CN111909312B - Flame retardant, synthetic method thereof and flame-retardant resin - Google Patents
Flame retardant, synthetic method thereof and flame-retardant resin Download PDFInfo
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- CN111909312B CN111909312B CN202010576907.8A CN202010576907A CN111909312B CN 111909312 B CN111909312 B CN 111909312B CN 202010576907 A CN202010576907 A CN 202010576907A CN 111909312 B CN111909312 B CN 111909312B
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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
- 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
- C08F230/02—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 phosphorus
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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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention provides a flame retardant, which adopts the copolymerization of phosphonate flame retardant with carbon-carbon double bond and acrylic resin to achieve the purpose of flame retardance. The invention starts from a reactive flame retardant, firstly synthesizes the phosphorus-containing flame retardant with unsaturated active groups, so that the phosphorus-containing flame retardant can be used as a reaction monomer to participate in polymerization reaction, overcomes the defect that the flame retardant migrates or volatilizes from the surface of a polymer, and can ensure the flame retardant effect and simultaneously keep the original physicochemical mechanical property of the polymer. The invention also provides a preparation method of the flame retardant.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to a flame retardant, a synthetic method thereof and flame-retardant resin.
Background
Polymethyl methacrylate (PMMA) resin is less likely to generate sharp fragments when broken, and in countries such as the united states and japan, it is mandatory to use PMMA resin for architectural glass in primary and secondary schools and kindergarten. China is in rapid urbanization construction pace, street signs, advertising light boxes, telephone boxes and the like are abundant, and a considerable part of materials are PMMA resin. Pure PMMA is however extremely flammable, has a Limiting Oxygen Index (LOI) of only 17, and once ignited, uncontrolled combustion occurs. Currently, in some fields characterized by the use of PMMA resins, such as building materials, flame retardancy is mandatory by regulations.
In order to impart flame retardancy to PMMA resins and ensure a certain light transmittance, a method of adding a low molecular monomer phosphonate flame retardant, such as tris (2-chloroethyl) phosphonate (TCEP), tris (chloroisopropyl) phosphonate (TCPP), is generally used. However, these flame retardants are added by physical mixing, which reduces the hardness of the plate, and since the PMMA resin containing such small molecular flame retardants has a low molecular weight and is easily vaporized and volatilized at high temperature, when the PMMA resin containing such small molecular flame retardants is used for a building plate, a fogging phenomenon is easily generated due to high-temperature solarization in summer, which reduces the flame retardancy of the plate, and the volatilized substances also have an adverse effect on human bodies. Thus, to reduce the amount of volatilization of the vaporized flame retardant, phosphonate oligomers of additive flame retardants can be used, however, while conventional additive flame retardants can improve the flame retardancy of the material to some extent, these highly condensed phosphonates do not meet the transparency requirements and suffer from loss of physical and mechanical properties.
The patent (CN101899125B) proposes a preparation method of an additive halogen-free sulfonate fire retardant, the method is an additive fire retardant, uneven mixing is easy to occur during screw granulation and mixing, and the fire retardant can ensure the light transmission performance only by a certain particle size requirement. The patent (CN107903440A) proposes a halogen-free alkyl phosphonate oligomer organic flame retardant, and does not relate to the control of the molecular weight of the flame retardant. In the patent (CN 101597350B), the composite material is prepared by taking methyl methacrylate as a raw material and taking sodium-based montmorillonite and magnesium hydroxide as flame retardants, and the light transmittance of the material is low. In the patent (CN107522885A), the polymethyl methacrylate microspheres pretreated by isopropanol are respectively and sequentially soaked in a graphite-phase carbon nitride suspension and a graphene oxide dispersion liquid, and layer-by-layer self-assembly is carried out to obtain the flame-retardant modified polymethyl methacrylate microspheres, and then surface treatment is carried out, so that the cost is high.
In view of the above, it is desirable to provide a novel flame retardant that can be used for acrylic resin-containing resins.
Disclosure of Invention
In order to solve the technical problem, the invention provides a flame retardant, which has the following structural general formula:
wherein R is1Is one of the following groups:
C1-C16alkyl radical, C2-C16-alkenyl, C2-C16-alkynyl, C1-C16-alkoxy, C2-C16-alkenyloxy, C2-C16-alkynyloxy, C3-C10-cycloalkyl, C3-C10Cycloalkoxy, C1-C16Alkylene radical, C2-C16-alkenylene, C2-C16-alkynylene, C1-C16Alkylene oxide radical, C2-C16-alkenylene oxy, C2-C16-alkynyloxy, C3-C10-cycloalkyl, C3-C10-a cycloalkoxy group; aryl, aryloxy; c6-C10-aryl-C1-C16Alkyl radical, C6-C10-aryl-C1-C16-alkoxy, C1-C16-alkyl-C6-C10-aryl, C1-C16-alkyl-C6-C10Aryloxy group, C6-C10-aryl-C1-C16Alkylene radical, C6-C10-aryl-C1-C16Alkylene oxide and C1-C16alkylene-C6-C10-an aryl group;
x, Y is Cl, Br or I, m is 1 or 0;
R2、R3is C1-C16Alkyl radical, C2-C16-alkenyl, C2-C16-one of an alkynyl group;
R4is one of the following groups:
C1-C16alkyl radical, C2-C16-alkenyl, C2-C16-alkynyl, C1-C16-alkoxy, C2-C16-alkenyloxy, C2-C16-alkynyloxy, C3-C10-cycloalkyl, C3-C10-a cycloalkoxy group; aryl, aryloxy; c6-C10-aryl-C1-C16Alkyl radical, C6-C10-aryl-C1-C16-alkoxy, C1-C16-alkyl-C6-C10-aryl and C1-C16-alkyl-C6-C10-an aryloxy group.
In one mode, the viscosity of the flame retardant is 20-10000 cp, and the acid value is less than 0.1 mgKOH/g.
The invention also provides flame-retardant resin which is prepared by reacting the unsaturated carbon-carbon bond-containing resin monomer or the monomer prepolymer with the flame retardant.
As one mode, the unsaturated carbon-carbon bond-containing resin monomer or monomer prepolymer is an acrylic resin monomer or acrylic prepolymer.
In one embodiment, the amount of the flame retardant is preferably 15 to 20% by mass of the acrylic resin.
The invention also provides a synthesis method of the flame retardant, which is characterized in that phosphonate, phosphorus pentoxide and acrylic ester containing epoxy group are used as raw materials to prepare the flame retardant.
As one mode, the synthesis method comprises the following steps:
s1, Synthesis of intermediates
Under the protection of inert gas, adding an antioxidant and phosphorus pentoxide into phosphonate, heating and carrying out heat preservation reaction to obtain polyphosphonate oligomer with P-O-P as a framework; dripping a viscosity regulator into the polyphosphonate oligomer, and preserving heat to prepare an intermediate of the flame retardant, wherein the reaction process is as follows:
R1is the following radicalOne of the clusters:
C1-C16alkyl radical, C2-C16-alkenyl, C2-C16-alkynyl, C1-C16-alkoxy, C2-C16-alkenyloxy, C2-C16-alkynyloxy, C3-C10-cycloalkyl, C3-C10Cycloalkoxy, C1-C16Alkylene radical, C2-C16-alkenylene, C2-C16-alkynylene, C1-C16Alkylene oxide radical, C2-C16-alkenylene oxy, C2-C16-alkynyloxy, C3-C10-cycloalkyl, C3-C10-a cycloalkoxy group; aryl, aryloxy; c6-C10-aryl-C1-C16Alkyl radical, C6-C10-aryl-C1-C16-alkoxy, C1-C16-alkyl-C6-C10-aryl, C1-C16-alkyl-C6-C10Aryloxy group, C6-C10-aryl-C1-C16Alkylene radical, C6-C10-aryl-C1-C16Alkylene oxide and C1-C16alkylene-C6-C10-an aryl group;
R5is hydroxy, C1-C12Alkoxy group of (a);
x is Cl, Br or I, and m is 1 or 0;
s2 synthetic flame retardant
Adding a catalyst into the obtained intermediate, heating, adding epoxy alkyl-containing alkenoic acid ester with the formula amount, reacting for a certain time, and performing low-removing aftertreatment, wherein the reaction process is as follows:
wherein X, Y is Cl, Br or I, and m is 1 or 0;
R2、R3is C1-C16Alkyl radical, C2-C16-alkenyl, C2-C16-an alkynyl group;
R4is C1-C16Alkyl radical, C2-C16-alkenyl, C2-C16-alkynyl, C1-C16-alkoxy, C2-C16-alkenyloxy, C2-C16-alkynyloxy, C3-C10-cycloalkyl, C3-C10Cycloalkoxy, aryl, aryloxy, C6-C10-aryl-C1-C16Alkyl radical, C6-C10-aryl-C1-C16-alkoxy, C1-C16-alkyl-C6-C10-aryl, C1-C16-alkyl-C6-C10-an aryloxy group.
In one mode, in step S1:
the removing temperature of the phosphonate is 50-100 ℃, and preferably 60-80 ℃.
In one embodiment, the inert gas is nitrogen or argon.
In one embodiment, the antioxidant includes one or a combination of at least two of alkyl phosphite, phosphorous acid derivatives, diethyl ethylphosphonate, vitamin a, vitamin C, vitamin E, tea polyphenol, flavonoids, butyl hydroxyanisole, dibutyl hydroxytoluene, tert-butyl hydroquinone, antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 168, antioxidant 164, antioxidant DNP, antioxidant DLTP, antioxidant TNP, antioxidant TPP, and antioxidant MB, and more preferably alkyl phosphite or antioxidant 1010.
In one embodiment, the antioxidant is added in an amount of 0.1 to 5% by mass, more preferably 0.3 to 2% by mass, based on the total mass of the phosphonate and the phosphorus pentoxide.
In one embodiment, the molar ratio of the phosphonate ester to the phosphorus pentoxide is 0.5 to 3.5, more preferably 0.9 to 1.5.
In one embodiment, in step S1, the antioxidant, phosphorus pentoxide, and phosphonate are mixed uniformly, heated to 30 to 150 ℃, more preferably 50 to 110 ℃, and reacted while maintaining the temperature.
In one embodiment, in the step S1, the reaction time is maintained for 0.2 to 3 hours, and more preferably 0.5 to 2 hours.
In one mode, in step S1:
the viscosity regulator comprises one or a mixture of at least two of water, alkyl alcohol with the carbon atom number n being 1-12, polyhydric alcohol with the carbon atom number n being 1-12, phenol, benzyl alcohol or phenethyl alcohol, and more preferably one or a mixture of ethanol, isopropanol, pentaerythritol, dipentaerythritol or benzyl alcohol.
In one embodiment, the mass ratio of the viscosity modifier to the phosphonate oligomer is 0.01 to 0.5, and more preferably 0.05 to 0.3.
As a mode, the temperature of the reaction of the viscosity regulator and the phosphonate oligomer taking P-O-P as a framework is 20-100 ℃, and more preferably 30-60 ℃.
Preferably, the reaction heat preservation time of the viscosity regulator and the phosphonate oligomer taking P-O-P as a framework is 0.1 to 3 hours, and more preferably 0.5 to 2 hours.
In one mode, in step S2:
the catalyst is one of Lewis acid, organic tin, primary amine, tertiary amine or quaternary ammonium salt or alkyl aluminum.
In one embodiment, the lewis acid is AlCl3、MgCl2、BF2、SbCl5、FeBr3、FeCl3、SnCl4、TiCl4、ZnCl2Benzene sulfonic acid or toluene sulfonic acid.
In one form, the primary, tertiary or quaternary amine is cyclohexylamine, methylcyclohexylamine or benzyltriethylammonium chloride.
In one embodiment, the organotin is stannous octoate or dibutyltin laurate.
In one mode, in step S2:
the addition amount of the catalyst is 0.1-5% of the total mass of the intermediate and the epoxyalkyl-containing component.
In one embodiment, the mass ratio of the acrylate of the epoxy group to the intermediate is 0.05 to 0.6.
In one embodiment, the temperature is raised to 20 to 100 ℃, and more preferably 30 to 60 ℃.
In one embodiment, the reaction time is 2 to 72 hours, and more preferably 3 to 36 hours.
As a mode, the temperature for removing the low temperature is 50-150 ℃, and the temperature is more preferably 70-120 ℃.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts the copolymerization of the phosphonate flame retardant with carbon-carbon double bonds and the acrylic resin to achieve the purpose of flame retardance. The invention starts from a reactive flame retardant, firstly synthesizes a phosphorus-containing flame retardant with unsaturated active groups, and enables the phosphorus-containing flame retardant to be used as a reaction monomer to participate in polymerization reaction, so that effective flame retardant components can be uniformly distributed on a polymer molecular chain in a molecular form, the defect that the flame retardant migrates or volatilizes from the surface of a polymer is overcome, and the original physicochemical mechanical property of the polymer can be kept while the flame retardant effect is ensured.
2. The invention provides an addition type flame retardant for PMMA and an acrylic resin system thereof, and PMMA with flame retardant performance prepared by the addition type flame retardant has transparent appearance and keeps the original mechanical and mechanical properties of PMMA.
3. The invention provides a synthesis method of an addition type flame retardant for PMMA and acrylic resin systems thereof, which has simple process and can prepare flame retardants with different viscosities through a molecular weight regulator. The flame retardant has wider viscosity distribution, can be suitable for different acrylic resin systems, can be added into acrylic resin monomers or acrylic prepolymer, and is more flexible to use, so that the flame retardant can meet the process requirements of manufacturers without acrylic resin in the market to a greater extent.
In addition, the synthesis method hardly generates three wastes, and is an environment-friendly process. The V-0 grade flame retardant requirement of the 3mm plate can be met by adding 15-20 wt% of PMMA.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention are clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
The invention provides a flame retardant, which has the following structural general formula:
wherein R is1Is one of the following groups:
C1-C16alkyl radical, C2-C16-alkenyl, C2-C16-alkynyl, C1-C16-alkoxy, C2-C16-alkenyloxy, C2-C16-alkynyloxy, C3-C10-cycloalkyl, C3-C10Cycloalkoxy, C1-C16Alkylene radical, C2-C16-alkenylene, C2-C16-alkynylene, C1-C16Alkylene oxide radical, C2-C16-alkenylene oxy, C2-C16-alkynyloxy, C3-C10-cycloalkyl, C3-C10-a cycloalkoxy group; aryl, aryloxy; c6-C10-aryl-C1-C16Alkyl radical, C6-C10-aryl-C1-C16-alkoxy, C1-C16-alkyl-C6-C10-aryl, C1-C16-alkyl-C6-C10Aryloxy group, C6-C10-aryl-C1-C16Alkylene radical, C6-C10-aryl-C1-C16Alkylene oxide and C1-C16alkylene-C6-C10-an aryl group;
x, Y is Cl, Br or I, m is 1 or 0;
R2、R3is C1-C16Alkyl radical, C2-C16-alkenyl, C2-C16-one of an alkynyl group;
R4is one of the following groups:
C1-C16alkyl radical, C2-C16-alkenyl, C2-C16-alkynyl, C1-C16-alkoxy, C2-C16-alkenyloxy, C2-C16-alkynyloxy, C3-C10-cycloalkyl, C3-C10-a cycloalkoxy group; aryl, aryloxy; c6-C10-aryl-C1-C16Alkyl radical, C6-C10-aryl-C1-C16-alkoxy, C1-C16-alkyl-C6-C10-aryl and C1-C16-alkyl-C6-C10-an aryloxy group.
In the above, C1-C16Alkyl means an alkyl group having 1 to 16 carbon atoms, C2-C16Alkenyl means alkenyl having 2 to 16 carbon atoms, and the like.
In the above, C6-C10-aryl-C1-C16The alkyl group means a group formed by connecting an aryl group having 6 to 10 carbon atoms to an alkyl group having 1 to 16 carbon atoms, C6-C10-aryl-C1-C16Alkoxy means a group formed by an aryl group having 6 to 10 carbon atoms linked to an alkoxy group having 1 to 16 carbon atoms, and so on.
The invention also provides a synthesis method of the flame retardant, which comprises the following steps:
s1, Synthesis of intermediates
Under the protection of inert gas, adding an antioxidant and phosphorus pentoxide into phosphonate, heating and carrying out heat preservation reaction to obtain polyphosphonate oligomer with P-O-P as a framework; dripping a viscosity regulator into the polyphosphonate oligomer, and preserving heat to prepare an intermediate of the flame retardant, wherein the reaction process is as follows:
R1is one of the following groups:
C1-C16alkyl radical, C2-C16-alkenyl, C2-C16-alkynyl, C1-C16-alkoxy, C2-C16-alkenyloxy, C2-C16-alkynyloxy, C3-C10-cycloalkyl, C3-C10Cycloalkoxy, C1-C16Alkylene radical, C2-C16-alkenylene, C2-C16-alkynylene, C1-C16Alkylene oxide radical, C2-C16-alkenylene oxy, C2-C16-alkynyloxy, C3-C10-cycloalkyl, C3-C10-a cycloalkoxy group; aryl, aryloxy; c6-C10-aryl-C1-C16Alkyl radical, C6-C10-aryl-C1-C16-alkoxy, C1-C16-alkyl-C6-C10-aryl, C1-C16-alkyl-C6-C10Aryloxy group, C6-C10-aryl-C1-C16Alkylene radical, C6-C10-aryl-C1-C16Alkylene oxide and C1-C16alkylene-C6-C10-an aryl group;
R5is hydroxy, C1-C12Alkoxy group of (a);
x is Cl, Br or I, and m is 1 or 0;
s2 synthetic flame retardant
Adding a catalyst into the obtained intermediate, heating, adding epoxy alkyl-containing alkenoic acid ester with the formula amount, reacting for a certain time, and performing low-removing aftertreatment, wherein the reaction process is as follows:
wherein X, Y is Cl, Br or I, and m is 1 or 0;
R2、R3is C1-C16Alkyl radical, C2-C16-alkenyl, C2-C16-an alkynyl group;
R4is C1-C16Alkyl radical, C2-C16-alkenyl, C2-C16-alkynyl, C1-C16-alkoxy, C2-C16-alkenyloxy, C2-C16-alkynyloxy, C3-C10-cycloalkyl, C3-C10Cycloalkoxy, aryl, aryloxy, C6-C10-aryl-C1-C16Alkyl radical, C6-C10-aryl-C1-C16-alkoxy, C1-C16-alkyl-C6-C10-aryl, C1-C16-alkyl-C6-C10-an aryloxy group.
In one embodiment, the mass ratio of the viscosity modifier to the phosphonate oligomer is 0.01 to 0.5, and more preferably 0.05 to 0.3.
When the mass ratio of the viscosity modifier to the phosphonate oligomer is more than 0.5, the viscosity of the finally obtained flame retardant product is reduced to 50cp, and the flame retardant product can be added only in an application mode of adding during the polymerization of methyl methacrylate monomers, and is suitable for being added at the stage of methyl methacrylate prepolymer when the viscosity is higher.
Example 1
S1 intermediate for synthesizing flame retardant
In a normal-temperature water bath, 10g of triethyl phosphite (antioxidant) is put into a flask containing 1200g of dehydrated triethyl phosphate, stirred, 800g of phosphorus pentoxide is added into the flask in batches, a heating jacket is replaced after half an hour, the temperature is raised to 80 ℃, and the reaction is carried out for 5 hours, so that polyphosphonate oligomer with P-O-P as a framework is obtained; and then cooling to 50 ℃, dropwise adding 50g of absolute ethyl alcohol (viscosity regulator) into the polyphosphonate oligomer, and keeping the temperature for 30min after dropwise adding to prepare colorless transparent liquid with the viscosity of 1000cp, namely an intermediate of the flame retardant.
Example 2
S1 intermediate for synthesizing flame retardant
In a normal-temperature water bath, 15g of triphenyl phosphite (antioxidant) is put into a flask containing 1100g of dehydrated diethyl ethylphosphonate, stirred, 900g of phosphorus pentoxide is added into the flask in batches, after half an hour, a heating jacket is replaced, the temperature is raised to 90 ℃, and the reaction is carried out for 4 hours, so that polyphosphonate oligomer with P-O-P as a framework is obtained; and then cooling to 50 ℃, dropwise adding 100g of isopropanol as a viscosity modifier into the polyphosphonate oligomer, and keeping the temperature for 1h after dropwise adding to prepare colorless transparent liquid with the viscosity of 560cp, namely an intermediate of the flame retardant.
Example 3
S1 intermediate for synthesizing flame retardant
In a normal-temperature water bath, 10g of antioxidant triethyl phosphite is put into a flask containing 1200g of dehydrated triethyl phosphate, stirring is carried out, 800g of phosphorus pentoxide is added into the flask in batches, after half an hour, a heating jacket is replaced, the temperature is raised to 80 ℃, and reaction is carried out for 5 hours, so as to obtain polyphosphonate oligomer with P-O-P as a framework; then cooling to 50 ℃, dropwise adding 50g of viscosity regulator absolute ethyl alcohol into the polyphosphonate oligomer, and keeping the temperature for 30min after dropwise adding to prepare colorless transparent liquid with the viscosity of 1000cp, namely an intermediate of the flame retardant;
s2 synthetic flame retardant
Adding 3.7g of catalyst titanium tetrachloride into the intermediate, slowly dropwise adding 670g of glycidyl methacrylate, heating to 100 ℃ for reaction for more than 6 hours, and finally removing low-boiling-point substances to obtain viscous liquid, namely the flame retardant.
Example 4
S1 intermediate for synthesizing flame retardant
In a normal-temperature water bath, adding 120g of phosphorus pentoxide into 233g of diethyl ethylphosphonate in batches at 50 ℃, heating to 80-90 ℃ after half an hour, and reacting for 5 hours to obtain a polyphosphonate oligomer with a P-O-P skeleton, namely an intermediate of the flame retardant;
s2 synthetic flame retardant
And (3) cooling to ensure that the temperature of the reaction system is lower than 45 ℃, adding 0.4g of stannous octoate serving as a catalyst, slowly and dropwise adding 170g of maleopimaric acid glycidyl ester, heating to 120 ℃, reacting for more than 6 hours, and finally removing low-boiling-point substances to obtain viscous liquid, namely the flame retardant.
Example 5
S1 intermediate for synthesizing flame retardant
In a normal-temperature water bath, adding 345g of phosphorus pentoxide into 760g of trichloroethyl phosphate in batches at 50 ℃, heating to 80-90 ℃ after half an hour, and reacting for 5 hours to obtain a polyphosphonate oligomer with P-O-P as a skeleton, wherein the polyphosphonate oligomer is a light yellow liquid with the viscosity of 800cp, namely an intermediate of a flame retardant;
s2 synthetic flame retardant
And then cooling, wherein the temperature of a reaction system is lower than 45 ℃, adding 2.1g of benzyltriethylammonium chloride serving as a catalyst, slowly dropwise adding 600g of glycidyl acrylate, heating to 120 ℃, reacting for more than 6 hours, and finally removing low-boiling-point substances to obtain viscous liquid, namely the flame retardant.
Example 6
S1, intermediates for synthesizing flame retardants
In a normal-temperature water bath, 345g of phosphorus pentoxide is added into 550g of dichloroethyl phosphate in batches at 60 ℃, after half an hour, the temperature is raised to 80-90 ℃, and the reaction is carried out for 5 hours, so as to obtain polyphosphonate oligomer with P-O-P as a framework, namely an intermediate of the flame retardant;
s2 synthetic flame retardant
Then cooling, adding 1.2g of benzyltriethylammonium chloride serving as a catalyst into a reaction system at the temperature of lower than 45 ℃, slowly dropwise adding 450g of glycidyl acrylate, heating to 120 ℃, reacting for more than 6 hours, and finally removing low-boiling-point substances to obtain viscous liquid, namely an intermediate of the flame retardant.
Example 7
This comparative example differs from example 3 only in that: the obtained polyphosphonate oligomer with P-O-P skeleton was not added dropwise with absolute ethanol as a viscosity modifier, and the rest was the same as in example 3.
Example 8
This example differs from example 3 only in that: the catalyst in step S2 was changed from titanium tetrachloride to anhydrous aluminum chloride, and the rest was the same as in example 3.
Example 9
This example differs from example 3 only in that: the mass ratio of the glycidyl methacrylate to the intermediate of the flame retardant is different, that is, 870g of glycidyl methacrylate is added to the intermediate of the same mass prepared in step S1, and the rest is the same as that in example 3.
Example 10
This example differs from example 3 only in that: the ratio of glycidyl methacrylate to the intermediate of the flame retardant was varied, that is, 470g of glycidyl methacrylate was added to the comparative example for the same mass of intermediate prepared in step S1, and the rest was the same as in example 3.
Test example 1
This test tested the viscosity, acid number and color number of the unsaturated resin flame retardant prepared in examples 3-10, the minimum addition required to meet the requirements of UL94V-0 and the hardness of the flame retardant PMMA board tested on PMMA flame retardant boards. Meanwhile, the flame retardant is compared with two types of flame retardants commonly used in the market. The specification of the burning test sample bar is 13mm 125mm 3mm, and the specific test method is the conventional test method commonly used in the prior art. The transparency of the flame retardant is represented by a platinum-cobalt color number, and specifically according to the test method of GB/T9282-. The test results are shown in table 1.
TABLE 1
As can be seen from the data in Table 1, the flame retardant prepared by the invention has better flame retardant effect than two types sold on the market, and has less addition amount required for reaching V-0 grade and less hardness reduction. The proportion of methacrylic acid derivatives is improved, unsaturated groups are increased, the crosslinking degree is improved, and the influence on the surface hardness of the prepared acrylic plate is enhanced.
The flame retardant can enable a 3mm acrylic plate to reach V0-grade flame retardant, and can ensure the transparency of the acrylic plate, the light transmittance is greater than 90%, and the light transmittance is good.
Although the embodiments of the present invention have been described above, the above description is only for the convenience of understanding the present invention, and is not intended to limit the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (39)
1. A flame retardant characterized by the following general structural formula:
wherein R is1Is one of the following groups:
C2-C16alkyl radical, C2-C16-alkenyl, C2-C16-alkynyl, C1-C16-alkoxy, C2-C16-alkenyloxy, C2-C16-alkynyloxy, C3-C10-cycloalkyl, C3-C10Cycloalkoxy, C1-C16Alkylene radical, C2-C16-alkenylene, C2-C16-alkynylene, C1-C16Alkylene oxide radical, C2-C16-alkenylene oxy, C2-C16-alkynyloxy; aryl, aryloxy; c6-C10-aryl-C1-C16Alkyl radical, C6-C10-aryl-C1-C16-alkoxy, C1-C16-alkyl-C6-C10-aryl, C1-C16-alkyl-C6-C10Aryloxy group, C6-C10-aryl-C1-C16Alkylene radical, C6-C10-aryl-C1-C16Alkylene oxide and C1-C16alkylene-C6-C10-an aryl group;
x, Y is Cl, Br or I, m is 1 or 0, n represents polymerization degree;
R2、R3is C2-C16Alkyl radical, C2-C16-alkenyl, C2-C16-one of an alkynyl group;
R4is one of the following groups:
C2-C16alkyl radical, C2-C16-alkenyl, C2-C16-alkynyl, C1-C16-alkoxy, C2-C16-alkenyloxy, C2-C16-alkynyloxy, C3-C10-cycloalkyl, C3-C10-a cycloalkoxy group; aryl, aryloxy; c6-C10-aryl-C1-C16Alkyl radical, C6-C10-aryl-C1-C16-alkoxy, C1-C16-alkyl-C6-C10-aryl and C1-C16-alkyl-C6-C10-an aryloxy group;
R5is hydroxy, C1-C12Alkoxy group of (a);
the viscosity of the flame retardant is 20-10000 cp, and the acid value is less than 0.1 mgKOH/g.
2. A flame-retardant resin, which is prepared by reacting a resin monomer or a monomer prepolymer containing unsaturated carbon-carbon bonds with the flame retardant of claim 1.
3. The flame-retardant resin according to claim 2, wherein the unsaturated carbon-carbon bond-containing resin monomer or monomer prepolymer is an acrylic resin monomer or acrylic prepolymer.
4. The flame-retardant resin according to claim 3, wherein the amount of the flame retardant is 15 to 20% by mass based on the mass of the acrylic resin.
5. The method for synthesizing the flame retardant according to claim 1, wherein the flame retardant is prepared by using phosphonate ester, phosphorus pentoxide and acrylic ester containing epoxy group as raw materials.
6. The method of synthesis according to claim 5, comprising the steps of:
s1, Synthesis of intermediates
Under the protection of inert gas, adding an antioxidant and phosphorus pentoxide into phosphonate, heating and carrying out heat preservation reaction to obtain polyphosphonate oligomer with P-O-P as a framework; dripping a viscosity regulator into the polyphosphonate oligomer, and preserving heat to prepare an intermediate of the flame retardant, wherein the reaction process is as follows:
R1is one of the following groups:
C2-C16alkyl radical, C2-C16-alkenyl, C2-C16-alkynyl, C1-C16-alkoxy, C2-C16-alkenyloxy, C2-C16-alkynyloxy, C3-C10-cycloalkyl, C3-C10Cycloalkoxy, C1-C16Alkylene radical, C2-C16-alkenylene, C2-C16-alkynylene, C1-C16Alkylene oxide radical, C2-C16-alkenylene oxy, C2-C16-alkynyloxy; aryl, aryloxy; c6-C10-aryl-C1-C16Alkyl radical, C6-C10-aryl-C1-C16-alkoxy, C1-C16-alkyl-C6-C10-aryl, C1-C16-alkyl-C6-C10Aryloxy group, C6-C10-aryl-C1-C16Alkylene radical, C6-C10-aryl-C1-C16Alkylene oxide and C1-C16alkylene-C6-C10-an aryl group;
R5is hydroxy, C1-C12Alkoxy group of (a);
x is Cl, Br or I, and m is 1 or 0;
s2 synthetic flame retardant
Adding a catalyst into the obtained intermediate, heating, adding epoxy alkyl-containing alkenoic acid ester with the formula amount, reacting for a certain time, and performing low-removing aftertreatment, wherein the reaction process is as follows:
wherein X, Y is Cl, Br or I, and m is 1 or 0;
R2、R3is C2-C16Alkyl radical, C2-C16-alkenyl, C2-C16-an alkynyl group;
R4is C2-C16Alkyl radical, C2-C16-alkenyl, C2-C16-alkynyl, C1-C16-alkoxy, C2-C16-alkenyloxy, C2-C16-alkynyloxy, C3-C10-cycloalkyl, C3-C10Cycloalkoxy, aryl, aryloxyBase, C6-C10-aryl-C1-C16Alkyl radical, C6-C10-aryl-C1-C16-alkoxy, C1-C16-alkyl-C6-C10-aryl, C1-C16-alkyl-C6-C10-an aryloxy group.
7. The synthesis method according to claim 6, wherein in step S1: the removing temperature of the phosphonate is 50-100 ℃.
8. The synthesis method according to claim 7, wherein the removal temperature of the phosphonate is 60-80 ℃.
9. The method of synthesis according to claim 6, wherein the inert gas is nitrogen or argon.
10. The synthesis method of claim 6, wherein the antioxidant comprises any one or a combination of at least two of alkyl phosphite, phosphorous acid derivatives, diethyl ethylphosphonate, vitamin A, vitamin C, vitamin E, tea polyphenols, flavonoids, butyl hydroxyanisole, dibutyl hydroxytoluene, tert-butyl hydroquinone, antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 168, antioxidant 164, antioxidant DNP, antioxidant DLTP, antioxidant TNP, antioxidant TPP, or antioxidant MB.
11. The method as claimed in claim 10, wherein the antioxidant is alkyl phosphite or antioxidant 1010.
12. The synthesis method according to claim 6, wherein the added mass of the antioxidant is 0.1-5% of the total mass of the phosphonate and the phosphorus pentoxide.
13. The synthesis method according to claim 6, wherein the added mass of the antioxidant is 0.3-2% of the total mass of the phosphonate and the phosphorus pentoxide.
14. The method of claim 13, wherein the molar ratio of phosphonate to phosphorus pentoxide is 0.5 to 3.5.
15. The method of claim 14, wherein the molar ratio of phosphonate to phosphorus pentoxide is 0.9-1.5.
16. The synthesis method of claim 6, wherein in step S1, the antioxidant, the phosphorus pentoxide and the phosphonate are uniformly mixed, heated to 30-150 ℃ and subjected to heat preservation reaction.
17. The synthesis method of claim 6, wherein in step S1, the antioxidant, the phosphorus pentoxide and the phosphonate are uniformly mixed, heated to 50-110 ℃, and subjected to heat preservation reaction.
18. The synthesis method according to claim 6, wherein in the step S1, the reaction time is 0.2-3 hours.
19. The synthesis method according to claim 18, wherein in step S1, the reaction time is 0.5-2 hours.
20. The synthesis method according to claim 6, wherein in step S1: the viscosity regulator comprises one or a mixture of at least two of water, alkyl alcohol with the carbon atom number n =1-12, polyhydric alcohol with the carbon atom number n =1-12, phenol, benzyl alcohol or phenethyl alcohol.
21. The synthesis method of claim 20, wherein the viscosity modifier comprises one or more of ethanol, isopropanol, pentaerythritol, dipentaerythritol, and benzyl alcohol.
22. The synthesis method of claim 6, wherein the mass ratio of the viscosity modifier to the phosphonate oligomer is 0.01-0.5.
23. The synthesis method of claim 22, wherein the mass ratio of the viscosity modifier to the phosphonate oligomer is 0.05-0.3.
24. The synthesis method of claim 6, wherein the reaction temperature of the viscosity modifier and the phosphonate oligomer with the P-O-P as the skeleton is 20-100 ℃.
25. The synthesis method of claim 24, wherein the reaction temperature of the viscosity modifier and the phosphonate oligomer with the P-O-P as the skeleton is 30-60 ℃.
26. The synthesis method of claim 6, wherein the reaction time of the viscosity modifier and the phosphonate oligomer with the P-O-P as the skeleton is 0.1-3 hours.
27. The synthesis method of claim 26, wherein the reaction time of the viscosity modifier and the phosphonate oligomer with the P-O-P as the skeleton is 0.5-2 hours.
28. The synthesis method according to claim 6, wherein in step S2: the catalyst is one of Lewis acid, organic tin, primary amine, tertiary amine or quaternary ammonium salt or alkyl aluminum.
29. The method of claim 28, wherein the lewis acid is AlCl3、MgCl2、BF2、SbCl5、FeBr3、FeCl3、SnCl4、TiCl4、ZnCl2Benzene sulfonic acid or toluene sulfonic acid.
30. The method of claim 28, wherein the primary, tertiary or quaternary amine is cyclohexylamine, methylcyclohexylamine or benzyltriethylammonium chloride.
31. The synthesis method according to claim 28, wherein the organotin is stannous octoate or dibutyltin laurate.
32. The synthesis method according to claim 6, wherein in step S2: the addition amount of the catalyst is 0.1-5% of the total mass of the intermediate and the epoxyalkyl-containing component.
33. The method of claim 32, wherein the mass ratio of the acrylate of the epoxy group to the intermediate is 0.05 to 0.6.
34. The synthesis method according to claim 6, wherein in step S2: heating to 20-100 ℃.
35. The synthesis method according to claim 34, wherein the temperature is raised to 30-60 ℃.
36. The method of synthesizing of claim 34 wherein in step S2: the reaction time is 2-72 h.
37. The method of synthesizing according to claim 36 wherein in step S2: the reaction time is 3-36 h.
38. The synthesis method according to claim 6, wherein in step S2: the temperature for removing the low temperature is 50-150 ℃.
39. The method of synthesizing according to claim 38 wherein in step S2: the temperature for removing the low temperature is 70-120 ℃.
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| EP0302827A2 (en) * | 1987-08-05 | 1989-02-08 | Ciba-Geigy Ag | Process for the formation of images |
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