CN111285902A - Synthesis method of flame-retardant acrylate monomer and flame-retardant diffusion film thereof - Google Patents
Synthesis method of flame-retardant acrylate monomer and flame-retardant diffusion film thereof Download PDFInfo
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- CN111285902A CN111285902A CN202010169723.XA CN202010169723A CN111285902A CN 111285902 A CN111285902 A CN 111285902A CN 202010169723 A CN202010169723 A CN 202010169723A CN 111285902 A CN111285902 A CN 111285902A
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- 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 94
- 239000003063 flame retardant Substances 0.000 title claims abstract description 90
- 238000009792 diffusion process Methods 0.000 title claims abstract description 61
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 40
- 239000000178 monomer Substances 0.000 title claims abstract description 37
- 238000001308 synthesis method Methods 0.000 title description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000002245 particle Substances 0.000 claims abstract description 71
- 239000000463 material Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 33
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 27
- -1 hydroxyalkyl acrylate Chemical compound 0.000 claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012074 organic phase Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012528 membrane Substances 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000012071 phase Substances 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 230000003678 scratch resistant effect Effects 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- 229910001882 dioxygen Inorganic materials 0.000 claims description 8
- 238000011010 flushing procedure Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- VXTFGYMINLXJPW-UHFFFAOYSA-N phosphinane Chemical compound C1CCPCC1 VXTFGYMINLXJPW-UHFFFAOYSA-N 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 238000007790 scraping Methods 0.000 claims description 8
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical group OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 claims description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006120 scratch resistant coating Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims 1
- 229920000647 polyepoxide Polymers 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000002834 transmittance Methods 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
- G02B5/0242—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Optics & Photonics (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
A method for synthesizing flame-retardant acrylate monomers and a flame-retardant diffusion film thereof are disclosed, wherein the method for synthesizing the flame-retardant acrylate monomers comprises the following steps: step 1: adding DDSP, hydroxyalkyl acrylate, toluene and an acid binding agent into a reaction container; step 2: heating the reaction container and then reacting; and step 3: and cooling to room temperature, transferring the solution into a separating funnel, adding isovolumetric deionized water, shaking uniformly, standing for layering, removing the lower water phase to obtain an organic phase, and putting the organic phase into a rotary evaporator to evaporate toluene. A flame retardant diffusion membrane comprising: the anti-scratch coating comprises a base material layer, an anti-scratch layer and a diffusion layer, wherein the anti-scratch layer consists of flame-retardant resin and ZnO particles; the diffusion layer consists of flame-retardant resin and polymethyl methacrylate particles; the flame-retardant resin is composed of the following components: the flame-retardant acrylate monomer, the flame-retardant acrylate oligomer, the flame-retardant acrylate acrylic acid, the flame-retardant 2-phenoxyethyl acrylate and the flame-retardant azobisisobutyronitrile prepared by the method. The invention provides a flame-retardant acrylate monomer and a flame-retardant diffusion film thereof, which have a flame-retardant function.
Description
Technical Field
The invention relates to a flame-retardant acrylate monomer and a diffusion film thereof.
Background
The diffusion film is widely applied to the liquid crystal field and the display illumination field, and light is subjected to non-directional reflection and refraction by the diffusion film through diffusion particles or a surface micro-lens structure, so that the effects of light homogenizing and flaw shading can be achieved. The diffusion film disclosed in patent CN102928901B has a good optical effect, but the diffusion film adhesive resin has no flame retardance, is easy to burn in production and storage, and has certain potential safety hazard. In the field of display illumination, especially some signs for safety exits, a diffusion film is required to have not only a light-homogenizing effect but also a certain flame-retardant effect. So that the indicator is not easy to burn under severe conditions such as high temperature of fire, thereby having better indicating effect.
The thiopyrophosphoric acid has excellent flame retardant effect in similar materials due to the flame retardant synergistic effect of sulfur and phosphorus. However, this material also has a disadvantage of being easily crystallized, and addition thereof to an optical resin easily affects the light transmittance of the resin. The acrylate material has excellent optical performance and high curing speed, and is widely applied to the field of optical films such as diffusion films and brightness enhancement films, but most of monomer and oligomer materials do not have flame retardance.
At present, no acrylate containing thiopyrophosphate groups exists, and the diffusion membrane has no flame retardant function.
Disclosure of Invention
In view of the fact that no acrylate containing thiopyrophosphate groups exists at present and a diffusion membrane does not have a flame retardant function, the invention provides a flame retardant acrylate monomer and a flame retardant diffusion membrane thereof.
The technical scheme for solving the technical problem is as follows: a method for synthesizing a flame-retardant acrylate monomer comprises the following steps:
step 1: adding 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxaphosphorinane (DDSP), hydroxyalkyl acrylate, toluene and an acid-binding agent into a reaction vessel;
wherein the molar ratio of the 5, 5-dimethyl-2-thio-2-chloro-1, 3, 2-dioxaphosphorinane to the hydroxyalkyl acrylate is 1: 1;
the molar ratio of the 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxygen phosphacyclohexane to the acid-binding agent is 1: 1-1: 100;
the amount of toluene used was: adding 1-4ml of toluene into each gram of 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxaphosphorinane;
step 2: heating the reaction container to 80-100 ℃, and flushing protective inert gas into the reaction container to react for 30-90 minutes;
and step 3: and (3) cooling the reaction vessel to room temperature, transferring the solution in the vessel to a separating funnel, adding isovolumetric deionized water, shaking up, standing for layering, removing the lower water phase to obtain an organic phase, and putting the organic phase into a rotary evaporator to evaporate toluene to obtain the flame-retardant acrylate monomer.
Preferably, the hydroxyalkyl acrylate is hydroxyethyl acrylate, or 3-hydroxypropyl acrylate, or 4-hydroxybutyl acrylate, or hydroxyethyl methacrylate, or 3-hydroxypropyl methacrylate, or 4-hydroxybutyl methacrylate.
Preferably, the acid-binding agent is pyridine or triethylamine.
A flame retardant diffusion membrane comprising: the scratch-resistant coating comprises a base material layer, a scratch-resistant layer and a diffusion layer, wherein the scratch-resistant layer is attached to the back surface of the base material layer, and the diffusion layer is attached to the front surface of the base material layer;
the anti-scraping layer consists of flame-retardant resin and ZnO particles, and the ZnO particles account for 0.1-0.3% of the total mass;
the diffusion layer is composed of flame-retardant resin and polymethyl methacrylate (PMMA) particles, and the polymethyl methacrylate particles account for 2% -5% of the total mass;
the flame-retardant resin comprises the following components in percentage by mass:
20-30 parts by mass of flame-retardant acrylate monomer prepared by the method
30 to 50 parts by mass of an oligomer
10 to 20 parts by mass of acrylic acid
30-40 parts by mass of 2-phenoxyethyl acrylate (PHEA)
3-5 parts by mass of azobisisobutyronitrile.
Preferably, the oligomer is a urethane acrylate oligomer, or an acrylic epoxy oligomer.
Preferably, the ZnO particle size is 100-500 microns, and the polymethyl methacrylate particle size is 200-300 microns.
The invention has the beneficial effects that: the flame-retardant acrylate monomer provided by the invention is colorless and transparent, has good compatibility with acrylic resin, and is simple in structure, low in cost and easy to obtain. Sulfur and phosphorus elements are adopted for synergetic flame retardance, and compared with a halogen-containing flame retardant, the flame retardant has excellent flame retardance and no irritant acid mist is generated in the combustion process. The flame-retardant diffusion film provided by the invention has better flame-retardant function and light diffusion function as well as low cost compared with the common diffusion film due to the flame-retardant acrylate monomer component, and is beneficial to industrial production.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example one
A method for synthesizing a flame-retardant acrylate monomer comprises the following steps:
step 1: adding 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxaphosphorinane, acrylic acid hydroxyalkyl ester, toluene and an acid-binding agent into a reaction container;
wherein the molar ratio of the 5, 5-dimethyl-2-thio-2-chloro-1, 3, 2-dioxaphosphorinane to the hydroxyalkyl acrylate is 1: 1;
the molar ratio of the 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxygen phospha cyclohexane to the acid-binding agent is 1: 50;
the amount of toluene used was: 2.5ml of toluene is added to each gram of 5, 5-dimethyl-2-thio-2-chloro-1, 3, 2-dioxaphosphorinane;
step 2: heating the reaction container to 80-100 ℃, and flushing protective inert gas into the reaction container to react for 60 minutes;
and step 3: and (3) cooling the reaction vessel to room temperature, transferring the solution in the vessel to a separating funnel, adding isovolumetric deionized water, shaking up, standing for layering, removing the lower water phase to obtain an organic phase, and putting the organic phase into a rotary evaporator to evaporate toluene to obtain the flame-retardant acrylate monomer.
In this example, the hydroxyalkyl acrylate is hydroxyethyl acrylate;
in this embodiment, the acid scavenger is pyridine.
A flame retardant diffusion membrane comprising: the anti-scratch coating comprises a base material layer, an anti-scratch layer and a diffusion layer, wherein the anti-scratch layer is attached to the back surface of the base material layer, the diffusion layer is attached to the front surface of the base material layer, and the base material layer is generally made of a PET material;
the anti-scraping layer is composed of flame-retardant resin and ZnO particles, and the ZnO particles account for 0.2% of the total mass;
the diffusion layer is composed of flame-retardant resin and polymethyl methacrylate particles, and the polymethyl methacrylate particles account for 3% of the total mass;
the flame-retardant resin comprises the following components in percentage by mass:
25 parts by mass of flame-retardant acrylate monomer prepared by the method
40 parts by mass of an oligomer
Acrylic acid 15 parts by mass
35 parts by mass of 2-phenoxyethyl acrylate
And 4 parts by mass of azobisisobutyronitrile.
In this embodiment, the oligomer is a urethane acrylate oligomer.
In the scratch-resistant layer, the particle size of the ZnO particles can be selected by those skilled in the art according to actual needs, and generally, the ZnO particle size is recommended to be 100 to 500 micrometers.
In the diffusion layer, the polymethyl methacrylate particles can be selected by those skilled in the art according to actual needs, and generally, the size of the polymethyl methacrylate particles is 200 to 300 micrometers.
Example two
A method for synthesizing a flame-retardant acrylate monomer comprises the following steps:
step 1: adding 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxaphosphorinane, acrylic acid hydroxyalkyl ester, toluene and an acid-binding agent into a reaction container;
wherein the molar ratio of the 5, 5-dimethyl-2-thio-2-chloro-1, 3, 2-dioxaphosphorinane to the hydroxyalkyl acrylate is 1: 1;
the molar ratio of the 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxygen phospha cyclohexane to the acid-binding agent is 1: 20;
the amount of toluene used was: adding 1ml of toluene into each gram of 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxaphosphorinane;
step 2: heating the reaction container to 80-100 ℃, and flushing protective inert gas into the reaction container to react for 50 minutes;
and step 3: and (3) cooling the reaction vessel to room temperature, transferring the solution in the vessel to a separating funnel, adding isovolumetric deionized water, shaking up, standing for layering, removing the lower water phase to obtain an organic phase, and putting the organic phase into a rotary evaporator to evaporate toluene to obtain the flame-retardant acrylate monomer.
In this example, the hydroxyalkyl acrylate is 3-hydroxypropyl acrylate;
in this embodiment, the acid-binding agent is triethylamine.
A flame retardant diffusion membrane comprising: the anti-scratch coating comprises a base material layer, an anti-scratch layer and a diffusion layer, wherein the anti-scratch layer is attached to the back surface of the base material layer, the diffusion layer is attached to the front surface of the base material layer, and the base material layer is generally made of a PET material;
the anti-scraping layer is composed of flame-retardant resin and ZnO particles, and the ZnO particles account for 0.15% of the total mass;
the diffusion layer is composed of flame-retardant resin and polymethyl methacrylate particles, and the polymethyl methacrylate particles account for 5% of the total mass;
the flame-retardant resin comprises the following components in percentage by mass:
20 parts by mass of flame-retardant acrylate monomer prepared by the method
Oligomer 35 parts by mass
Acrylic acid 12 parts by mass
40 parts by mass of 2-phenoxyethyl acrylate
3.5 parts by mass of azobisisobutyronitrile.
In this embodiment, the oligomer is an acrylic epoxy oligomer.
In the scratch-resistant layer, the particle size of the ZnO particles can be selected by those skilled in the art according to actual needs, and generally, the ZnO particle size is recommended to be 100 to 500 micrometers.
In the diffusion layer, the polymethyl methacrylate particles can be selected by those skilled in the art according to actual needs, and generally, the size of the polymethyl methacrylate particles is 200 to 300 micrometers.
EXAMPLE III
A method for synthesizing a flame-retardant acrylate monomer comprises the following steps:
step 1: adding 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxaphosphorinane, acrylic acid hydroxyalkyl ester, toluene and an acid-binding agent into a reaction container;
wherein the molar ratio of the 5, 5-dimethyl-2-thio-2-chloro-1, 3, 2-dioxaphosphorinane to the hydroxyalkyl acrylate is 1: 1;
the molar ratio of the 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxygen phospha cyclohexane to the acid-binding agent is 1: 80;
the amount of toluene used was: adding 3ml of toluene into each gram of 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxaphosphorinane;
step 2: heating the reaction container to 80-100 ℃, and flushing protective inert gas into the reaction container to react for 30 minutes;
and step 3: and (3) cooling the reaction vessel to room temperature, transferring the solution in the vessel to a separating funnel, adding isovolumetric deionized water, shaking up, standing for layering, removing the lower water phase to obtain an organic phase, and putting the organic phase into a rotary evaporator to evaporate toluene to obtain the flame-retardant acrylate monomer.
In this example, the hydroxyalkyl acrylate is 4-hydroxybutyl acrylate;
in this embodiment, the acid scavenger is pyridine.
A flame retardant diffusion membrane comprising: the anti-scratch coating comprises a base material layer, an anti-scratch layer and a diffusion layer, wherein the anti-scratch layer is attached to the back surface of the base material layer, the diffusion layer is attached to the front surface of the base material layer, and the base material layer is generally made of a PET material;
the anti-scraping layer is composed of flame-retardant resin and ZnO particles, and the ZnO particles account for 0.3% of the total mass;
the diffusion layer is composed of flame-retardant resin and polymethyl methacrylate particles, and the polymethyl methacrylate particles account for 2.5% of the total mass;
the flame-retardant resin comprises the following components in percentage by mass:
30 parts by mass of flame-retardant acrylate monomer prepared by the method
Oligomer 30 parts by mass
Acrylic acid 13 parts by mass
32 parts by mass of 2-phenoxyethyl acrylate
5 parts by mass of azobisisobutyronitrile.
In this embodiment, the oligomer is a urethane acrylate oligomer.
In the scratch-resistant layer, the particle size of the ZnO particles can be selected by those skilled in the art according to actual needs, and generally, the ZnO particle size is recommended to be 100 to 500 micrometers.
In the diffusion layer, the polymethyl methacrylate particles can be selected by those skilled in the art according to actual needs, and generally, the size of the polymethyl methacrylate particles is 200 to 300 micrometers.
Example four
A method for synthesizing a flame-retardant acrylate monomer comprises the following steps:
step 1: adding 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxaphosphorinane, acrylic acid hydroxyalkyl ester, toluene and an acid-binding agent into a reaction container;
wherein the molar ratio of the 5, 5-dimethyl-2-thio-2-chloro-1, 3, 2-dioxaphosphorinane to the hydroxyalkyl acrylate is 1: 1;
the molar ratio of the 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxygen phospha cyclohexane to the acid-binding agent is 1: 1;
the amount of toluene used was: adding 2ml of toluene into each gram of 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxaphosphorinane;
step 2: heating the reaction container to 80-100 ℃, and flushing protective inert gas into the reaction container to react for 90 minutes;
and step 3: and (3) cooling the reaction vessel to room temperature, transferring the solution in the vessel to a separating funnel, adding isovolumetric deionized water, shaking up, standing for layering, removing the lower water phase to obtain an organic phase, and putting the organic phase into a rotary evaporator to evaporate toluene to obtain the flame-retardant acrylate monomer.
In this example, the hydroxyalkyl acrylate is hydroxyethyl methacrylate;
in this embodiment, the acid-binding agent is triethylamine.
A flame retardant diffusion membrane comprising: the anti-scratch coating comprises a base material layer, an anti-scratch layer and a diffusion layer, wherein the anti-scratch layer is attached to the back surface of the base material layer, the diffusion layer is attached to the front surface of the base material layer, and the base material layer is generally made of a PET material;
the anti-scraping layer is composed of flame-retardant resin and ZnO particles, and the ZnO particles account for 0.1% of the total mass;
the diffusion layer is composed of flame-retardant resin and polymethyl methacrylate particles, and the polymethyl methacrylate particles account for 4% of the total mass;
the flame-retardant resin comprises the following components in percentage by mass:
22 parts by mass of flame-retardant acrylate monomer prepared by the method
Oligomer 50 parts by mass
Acrylic acid 10 parts by mass
36 parts by mass of 2-phenoxyethyl acrylate
Azobisisobutyronitrile 4.5 parts by mass.
In this embodiment, the oligomer is an acrylic epoxy oligomer.
In the scratch-resistant layer, the particle size of the ZnO particles can be selected by those skilled in the art according to actual needs, and generally, the ZnO particle size is recommended to be 100 to 500 micrometers.
In the diffusion layer, the polymethyl methacrylate particles can be selected by those skilled in the art according to actual needs, and generally, the size of the polymethyl methacrylate particles is 200 to 300 micrometers.
EXAMPLE five
A method for synthesizing a flame-retardant acrylate monomer comprises the following steps:
step 1: adding 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxaphosphorinane, acrylic acid hydroxyalkyl ester, toluene and an acid-binding agent into a reaction container;
wherein the molar ratio of the 5, 5-dimethyl-2-thio-2-chloro-1, 3, 2-dioxaphosphorinane to the hydroxyalkyl acrylate is 1: 1;
the molar ratio of the 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxygen phospha cyclohexane to the acid-binding agent is 1: 100;
the amount of toluene used was: adding 3.5ml of toluene into each gram of 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxaphosphorinane;
step 2: heating the reaction container to 80-100 ℃, and flushing protective inert gas into the reaction container to react for 70 minutes;
and step 3: and (3) cooling the reaction vessel to room temperature, transferring the solution in the vessel to a separating funnel, adding isovolumetric deionized water, shaking up, standing for layering, removing the lower water phase to obtain an organic phase, and putting the organic phase into a rotary evaporator to evaporate toluene to obtain the flame-retardant acrylate monomer.
In this example, the hydroxyalkyl acrylate was 3-hydroxypropyl methacrylate;
in this embodiment, the acid scavenger is pyridine.
A flame retardant diffusion membrane comprising: the anti-scratch coating comprises a base material layer, an anti-scratch layer and a diffusion layer, wherein the anti-scratch layer is attached to the back surface of the base material layer, the diffusion layer is attached to the front surface of the base material layer, and the base material layer is generally made of a PET material;
the anti-scraping layer is composed of flame-retardant resin and ZnO particles, and the ZnO particles account for 0.18% of the total mass;
the diffusion layer is composed of flame-retardant resin and polymethyl methacrylate particles, and the polymethyl methacrylate particles account for 2% of the total mass;
the flame-retardant resin comprises the following components in percentage by mass:
26 parts by mass of flame-retardant acrylate monomer prepared by the method
Oligomer 45 parts by mass
20 parts by mass of acrylic acid
30 parts by mass of 2-phenoxyethyl acrylate
3 parts by mass of azobisisobutyronitrile.
In this embodiment, the oligomer is a urethane acrylate oligomer.
In the scratch-resistant layer, the particle size of the ZnO particles can be selected by those skilled in the art according to actual needs, and generally, the ZnO particle size is recommended to be 100 to 500 micrometers.
In the diffusion layer, the polymethyl methacrylate particles can be selected by those skilled in the art according to actual needs, and generally, the size of the polymethyl methacrylate particles is 200 to 300 micrometers.
EXAMPLE six
A method for synthesizing a flame-retardant acrylate monomer comprises the following steps:
step 1: adding 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxaphosphorinane, acrylic acid hydroxyalkyl ester, toluene and an acid-binding agent into a reaction container;
wherein the molar ratio of the 5, 5-dimethyl-2-thio-2-chloro-1, 3, 2-dioxaphosphorinane to the hydroxyalkyl acrylate is 1: 1;
the molar ratio of the 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxygen phospha cyclohexane to the acid-binding agent is 1: 70;
the amount of toluene used was: adding 4ml of toluene into each gram of 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxaphosphorinane;
step 2: heating the reaction container to 80-100 ℃, and flushing protective inert gas into the reaction container to react for 80 minutes;
and step 3: and (3) cooling the reaction vessel to room temperature, transferring the solution in the vessel to a separating funnel, adding isovolumetric deionized water, shaking up, standing for layering, removing the lower water phase to obtain an organic phase, and putting the organic phase into a rotary evaporator to evaporate toluene to obtain the flame-retardant acrylate monomer.
In this example, the hydroxyalkyl acrylate is 4-hydroxybutyl methacrylate;
in this embodiment, the acid-binding agent is triethylamine.
A flame retardant diffusion membrane comprising: the anti-scratch coating comprises a base material layer, an anti-scratch layer and a diffusion layer, wherein the anti-scratch layer is attached to the back surface of the base material layer, the diffusion layer is attached to the front surface of the base material layer, and the base material layer is generally made of a PET material;
the anti-scraping layer is composed of flame-retardant resin and ZnO particles, and the ZnO particles account for 0.25% of the total mass;
the diffusion layer is composed of flame-retardant resin and polymethyl methacrylate particles, and the polymethyl methacrylate particles account for 3.5% of the total mass;
the flame-retardant resin comprises the following components in percentage by mass:
28 parts by mass of flame-retardant acrylate monomer prepared by the method
42 parts by mass of an oligomer
18 parts by mass of acrylic acid
38 parts by mass of 2-phenoxyethyl acrylate
3.2 parts by mass of azobisisobutyronitrile.
In this embodiment, the oligomer is an acrylic epoxy oligomer.
In the scratch-resistant layer, the particle size of the ZnO particles can be selected by those skilled in the art according to actual needs, and generally, the ZnO particle size is recommended to be 100 to 500 micrometers.
In the diffusion layer, the polymethyl methacrylate particles can be selected by those skilled in the art according to actual needs, and generally, the size of the polymethyl methacrylate particles is 200 to 300 micrometers.
Claims (7)
1. A method for synthesizing a flame-retardant acrylate monomer is characterized by comprising the following steps:
step 1: adding 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxaphosphorinane, acrylic acid hydroxyalkyl ester, toluene and an acid-binding agent into a reaction container;
wherein the molar ratio of the 5, 5-dimethyl-2-thio-2-chloro-1, 3, 2-dioxaphosphorinane to the hydroxyalkyl acrylate is 1: 1;
the molar ratio of the 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxygen phosphacyclohexane to the acid-binding agent is 1: 1-1: 100;
the amount of toluene used was: adding 1-4ml of toluene into each gram of 5, 5-dimethyl-2-sulfur-2-chlorine-1, 3, 2-dioxaphosphorinane;
step 2: heating the reaction container to 80-100 ℃, and flushing protective inert gas into the reaction container to react for 30-90 minutes;
and step 3: and (3) cooling the reaction vessel to room temperature, transferring the solution in the vessel to a separating funnel, adding isovolumetric deionized water, shaking up, standing for layering, removing the lower water phase to obtain an organic phase, and putting the organic phase into a rotary evaporator to evaporate toluene to obtain the flame-retardant acrylate monomer.
2. The method for synthesizing a flame retardant acrylate monomer according to claim 1, wherein: the hydroxyalkyl acrylate is hydroxyethyl acrylate, or 3-hydroxypropyl acrylate, or 4-hydroxybutyl acrylate, or hydroxyethyl methacrylate, or 3-hydroxypropyl methacrylate, or 4-hydroxybutyl methacrylate.
3. The method for synthesizing a flame retardant acrylate monomer according to claim 1 or 2, wherein: the acid-binding agent is pyridine or triethylamine.
4. A flame retardant diffusion membrane comprising: the scratch-resistant coating comprises a base material layer, a scratch-resistant layer and a diffusion layer, wherein the scratch-resistant layer is attached to the back surface of the base material layer, and the diffusion layer is attached to the front surface of the base material layer;
the method is characterized in that: the anti-scraping layer consists of flame-retardant resin and ZnO particles, and the ZnO particles account for 0.1-0.3% of the total mass;
the diffusion layer is composed of flame-retardant resin and polymethyl methacrylate particles, and the polymethyl methacrylate particles account for 2% -5% of the total mass;
the flame-retardant resin comprises the following components in percentage by mass:
20-30 parts by mass of a flame-retardant acrylate monomer prepared according to any one of claims 1-3
30 to 50 parts by mass of an oligomer
10 to 20 parts by mass of acrylic acid
30-40 parts by mass of 2-phenoxyethyl acrylate
3-5 parts by mass of azobisisobutyronitrile.
5. The flame retardant diffusion film of claim 4, wherein: the oligomer is urethane acrylate oligomer or acrylic epoxy resin oligomer.
6. The flame retardant diffuser film of claim 4 or 5, wherein: the ZnO particle size is 100-500 microns, and the polymethyl methacrylate particle size is 200-300 microns.
7. The flame retardant diffusion film of claim 6, wherein: the ZnO particle size is 100-500 microns, and the polymethyl methacrylate particle size is 200-300 microns.
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| US4041012A (en) * | 1976-06-01 | 1977-08-09 | Velsicol Chemical Corporation | Acrylate esters of dihaloneopentyl glycol phosphates (phosphorinanes) and their use as flame retardants |
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| CN108427153A (en) * | 2017-12-27 | 2018-08-21 | 深圳市长松科技有限公司 | A kind of optical diffusion film |
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| US4041012A (en) * | 1976-06-01 | 1977-08-09 | Velsicol Chemical Corporation | Acrylate esters of dihaloneopentyl glycol phosphates (phosphorinanes) and their use as flame retardants |
| CN104497051A (en) * | 2014-12-20 | 2015-04-08 | 王树礼 | Method for preparing reactive type halogen-free flame retardant for coating |
| CN108427153A (en) * | 2017-12-27 | 2018-08-21 | 深圳市长松科技有限公司 | A kind of optical diffusion film |
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