CN108359293B - Acryloyl phosphate containing nitrogen and hydroxyl and epoxy acrylate flame-retardant coating thereof - Google Patents
Acryloyl phosphate containing nitrogen and hydroxyl and epoxy acrylate flame-retardant coating thereof Download PDFInfo
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- CN108359293B CN108359293B CN201810063569.0A CN201810063569A CN108359293B CN 108359293 B CN108359293 B CN 108359293B CN 201810063569 A CN201810063569 A CN 201810063569A CN 108359293 B CN108359293 B CN 108359293B
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 19
- PWGIEBRSWMQVCO-UHFFFAOYSA-N phosphono prop-2-enoate Chemical compound OP(O)(=O)OC(=O)C=C PWGIEBRSWMQVCO-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000000576 coating method Methods 0.000 title abstract description 130
- 239000011248 coating agent Substances 0.000 title abstract description 120
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 54
- 239000003063 flame retardant Substances 0.000 title abstract description 54
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 title abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 41
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 2
- 238000003848 UV Light-Curing Methods 0.000 abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 7
- 239000003085 diluting agent Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 34
- 230000000694 effects Effects 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 238000001723 curing Methods 0.000 description 17
- 230000007423 decrease Effects 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000002329 infrared spectrum Methods 0.000 description 13
- 238000002834 transmittance Methods 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910004856 P—O—P Inorganic materials 0.000 description 2
- 101100194363 Schizosaccharomyces pombe (strain 972 / ATCC 24843) res2 gene Proteins 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 101150037117 pct-1 gene Proteins 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- -1 acryloyl Phosphazene Chemical compound 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000004786 cone calorimetry Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an acryloyl phosphate containing nitrogen and hydroxyl and an epoxy acrylate flame retardant coating thereof, wherein a P-containing product PEPI is prepared by reacting phosphoric acid with epoxy chloropropane, an P, N-containing active monomer PAEA is prepared by reacting the PEPI with acrylamide, the PAEA is compounded with epoxy acrylate and an active diluent, and the P, N-containing epoxy acrylate coating is prepared by UV curing.
Description
Technical Field
The invention belongs to the technical field of flame-retardant coatings, and particularly relates to an acryloyl phosphate containing nitrogen and hydroxyl and an epoxy acrylate flame-retardant coating thereof.
Background
Epoxy Acrylates (EA) are the most widely used resins in uv curable coatings. The UV-cured EA coating has the advantages of high hardness, excellent chemical resistance, environmental protection, energy conservation and quick curing, is developed into a novel green coating, and has a wide application range in the fields of buildings, bamboo and wood floor decoration and valuable wooden furniture. Particularly, the coating has high transparency and potential as a transparent coating of ancient wood buildings and valuable furniture, but the flame retardant effect is poor, so that the application prospect of the coating as the transparent coating of the ancient wood buildings and the valuable furniture is limited. The UV curing epoxy acrylate coating has poor heat resistance and flame retardant property, and the application of the UV curing technology is limited to a certain extent. Therefore, research and development of flame retardant UV curable EA coatings has become a new focus.
There are generally two methods for preparing flame retardant materials: the flame retardant is directly added in the post-treatment or forming processing of the high polymer material, and the flame retardant does not generally have chemical reaction with the high polymer material; the other chemical type, namely the reaction type flame retardant material, takes the flame retardant as a reactant to participate in the reaction of macromolecules in the preparation process. The additive type flame retardant material often has the problems of reduced compatibility, reduced mechanical properties of the material and the like. Therefore, the research on the reactive flame retardant material is very important, the flame retardant property of the material can be improved without sacrificing the mechanical property of the material, and the research is a hotspot of the research on the flame retardant material in recent years.
The existing method for improving the flame retardant effect of the epoxy acrylate coating is to add flame retardant monomers containing P, N or Si and the like, so that the adverse effects of easy migration of the flame retardant, short flame retardant effect and the like brought by the addition type flame retardant can be avoided, and the mechanical property of the material can be improved. The phosphorus-nitrogen synergistic system has good flame retardant effect, the flame retardant effect of the system is poorer than that of the P-containing flame retardant monomer by adding the Si-containing flame retardant monomer, the cost is high, and the material can keep good mechanical property but is not practical. Therefore, in order to improve the flame retardant property of the UV-curable acrylate coating, an acrylate active flame retardant monomer with high P, N content needs to be designed and prepared, and is used for preparation and performance improvement of the UV-curable epoxy acrylate coating, so that the UV-curable epoxy acrylate coating with excellent flame retardant effect is prepared, and the application range of the material is further expanded.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the acryloyl phosphate containing nitrogen and hydroxyl and the epoxy acrylate flame-retardant coating thereof.
One of the technical schemes adopted by the invention for solving the technical problems is as follows:
a nitrogen and hydroxyl containing acryloyl phosphate monomer having the formula:
the second technical scheme adopted by the invention for solving the technical problems is as follows:
the preparation method of the nitrogen and hydroxyl contained acryloyl phosphate monomer comprises the following steps:
1) dropwise adding acetone dissolved with epoxy chloropropane into phosphoric acid at the temperature of-5 ℃, wherein the molar ratio of the phosphoric acid to the epoxy chloropropane is 1: 2-4, and controlling the dropwise adding speed to ensure that the temperature of a reaction system is kept stable in the dropwise adding process; after the dropwise addition is finished, adding methoxyphenol, and reacting at 75-85 ℃ for 9-11 h to obtain PEPI;
2) dissolving the PEPI prepared in the step 1) and acrylamide in acetone, and adding AlCl while stirring3The PEPI and the acrylamideWith AlCl3The molar ratio of (1) to (2) is 0.8-1.2: 0.8-1.2, the reaction is carried out at 35-55 ℃, and when no gas is generated, the reaction is completed to obtain the nitrogen and hydroxyl contained acryloyl phosphate monomer.
The third technical scheme adopted by the invention for solving the technical problems is as follows:
the epoxy acrylate flame-retardant coating containing the nitrogen-containing and hydroxyl-containing acryloyl phosphate monomer comprises the following components in parts by mass: 10-90 parts of nitrogen and hydroxyl-containing acryloyl phosphate monomer, 0.5-4 parts of PCT, and 10-85 parts of epoxy acrylate.
In one embodiment: the method comprises the following steps of: 55-65 parts of nitrogen and hydroxyl-containing acryloyl phosphate monomer, PCT 1-3 parts and 35-40 parts of epoxy acrylate.
In one embodiment: the method comprises the following steps of: 75-85 parts of nitrogen and hydroxyl-containing acryloyl phosphate monomer, 75-3 parts of PCT1 and 15-20 parts of epoxy acrylate.
In one embodiment: the method comprises the following steps of: 35-45 parts of nitrogen and hydroxyl-containing acryloyl phosphate monomer, PCT 1-3 parts, and 55-60 parts of epoxy acrylate.
In one embodiment: the method comprises the following steps of: 15-25 parts of nitrogen and hydroxyl-containing acryloyl phosphate monomer, 75-80 parts of PCT1 and epoxy acrylate.
In one embodiment: the paint also comprises an initiator accounting for 3-5% of the total mass of the paint system.
In one embodiment: the initiator is a photoinitiator 1173.
The fourth technical scheme adopted by the invention for solving the technical problems is as follows:
the preparation method of the epoxy acrylate flame-retardant coating comprises the step of mixing epoxy acrylate, PCT and an acryloyl phosphate monomer containing nitrogen and hydroxyl into a uniform system according to the mass parts.
Compared with the background technology, the technical scheme has the following advantages:
according to the invention, a product (PEPI) containing P is prepared by reacting phosphoric acid with epoxy chloropropane, an P, N-containing active monomer (PAEA) is prepared by reacting PEPI with acrylamide, the PAEA-containing active monomer (PAEA) is compounded with Epoxy Acrylate (EA) and an active diluent, and the EA coating containing P, N is prepared by UV curing.
Drawings
The invention is further illustrated by the following figures and examples.
Fig. 1 is an infrared spectrum of epichlorohydrin.
FIG. 2 is an infrared spectrum of PEPI during the reaction.
FIG. 3 is an infrared spectrum of PEPI and PAEA.
Fig. 4 is an ir spectrum of EA2 coating at different UV cure times.
FIG. 5 is a graph showing the relationship between the conversion of double bonds of a UV-curable coating film and the curing time.
FIG. 6 shows the effect of PAEA content on coating transmittance (a-EA 1, b-EA2, c-EA3, d-EA4, e-EA 5).
FIG. 7 is a photograph showing the degree of transparency of the coating (a-EA 1, b-EA2, c-EA3, d-EA4, e-EA 5).
FIG. 8 is a plot of PAEA content versus water absorption.
FIG. 9 is a TG curve of a UV-cured EA coating containing PAEA (a-EA 1, b-EA4 in the figure).
Fig. 10 is a digital photograph of the UV cured EA coating film after burning.
FIG. 11 is a plot of heat release rate for an EA-cured coating containing PAEA.
FIG. 12 is an infrared spectrum analysis of the thermal degradation process of EA 1.
FIG. 13 is an infrared spectrum analysis of the thermal degradation process of EA 2.
Detailed Description
The present invention will be described in detail with reference to the following examples:
example 1: preparation of PEPI
Adding 0.1mol of phosphoric acid into a 250m L three-neck flask, placing the three-neck flask in an ice bath, dissolving 0.3mol of epichlorohydrin in 100m L of acetone, slowly adding the epichlorohydrin into the three-neck flask by using a dropping funnel at a speed which is suitable for keeping the temperature of a reaction system stable and not suddenly rising, after the dropwise addition is completed, adding a small amount of p-methoxyphenol into the system, transferring the system into a water bath kettle, heating to 80 ℃, reacting for about 10h, transferring a reaction product into a distillation flask, carrying out reduced pressure distillation, and purifying to obtain PEPI, wherein the reaction formula is as follows:
example 2: preparation of PAEA monomer
0.05mol PEPI, 0.05mol acrylamide and 100m L of acetone are added into a three-neck flask with the diameter of 250m L, stirred until the solution becomes clear, and then 0.05mol AlCl is added into the solution under stirring3And when the solution becomes turbid, HCl gas is released during reaction, the temperature is controlled to be 40-50 ℃, the reaction is completed when no gas is generated during the reaction by using pH test paper, and the obtained product is subjected to rotary evaporation to obtain a pure acryloyl phosphate monomer (PAEA monomer) containing nitrogen and hydroxyl. The reaction formula is as follows:
example 3: preparation of PAEA-containing epoxy acrylate UV-cured flame-retardant coating
Mixing Epoxy Acrylate (EA), acryloyl Phosphazene (PCT) and PAEA monomer, adding Darocur 1173 accounting for 4 wt% of the total mass of EA, PCT and PAEA, and stirring to obtain a uniform solution (if necessary, slightly heating or ultrasonic oscillating can be carried out to uniformly disperse materials). The content of the PAEA flame retardant monomer in the epoxy acrylate system is respectively 0 wt.%, 20 wt.%, 40 wt.%, 60 wt.%, 80 wt.%, EA and monomer are mixed and coated on a glass plate, the coating thickness is 100 μm, and then 800W/cm is used2The UV-curable coating formulation is shown in Table 1.
TABLE 1 formulation of PAEA-containing epoxy acrylate UV-cured flame retardant coatings
The above examples were applied to the following experimental examples:
experimental example 1: determination of Water absorption of coating
Cutting the cured coating into 3 pieces of 10mm × 10mm samples, drying and weighing to obtain W1Soaking in deionized water for 6 hr, wiping off the adsorbed water on the surface, and weighing to obtain W2The water absorption W was calculated according to the following formula:
W＝(W2-W1)/W1×100％
experimental example 2: measurement of hardness
The hardness of the cured film is measured by a pencil hardness method, according to the test of GB/T6739-. The test selects the Chinese pencil, and the hardness range is HB-6H.
Experimental example 3: adhesion measurement
GB/T9286-1998 grid test for paint films of colored paint and varnish is adopted as a determination standard, and the test result can be divided into six grades of 0-5, wherein the adhesion performance of the grade 0 is the best, and the adhesion performance of the grade 5 is the worst.
Experimental example 4: acid and alkali resistance measurement
Preparing 20% and 30% sulfuric acid solution and sodium hydroxide solution, respectively soaking the coating in the sulfuric acid solution and the sodium hydroxide solution, observing the surface color and state every 8h, comparing the surface color and state with the un-soaked sample, and comparing the color and state change. When the soaking time is more than 8h and less than 24h, the medium resistance of the coating is normal if the coating is unchanged; when the soaking time is longer than 24 hours, the coating film is excellent in the dielectric resistance without significant change.
Experimental example 5: impact resistance measurement
The impact resistance of the samples was determined according to GB/T1732-1993 "determination of impact resistance of paint films".
Experimental example 6: thermogravimetric analysis
Carrying out thermogravimetric analysis on the sample by using a thermogravimetric analyzer, wherein the temperature range is from room temperature to 700 ℃, the heating rate is 10 ℃/min, and the sample is in an air atmosphere.
Experimental example 7 limiting oxygen index (L OI) test
L OI test specimen with size of 100 × 6.5.5 6.5 × 3mm3Then, the test is carried out on an oxygen index instrument according to the standard of GB/T2406-93.
Experimental example 8 vertical Combustion (U L-94) test
The U L-94 test was carried out on a horizontal vertical burning test apparatus according to the standard GB 2408-80, the dimensions of the bars being 100 × 12.7.7 12.7 × 3mm3。
Experimental example 9: scrub resistance measurement
The scrub resistance of the coating was determined using GB/T9266-88 as a standard.
Experimental example 10: FT-IR analysis
And testing the change condition of the absorption peak of the synthesized product after UV curing by using an infrared spectrometer, thereby monitoring the photocuring kinetics of the coating. Wherein the solid powder and KBr pellet are tested, the coating film is directly tested, and the liquid is smeared on a KBr wafer for testing.
Experimental example 11: measurement of transmittance
Measuring the UV-V of the coating in the range of 200-900 nm by using an ultraviolet/visible spectrophotometerisA transmission spectrum.
Experimental example 12: determination of Heat Release Rate
Cone calorimeter test specimens having dimensions of 100 × 100 × 3mm were tested on a cone calorimeter in accordance with ISO 5660 Standard test method3The radiant heat flux used in the test was 35kW/m2。
Experimental example 13: determination of conversion of carbon-carbon double bond
And calculating the conversion rate of C-C double bonds according to a formula. In the formula, A0、AtThe peak areas of C ═ C double bonds at t ═ 0s and t respectively; s0、StThe peak areas of C ═ O at t ═ 0s and t, respectively. The formula is as follows:
the results of the above experimental examples are as follows:
infrared analysis of PEPI
FIG. 1 is an infrared spectrum of epichlorohydrin, and FIG. 2 is an infrared spectrum of PEPI at different reaction times. As can be seen from FIG. 1, the epoxy group is 927cm-1、856cm-1Has obvious expansion and contraction vibration absorption peak. Compared with fig. 1, fig. 2 shows that, since epoxy groups in epichlorohydrin are easy to open rings, and undergo a ring-opening addition reaction with phosphoric acid, a spectrum undergoes a series of changes: the epoxy group in FIG. 1 was 927cm-1、856cm-1The characteristic absorption peak of (A) is basically disappeared, which indicates that the epichlorohydrin is basically completely reacted. In FIG. 2, 3354cm with increasing reaction time-1(ii) peak of stretching vibration of-OH bond at 2983cm-1the-OH stretching vibration absorption peak on P is obviously reduced, which shows that-OH on phosphoric acid and epoxy group have addition reaction and the reaction is complete. 1224cm in FIG. 2-1Is a stretching vibration absorption peak of-P ═ O double bond, 1049cm-1Is a-O-C single bond stretching vibration absorption peak on P, which indicates that phosphate groups exist in the product structure after the reaction, and the PEPI is synthesized.
Infrared analysis of PAEA monomers
FIG. 3 is an infrared spectrum of the prepared PEPI and PAEA. The figure shows that the PAEA monomer is 1672cm more-11625cm as a stretching vibration absorption peak of amide bond-1Indicates that-Cl on the PEPI monomer undergoes a substitution reaction with an amino group.
Effect of PAEA content on the curing kinetics of UV-cured EA coatings
Taking a UV-cured coating (namely EA2) with the PAEA addition amount accounting for 20% of the system content as an example, the infrared spectrums of the coating at different curing times are observed, as shown in FIG. 4, as the curing time increases, the C ═ C double bond is 1635.5cm-1The absorption peak becomes smaller, and when the curing time is 20s, the absorption peak is substantially disappeared and the curing tends to be complete. FIG. 5 shows UV curingThe relationship between the double bond conversion rate of the chemical coating and the curing time can be seen from fig. 5, the double bond conversion rate increases with the increase of the curing time, and becomes stable to a certain extent, mainly because the system forms a cross-linked network structure to hinder the migration of macromolecular free radicals, so that the number of the free radicals is increased, and the double bond conversion rate is increased. When the reaction is carried out to a certain extent, the rate of crosslinking decreases due to the increasingly limited migration of free radicals and the decrease in the number of active radicals, some unreacted reactive monomers and free radicals remaining in the structure of the network. The double bond conversion rate increases with the curing time before 20s and increases with the PAEA content along with the change of the PAEA content, the curing time exceeds 20s, and finally the double bond conversion rate shows a descending trend with the increase of the PAEA content, which is mainly because the double bond content is increased by adding the monomer, the viscosity of the system is reduced, the system reaches the maximum reaction rate more quickly, gel is formed in the system earlier, the rest double bonds are difficult to polymerize further, and therefore, the double bond conversion rate is reduced finally.
Effect of PAEA content on UV-cured film transmittance
Fig. 6 is a uv-vis-spectrum of an EA coating containing PAEA. As can be seen from the figure, in the ultraviolet light region of 200-300 nm, the light transmittance of the coating is almost 0, which indicates that the coating has a good ultraviolet-proof function; the light transmittance of the coating is increased along with the increase of the wavelength within 300-400 nm; in a visible light area of 400-700 nm, the measured transmittance of the coating exceeds 80%, but the visible light transmittance of the coating tends to decrease with the increase of the addition amount of the PAEA, mainly because the PAEA is a trifunctional monomer, the crosslinking degree of the monomer increases with the increase of the content of the PAEA, the hardness correspondingly increases, the system structure is more compact, and the light transmittance is reduced. This indicates that the higher the PAEA content, the greater the effect on the light transmittance of the coating film.
Fig. 7 is a digital photograph of UV cured EA coating overlaid on top of text. Wherein a, b, c, d and e are respectively epoxy acrylate coatings with PAEA content of 0%, 20%, 40%, 60% and 80% of the system. As can be seen, the class 5 UV cured coatings all have good transparency and clear visibility of the text underneath the coating. The transparency of the coating decreases with increasing PAEA content, with the worst transparency of the coating at 80% PAEA content.
Influence of PAEA content on physical properties and chemical resistance of UV-cured EA coating film
TABLE 2 influence of PAEA content on physical and chemical resistance of UV-cured coating films
It can be seen from table 2 that the pencil hardness of the cured coating gradually increases with the increase of the content of PAEA in the cured coating, but the impact resistance gradually decreases, and when the content of PAEA is 60% of the total system (i.e. EA4), the hardness reaches 4H and tends to be stable, the acid resistance and alkali resistance is more than 40H without corrosion, the number of washing and brushing times is the highest and reaches 13730 times, but the impact resistance gradually decreases because the flexibility of the coating is determined by the properties of the film-forming material, the combined force of the epoxy acrylate resin is strong, the creep is small, and the flexibility of the coating is better, but the impact strength of the coating decreases and the hardness increases with the increase of the content of PAEA, and the crosslinking density of the coating increases with the increase of the content of the PAEA. It can be seen from table 2 that the acid resistance of the coating is better than the alkali resistance, and the acid resistance and the alkali resistance of the coating containing PAEA are stronger than those of the coating without PAEA, and the main reason is that the swelling degree of the system is limited along with the increase of the content of PAEA, so that the acid resistance and the alkali resistance are correspondingly improved.
Influence of PAEA content on Water absorption of UV-cured coating film
From fig. 8, it can be seen that the water absorption of the coating film decreases with the increase of the PAEA content, i.e. the water resistance of the coating film increases, because the PAEA active monomer is a trifunctional monomer, and the crosslinking density of the coating film increases with the increase of the content, so that the coating film is not easy to swell, and when the PAEA content is 60% of the system, the water absorption of the coating film is 0.31%, and then the water absorption of the coating film decreases gradually.
Effect of PAEA content on thermal stability of UV-cured coating films
FIG. 9 is a TG curve of a UV-cured epoxy acrylate coating containing PAEA, reflecting the weight percent of coating versus temperature for different PAEA contents. With the addition of PAEA there is essentially no significant loss of weight of the system before 275 ℃, in which case the mass loss of the coating may be due to the loss of the coating itself at this stage due to the absorption of a small portion of the water; the mass loss of the coating is increased and the loss rate is maximum at 275-390 ℃; the thermal stability of the coating gradually increases with the addition of PAEA at 390-700 ℃. This indicates that the EA coating containing PAEA monomer has significant interaction in the degradation process, and the amount of carbon residue gradually decreases with the increase of temperature, which indicates that the carbon generated in the thermal degradation process of PAEA flame-retardant EA is an unstable amorphous structure and can continue to generate oxidation reaction in the presence of heat and oxygen. After 340 ℃, the weight percentage of EA4 is higher than that of EA1, because the addition of PAEA monomer can catalyze the polymer coating to form carbon, and the carbon layer can play a good role in heat insulation and oxygen insulation, thus leading to the reduction of quality loss.
FIG. 10 is a digital photograph of carbon residue after combustion of a UV cured epoxy resin, wherein a and b are pictures of carbon residue after combustion of an EA coating having a PAEA content of 0% and 60% by mass of the system, respectively. As can be seen from the figure, the EA coating with the PAEA content of 0 percent has loose structure after combustion, lower carbon residue rate and no expansion effect on the carbon layer; the EA coating with the PAEA content of 60% has a compact structure after combustion, high carbon residue rate and a remarkable expansion effect, and the expansion multiple is about 80 times, so that the phenomenon can show that the addition of the PAEA-containing monomer can improve the compactness of carbon residue, improve the heat and oxygen isolation capability of the coating, further improve the flame retardant property of the coating, and indirectly reflect that the flame retardant effect of the PAEA-containing EA coating is better.
Analysis of Heat Release Curve of UV-cured coating film
The limiting oxygen index (L OI) and U L-94 vertical burn tests are widely used to evaluate the flame retardant properties of materials, particularly for flame retardant polymeric materials, and cone calorimetry is capable of providing more useful information about the burning behavior of materialsEA cured coating heat release rate profile. EA1 burned very rapidly after ignition, and was a sharp peak in heat release rate, corresponding to a peak of 620kW/m2. For the EA2 and EA4 coatings, the peak values of the heat release rate are greatly reduced and are reduced along with the increase of the addition amount of the PAEA, the heat release rate of the PAEA/EA system can be reduced by 54.0 percent and 59.7 percent respectively by 20 wt.% and 60 wt.% of the PAEA, and meanwhile, the combustion time of the flame-retardant EA is greatly prolonged. It is worth noting that the ignition time of the flame retardant EA coating is shorter than that of the non-flame retardant one, probably because the phosphate structure degrades first, releasing some small molecule flammable gas at lower temperatures. In the combustion process, a compact protective carbon layer is generated on the surface of the sample, and the oxygen insulation and the heat insulation can be effectively realized.
Dynamic infrared of UV-cured coating film
The thermo-oxidative degradation processes of EA1 and EA2 were examined by dynamic infrared spectroscopy, and the results are shown in fig. 12 and fig. 13, respectively. Usually, 2500-3200 cm is selected-1Characteristic absorption peaks of the aliphatic chains (C-H) in between study the thermal oxidation degradation process of the high molecular material. As can be seen from FIG. 12, the transmission of the IR spectrum hardly changed before 350 ℃, which corresponds to the sample still having very good thermal stability at 350 ℃. 1184cm-1And 1246cm-1The characteristic absorption peak at the ester group is still strong at 350 ℃. As the temperature is further increased, the relative intensity of the absorption peaks decreases. At 470 ℃, all absorption peaks disappeared, which means that EA1 was completely degraded. And, no new absorption peaks appear during thermal degradation.
FIG. 13 is an IR spectrum of EA2 during thermo-oxidative degradation. The transmission of the infrared spectrum hardly changed before 320 c, indicating that the sample still has very good thermal stability at 320 c. With further increase in temperature, the relative intensity of the absorption peaks decreases. The main infrared spectrum peaks in the figure are as follows: 2972cm-1Is CH2Vibration of (2); 1452cm-1And 1385cm-1Deformation vibration of C-H; 830cm-1And 750cm-1C-H vibration; 1734cm-1Stretching vibration of C ═ O; 1037cm-1Stretching vibration of P-O-C；1245cm-1And 1174cm-1The stretching vibration is P ═ O. With increasing temperature, at 1037cm-1The stretching vibration of P-O-C is rapidly degraded above 230 ℃ and completely disappears at 320 ℃, which indicates that the phosphate starts to degrade at 230 ℃ and completely degrades at 320 ℃, wherein the phosphate (P-O-C) structure is degraded at 320 ℃ to generate the P-O-P structure. 1245cm when the temperature is raised to 350 deg.C-1The characteristic absorption peak at P ═ O is shifted to high wavenumber and to 1260cm-1To (3). 2972cm-1Characteristic absorption peak at C-H and 1734cm-1The characteristic peak at C ═ O was almost unchanged before 320 ℃, indicating that the EA/PAEA hybrid system was mainly degraded by P — O — C before 320 ℃. The thermal degradation process of the flame retardant EA2 cured film is much more complicated than that of the EA1 cured film.
2972cm-1(C-H) and 1734cm-1The absorption peak of (C ═ O) rapidly decreases with increasing temperature, and some new absorption peaks also appear. At 1150cm-1A new absorption peak appears, which is attributed to P-O-C. 875cm when the temperature rises to 350 deg.C-1A new absorption peak of 875cm appears at-1An asymmetric absorption peak at P-O-P of 1260cm-1The absorption peak at (f) is assigned to the absorption peak of (P ═ O) -O-P. These newly appearing absorption peaks are particularly pronounced at 470 ℃. This indicates that the thermal degradation history of EA2 and EA1 are completely different. In the EA2 cured material, P-O-C functional groups are firstly degraded to generate polyphosphoric acid, which further catalyzes EA degradation and is crosslinked into carbon.
Effect of PAEA content on flame retardant Effect of acrylate coatings
TABLE 3 limiting oxygen index and vertical burn results for acrylate coatings containing PAEA
The limited oxygen index (L OI) and the vertical burning test (U L-94) are two methods which are most widely applied to the flame retardant property test of materials, as can be seen from Table 3, the limited oxygen index of the coating increases with the increase of the content of PAEA, when the PAEA is not added, the coating is flammable, when the addition amount reaches 40%, the oxygen index of the EA can be increased from 18.0 to 32.0, the flame retardant property of the coating is greatly improved and belongs to a flame retardant level, the vertical burning level of the coating increases with the increase of the content of PAEA, until the addition amount of the PAEA reaches 60%, the vertical burning level reaches V-0 level, because of the synergistic flame retardant of P, N elements, the compactness of residual carbon is improved, the content of the residual carbon is increased, and the carbon layer plays a physical barrier role, thereby improving the capability of the coating for insulating oxygen and heat, and improving the flame retardant property of the whole system.
And (4) conclusion:
(1) the PAEA monomer is prepared, the epoxy acrylate coating containing PAEA is synthesized by adopting an ultraviolet curing method, and experiments show that the comprehensive performance of the coating containing PAEA is better than that of the coating not containing PAEA. When the addition amount of the PAEA reaches 60%, the mechanical property is optimal, the pencil hardness of the coating can reach 4H, the acid resistance and the alkali resistance both exceed 40H, the water absorption rate is only 0.31%, the impact resistance is 50 kg-cm, the washing resistance can reach 13730 times, the adhesive force is level 1, and the thermal stability is good.
(2) The transmittance of the EA coating containing PAEA in a visible light region of 400-700 nm exceeds 80%, but the transmittance of the coating in the visible light region tends to decrease with the increase of the addition amount of PAEA, which shows that the higher the content of PAEA is, the greater the influence on the transmittance of the coating is.
(3) The EA coating is added with PAEA, the system weight is basically not greatly lost before 275 ℃, and the mass loss of the coating is increased between 275 ℃ and 390 ℃; the thermal stability of the coating gradually increases with the addition of PAEA between 390 ℃ and 700 ℃. After the EA coating with high PAEA content is combusted, the carbon layer structure is compact, and the carbon residue rate is high.
(4) The conversion rate of double bonds of the UV curing coating film is obviously increased along with the increase of curing time; before the curing time is 20s, the double bond conversion rate increases with the increase of the PAEA content, the curing time exceeds 20s, and finally the double bond conversion rate of the UV-cured coating film tends to decrease with the increase of the PAEA monomer content.
(5) The UV-cured acrylate coating containing the PAEA has good flame-retardant effect, the limit oxygen index of the UV-cured acrylate coating is in an ascending trend along with the increase of the content of the PAEA, and the vertical burning level of the UV-cured acrylate coating is increased along with the increase of the content of the PAEA. The heat release rate is reduced along with the increase of the PAEA content, the peak value of the heat release rate is greatly reduced compared with that of the EA curing coating without the PAEA, the ignition time of the heat release rate is shorter than that of the EA curing coating without flame retardance, and meanwhile, the combustion time is greatly prolonged.
(6) In conclusion, the PAEA monomer can improve the compactness of burning carbon residue of the coating, improve the heat and oxygen isolation capability of the coating, further improve the flame retardant property of the coating, and indirectly reflect that the epoxy acrylate coating containing PAEA has better flame retardant effect. The UV curing coating added with PAEA has better flame retardant effect, and the thermal stability and the mechanical property of the UV curing coating are better than those of the UV coating without PAEA.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (2)
1. An acryloyl phosphate monomer containing nitrogen and hydroxyl, which is characterized in that: the structural formula is shown as the following formula:
2. a method for preparing the nitrogen and hydroxyl group-containing acryloyl phosphate monomer of claim 1, wherein the method comprises the following steps: the method comprises the following steps:
1) dropwise adding acetone dissolved with epoxy chloropropane into phosphoric acid at the temperature of-5 ℃, wherein the molar ratio of the phosphoric acid to the epoxy chloropropane is 1: 2-4, and controlling the dropwise adding speed to ensure that the temperature of a reaction system is kept stable in the dropwise adding process; after the dropwise addition is finished, adding methoxyphenol, and reacting at 75-85 ℃ for 9-11 h to obtain PEPI;
2) dissolving the PEPI prepared in the step 1) and acrylamide in acetone, and adding AlCl while stirring3The PEPI, the acrylamide and the AlCl3The molar ratio of (A) to (B) is 0.8-1.2: 08-1.2, reacting at 35-55 ℃, and finishing the reaction when no gas is generated to obtain the acryloyl phosphate monomer containing nitrogen and hydroxyl.
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