CN111234092A - Transparent flame-retardant organic glass and preparation method thereof - Google Patents

Transparent flame-retardant organic glass and preparation method thereof Download PDF

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Publication number
CN111234092A
CN111234092A CN202010151040.1A CN202010151040A CN111234092A CN 111234092 A CN111234092 A CN 111234092A CN 202010151040 A CN202010151040 A CN 202010151040A CN 111234092 A CN111234092 A CN 111234092A
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organic glass
phosphate
flame retardant
transparent flame
retardant organic
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王振卫
窦桂桂
李昀谦
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Shanghai Institute of Technology
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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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/136—Phenols containing halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The invention relates to a transparent flame-retardant organic glass and a preparation method thereof, wherein the transparent flame-retardant organic glass is prepared from the following components in parts by weight: methyl methacrylate, phosphate, a brominated flame retardant, an epoxy acrylate monomer, active amine, an initiator and a release agent. Compared with the prior art, the bromine-containing flame retardant is copolymerized with the epoxy acrylate monomer under the catalytic action of the active amine, and then is stably grafted to the macromolecular chain of the polymethyl methacrylate through the copolymerization of the epoxy acrylate monomer and the methyl methacrylate, so that the transparent flame-retardant organic glass which is free of precipitation, good in transparency and flame-retardant to reach UL 94V 2-V0 grades is obtained.

Description

Transparent flame-retardant organic glass and preparation method thereof
Technical Field
The invention relates to the technical field of casting organic glass plates, in particular to transparent flame-retardant organic glass and a preparation method thereof.
Background
Polymethyl methacrylate (PMMA) is also known as plexiglass and also as acrylic. The method can be divided into an extrusion plate and a casting plate according to the manufacturing method, wherein the extrusion plate is made of granular raw materials by extrusion molding after high-temperature dissolution, and the casting plate is a high molecular compound synthesized by taking Methyl Methacrylate (MMA) as a monomer through three steps of bulk polymerization, prepolymerization, casting and post-polymerization. Compared with an extrusion plate, the casting plate has the advantages of high molecular weight, good mechanical property, strong light transmittance and more flexible specification adjustment. Due to the characteristics of the product, the product is widely applied to the fields of buildings, advertisements, traffic, medicine, industry, home furnishing and the like; however, the limited oxygen index of the organic glass is low, the organic glass is extremely easy to burn, the combustion mechanism of the organic glass is a free radical chain fracture mechanism, the decomposed monomer meets flame under the heated condition to promote delayed combustion, once ignited, the monomer can continuously burn until the monomer is burnt out, and the organic glass also has high heat release rate.
Due to the excellent flame retardant effect of the brominated flame retardant, the brominated flame retardant is still mainly used in the market of the flame retardant at present, but the brominated flame retardant is generally a solid and can be seriously separated out in the later polymerization stage of PMMA, so that the flame retardant effect is achieved on an organic glass plate, the surface haze of the plate is also high, and the transparency is poor.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, the mutual dissolving effect of a brominated flame retardant and methyl methacrylate is not ideal, and the obtained transparent acrylic has serious precipitation, and provides transparent flame-retardant organic glass and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a transparent flame-retardant organic glass, which is prepared from the following components in parts by weight:
Figure BDA0002402450970000021
preferably, the bromine-based flame retardant comprises one or more of dibromophenol, 2,4, 6-tribromophenol, tetrabromobisphenol A bis (hydroxyethyl ether) and tetrabromophthalic acid diethylene glycol propylene glycol diester/diol.
Preferably, the epoxy acrylate monomer comprises glycidyl acrylate or glycidyl methacrylate.
Preferably, the active amine is a tertiary amine catalyst, including dodecyl/tetradecyl dimethyl tertiary amine, hexadecyl/octadecyl dimethyl tertiary amine, N-dimethylaminoethyl methacrylate, triethylamine or N, N-dimethylbenzylamine.
Preferably, the initiator comprises azobisisobutyronitrile, azobisisoheptonitrile or dibenzoyl peroxide.
Preferably, the phosphate ester comprises one or more of tris (2-chloropropyl) phosphate, tris (1, 3-dichloroisopropyl) phosphate, tris (2-carboxyethyl) phosphine, dimethyl methylphosphonate, triphenyl phosphate, bisphenol a-bis (diphenyl phosphate), resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate ], cyclic phosphate, tris (2, 3-dibromopropyl) phosphate, and polyphosphate.
Preferably, the release agent is one or more of stearic acid, sodium stearate, polymethylsiloxane liquid, polydimethylsiloxane oil and benzyl silicone oil.
Preferably, the mass ratio of the epoxy acrylate monomer to the brominated epoxy resin is 1 (1-10).
Preferably, the flame retardant performance of the transparent flame retardant organic glass reaches UL 94V2 to V0 grades, and the light transmittance is not lower than 90%.
The invention also provides a preparation method of the transparent flame-retardant organic glass, which comprises the following steps:
(1) taking a methyl methacrylate monomer, brominated epoxy resin, an epoxy acrylate monomer, active amine and a part of initiator according to the proportion, and stirring and heating;
(2) stopping heating and stirring at the constant temperature after the system is boiled;
(3) taking out the system after the viscosity of the system reaches the preset viscosity, and cooling to room temperature;
(4) when the system is cooled to room temperature, the rest initiator, the release agent and the phosphate are added into the system, and the mixture is stirred uniformly at the room temperature;
(5) performing vacuum defoaming on the uniformly stirred mixture in the step (4) to obtain a pre-polymerized material;
(6) pouring the pre-polymerized material into a mold, and heating the mold to solidify the pre-polymerized material;
(7) and after the prepolymer is solidified, further solidifying the mold at a high temperature, cooling to room temperature, and demolding to obtain the transparent flame-retardant organic glass.
Preferably, in the step (2), the stirring time is 20-30 min.
Preferably, in step (3), the preset viscosity is 60-80s (4 cups coated, 23. + -. 1 ℃ C.).
Preferably, in the step (5), the vacuum defoaming conditions are as follows: the pressure is between-0.04 and-0.06 MPa, and the time is between 0.5 and 2 hours.
Preferably, in the step (6), the temperature for heating and curing is 50-65 ℃ and the time is 2-6 h.
Preferably, in the step (7), the temperature for further curing at high temperature is 110-120 ℃ and the time is 1-5 h.
Compared with the prior art, the bromine-containing flame retardant is copolymerized with the epoxy acrylate monomer under the catalytic action of the active amine, and then is stably added into the methyl methacrylate through the copolymerization of the epoxy acrylate monomer and the methyl methacrylate, so that the transparent flame-retardant organic glass which is free of precipitation, good in transparency and flame-retardant to reach the UL 94V 2-V0 level is obtained.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
A transparent organic glass flame-retardant plate is prepared from the following raw materials in parts by weight: 76.33g of methyl methacrylate monomer, 23g of bisphenol A-bis (diphenyl phosphate) (BDP), 0.5g of 2,4, 6-tribromophenol, 0.17g of Glycidyl Methacrylate (GMA), and 0.5X 10g of hexadecyl dimethyl tertiary amine-2g. Dibenzoyl peroxide (BPO) 7.6X 10-3g. Sodium stearate 0.07 g.
The preparation steps are as follows:
(1) taking methyl methacrylate monomer, 2,4, 6-tribromophenol, hexadecyl dimethyl tertiary amine and a part of dibenzoyl peroxide (BPO) according to the mixture ratio, stirring and heating to 95 ℃;
(2) stopping heating after the system is heated to 95 ℃, and stirring for 20-30min under heat preservation;
(3) taking out the system after the viscosity of the system reaches 60-80s, and cooling to room temperature;
(4) when the system is cooled to normal temperature, supplementing the rest dibenzoyl peroxide (BPO), sodium stearate and tris (2-chloropropyl) phosphate into the system according to the proportion and stirring for 25 min;
(5) carrying out vacuum defoamation on the uniformly stirred mixture in the step (4) under-0.05 MPa for 0.5h to obtain a pre-polymerization material;
(6) pouring the prepolymer into a mould, and heating the mould in a water bath at 60 ℃ for 4 hours;
(7) and after the prepolymer is solidified, further solidifying the mold for 1.5 hours at the high temperature of 120 ℃, cooling and demolding to obtain the transparent flame-retardant organic glass.
The transparent flame-retardant organic glass obtained in the embodiment is easy to demould, the Shore hardness D reaches 88, the pencil scratch hardness reaches H, the light transmittance reaches 93%, and the UL 94 vertical burning test reaches the V1 grade.
Example 2
A transparent organic glass flame-retardant plate is composed ofThe material by weight portion is: 72.43g of methyl methacrylate monomer, 25g of dimethyl methylphosphonate (DMMP), 2g of dibromophenol, 0.57g of glycidyl acrylate and 1.71X 10 of dodecyl dimethyl tertiary amine-4g. Azobisisobutyronitrile (AIBN) 1.44X 10-3g. Azobisisoheptonitrile (ABVN) 1.44X 10-4g. 0.07g of polymethylsiloxane fluid.
The preparation steps are as follows:
(1) taking methyl methacrylate monomer, 2,4, 6-tribromophenyl glycidyl ether, hydroxypropyl methacrylate, dodecyl dimethyl tertiary amine and azo-bis-iso-heptonitrile (ABVN) according to the proportion, stirring and heating to 95 ℃;
(2) stopping heating after the system is heated to 95 ℃, and stirring for 20-30min under heat preservation;
(3) taking out the system after the viscosity of the system reaches 60-80s, and cooling to room temperature;
(4) when the system is cooled to normal temperature, adding Azodiisobutyronitrile (AIBN), polymethylsiloxane liquid and dimethyl methylphosphonate (DMMP) into the system according to the proportion and stirring for 20 min;
(5) defoaming the uniformly stirred mixture in the step (4) for 1.5h under-0.05 MPa in vacuum to obtain a pre-polymerization material;
(6) pouring the prepolymer into a mold, and heating the mold in a water bath at 60 ℃ for 2.5 hours;
(7) and after the prepolymer is solidified, further solidifying the mold for 2 hours at the high temperature of 120 ℃, cooling and demolding to obtain the transparent flame-retardant organic glass.
The transparent flame-retardant organic glass obtained in the embodiment is easy to demould, the Shore hardness D reaches 86, the pencil scratch hardness H and the light transmittance are 92%, and the UL 94 vertical burning test reaches the V0 grade.
Example 3
A transparent organic glass flame-retardant plate is prepared from the following raw materials in parts by weight: 64.71g of methyl methacrylate monomer, 25g of tris (2-chloropropyl) phosphate, 8g of tetrabromobisphenol A, 2.29g of glycidyl acrylate, 0.14g of dodecyl dimethyl tertiary amine and 6.5X 10 of dibenzoyl peroxide (BPO)-3g. Azobisisoheptonitrile (ABVN) 1.2X 10-3g. 0.024g of polydimethyl silicone oil and benzyl silicone oil0.05g。
The preparation steps are as follows:
(1) taking a methyl methacrylate monomer, a tetrabromobisphenol A epoxy oligomer, N-hydroxymethyl acrylamide, dodecyl dimethyl tertiary amine and azo-diisoheptanonitrile (ABVN) according to the mixture ratio, stirring and heating to 90 g;
(2) stopping heating and stirring for 30min after the system is heated to 90 ℃;
(3) taking out the system after the viscosity of the system reaches 60-80s, and cooling to room temperature;
(4) when the system is cooled to normal temperature, adding dibenzoyl peroxide (BPO), polydimethylsiloxane oil, benzyl silicone oil and phosphate into the system according to the proportion, and stirring for 25min to obtain a prepolymer;
(5) carrying out vacuum defoamation on the uniformly stirred mixture in the step (4) under-0.06 MPa for 2h to obtain a pre-polymerization material;
(6) pouring the prepolymer into a mould, and heating the mould in water bath at 58 ℃ for 4 hours;
(7) and after the prepolymer is solidified, further solidifying the mold for 1.5 hours at the high temperature of 120 ℃, cooling and demolding to obtain the transparent flame-retardant organic glass.
The transparent flame-retardant organic glass obtained in the embodiment is easy to demould, the Shore hardness D reaches 78, the pencil scratch hardness is 2B, the light transmittance is 90%, and the UL 94 vertical burning test reaches the V0 grade.
Example 4
A transparent organic glass flame-retardant plate is prepared from the following raw materials in parts by weight: methyl methacrylate monomer 65.75g, resorcinol-bis (diphenyl phosphate) (RDP)28g, diethylene glycol propylene glycol tetrabromophthalate diester 5g, Glycidyl Methacrylate (GMA)1.25g, triethylamine 2.5X 10-3g. 0.025g of dibenzoyl oxide (BPO) and 0.015g of polydimethylsiloxane.
The preparation steps are as follows:
(1) taking methyl methacrylate monomer, tetrabromophthalic acid diethylene glycol propylene glycol diester, methyl (GMA), triethylamine and a part of dibenzoyl peroxide (BPO) according to the mixture ratio, stirring and heating to 92 ℃;
(2) stopping heating after the system is heated to 92 ℃, and stirring for 20-30min under heat preservation;
(3) taking out the system after the viscosity of the system reaches 60-80s, and cooling to room temperature;
(4) when the system is cooled to normal temperature, the rest dibenzoyl peroxide (BPO), polydimethylsiloxane oil and resorcinol-bis (diphenyl phosphate) (RDP) are added into the system according to the proportion and stirred for 20 min;
(5) carrying out vacuum defoamation on the uniformly stirred mixture in the step (4) under-0.06 MPa for 3 hours to obtain a pre-polymerization material;
(6) pouring the prepolymer into a mould, and heating the mould in a water bath at 60 ℃ for 4 hours;
(7) and after the prepolymer is solidified, further solidifying the mold for 1.5 hours at the high temperature of 120 ℃, cooling and demolding to obtain the transparent flame-retardant organic glass.
The transparent flame-retardant organic glass obtained in the embodiment is easy to demould, the Shore hardness D reaches 87, the pencil scratch hardness H and the light transmittance are 92%, and the UL 94 vertical burning test reaches the V1 grade.
Example 5
A transparent organic glass flame-retardant plate is prepared from the following raw materials in parts by weight: 74.7g of methyl methacrylate monomer, 10g of tris (1, 3-dichloroisopropyl) phosphate (TDCPP), 10g of dimethyl methylphosphonate (DMMP), 4.3g of 2,4, 6-tribromophenol, 1g of glycidyl acrylate, 0.001g of N, N-dimethylaminoethyl methacrylate, and 1.44X 10 of Azobisisobutyronitrile (AIBN)-3g. Azobisisoheptonitrile (ABVN) 1.44X 10-40.03g of stearic acid.
The preparation steps are as follows:
(1) taking methyl methacrylate monomer, tetrabromobisphenol A epoxy oligomer, hydroxyethyl acrylate, n-dimethylaminoethyl methacrylate and azodiisoheptanonitrile according to the proportion, stirring and heating to 95 ℃;
(2) stopping heating after the system is heated to 95 ℃, and stirring for 20-30min under heat preservation;
(3) taking out the system after the viscosity of the system reaches 60-80s, and cooling to room temperature;
(4) when the system is cooled to normal temperature, adding azodiisobutyronitrile, stearic acid, tris (1, 3-dichloroisopropyl) phosphate (TDCPP) and dimethyl methyl phosphonate (DMMP) into the system according to the proportion and stirring for 20 min;
(5) carrying out vacuum defoamation on the uniformly stirred mixture in the step (4) under-0.05 MPa for 1h to obtain a pre-polymerization material;
(6) pouring the prepolymer into a mould, and heating the mould in a water bath at 60 ℃ for 4 hours;
(7) and after the prepolymer is solidified, further solidifying the mold for 1.5 hours at the high temperature of 120 ℃, cooling and demolding to obtain the transparent flame-retardant organic glass.
The transparent flame-retardant organic glass obtained in the embodiment is easy to demould, the Shore hardness D reaches 88, the pencil scratch hardness is 3B, the light transmittance is 90%, and the UL 94 vertical burning test reaches the V0 grade.
Example 6
A transparent organic glass flame-retardant plate is prepared from the following raw materials in parts by weight: 72.3g of methyl methacrylate monomer, 20g of bisphenol A bis (diphenyl phosphate) (BDP), 15g of tris (2-chloropropyl) phosphate (TCPP), 3.6g of tetrabromobisphenol A bis (allyl ether), 6.4g of brominated epoxy resin, 4.36g of Glycidyl Methacrylate (GMA), 0.021g of N, N-dimethylbenzylamine, and 1.44X 10 of Azobisisobutyronitrile (AIBN)-3g. Dibenzoyl peroxide (BPO) 7.2X 10-4g. Stearic acid 0.06 g.
The preparation steps are as follows:
(1) taking methyl methacrylate monomer, tetrabromobisphenol A bis (allyl ether), hydroxypropyl acrylate, N-dimethylbenzylamine and dibenzoyl peroxide (BPO) according to the mixture ratio, stirring and heating to 90 ℃;
(2) stopping heating after the system is heated to 90 ℃, and stirring for 20-30min under heat preservation;
(3) taking out the system after the viscosity of the system reaches 60-80s, and cooling to room temperature;
(4) when the system is cooled to normal temperature, adding Azodiisobutyronitrile (AIBN), stearic acid, bisphenol A-bis (diphenyl phosphate) (BDP) and tris (2-chloropropyl) phosphate (TCPP) into the system according to the proportion, and stirring for 25 min;
(5) defoaming the uniformly stirred mixture in the step (4) for 1.5h under-0.06 MPa in vacuum to obtain a pre-polymerization material;
(6) pouring the prepolymer into a mould, and heating the mould in water bath at 50 ℃ for 6 hours;
(7) and after the prepolymer is solidified, further solidifying the mold for 2 hours at the high temperature of 120 ℃, cooling and demolding to obtain the transparent flame-retardant organic glass.
The transparent flame-retardant organic glass obtained in the embodiment is easy to demould, the Shore hardness D reaches 80, the pencil scratch hardness HB and the light transmittance are 90%, and the UL 94 vertical burning test reaches the V0 grade.
Example 7
This example is essentially the same as example 1, except that tris (2-carboxyethyl) phosphine (TCEP) is used as the phosphate in this example.
Example 8
This example is substantially the same as example 1 except that triphenyl phosphate (TPP) is used as the phosphate in this example.
Example 9
This example is substantially the same as example 1 except that resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate ] (RDX) is used as the phosphate in this example.
Example 10
This example is substantially the same as example 1 except that the cyclic phosphoric acid ester tris (2, 3-dibromopropyl) phosphate (TDBPP) is used as the phosphoric acid ester in this example.
Example 11
This example is substantially the same as example 1, except that polyphosphate is used as the phosphate in this example.
Example 12
This example is substantially the same as example 1, except that benzyl silicone oil is used as the release agent in this example.
Example 13
This example is substantially the same as example 1, except that in step (5) of the preparation process of this example, the uniformly stirred mixture in step (4) was subjected to vacuum defoamation at about-0.04 MPa for 0.5h to obtain a prepolymer.
Example 14
This example is substantially the same as example 1, except that in step (5) of the preparation process of this example, the uniformly stirred mixture in step (4) was subjected to vacuum defoamation at about-0.05 MPa for 2 hours to obtain a prepolymer.
Example 15
This example is substantially the same as example 1 except that in step (6) of the production method of this example, the mold was heated in a water bath at 50 ℃ for 6 hours.
Example 16
This example is substantially the same as example 1 except that in step (6) of the production method of this example, the mold was heated in a water bath at 65 ℃ for 2 hours.
Example 17
This example is substantially the same as example 1 except that in step (7) of the production method of this example, the mold is further cured at a high temperature of 110 ℃ for 5 hours.
Example 18
This example is substantially the same as example 1 except that in step (7) of the production method of this example, the mold was further cured at a high temperature of 115 ℃ for 1 hour.
Example 19
The present embodiment is substantially the same as embodiment 1, except that the transparent flame retardant organic glass made in the present embodiment comprises the following components: 80 parts of methyl methacrylate, 15 parts of phosphate, 10 parts of brominated flame retardant, 0.01 part of epoxy acrylate monomer, 0.05 part of active amine, 0.001 part of initiator and 0.5 part of release agent.
Example 20
The present embodiment is substantially the same as embodiment 1, except that the transparent flame retardant organic glass made in the present embodiment comprises the following components: 50 parts of methyl methacrylate, 35 parts of phosphate, 0.1 part of brominated flame retardant, 5 parts of epoxy acrylate monomer, 0.001 part of active amine, 0.1 part of initiator and 0.01 part of release agent.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. The transparent flame-retardant organic glass is characterized by being prepared from the following components in parts by weight:
Figure FDA0002402450960000011
2. the transparent flame retardant organic glass according to claim 1, wherein the brominated flame retardant comprises one or more of dibromophenol, 2,4, 6-tribromophenol, tetrabromobisphenol a bis (hydroxyethyl ether), and tetrabromophthalic acid diethylene glycol propylene glycol diester/diol.
3. The transparent flame retardant plastic glazing of claim 1, wherein the epoxy acrylate monomer comprises glycidyl acrylate or glycidyl methacrylate.
4. The transparent flame retardant organic glass according to claim 1, wherein the active amine is a tertiary amine catalyst comprising dodecyl/tetradecyl dimethyl tertiary amine, hexadecyl/octadecyl dimethyl tertiary amine, N-dimethylaminoethyl methacrylate, triethylamine or N, N-dimethylbenzylamine.
5. The transparent flame retardant plastic glazing of claim 1, wherein the initiator comprises azobisisobutyronitrile, azobisisoheptonitrile, or dibenzoyl peroxide.
6. The transparent flame retardant organic glass according to claim 1, wherein the phosphate ester comprises one or more of tris (2-chloropropyl) phosphate, tris (1, 3-dichloroisopropyl) phosphate, tris (2-carboxyethyl) phosphine, dimethyl methylphosphonate, triphenyl phosphate, bisphenol a-bis (diphenyl phosphate), resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate ], cyclic phosphate tris (2, 3-dibromopropyl) phosphate, and polyphosphate.
7. The transparent flame-retardant organic glass according to claim 1, wherein the release agent is one or more of stearic acid, sodium stearate, polymethylsiloxane fluid, polydimethylsiloxane oil and benzyl silicone oil.
8. The transparent flame retardant organic glass according to claim 1, comprising any one or more of the following conditions:
(i) the mass ratio of the epoxy acrylate monomer to the brominated flame retardant is 1 (1-10);
(ii) the flame retardant property of the transparent flame-retardant organic glass reaches UL 94V 2-V0 level, and the light transmittance is not lower than 90%.
9. The method of making a transparent flame retardant organic glass according to claim 1, comprising the steps of:
(1) taking methyl methacrylate, a brominated flame retardant, an epoxy acrylate monomer, active amine and a part of initiator according to the proportion, and stirring and heating;
(2) stopping heating and stirring at the constant temperature after the system is boiled;
(3) taking out the system after the viscosity of the system reaches the preset viscosity, and cooling to room temperature;
(4) when the system is cooled to room temperature, the rest initiator, the release agent and the phosphate are added into the system, and the mixture is stirred uniformly at the room temperature;
(5) performing vacuum defoaming on the uniformly stirred mixture in the step (4) to obtain a pre-polymerized material;
(6) pouring the pre-polymerized material into a mold, and heating the mold to solidify the pre-polymerized material;
(7) and after the prepolymer is solidified, further solidifying the mold at a high temperature, cooling to room temperature, and demolding to obtain the transparent flame-retardant organic glass.
10. The method of making a transparent flame retardant organic glass according to claim 9, characterized in that it comprises any one or more of the following conditions:
(i) in the step (2), the stirring time is 20-30 min;
(ii) in the step (3), the preset viscosity is 60-80s (4 cups are coated, and the temperature is 23 +/-1 ℃);
(iii) in the step (5), the vacuum defoaming conditions are as follows: the pressure is between-0.04 and-0.06 MPa, and the time is between 0.5 and 2 hours;
(iv) in the step (6), the temperature for heating and curing is 50-65 ℃ and the time is 2-6 h;
(v) in the step (7), the temperature for further curing at high temperature is 110-.
CN202010151040.1A 2020-03-06 2020-03-06 Transparent flame-retardant organic glass and preparation method thereof Pending CN111234092A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101531572A (en) * 2009-03-20 2009-09-16 淮海工学院 Method for co-producing tetrabromobisphenol A sodium salt and tetrabromobisphenol A
CN103525034A (en) * 2012-07-02 2014-01-22 青岛欣展塑胶有限公司 Toughened flame-retardant ABS/PBT (acrylonitrile-butadiene-styrene/polybutylene terephthalate) alloy material
CN108864353A (en) * 2018-06-26 2018-11-23 浙江工业大学 A kind of antistatic PMMA composite material and preparation method of transparent flame-retarding
US10227482B2 (en) * 2012-12-20 2019-03-12 Byk Usa Inc. Flame retardant polymer compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101531572A (en) * 2009-03-20 2009-09-16 淮海工学院 Method for co-producing tetrabromobisphenol A sodium salt and tetrabromobisphenol A
CN103525034A (en) * 2012-07-02 2014-01-22 青岛欣展塑胶有限公司 Toughened flame-retardant ABS/PBT (acrylonitrile-butadiene-styrene/polybutylene terephthalate) alloy material
US10227482B2 (en) * 2012-12-20 2019-03-12 Byk Usa Inc. Flame retardant polymer compositions
CN108864353A (en) * 2018-06-26 2018-11-23 浙江工业大学 A kind of antistatic PMMA composite material and preparation method of transparent flame-retarding

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