CN117624228A - Phosphorus-based bulk flame-retardant UV (ultraviolet) photocuring active monomer as well as preparation method and application thereof - Google Patents
Phosphorus-based bulk flame-retardant UV (ultraviolet) photocuring active monomer as well as preparation method and application thereof Download PDFInfo
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- CN117624228A CN117624228A CN202311600416.2A CN202311600416A CN117624228A CN 117624228 A CN117624228 A CN 117624228A CN 202311600416 A CN202311600416 A CN 202311600416A CN 117624228 A CN117624228 A CN 117624228A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 72
- 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 claims abstract description 71
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 51
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000011574 phosphorus Substances 0.000 title claims abstract description 50
- 239000000178 monomer Substances 0.000 title claims abstract description 49
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 36
- -1 acryloyloxy substituent Chemical group 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 4
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- QPQGTZMAQRXCJW-UHFFFAOYSA-N [chloro(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(Cl)C1=CC=CC=C1 QPQGTZMAQRXCJW-UHFFFAOYSA-N 0.000 claims description 2
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000000979 retarding effect Effects 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/1411—Esters of phosphorous acids with hydroxyalkyl compounds with further substituents on alkyl
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
- C07F9/4808—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
- C07F9/4841—Aromatic acids or derivatives (P-C aromatic linkage)
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
- C07F9/4866—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the ester moiety containing a substituent or structure which is considered as characteristic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a phosphorus-based bulk flame-retardant UV (ultraviolet) photocuring active monomer, a preparation method and application thereof, wherein the phosphorus-based bulk flame-retardant UV photocuring active monomer has a chemical structural formula as follows:wherein n=1, or 2, or 3, p is a phosphorus-containing group in the chlorophosphoric compound; r1 is an acryloyloxy substituent generated by the reaction of a P-Cl bond of a chlorophosphoric compound and hydroxy acrylic ester. The phosphorus-based bulk flame-retardant UV photo-curing active monomer is prepared by introducing phosphorus atoms into hydroxy acrylic ester through chlorination reaction, has the characteristics of high phosphorus content, low viscosity and adjustable functionality, has bulk flame retardance, and is used for flame retarding UVThe field of photo-curing materials has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a phosphorus-based bulk flame-retardant UV (ultraviolet) photocuring active monomer, and a preparation method and application thereof.
Background
Compared with heat-curing paint, the Ultraviolet (UV) curing technology is more environment-friendly, and the emission of Volatile Organic Compounds (VOCs) and the energy consumption for film formation are lower. Not only has excellent film forming performance, but also greatly reduces environmental pollution. The UV light-cured coating has the performance and environmental requirements required by industrial application as a substrate protective agent, and is applied in large scale in the fields of wood, metal, automobile parts, synthetic leather, fabric, paper and the like.
Reactive monomers are compounds which can dissolve or disperse the film-forming material and can participate in the film-forming reaction in the film-forming process of the coating to form nonvolatile components which remain in the coating film. The use of the functional active monomer provides an effective path capable of flexibly adjusting the construction process, improving the coating performance and carrying out functional modification on the coating.
The UV material has the characteristics of low thermal stability and high combustibility, which greatly limits the application of the UV material in the fields of construction, traffic, electronic appliances and the like, and has the necessity of improving the flame retardance of the material in the special application field. At present, the flame retardant mode of the UV material mainly comprises additive flame retardant, namely, the flame retardant is physically mixed with a material matrix, and the flame retardant and the matrix do not react chemically, but are dispersed in the material matrix through physical action. The flame retardant method has the advantages of simple process, rich types of flame retardants and flexible formula. But the flame retardant efficiency is low, the using amount of the flame retardant is too high, and the influence of the mechanical properties of the material is large. And due to the compatibility problem, the flame retardant is easy to separate out in the process of processing or using the material, so that the appearance and the performance of the product are affected.
The reactive flame retardant is a technical scheme for introducing flame retardant components in the preparation process of materials, and flame retardant elements such as P, halogen (Br and the like), N, si and the like are combined into the chemical structure of the materials in a chemical bonding mode, so that the materials have the flame retardance of the bodies.
At present, the development of flame retardance of a UV light-cured material body mainly focuses on the field of flame retardance modification of resin, namely, introduction of flame retardance elements in the preparation process of the resin. Patent CN112538156a discloses a smoke end scalding resistant flame-retardant photo-curing resin and photo-curing paint, hydroxyl acrylic ester and tetrabromophthalic anhydride are reacted under the action of a catalyst to obtain a hydroxyl-terminated acrylic ester compound, then the hydroxyl-terminated acrylic ester compound is reacted with phenolic epoxy resin to obtain a compound with epoxy groups, and finally the epoxy-terminated epoxy resin is reacted with tetrabromophthalic anhydride and hydroxyl-terminated organosilicon fluorine polyol to obtain the smoke end scalding resistant, stain resistant and flame-retardant photo-curing resin. However, the prepared flame-retardant resin has a narrow application field and is difficult to be applied to flame retardance of other UV materials.
Different from flame retardant modification of resin, the active monomer with the main body flame retardant property is more flexible to use in the preparation of the UV flame retardant material, the phosphorus content and the functionality can be flexibly adjusted, and the application is wider. Meanwhile, in the film curing process, the active monomer is copolymerized with the resin, so that the flame retardant property of the whole material body can be simultaneously endowed by adding and using the active monomer. However, currently there is less investigation of bulk flame retardant reactive monomers.
Therefore, the preparation method of the simple phosphorus-based bulk flame-retardant UV photo-curing active monomer is provided, and the preparation method is used for flame retardance of UV materials, and has important significance.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention provides a phosphorus-based body flame-retardant UV photo-curing active monomer, a preparation method and application thereof, wherein phosphorus atoms are introduced into hydroxy acrylic ester through chlorination reaction, and the phosphorus-based body flame-retardant UV photo-curing active monomer has the characteristics of high phosphorus content, low viscosity and adjustable functionality, has body flame retardance, and has wide application prospect in the field of flame-retardant UV photo-curing materials.
In order to achieve the above purpose, the present invention provides a phosphorus-based bulk flame retardant UV photo-curing reactive monomer, wherein the chemical structural formula of the phosphorus-based bulk flame retardant UV photo-curing reactive monomer is:
wherein n=1, or 2, or 3,
p is a phosphorus-containing group in the chlorophosphoric compound;
r1 is an acryloyloxy substituent generated by the reaction of a P-Cl bond of a chlorophosphoric compound and hydroxy acrylic ester.
Further, in the above technical scheme, the chlorinated phosphorus compound is selected from one of phosphorus trichloride, phenyl phosphorus dichloride, diphenyl phosphorus chloride, phosphorus oxychloride, phenylphosphonic dichloride and diphenyl phosphinic chloride.
Further, in the above technical scheme, the hydroxy acrylate compound is selected from any one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate or pentaerythritol triacrylate.
Further, in the above technical solution, the chemical structural formula of R1 is:
further, in the above technical scheme, the functionality of the phosphorus-based bulk flame-retardant UV light-cured active monomer is 1-9.
The invention also provides a preparation method of the phosphorus-based bulk flame-retardant UV light-cured active monomer, which comprises the following steps: dissolving a hydroxy acrylic ester compound in a solvent, maintaining the temperature of the material below 10 ℃, dropwise adding a chlorophosphoric compound, maintaining the temperature of the material at 30-60 ℃ after the dropwise adding is completed, performing reaction, washing with water after the reaction is completed, layering, and removing the solvent from an upper organic phase through reduced pressure concentration to obtain the phosphorus-based bulk flame-retardant UV photo-curing active monomer.
Further, in the above technical scheme, the solvent is any one of ethyl acetate, dichloromethane, 1, 2-dichloroethane, toluene, benzene, petroleum ether or n-hexane.
Further, in the technical scheme, HCl generated by the chlorination reaction is removed by vacuum, and the vacuum degree is more than or equal to 0.09Mpa.
Further, in the technical scheme, the temperature is raised to 30-60 ℃ and the reaction time is 1-10h.
The invention also provides application of the phosphorus-based body flame-retardant UV photo-curing active monomer in preparing a flame-retardant UV photo-curing material.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the phosphorus atom chemical bond is added into the hydroxy acrylic ester by a chemical modification method, so that the material has the main flame retardance, and the prepared phosphorus main flame-retardant UV light-cured active monomer has the characteristics of high phosphorus content, low viscosity, adjustable functionality, good flame-retardant effect and the like, the functionality can be flexibly adjusted between 1 and 9, and the phosphorus main flame-retardant UV light-cured active monomer has wide application prospect in the field of flame-retardant UV light-cured materials;
2. the invention has simple synthesis process and short production period; the byproduct HCl is pumped out in vacuum, so that an acid binding agent is avoided, and the process is environment-friendly and free of solid waste.
Detailed Description
The experimental methods in the following examples are conventional methods unless otherwise specified. The raw materials used in the following examples are all commercially available and commercially available unless otherwise specified.
The above technical features of the present invention and the technical features specifically described in the following (embodiment) may be combined with each other to form a new or preferred technical solution.
The phosphorus-based bulk flame-retardant UV photocuring active monomer prepared by the invention takes chlorinated phosphorus compounds and hydroxy acrylic ester as raw materials, phosphorus-containing groups are introduced into acrylic ester through substitution reaction between P-Cl bond and hydroxy, HCl which is a byproduct generated by the reaction is extracted through vacuum, and the phosphorus-based bulk flame-retardant UV photocuring active monomer with the functionality of 1-9 can be prepared, and the prepared product has the characteristics of high phosphorus content, low viscosity, adjustable functionality, good flame-retardant effect and the like.
The starting materials involved in the various embodiments of the present invention are either existing commercially available products or can be prepared according to existing methods.
Example 1: preparation of monofunctional phosphorus-based bulk flame-retardant UV photo-curing active monomer
Hydroxyethyl acrylate (100 g,0.86 mol) is added into 200mL of dichloromethane solvent, the temperature of the material is maintained below 10 ℃, diphenyl phosphorus chloride (189.8 g,0.86 mol) is added dropwise, HCl generated by the reaction is removed through vacuum, the vacuum degree of the system is maintained to be 0.095MPa, the temperature of the material is maintained to be 50 ℃ after the dripping is finished, the reaction is carried out, water washing delamination is carried out for 2 times, the solvent is removed from the upper organic phase through reduced pressure concentration, and the monofunctional phosphorus-based flame-retardant UV photo-curing active monomer is obtained.
The chemical structural formula of the prepared monofunctional phosphorus-based body flame-retardant UV photo-curing active monomer is shown as follows:
the product data are characterized as follows:
1 H NMR(400MHz,DMSO-d6)δ:7.42(tt,J＝9.8,1.4Hz,6H),7.15(dd,J＝7.7,9H),6.41(s,1H),6.12(s,1H),5.83(dd,J＝7.7，1.4Hz,1H),4.29(d,J＝5.5,1.3Hz,2H),3.81(q,J＝5.1,1.4Hz,2H).
the liquid chromatogram is shown in fig. 1, and the characterization result is that: the residence time of the product is 11.207min, and the purity is 99.2%. Wherein, liquid phase condition-chromatographic column: c18,5 μm, 250X 4.6mm;
wavelength: 254nm;
flow rate: 1.0mL/min;
column temperature: room temperature;
sample injection amount: 20. Mu.L;
mobile phase: water/acetonitrile=45/55, filtered, degassed.
Example 2: preparation of difunctional phosphorus-based bulk flame-retardant UV (ultraviolet) photocuring active monomer
Hydroxyethyl acrylate (100 g,0.86 mol) is added into 200mL of dichloromethane solvent, the temperature of the material is maintained below 10 ℃, phenyl phosphorus dichloride (77.0 g,0.43 mol) is added dropwise, HCl generated by the reaction is removed in vacuum, the vacuum degree of the system is maintained at 0.095MPa, the temperature of the material is maintained at 50 ℃ after the dropwise addition is finished, the reaction is carried out for 2 times, water washing delamination is carried out after the reaction is finished, the solvent is removed from the upper organic phase through reduced pressure concentration, and the tri-functionality phosphorus-based flame-retardant UV photo-curing active monomer is obtained.
The chemical structural formula of the prepared difunctional phosphorus-based bulk flame-retardant UV photo-curing active monomer is shown as follows:
the product data are characterized as follows:
1 H NMR(400MHz,DMSO-d6)δ:7.42(m,3H),7.15(m,2H),6.41(dd,J＝7.7,1.4Hz,1.4Hz,2H),6.12(q,J＝5.5,1.3Hz,2H),5.83(dd,J＝7.7,1.4Hz,2H),4.29(d,J＝6.5,1.4Hz,4H),3.81(m,J＝5.1,4H).
the liquid chromatogram is shown in fig. 2, and the characterization result is as follows: the product residence time was 10.933min and purity 98.9%.
Wherein, liquid phase condition-chromatographic column: c18,5 μm, 250X 4.6mm;
wavelength: 254nm;
flow rate: 1.0mL/min;
column temperature: room temperature;
sample injection amount: 20. Mu.L;
mobile phase: water/acetonitrile=45/55, filtered, degassed.
Example 3: preparation of hexafunctional phosphorus-based bulk flame-retardant UV photo-curing active monomer
Pentaerythritol triacrylate (100 g,0.34 mol) is added into 200mL of dichloromethane solvent, the temperature of the mixture is maintained below 10 ℃, phenyl phosphorus dichloride (30.4 g,0.17 mol) is dropwise added, HCl generated by the reaction is removed through vacuum, the vacuum degree of the system is maintained at 0.095MPa, the temperature of the mixture is maintained at 50 ℃ after the dropwise addition is completed, the reaction is completed, water washing and layering are carried out for 2 times, the solvent is removed from the upper organic phase through reduced pressure concentration, and the hexafunctional phosphorus-based flame-retardant UV photo-curing active monomer is obtained.
The chemical structural formula of the prepared hexafunctional phosphorus-based bulk flame-retardant UV photo-curing active monomer is shown as follows:
the product data are characterized as follows:
1 H NMR(400MHz,DMSO-d6)δ:7.42(m,3H),7.15(m,2H),6.41(dd,J＝7.7,1.4Hz,6H),6.12(q,J＝5.5,6H),5.83(dd,J＝7.7,1.4Hz,6H),4.01(d,J＝6.5,1.4Hz,12H),3.39(q,J＝5.1,1.4Hz,4H).
the liquid chromatogram is shown in fig. 3, and the characterization result is as follows: the residence time of the product was 11.952min and the purity was 94.0%.
Wherein, liquid phase condition-chromatographic column: c18,5 μm, 250X 4.6mm;
wavelength: 254nm;
flow rate: 1.0mL/min;
column temperature: room temperature;
sample injection amount: 20. Mu.L;
mobile phase: water/acetonitrile=45/55, filtered, degassed.
Example 4: preparation of nine-functionality phosphorus-series bulk flame-retardant UV photo-curing active monomer
Pentaerythritol triacrylate (100 g,0.34 mol) is added into 200mL of dichloromethane solvent, the temperature of the material is maintained below 0 ℃, phosphorus trichloride (15.6 g,0.11 mol) is dripped, HCl generated by the reaction is removed through vacuum, the vacuum degree of the system is maintained to be 0.095MPa, the temperature of the material is maintained to be 50 ℃ after the dripping is finished, the reaction is finished, water washing layering is carried out for 2 times, the solvent is removed from the upper organic phase through reduced pressure concentration, and the nine-functionality phosphorus-based flame-retardant UV photo-curing active monomer is obtained.
The chemical structural formula of the prepared nine-functionality phosphorus-based bulk flame-retardant UV photo-curing active monomer is shown as follows:
the product data are characterized as follows:
1 H NMR(400MHz,DMSO-d6)δ:6.48(d,J＝7.2,4Hz,2H),6.41(d,J＝6.5,1.4Hz,10H),6.40(t,J＝7.5,1.4Hz,2H),6.12(m,10H),5.83(tt,J＝8.5,1.4Hz,3H),4.94(d,J＝6.5,1.4Hz,3H),4.77(m,2H),4.29(t,J＝7.5,1.4Hz,2H),4.01(s,2H),3.68(m,4H),3.54(m,2H),3.39(dd,J＝7.7.1.4Hz,6H),2.01(s,6H),1.3(d,J＝6.5,1.4Hz,6H).
the liquid chromatogram is shown in fig. 4, and the characterization result is as follows: the product residence time was 12.126min and purity 92.4%.
Wherein, liquid phase condition-chromatographic column: c18,5 μm, 250X 4.6mm;
wavelength: 254nm;
flow rate: 1.0mL/min;
column temperature: room temperature;
sample injection amount: 20. Mu.L;
mobile phase: water/acetonitrile=45/55, filtered, degassed.
The properties of the four phosphorus-based bulk flame-retardant UV light-curing active monomers with different functionality degrees, hydroxyethyl acrylate and pentaerythritol triacrylate prepared in examples 1-4 were tested, and the results are shown in Table 1.
TABLE 1
As can be seen from the results of table 1, the phosphorus based bulk flame retardant UV photo-curable reactive monomer has the following characteristics compared with the conventional mono-functional acrylate diluent hydroxyethyl acrylate and the tri-functional acrylate diluent pentaerythritol triacrylate: the viscosity is low, the viscosity is still lower under higher functionality, and the advantages are obvious in the application field of the high-functionality low-viscosity reactive diluent; the introduction of the P element endows the material body with flame retardant property, and the monofunctional, difunctional and hexa functional monomers can pass the UV-94 test V-0 level, and the LOI oxygen index reaches the flame retardant level, so that the material has outstanding flame retardant property and wide application prospect in the field of flame retardant UV photo-curing materials.
Finally, it should be emphasized that the foregoing description is merely illustrative of the preferred embodiments of the invention, and that various changes and modifications can be made by those skilled in the art without departing from the spirit and principles of the invention, and any such modifications, equivalents, improvements, etc. are intended to be included within the scope of the invention.
Claims (10)
1. The phosphorus-based bulk flame-retardant UV photo-curing active monomer is characterized by comprising the following chemical structural formula:
wherein n=1, or 2, or 3,
p is a phosphorus-containing group in the chlorophosphoric compound;
r1 is an acryloyloxy substituent generated by the reaction of a P-Cl bond of a chlorophosphoric compound and hydroxy acrylic ester.
2. The phosphorus-based bulk flame-retardant UV light-curable active monomer according to claim 1, wherein the chlorinated phosphorus compound is one selected from phosphorus trichloride, phenyl phosphorus dichloride, diphenyl phosphorus chloride, phosphorus oxychloride, phenylphosphonyl dichloride and diphenylphosphinyl chloride.
3. The phosphorus-based bulk flame-retardant UV light-curable reactive monomer of claim 1, wherein the hydroxy acrylate compound is selected from any one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, or pentaerythritol triacrylate.
4. The phosphorus-based bulk flame retardant UV photo-curing reactive monomer of claim 1, wherein said R1 has the chemical formula:
5. the phosphorus-based bulk flame retardant UV photo-curable reactive monomer of claim 1, wherein the phosphorus-based bulk flame retardant UV photo-curable reactive monomer has a functionality of 1-9.
6. The method for preparing the phosphorus-based bulk flame-retardant UV light-curable reactive monomer as claimed in any one of claims 1 to 5, comprising the steps of: dissolving a hydroxy acrylic ester compound in a solvent, maintaining the temperature of the material below 10 ℃, dropwise adding a chlorophosphoric compound, maintaining the temperature of the material at 30-60 ℃ after the dropwise adding is completed, performing reaction, washing with water after the reaction is completed, layering, and removing the solvent from an upper organic phase through reduced pressure concentration to obtain the phosphorus-based bulk flame-retardant UV photo-curing active monomer.
7. The method according to claim 6, wherein the solvent is any one of ethyl acetate, methylene chloride, 1, 2-dichloroethane, toluene, benzene, petroleum ether, and n-hexane.
8. The process according to claim 6, wherein HCl produced by the chlorination reaction is removed by vacuum, and the vacuum degree is not less than 0.09MPa.
9. The preparation method according to claim 6, wherein the temperature is raised to 30-60 ℃ and the reaction time is 1-10h.
10. Use of the phosphorus-based bulk flame retardant UV photo-curable active monomer according to any one of claims 1 to 5 or prepared by the preparation method according to any one of claims 6 to 9 in the preparation of flame retardant UV photo-curable materials.
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