CN111909302B - Phosphorus/silicon-containing flame-retardant transparent acrylic resin and preparation method thereof - Google Patents
Phosphorus/silicon-containing flame-retardant transparent acrylic resin and preparation method thereof Download PDFInfo
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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Abstract
The invention discloses a phosphorus/silicon-containing flame-retardant transparent acrylic resin and a preparation method thereof, belonging to the field of flame retardance of high polymer materials. The transparent acrylic resin comprises a polymer shown as a formula (I). The flame retardant performance of the acrylic resin reaches UL 94-V0 grade through the synergistic effect of phosphorus/silicon. The light transmittance of the material is up to 93 percent through the introduction of silicon substituent groups. The acrylic resin is prepared by methyl methacrylate and a phosphorus/silicon reaction type flame retardant through prepolymerization, low-temperature polymerization in a mold, high-temperature post-treatment and demolding in the presence of an initiator. The transparent acrylic resin has high thermal stability and good mechanical property, can effectively prevent the further degradation of the lower polymer material, and has the function of inhibiting the release of toxic gas. In addition, the phosphorus/silicon-containing flame retardant can also improve the characteristics of the processability, the mechanical property and the heat resistance of the polymer.
Description
Technical Field
The invention belongs to the field of flame retardance of high polymer materials, and particularly relates to a phosphorus/silicon-containing flame-retardant transparent acrylic resin and a preparation method thereof.
Background
Polymethyl methacrylate (PMMA), commonly known as organic glass, is a typical colorless transparent polymer material, has good transparency, weather resistance, electrical insulation and processability, does not generate sharp fragments when being crushed, has high safety factor in use, is widely applied to the aspects of airplanes, automobiles, buildings, electronic devices, advertising lighting, indoor decoration and the like, and particularly promotes the great increase of the demand of PMMA due to the rapid development of the electronic product market, the automobile industry and the solar energy industry in recent years. However, PMMA is extremely flammable, and when burned, it drips and releases a large amount of heat and toxic gases, which seriously threatens human life and property safety, thus greatly limiting the application range of PMMA. Therefore, the research on how to improve the heat resistance and the flame resistance of the PMMA has important theoretical and practical significance on the premise of keeping the excellent transparency and the mechanical property of the PMMA.
In application nos. CN200910074574.2, CN201110129445.6, CN201110320469.x, CN201610409978.2, and the like, PMMA having excellent flame retardancy is obtained by mixing PMMA with sodium montmorillonite, magnesium hydroxide, basic magnesium chloride, modified basic magnesium chloride, or the like. However, the addition of the inorganic flame retardant not only affects the transparency of PMMA, but also has the problems of uneven dispersion and easy agglomeration of the additive in the process of forming products. The products prepared by adding small molecule organic phosphorus flame retardant such as methyl phosphonic acid dimethyl ester, triphenyl phosphate, phenethyl bridge chain 9' 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DIDOPO) and the like in the application numbers CN201210386432.1, CN201310290827.6, CN201510251965.2, CN201510408210.9, CN201510810563.1, CN201610487840.4, CN201610779344.6 and the like in the polymerization process have good transparency. However, the addition of small organic molecules significantly affects the mechanical properties of PMMA. The application numbers CN201310245018.3, CN201410532118.9, CN201510183772.8 and CN201611183583.1 adopt vinyl phosphorus-containing monomers, such as ethyl (methacryloyloxymethyl) phosphonate, 2- (2-methyl 3- (6-oxygen-6H-dibenzo [ c, e ] [1,2] phosphine oxide-6-yl) propionyloxy) ethyl acrylate and other reactive flame retardants to copolymerize with methyl methacrylate, and products with high transparency are obtained. Generally, the phosphorus-containing moiety degrades from the polymer matrix at low temperatures to form a phosphorus-containing char layer that acts as a thermal barrier and prevents the escape of combustible gases when burned. The phosphorus-containing flame retardant has the problems of poor flame retardance, large addition amount and the like, and further influences the production cost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides various phosphorus/silicon-containing flame-retardant transparent acrylic resins and a preparation method thereof, and the phosphorus/silicon-containing flame retardant is environment-friendly and does not emit VOC (volatile organic compound) gas, so that the phosphorus/silicon-containing flame retardant can migrate to the surface of a material to generate a silicon-carbon compound due to lower surface energy in the pyrolysis process, and the compound has high thermal stability and good mechanical property, can effectively prevent the further degradation of a lower-layer polymer material, and has the effect of inhibiting the release of toxic gas. In addition, the phosphorus/silicon-containing flame retardant can also improve the processing property, the mechanical property and the heat resistance of the polymer.
The invention is realized by the following technical scheme: a phosphorus/silicon-containing flame-retardant transparent acrylic resin comprises a polymer shown as a formula (I):
wherein R is1＝-H，-CH3，R2＝-CnH2n+1，n≤3。
Further, the transparent acrylic resin is prepared by the following method:
adding 40-80 parts by mass of methyl methacrylate, 20-60 parts by mass of phosphorus/silicon-containing reactive flame retardant and 0.05-0.2 part by mass of free radical initiator into a reaction vessel, carrying out prepolymerization at 75-95 ℃ to obtain a prepolymer, taking out until the prepolymer is sticky, pouring the prepolymer into a mold, carrying out heat preservation at 45-65 ℃ for 7-11h, then heating to 90-120 ℃, and carrying out heat preservation for 2-5h to obtain the phosphorus/silicon-containing flame retardant transparent acrylic resin.
Further, the radical initiator is azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, cumene hydroperoxide or tert-butyl hydroperoxide.
Further, the phosphorus/silicon-containing reactive flame retardant has a structure represented by formula II:
wherein R is1＝-H，-CH3，R2＝-CnH2n+1，n≤3。
Further, the phosphorus/silicon-containing reactive flame retardant is synthesized by the following method:
1mol of phosphate, 2 to 2.5mol of chlorosilane and 2 to 2.5mol of anhydrous lithium bromide are added into 100-300mL of dry acetonitrile and stirred. Reacting at 45-75 ℃ for 8-15h, then cooling the reaction temperature to room temperature, filtering to remove excessive lithium bromide and lithium chloride generated in the reaction, removing acetonitrile under reduced pressure, adding a free radical polymerization inhibitor, and distilling under reduced pressure to obtain the phosphorus/silicon reaction type flame retardant (II).
Further, the chlorosilane is methyl chlorosilane, ethyl chlorosilane or phenyl chlorosilane.
Further, the phosphate ester has a structure represented by formula III:
wherein R is1＝-H，-CH3。
Further, the phosphate ester (III) is synthesized by the following method:
adding 1mol of dimethyl phosphoryl chloride and 1-1.3mol of acrylic acid hydroxy ester into 300mL of 100-one ethyl ether, adding 1-1.3mol of triethylamine at-10-10 ℃, reacting at room temperature for 5-10h after the dropwise addition is finished, filtering to remove the quaternary ammonium salt generated by the reaction, and removing the ethyl ether under reduced pressure to obtain the phosphate (III).
Further, the hydroxyl acrylate is hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate.
Compared with the prior art, the invention has the following beneficial effects: the phosphorus/silicon reaction type flame retardant is adopted, the addition amount is low, and the flame retardant property of the polymethacrylate is obviously improved on the premise of not influencing the mechanical property and transparency of the polymethacrylate.
Drawings
FIG. 1 is a schematic diagram of the structure of phosphate esters: FIG. 1A is a schematic structural diagram of a phosphate ester according to example 1, FIG. 1B is a schematic structural diagram of a phosphate ester according to example 2, FIG. 1C is a schematic structural diagram of a phosphate ester according to example 3, FIG. 1D is a schematic structural diagram of a phosphate ester according to example 4, FIG. 1E is a schematic structural diagram of a phosphate ester according to example 5, and FIG. 1F is a schematic structural diagram of a phosphate ester according to example 6;
FIG. 2 is a schematic structural diagram of a phosphorus/silicon-containing reactive flame retardant: fig. 2G is a schematic structural view of the phosphorus/silicon-containing reactive flame retardant prepared in example 7, fig. 2H is a schematic structural view of the phosphorus/silicon-containing reactive flame retardant prepared in example 8, fig. 2I is a schematic structural view of the phosphorus/silicon-containing reactive flame retardant prepared in example 9, fig. 2J is a schematic structural view of the phosphorus/silicon-containing reactive flame retardant prepared in example 10, fig. 2K is a schematic structural view of the phosphorus/silicon-containing reactive flame retardant prepared in example 11, and fig. 2L is a schematic structural view of the phosphorus/silicon-containing reactive flame retardant prepared in example 12.
Detailed Description
In order that the objects and effects of the present invention will become more apparent, the present invention will be further described with reference to the following examples.
Example 1
0.1mol of dimethylphosphoryl chloride and 0.1mol of hydroxymethyl acrylate are added to 200mL of diethyl ether. At-10 deg.C, 0.11mol of triethylamine was added slowly. After the completion of the dropwise addition, the reaction was carried out at room temperature for 7 hours. The quaternary ammonium salt formed by the reaction was removed by filtration. Removing ether under reduced pressure to obtain phosphate with structural formula shown in figure 1A.
Example 2
0.1mol of dimethylphosphoryl chloride and 0.12mol of hydroxypropyl methacrylate were added to 200mL of diethyl ether. At 0 ℃ 0.13mol of triethylamine are slowly added. After the completion of the dropwise addition, the reaction was carried out at room temperature for 8 hours. The quaternary ammonium salt formed by the reaction was removed by filtration. Removing ether under reduced pressure to obtain phosphate with structural formula shown in figure 1B.
Example 3
0.1mol of dimethylphosphoryl chloride and 0.11mol of hydroxyethyl methacrylate are added to 100mL of diethyl ether. At 5 ℃ 0.12mol of triethylamine are slowly added. After the completion of the dropwise addition, the reaction was carried out at room temperature for 10 hours. The quaternary ammonium salt formed by the reaction was removed by filtration. Removing ether under reduced pressure to obtain phosphate with structural formula shown in figure 1C.
Example 4
0.1mol of dimethylphosphoryl chloride and 0.1mol of hydroxymethyl methacrylate are added to 200mL of diethyl ether. At-10 deg.C, 0.10mol of triethylamine was slowly added. After the completion of the dropwise addition, the reaction was carried out at room temperature for 7 hours. The quaternary ammonium salt formed by the reaction was removed by filtration. Removing ether under reduced pressure to obtain phosphate with structural formula shown in figure 1D.
Example 5
0.1mol of dimethylphosphoryl chloride and 0.13mol of hydroxypropyl acrylate were added to 300mL of diethyl ether. 0.13mol of triethylamine are slowly added at 10 ℃. After the completion of the dropwise addition, the reaction was carried out at room temperature for 8 hours. The quaternary ammonium salt formed by the reaction was removed by filtration. Removing ether under reduced pressure to obtain phosphate with structural formula shown in figure 1E.
Example 6
0.1mol of dimethylphosphoryl chloride and 0.11mol of hydroxyethyl acrylate are added to 200mL of diethyl ether. At 5 ℃ 0.12mol of triethylamine are slowly added. After completion of the dropwise addition, the reaction was carried out at room temperature for 5 hours. The quaternary ammonium salt formed by the reaction was removed by filtration. Removing ether under reduced pressure to obtain phosphate with structural formula shown in figure 1F.
The structural formula of the phosphate esters prepared in examples 1 to 6 is shown in FIG. 1, and it is confirmed by infrared analysis that the phosphate esters are indeed phosphate esters.
Example 7
0.1mol of the phosphoric ester A obtained in example 1, 0.2mol of methylchlorosilane and 0.2mol of anhydrous lithium bromide were added to 300mL of dry acetonitrile and stirred vigorously. After 15 hours at 45 ℃ the reaction was allowed to cool to room temperature. The excess lithium bromide and the lithium chloride formed in the reaction are removed by filtration. Removing acetonitrile under reduced pressure, adding free radical polymerization inhibitor, and distilling under reduced pressure to obtain phosphorus/silicon reaction type flame retardant, as shown in FIG. 2G.
Example 8
0.1mol of the phosphoric ester B prepared in example 2, 0.21mol of ethylchlorosilane and 0.22mol of anhydrous lithium bromide were added to 100mL of dry acetonitrile and stirred vigorously. After 13 hours at 55 ℃ the reaction was allowed to cool to room temperature. The excess lithium bromide and the lithium chloride formed in the reaction are removed by filtration. Removing acetonitrile under reduced pressure, adding free radical polymerization inhibitor, and distilling under reduced pressure to obtain phosphorus/silicon reaction type flame retardant, as shown in FIG. 2H.
Example 9
0.1mol of the phosphoric ester C prepared in example 3, 0.23mol of phenylchlorosilane and 0.25mol of anhydrous lithium bromide were added to 300mL of dry acetonitrile and stirred vigorously. After 11 hours at 60 ℃ the reaction was allowed to cool to room temperature. The excess lithium bromide and the lithium chloride formed in the reaction are removed by filtration. Removing acetonitrile under reduced pressure, adding polymerization inhibitor, and distilling under reduced pressure to obtain phosphorus/silicon reaction type flame retardant, as shown in FIG. 2I.
Example 10
0.1mol of the phosphoric ester D prepared in example 4, 0.25mol of ethylchlorosilane and 0.25mol of anhydrous lithium bromide were added to 300mL of dry acetonitrile and stirred vigorously. After 8 hours at 75 ℃, the reaction was allowed to cool to room temperature. The excess lithium bromide and the lithium chloride formed in the reaction are removed by filtration. Removing acetonitrile under reduced pressure, adding free radical polymerization inhibitor, and distilling under reduced pressure to obtain phosphorus/silicon reaction type flame retardant J, as shown in figure 2.
Example 11
0.1mol of the phosphoric ester E obtained in example 5, 0.23mol of methylchlorosilane and 0.25mol of anhydrous lithium bromide were added to 300mL of dry acetonitrile and stirred vigorously. After 12 hours at 58 ℃ the reaction was allowed to cool to room temperature. The excess lithium bromide and the lithium chloride formed in the reaction are removed by filtration. Removing acetonitrile under reduced pressure, adding free radical polymerization inhibitor, and distilling under reduced pressure to obtain phosphorus/silicon reaction type flame retardant, as shown in FIG. 2K.
Example 12
0.1mol of the phosphoric ester F prepared in example 6, 0.22mol of phenylchlorosilane and 0.24mol of anhydrous lithium bromide were added to 300mL of dry acetonitrile and stirred vigorously. After 8 hours at 75 ℃, the reaction was allowed to cool to room temperature. The excess lithium bromide and the lithium chloride formed in the reaction are removed by filtration. Removing acetonitrile under reduced pressure, adding free radical polymerization inhibitor, and distilling under reduced pressure to obtain phosphorus/silicon reaction type flame retardant, as shown in FIG. 2L.
The structural formula of the phosphorus/silicon reactive flame retardant prepared in examples 7 to 12 is shown in FIG. 2, and infrared analysis proves that the phosphorus/silicon reactive flame retardant is really a phosphorus/silicon reactive flame retardant.
Example 13
Adding 80 parts by mass of methyl methacrylate, 20 parts by mass of the phosphorus/silicon reaction type flame retardant G prepared in example 7 and 0.20 part by mass of azobisisobutyronitrile into a three-necked bottle, carrying out prepolymerization at 75 ℃ for 50min, taking out the prepolymer after the system is sticky, pouring the prepolymer into a mold, keeping the temperature at 45 ℃ for 11 hours, and then heating to 90 ℃ for 5 hours to obtain the flame-retardant transparent acrylic resin.
The light transmittance of the flame-retardant transparent acrylic resin prepared by the method is 90% according to the national standard GB/T2410-2008. The Vicat softening point of the flame-retardant transparent acrylic resin is measured to be 90 ℃ according to the national standard GB/T1633-2000. The flame retardant rating of the resin was V1 as measured by UL94 vertical burning method.
Example 14
75 parts by mass of methyl methacrylate, 25 parts by mass of the phosphorus/silicon reaction type flame retardant H prepared in example 8 and 0.18 part by mass of azobisisoheptonitrile are added into a three-necked bottle, prepolymerization is carried out for 50min at 75 ℃, the prepolymer is taken out after the system is sticky, the prepolymer is poured into a mold, the temperature is kept for 10 hours at 50 ℃, and then the temperature is raised to 100 ℃ and kept for 4 hours, so that the flame-retardant transparent acrylic resin is obtained.
The light transmittance of the flame-retardant transparent acrylic resin prepared by the method is 90% according to the national standard GB/T2410-2008. The Vicat softening point of the flame-retardant transparent acrylic resin is measured to be 93 ℃ according to the national standard GB/T1633-2000. The flame retardant rating of the resin was V1 as measured by UL94 vertical burning method.
Example 15
Adding 65 parts by mass of methyl methacrylate, 35 parts by mass of the phosphorus/silicon reaction type flame retardant I prepared in the example 9 and 0.14 part by mass of benzoyl peroxide into a three-necked bottle, carrying out prepolymerization at 95 ℃ for 20min, taking out a prepolymer after the system is sticky, pouring the prepolymer into a mold, carrying out heat preservation at 55 ℃ for 9 hours, and then heating to 120 ℃ for 2 hours to obtain the flame-retardant transparent acrylic resin.
The light transmittance of the flame-retardant transparent acrylic resin prepared by the method is 90% according to the national standard GB/T2410-2008. The Vicat softening point of the flame-retardant transparent acrylic resin is measured to be 98 ℃ according to the national standard GB/T1633-2000. The flame retardant rating of the resin was V0 as measured by UL94 vertical burning method.
Example 16
50 parts by mass of methyl methacrylate, 50 parts by mass of the phosphorus/silicon reaction type flame retardant J prepared in example 10 and 0.10 part by mass of cumene hydroperoxide are added into a three-necked bottle, prepolymerization is carried out for 35min at 85 ℃, the prepolymer is taken out after the system is sticky, the prepolymer is poured into a mold, the temperature is kept for 9 hours at 60 ℃, and then the temperature is raised to 110 ℃ and kept for 3 hours, thus obtaining the flame-retardant transparent acrylic resin.
The light transmittance of the flame-retardant transparent acrylic resin prepared by the method is 91% according to the national standard GB/T2410-2008. The Vicat softening point of the flame-retardant transparent acrylic resin is 100 ℃ according to the national standard GB/T1633-2000. The flame retardant rating of the resin was V0 as measured by UL94 vertical burning method.
Example 17
Adding 45 parts by mass of methyl methacrylate, 55 parts by mass of the phosphorus/silicon reaction type flame retardant K prepared in example 11 and 0.08 part by mass of tert-butyl hydroperoxide into a three-necked bottle, carrying out prepolymerization at 80 ℃ for 40min, taking out the prepolymer after the system is sticky, pouring the prepolymer into a mold, keeping the temperature at 60 ℃ for 8 hours, and then heating to 115 ℃ for 3 hours to obtain the flame-retardant transparent acrylic resin.
The light transmittance of the flame-retardant transparent acrylic resin prepared by the method is 92% according to the national standard GB/T2410-2008. The Vicat softening point of the flame-retardant transparent acrylic resin is measured to be 105 ℃ according to the national standard GB/T1633-2000. The flame retardant rating of the resin was V0 as measured by UL94 vertical burning method.
Example 18
Adding 40 parts by mass of methyl methacrylate, 60 parts by mass of the phosphorus/silicon reaction type flame retardant L prepared in example 12 and 0.05 part by mass of tert-butyl hydroperoxide into a three-necked bottle, carrying out prepolymerization at 95 ℃ for 20min, taking out the prepolymer after the system is sticky, pouring the prepolymer into a mold, keeping the temperature at 65 ℃ for 9 hours, and then heating to 120 ℃ for 2 hours to obtain the flame-retardant transparent acrylic resin.
The light transmittance of the flame-retardant transparent acrylic resin prepared by the method is 93 percent according to the national standard GB/T2410-2008. The Vicat softening point of the flame-retardant transparent acrylic resin is measured to be 110 ℃ according to the national standard GB/T1633-2000. The flame retardant rating of the resin was V0 as measured by UL94 vertical burning method.
Claims (7)
1. The phosphorus/silicon-containing flame-retardant transparent acrylic resin is characterized by being prepared by the following method:
adding 40-80 parts by mass of methyl methacrylate, 20-60 parts by mass of phosphorus/silicon-containing reactive flame retardant and 0.05-0.2 part by mass of free radical initiator into a reaction vessel, carrying out prepolymerization at 75-95 ℃ to obtain a prepolymer, taking out the prepolymer until the prepolymer is sticky, pouring the prepolymer into a mold, carrying out heat preservation at 45-65 ℃ for 7-11h, then heating to 90-120 ℃, and carrying out heat preservation for 2-5h to obtain phosphorus/silicon-containing flame retardant transparent acrylic resin;
the phosphorus/silicon-containing reactive flame retardant has a structure shown as a formula II:
wherein R is1＝-H，-CH3，R2＝-CnH2n+1，n≤3。
2. The phosphorus/silicon-containing flame retardant transparent acrylic resin according to claim 1, wherein the radical initiator is azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, cumene hydroperoxide or tert-butyl hydroperoxide.
3. The phosphorus/silicon-containing flame-retardant transparent acrylic resin according to claim 1, wherein the phosphorus/silicon-containing reactive flame retardant is synthesized by the following method:
adding 1mol of phosphate, 2-2.5mol of chlorosilane and 2-2.5mol of anhydrous lithium bromide into 100-300mL of dry acetonitrile, stirring, reacting at 45-75 ℃ for 8-15h, then cooling the reaction temperature to room temperature, filtering to remove excessive lithium bromide and lithium chloride generated by the reaction, removing acetonitrile under reduced pressure, adding a free radical polymerization inhibitor, and distilling under reduced pressure to obtain the phosphorus/silicon-containing reactive flame retardant (II).
4. The phosphorus/silicon-containing flame-retardant transparent acrylic resin according to claim 3, wherein the chlorosilane is methylchlorosilane or ethylchlorosilane.
5. The phosphorus/silicon containing flame retardant transparent acrylic resin of claim 3 wherein the phosphate ester has the structure of formula III:
wherein R is1＝-H，-CH3。
6. The phosphorus/silicon-containing flame-retardant transparent acrylic resin according to claim 5, wherein the phosphate ester (III) is synthesized by the following method:
adding 1mol of dimethyl phosphoryl chloride and 1-1.3mol of acrylic acid hydroxy ester into 300mL of 100-one ethyl ether, adding 1-1.3mol of triethylamine at-10-10 ℃, reacting at room temperature for 5-10h after the dropwise addition is finished, filtering to remove the quaternary ammonium salt generated by the reaction, and removing the ethyl ether under reduced pressure to obtain the phosphate (III).
7. The phosphorus/silicon containing flame retardant transparent acrylic resin of claim 6 wherein the hydroxy acrylate is hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate.
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