpu instruments and meters manufacturing Co., ltd. Ultrapure water machine, type GWB-1B, beijing general instrument responsibility company. Air compressor, KMS, eternal health market, fine beauty household articles limited. Emulsifying mixer, EUROSTAR type 20, ai Ka (guangzhou) instruments, inc. Electrochemical analyzer, CHI660E, shanghai Chen Hua instruments Co.
High-strength degradable flame-retardant waterborne polyurethane test characterization
Mechanical property test
The mechanical tensile test adopts a WDW-02 type electronic universal tester, the tensile speed is20 mm & min-1 at room temperature, the thickness of a test piece is 0.02mm, and the stress-strain curve is measured. According to the national standard 36363, an INSTRON 5982 universal mechanical testing machine is adopted, and the puncture speed is 10mm & min at room temperature -1 The test piece had a thickness of 0.3mm, and the penetration strength of the test piece was measured.
Differential scanning calorimetry DSC measurements were performed on a mertrer-tolidodsc 1 STARe differential scanning calorimeter and FRS5 sensor to determine the thermal behavior of the samples. All experiments were performed under a dry nitrogen atmosphere, with the samples first heated to 150 ℃ and held for 2 minutes to remove the heat history, then cooled to-80 ℃ and then heated to 150 ℃ with a heating/cooling rate of 10 ℃/min. The second heating scan takes the glass transition temperature Tg as the midpoint of the heat flow change.
Flame retardant Performance test
According to ISO 5660 standard, the paper size before modification is 10cm×10cm×0.55mm, the paper size after modification is 10cm×10cm×2mm, and the heat flow is 35 kw.m-2. Cone calorimeter tests were performed using an FTT0007 cone calorimeter in the uk. According to GB/T2408-2008 standard, a vertical burn test was performed using FTT0082 (Instrument, UK) with dimensions of 15cm by 3cm by 2cm. Limiting oxygen index tests were performed according to ASTM D2863 using an british FTT0077 oxygen index tester. Samples of 15cm by 3cm by 2cm in size were measured and 15 parallel experiments were performed to ensure accuracy of the data.
Degradation Performance test
Fourier Transform Infrared (FTIR) spectra were used for infrared characterization using Thermo Scientific Nicolet iS, and the thickness of the characterization films were all 0.05mm. The degraded film cannot reach the designated film thickness due to uncontrollable degradation, and each test is repeated for more than 3 times, so that the accuracy of the experimental result is ensured.
Scanning Electron Microscopy (SEM) scanning electron microscopy images were taken under vacuum using a Hitachi regulatory 8220 specification scanning electron microscope. A thin layer of gold (2-3 nm) is coated on the cross section of the sample, and the cross section area of natural fracture is selected for photographing.
Corrosion resistance test
Electrochemical measurements the coatings were electrochemically measured in a CASS (ASTM B368) environment. The coatings were electrochemically tested at a steady open circuit voltage using a CHI 660D electrochemical workstation (china Shanghai aging). The test area of the coating was 38.465cm 2 Ag/Agcl is a reference electrode, and Pt is a counter electrode. Polarization curve scan rate of 1 mV.s -1 Electrochemical impedance spectrum at 10 -2 Hz～10 5 In the Hz frequency range, the sinusoidal signal disturbance is 5mV. Each test is repeated for more than 3 times to ensure the accuracy of the test result.
x-ray photoelectron spectroscopy (XPS) XPS was performed in escalabxi+ at voltages of 12mA and 12kV using a monochromatic aluminum source. The chamber pressure was 5X 10-9mbar. To detect spectra at different depths, an Ar gun was used at 1.5X10 before measurement -6 The grating dimensions were 2X 2mm at mbar and 3kV pressure 2 Samples were subjected to different etching times (0, 10, 20, 30, 40 and 50 nm). The data were analyzed in casxps software. All binding energies are associated with the c1s peak at 285eV for surface indefinite carbon. The etching depth is proportional to the increase of etching time.
Thermogravimetric analysis (TGA) using a TGAQ50 thermogravimetric analyzer, placing a sample in a crucible with a temperature rise rate of 10 ℃/min under nitrogen atmosphere, and analyzing the pyrolysis behavior of the material at 0 ℃ to 800 ℃. Tests show that the addition of the flame retardant has little effect on the thermal stability.
An x-ray diffractometer (XRD) was used with a Rigaku D/max-2500 diffractometer equipped with a Cu ka radiation (λ= 0.15406 nm) source (40 kv,200 ma). The morphology and structure of SIPCs were characterized by field emission.
The following examples are further illustrative of the invention, but the invention is not limited thereto.
EXAMPLE 1 Synthesis of flame retardant Waterborne Polyurethane (WPU)
Degradable WPU is designed and prepared by taking degradable CO and PCL as soft segments. The rigid structure 1, 4-di (2-hydroxyethyl) benzene (HQEE) is adopted as a chain extender, so that the mechanical property of the material molecular chain is improved. 2, 2-dimethylolbutanoic acid (DMBA) containing hydrophilic groups is introduced into the molecular chain, so that the emulsification process is promoted, and finally, a polymer network with high molecular weight is prepared. It is believed that the presence of hydrogen bonds within the system is responsible for the high mechanical strength of the overall network, i.e. dense hydrogen bonds are distributed in the polymer network, and the strong synergy of the hydrogen bonds of the different components gives the polymer network excellent mechanical strength (figure 1).
The synthesis steps are as follows:
1) Castor Oil (CO), polycaprolactone diol (PCL), OP550, 1, 4-bis (2-hydroxyethoxy) benzene (HQEE), 2-dimethylolbutyric acid (DMBA) were placed in a vacuum oven and dried for 1.5 hours under vacuum at 110deg.C;
the vacuum degree is 133Pa (gauge pressure is-90 KPa, absolute pressure is 10 KPa)
2) Dried CO, PCL, OP was placed in a three-necked flask, 5ml of Tetrahydrofuran (THF) was added thereto, and the mixture was placed in an oil bath at 30 ℃. The condensation reflux apparatus was assembled, nitrogen was introduced into the system to exhaust the air inside, and then IPDI was slowly dropped into a three-necked flask having CO, PCL, OP550,550 with a constant pressure funnel, followed by dropping 50 μl of catalyst (DBTDL), and finally the temperature of the oil bath was raised to 80 ℃ for 2 hours of reaction.
The entire reaction was applied to both solvents. Tetrahydrofuran was used as a solvent throughout the reaction, and acetone was also used as a solvent. The effect of acetone is to dissolve 2, 2-dimethylolbutanoic acid (DMBA) because 2, 2-dimethylolbutanoic acid (DMBA) is much more soluble in acetone than tetrahydrofuran. Because of the small amount of DMBA, the amount of acetone is much smaller than tetrahydrofuran. The dried DMBA was dissolved in acetone and then added to the reaction system.
The molar ratio of CO, PCL, OP 550:550 and IPDI is controlled at 48:12:3:328, 48:12:7:386, 48:12:14:473, 48:12:20:553.
3) HQEE and DMBA dissolved in acetone were added, followed by 50. Mu.L DBTDL. The reaction was carried out for another 4 hours.
Tetrahydrofuran (THF) was added during the reaction to reduce viscosity. The purpose of this tetrahydrofuran as a solvent is to reduce the viscosity of the system during the reaction, since once too viscous the magnet is easily stirred, which eventually leads to experimental failure. Regarding the addition at which step, the addition amount can be completely seen that the magnet can not rotate normally, and the addition can be omitted, otherwise, the addition is performed.
4) The temperature of the oil bath is firstly reduced to 40 ℃, then 0.553 to 0.984g of triethylamine is added under the environment of 40 ℃ and stirred for 30min.
After the third step of preparation, the polyurethane is prepared and molded, at the moment, carboxyl groups still exist on the polyurethane molecular chain, and at the moment, triethylamine is added for neutralization with the carboxyl groups on the polyurethane molecular chain, wherein the molar ratio of the triethylamine to the DMBA is 1:1.
The OP550 content in the WPU was 5, 10, 15, 20wt% respectively. The resulting WPU was designated as 5wt% OP550 (designated S1), 10wt% OP550 (designated S2), 15wt% OP550 (designated S3) and 20wt% OP550 (designated S4) samples.
The influence of different components on the mechanical properties of polyurethane is explored by regulating the proportion of soft segment raw materials, a series of flame-retardant WPU is synthesized by regulating the mole ratio of PCL and CO, and the tensile strength is obviously reduced and the elongation at break is simultaneously improved along with the increase of the mole ratio of PCL and CO. This is because CO has more reactive sites as a tertiary alcohol, and an increase in CO results in a significant increase in the polymer crosslink density, thus exhibiting higher mechanical strength. To verify this point, we characterized the verification by FTIR test, which observed 1700cm -1 The peak area at this point increases, which is related to the increase in the number and density of hydrogen bonds, demonstrating that an increase in the CO content has a positive effect on the tensile strength. When PCL: co=1:9, the tensile strength is as high as 49.94MPa, and the elongation at break is only 60%.
To verify that we successfully synthesized WPU, we performed FTIR testing of the prepared material to detect 2230-2270 cm -1 The disappearance of the peak at isocyanate (-n=c=o) in the FTIR spectrum demonstrates the successful synthesis of the series of flame retardant WPUs.
Example 2: synthesis and monomer proportion regulation and control research of high-strength degradable flame-retardant Waterborne Polyurethane (WPU)
The synthesis steps are as follows:
1) Castor Oil (CO), polycaprolactone diol (PCL), OP550, 1, 4-bis (2-hydroxyethoxy) benzene (HQEE), 2-dimethylolbutyric acid (DMBA) were placed in a vacuum oven and dried for 1.5 hours under vacuum at 110deg.C;
the vacuum degree is 133Pa (gauge pressure is-90 KPa, absolute pressure is 10 KPa)
2) Dried CO, PCL, OP was placed in a three-necked flask, 5ml of Tetrahydrofuran (THF) was added thereto, and the mixture was placed in an oil bath at 30 ℃. The condensation reflux apparatus was assembled, nitrogen was introduced into the system to exhaust the air inside, and then IPDI was slowly dropped into a three-necked flask having CO, PCL, OP550,550 with a constant pressure funnel, followed by dropping 50 μl of catalyst (DBTDL), and finally the temperature of the oil bath was raised to 80 ℃ for 2 hours of reaction.
The entire reaction was applied to both solvents. Tetrahydrofuran was used as a solvent throughout the reaction, and acetone was also used as a solvent. The effect of acetone is to dissolve 2, 2-dimethylolbutanoic acid (DMBA) because 2, 2-dimethylolbutanoic acid (DMBA) is much more soluble in acetone than tetrahydrofuran. Because of the small amount of DMBA, the amount of acetone is much smaller than tetrahydrofuran. The dried DMBA was dissolved in acetone and then added to the reaction system.
The molar ratio of CO, PCL, OP 550:550 and IPDI is controlled at 48:12:3:328, 48:12:7:386, 48:12:14:473, 48:12:20:553.
The full name of IPDI is isophorone diisocyanate (Isophorone Diisocyanate).
The catalyst is dibutyl tin dilaurate (DBTDL), and the catalyst is used for improving the reaction rate. Dibutyl tin dilaurate is the most commonly used catalyst in polyurethane preparation, and other catalysts may be used in commercial processes. The ratio of the catalyst to be added is not particularly limited, and the amount of the catalyst to be added in each case in the present invention is 50. Mu.L, and can be adjusted as required by those skilled in the art.
3) HQEE and DMBA dissolved in acetone were added, followed by 50. Mu.L DBTDL. The reaction was carried out for another 4 hours.
Tetrahydrofuran (THF) was added during the reaction to reduce viscosity. The purpose of this tetrahydrofuran as a solvent is to reduce the viscosity of the system during the reaction, since once too viscous the magnet is easily stirred, which eventually leads to experimental failure. Regarding the addition at which step, the addition amount can be completely seen that the magnet can not rotate normally, and the addition can be omitted, otherwise, the addition is performed.
4) The temperature of the oil bath is firstly reduced to 40 ℃, then 0.553 to 0.984g of triethylamine is added under the environment of 40 ℃ and stirred for 30min.
After the third step of preparation, the polyurethane is prepared and molded, at the moment, carboxyl groups still exist on the polyurethane molecular chain, and at the moment, triethylamine is added for neutralization with the carboxyl groups on the polyurethane molecular chain, wherein the molar ratio of the triethylamine to the DMBA is 1:1.
5) A predetermined amount of distilled water containing 3wt% THPO was added thereto and stirred at a speed of 1200 rpm for 1 hour. The final result was an aqueous emulsion of 33% solids.
THPO is trimethylol phosphorus oxide, and THPO is a phosphorus-containing flame retardant, which is equivalent to blending into a polyurethane system to improve the flame retardant property of the polyurethane material. OP550 is Exolit OP550, is a medium viscosity liquid, is based on non-halogenated phosphorus polyol, has a functionality of about 10%, and is mainly suitable for the production of flame retardant polyurethane foam; OP550 used in the present invention was purchased from clariant chemical industry, ltd.
The OP550 content in the WPU was 5, 10, 15, 20wt% respectively. The resulting WPU was designated as 5wt% op550+3% THPO (designated S6), 10wt% op550+3% THPO (designated S7), 15wt% op550+3% THPO (designated S8) and 20wt% op550+3% THPO (designated S9) samples.
Considering the higher toughness of WPUs, example 2 selects WPUs with PCL: co=1:4, and further synthesizes flame retardant WPUs by adding flame retardants OP550 and THPO.
EXAMPLE 3 study of flame retardant Properties and mechanical Properties
According to the invention, the excellent flame-retardant effect of the material is achieved by synergistic flame retardance of the OP550 and the THPO, and the existing flame-retardant effect cannot be achieved only by any one of the OP550 and the THPO. We control the addition amount of THPO to be 3%, and discuss the influence of OP550 with different contents on the mechanical property and flame retardant property of the material. The limiting oxygen index of the samples is shown in Table 1.
Table 1 limiting oxygen index of samples
The mechanical properties of the flame retardant WPU are shown in table 2. It was found that as the specific gravity of OP550 was gradually increased from 5wt% to 20wt%, the tensile strength was gradually decreased from 39MPa to 23MPa. The synthesized flame-retardant WPU is further analyzed, XRD tests prove that a series of flame-retardant WPUs are of amorphous structures (figure 2), and thermal degradation behaviors of the flame-retardant WPU are hardly changed along with the increase of the proportion of the flame retardant through thermogravimetric analysis, so that the addition of OP550 has no influence on the thermal stability of the whole material.
Table 2. Mechanical properties of flame retardant WPU.
To investigate the internal properties of the material, we further investigated the thermal properties of the S6-S9 sample flame retardant WPU synthesized in example 2 by Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA). The DSC curve shows that as the proportion of OP550 increases gradually from 5wt% to 20wt%, the glass transition temperature (Tg) decreases gradually from 57.37 ℃ to 39.79 ℃ (fig. 3 a), indicating that increasing the proportion of OP550, decreasing the proportion of castor oil, and decreasing the hydrogen bonds formed in the system, results in a decrease in Tg. The DMA results showed that the law of change in Tg was consistent with DSC, with the storage modulus (G') decreasing with increasing proportion of OP550, which was also consistent with the stretching results (fig. 3 b). We believe that the crosslink density of the network structure within WPU is strongly related to mechanical strength. The cross-linking density of the network structure inside the WPU has a direct relation with the ratio of CO and OP550 content, and therefore, in order to solve the influence of OP550 ratio on mechanical properties, the cross-linking density (N) is calculated (formula 1).
Ge＝NRT (1)
Ge is the plateau modulus G', R and T in the storage modulus curve, and are the gas constant and absolute temperature, respectively. As the proportion of OP550 increases from 5, 10, 15wt% to 20wt%, the N of the flame retardant WPU decreases from 1024.94, 642.77, 414.16 to 232.11mol·m-3, indicating that the increase in proportion of OP550 weakens its mechanical properties.
EXAMPLE 4 study of adhesion Strength of flame retardant waterborne polyurethane
The polyurethane is used as a traditional adhesive, the synthesized flame-retardant WPU also has excellent adhesive performance, the adhesive strength of the S7 sample (10 wt% of OP550) synthesized in the example 2 on a glass substrate can reach 4.6MPa, and the adhesive performance of the sample on various substrates is extremely high as shown in figure 4. The adhesion strength of the S7 sample synthesized in example 2 on the substrate is shown in Table 3.
TABLE 3 adhesion Strength of S7 samples on different substrates
EXAMPLE 5 flame retardant waterborne polyurethane flame retardant Property Studies
To test the flame retardancy of WPUs, a vertical burning test was performed. As shown in fig. 5, the degradable WPU (10 wt% op550 sample S7 in example 2) rapidly self-extinguishes after 10S ignition, and the cotton bed (cotton bed is commercially available cotton) is not ignited after the second ignition, demonstrating that the WPU has the highest "V0" level flame retardant performance, conforming to UL-94 test standard.
Limiting Oxygen Index (LOI), an important parameter in evaluating the flame retardancy of a material, is the minimum concentration of oxygen capable of supporting the combustion of a polymer, expressed as a volume percent of oxygen. Limiting oxygen index greater than the oxygen concentration in the atmosphere is one of the criteria for flame retardant materials. Materials with an index greater than the oxygen concentration in the atmosphere (21%), also known as flame retardant materials; but generally to ensure safety, the material is considered flame retardant when the LOI is 27. For our degradable WPU, the LOI of the WPU increased from 27.55 to 28.34 as the proportion of OP550 increased from 10wt% to 20wt% (table 2).
Example 6 flame retardant waterborne polyurethane modified flame retardant Material and test
To further investigate the steady state combustion behaviour of the material we measured heat flow at 35 kw.m using WPU modified cardboard -2 Exothermic properties at this time.
The preparation method of the WPU modified cardboard is that the WPU is used for completely wrapping the cardboard. Comprises the following steps:
the WPU emulsion was added dropwise to the cardboard uniformly, and after drying, a layer of polyurethane cured film was formed around the cardboard. The film thickness cured in the experiment was 0.72mm.
As can be seen from fig. 6a, the peak heat release rate (phr) of the modified cardboard was reduced by 32.15% compared to the cardboard before modification. Average Heat Release Rate (HRR) from 221.02 kW.m before modification -2 Reduced to 41.07 kW.m after modification -2 Reduced by 81.4% (fig. 6 b). A longer ignition time (Tig) means that the material itself is more difficult to ignite. As shown in fig. 6c, tig of the cardboard increased from 13s before modification to 21s after modification, by 61.5%. To further evaluate the real combustion behavior under fire conditions, we introduced two important parameters (fig. 6 d), fire Performance Index (FPI) and Fire Growth Index (FGI) (see equations 2 and 3);
tPHRR is the time to PHRR. In general, the higher the FPI value, the lower the FGI value, and the better the refractory properties of the material. In our work, the FPI and FGI values of the cardboard before and after modification varied from 0.03 and 14.41 to 0.033 and 12.96, respectively, indicating that flame retardant WPU has great potential in flame retardant applications.
The advantage of the degradable WPU was further demonstrated by igniting the modified cardboard with an alcohol burner (fig. 7). As shown in fig. 8, when the cardboard before modification was burned for 24s, the cardboard had been burned and the maximum surface temperature was 507.7 ℃, whereas the modified paper remained intact at 24s of combustion, the maximum surface temperature was reduced by 32%. Furthermore, the mechanical and flame retardant properties of our WPU were compared to previously reported flammable and flame retardant WPUs. Meanwhile, the stress of the WPU is 35MPa, and the LOI is 27.55. These values are the highest levels reported for most flammable and flame retardant WPUs.
Our WPU has good degradability in addition to flame retardancy and higher mechanical strength. The degradability of the WPU plastic is studied by adopting an enzyme solution soaking method and a soil burying method. Degrading enzyme (0.05 g enzyme and 1g WPU in phosphate buffer saline solution) was added at a rate of 0.05g/g, and the WPU plastic surface was obviously broken after soaking at 50 ℃ for 15 days. After soaking for 30 days, the WPU plastic will crack into small pieces. The mass loss rate of the WPU plastic after soaking for 40 days is 12.25%. Furthermore, adjusting the lipase dosage may accelerate the degradation process. When the enzyme addition amount was adjusted to 0.2g/g, the mass loss rate reached 15.2% after soaking for 40 days. And (3) burying the WPU plastic in campus soil for degradation performance test. The WPU plastic gradually cracks as the depth of burial increases. The mass loss rate of the WPU plastic after being buried for 3 months reaches 37 percent.
Claims (10)
1. A flame-retardant aqueous polyurethane emulsion is prepared from Castor Oil (CO), polycaprolactone diol (PCL), OP550, 1, 4-bis (2-hydroxyethoxy) benzene (HQEE) and 2, 2-dimethylolbutyric acid (DMBA), wherein the molar ratio of CO, PCL, OP, HQEE, DMBA and IPDI is controlled at 48:12: (3-20): (186-352): (55-97): (328-553).
2. A flame retardant waterborne polyurethane modified flame retardant material comprising a substrate and a film cured from the flame retardant waterborne polyurethane emulsion of claim 1 coated on the surface of the substrate.
3. The flame retardant waterborne polyurethane modified flame retardant material of claim 2, wherein said substrate comprises cardboard, wood, cotton, and the like.
4. The flame retardant aqueous polyurethane modified flame retardant material of claim 2, wherein the film cured from the flame retardant aqueous polyurethane emulsion has a film thickness of 0.5-2 mm.
5. The method for preparing a flame retardant material modified by flame retardant waterborne polyurethane according to any one of claims 2 to 4, comprising dripping, spraying or dipping the flame retardant waterborne polyurethane emulsion on or into a substrate.
6. The flame retardant aqueous polyurethane emulsion of claim 1,
the synthetic method of the flame-retardant Waterborne Polyurethane (WPU) emulsion comprises the following steps:
1) Placing Castor Oil (CO), polycaprolactone diol (PCL), OP550, 1, 4-bis (2-hydroxyethoxy) benzene (HQEE) and 2, 2-dimethylolbutyric acid (DMBA) in a vacuum oven, and drying;
2) Placing the dried CO, PCL, OP550,550 into a reaction vessel, adding a solvent, placing in an oil bath environment at 25-40 ℃, slowly dripping IPDI into a three-neck flask with CO, PCL, OP550,550, and then dripping a catalyst;
3) Raising the temperature of the oil bath to 70-90 ℃ and reacting for 1-3 hours.
4) HQEE and DMBA dissolved with acetone were added, followed by catalyst. The reaction is carried out for 3 to 5 hours.
5) Firstly, the temperature of the oil bath pot is reduced to 30-50 ℃, and then triethylamine is added in the environment of 30-50 ℃ and stirred for 20-40 min.
6) Adding a predetermined amount of distilled water containing 3wt% THPO, stirring at a speed of 1100-1300 rpm for 0.5-2 hours. Obtaining the flame-retardant Waterborne Polyurethane (WPU) emulsion.
7. The flame retardant aqueous polyurethane emulsion of claim 6, wherein the drying in step 1) is 100-120 ℃ for 1-3 hours.
The vacuum in the step 1) is 125-140 Pa.
8. The flame retardant aqueous polyurethane emulsion of claim 6, wherein in step 2), the molar ratio of CO, PCL, OP 550:550 to IPDI is controlled to be 48:12:3:328, 48:12:7:386, 48:12:14:473 or 48:12:20:553.
In step 4), the molar ratio of CO, PCL, OP, HQEE, DMBA and IPDI was controlled at 48:12: (3-20): (186-352): (55-97): (328-553); the OP550 content in the WPU is 5-20wt%. More preferably, the molar ratio of CO, PCL, OP, HQEE, DMBA and IPDI is controlled to be 48:12:3:186:55:328, 48:12:7:230:65:386, 48:12:14:294:81:473, or 48:12:20:352:97:553.
Preferably, in step 5), the molar ratio of triethylamine to DMBA is (0.8 to 1.5): 1. More preferably, in step 5), the molar ratio of triethylamine to DMBA is 1:1.
9. The flame-retardant aqueous polyurethane emulsion according to any one of claims 1, 6 to 8, wherein the obtained flame-retardant aqueous polyurethane has a high tensile stress of 35MPa, an elongation of 156% and a toughness of 48.69 mj.m -3 . The limiting oxygen index is 27.55% or more, preferably 27.55 to 28.34%.
10. Use of a flame retardant Waterborne Polyurethane (WPU) emulsion as claimed in any of claims 1, 6-9 for electrical insulation packaging materials, electrical component potting adhesive, waterproof coatings, anticorrosive coatings, cold resistant coatings, fire retardant intumescent seals, adhesives and the like.
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