CN110627974A - High-heat-resistance phosphorus-silicon flame retardant, and preparation method and application thereof - Google Patents
High-heat-resistance phosphorus-silicon flame retardant, and preparation method and application thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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Abstract
The invention relates to the technical field of flame retardants for PC/ABS alloys, in particular to a high heat-resistant phosphorus-silicon flame retardant, a preparation method and application thereof, wherein the preparation method of the high heat-resistant phosphorus-silicon flame retardant comprises the steps of firstly obtaining a silicon-containing DOPO derivative by initiating a reaction between DOPO and a vinyl silane coupling agent, introducing a silicon element, and improving the heat resistance and the flame retardance; adding ammonia water into the DOPO silicon-containing derivative for hydrolysis to obtain a DOPO silicon-containing hydrolysate, so that the DOPO silicon-containing hydrolysate can obtain-OH active groups, and can conveniently react with aromatic vinyl monomers; finally, the DOPO silicon-containing hydrolysate and the aromatic vinyl monomer are subjected to emulsion polymerization, so that the compatibility of the high-heat-resistance phosphorus-silicon flame retardant and the PC/ABS alloy is improved, and the heat resistance of the high-heat-resistance phosphorus-silicon flame retardant is improved by introducing phenyl. The preparation method has the advantages of simple operation, convenient control, high production efficiency and low production cost, and can be used for large-scale production.
Description
Technical Field
The invention relates to the technical field of flame retardants for PC/ABS alloys, in particular to a high-heat-resistance phosphorus-silicon flame retardant, and a preparation method and application thereof.
Background
The PC/ABS alloy with PC and ABS as main material is one important engineering plastic alloy with excellent forming performance, low temperature impact resistance, high heat deformation temperature and high light stability. Compared with PC, the PC/ABS alloy reduces the melt viscosity, improves the processing performance and greatly improves the stress cracking resistance of the product; compared with ABS, the PC/ABS alloy has improved heat resistance and weather resistance, and has good performances of the two.
The PC/ABS alloy is added with more than 20 wt% of the existing organic phosphorus-silicon flame retardant, and the flame retardant grade (UL-94) can reach V-0 grade (3.2 mm); however, the compatibility of the existing organophosphorus-silicon flame retardant and PC/ABS alloy is poor, and the obtained polymer alloy is difficult to really exert respective advantages.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the preparation method of the phosphorus-silicon flame retardant with high heat resistance, which is simple to operate, convenient to control, high in production efficiency and low in production cost and can be used for large-scale production.
The second purpose of the invention is to provide a high heat-resistant phosphorus-silicon flame retardant which has high heat resistance, good flame-retardant stability and good compatibility with PC/ABS alloy materials.
The invention also aims to provide an application of the high heat-resistant phosphorus-silicon flame retardant, wherein the high heat-resistant phosphorus-silicon flame retardant is applied to a PC/ABS alloy material, so that the compatibility of the high heat-resistant phosphorus-silicon flame retardant and the PC/ABS alloy material is improved, and the flame retardance of the high heat-resistant phosphorus-silicon flame retardant is also improved.
One of the purposes of the invention is realized by the following technical scheme: a preparation method of a high-heat-resistance phosphorus-silicon flame retardant comprises the following steps:
(S1) mixing 20-30 parts by weight of vinyl silane coupling agent, 10-15 parts by weight of DOPO and 1-1.5 parts by weight of initiator A, and reacting at 70-85 ℃ for 20-30h to obtain the silicon-containing DOPO derivative;
(S2) adding water into the DOPO silicon-containing derivative prepared in the step (S1) for dilution, then adding ammonia water to adjust the pH value to 9-11, and then carrying out hydrolysis reaction at the temperature of 40-60 ℃ for 5-7h to obtain a DOPO silicon-containing hydrolysate;
(S3) mixing 15-30 parts by weight of aromatic vinyl monomer, 30-50 parts by weight of DOPO silicon-containing hydrolysate prepared in the step (S2) and 50-80 parts by weight of emulsifier-water solution, adding an initiator B, heating to 85-98 ℃ under the condition of continuous stirring, reacting for 7-9h, demulsifying, filtering and drying to prepare the high-heat-resistance phosphorus-silicon flame retardant.
According to the preparation method of the high-heat-resistance phosphorus-silicon flame retardant, DOPO is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, the structure of the DOPO contains a P-H bond, the DOPO, the epoxy bond and the carbonyl group have high activity, and can react to generate a plurality of derivatives, and the DOPO and the derivatives thereof have higher heat stability and chemical stability than common organic phosphate without ring formation and better flame retardant performance because the molecular structure contains a biphenyl ring and a phenanthrene ring structure, particularly a side phosphorus group is introduced in a mode of a ring O ═ P-O bond; in the step (S1), because the DOPO structure contains P-H bonds and has activity on olefin, epoxy bonds and carbonyl groups, the DOPO and vinyl silane coupling agent are initiated to react under the action of an initiator A and 70-85 ℃ to obtain the DOPO silicon-containing derivative, so that silicon element is introduced into the DOPO silicon-containing derivative, and the heat resistance and the flame retardance of the high-heat-resistance phosphorus-silicon flame retardant are greatly improved. In the step (S2), ammonia water is added to adjust the pH value to 9-11, and the DOPO silicon-containing derivative is hydrolyzed to obtain a DOPO silicon-containing hydrolysate, so that the DOPO silicon-containing hydrolysate can obtain-OH active groups, and can further react with aromatic vinyl monomers; the reaction is promoted at a temperature of 40-60 ℃. In the step (S3), the DOPO silicon-containing hydrolysate and the aromatic vinyl monomer are subjected to emulsion polymerization under the action of an initiator B and at 85-98 ℃ to obtain the novel phosphorus-silicon flame retardant (namely the high heat-resistant phosphorus-silicon flame retardant), so that the compatibility of the high heat-resistant phosphorus-silicon flame retardant and the PC/ABS alloy is improved, and the phenyl is introduced to improve the heat resistance of the flame retardant.
Preferably, the vinyl silane coupling agent is vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tris (. beta. -methoxyethoxy) silane, vinyl phenyldimethoxysilane, vinyl diphenylmethoxysilane, divinylphenylmethoxysilane, vinyl phenyldiethoxysilane, vinyl diphenylethoxysilane, divinylphenylethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, vinyl methyldimethoxysilane, vinyl methyldiethoxysilane, vinyl ethyldimethoxysilane, vinyl ethyldiethoxysilane, vinyl propyldimethoxysilane, vinyl propyldiethoxysilane, p-vinylphenylmethylmethoxysilane, p-vinylphenylmethylethoxysilane, p-vinylphenylethylmethoxysilane, vinyl-phenyldimethoxysilane, vinyl-substituted vinylmethyldimethoxysilane, vinyl-substituted vinylmethyldimeth, P-vinylphenylethylethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldiethoxysilane, 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane, 3- (p-vinylbenzoyloxy) propylmethyldiethoxysilane.
According to the invention, by adopting the vinyl silane coupling agent, the vinyl in the vinyl silane coupling agent is combined with the DOPO through reaction, so that the DOPO introduces silicon element, the heat resistance and the flame retardance of the high heat-resistant phosphorus-silicon flame retardant are greatly improved, and the obtained DOPO silicon-containing derivative is yellow liquid. More preferably, the vinyl silane coupling agent is a mixture of vinyl trimethoxy silane, p-vinylphenylmethyl ethoxy silane and 3- (p-vinylbenzoyloxy) propylmethyl diethoxy silane in a weight ratio of 2-4: 1.5-2.5: 1, in a mixture of the components.
Preferably, the initiator A is at least one of benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate; the initiator B is at least one of benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.
By adopting the technical scheme, the initiating effect is good by strictly controlling the type, compounding and proportion of the initiating agent A, the polymerization of DOPO and the vinyl silane coupling agent in the step (S1) is promoted, the polymerization rate is improved, the polymerization temperature is reduced, the energy is saved, and the production efficiency is improved; by strictly controlling the type, compounding and proportion of the initiator B, the initiator B has good initiating effect, promotes the polymerization of the DOPO silicon-containing hydrolysate and the aromatic vinyl monomer in the step (S2), improves the polymerization rate, reduces the polymerization temperature, saves energy and improves the production efficiency. More preferably, the initiator A is a mixture of benzoyl peroxide and azobisisobutyronitrile in a weight ratio of 2: 1.5-2.5; the initiator B is a mixture of di-tert-butyl peroxide, dicumyl peroxide and azobisisobutyronitrile in a weight ratio of 1:0.5-1.5: 1.5-2.5.
Preferably, in the step (S2), the ratio of the weight of the silicon-containing derivative of DOPO to the weight of water is 1: 5-10; the concentration of the ammonia water is 15-20 wt%.
By adopting the technical scheme, the weight ratio of the OPO silicon-containing derivative to the water is controlled to be 1: 5-10, the hydrolysis degree is larger, and the hydrolysis of the silicon-containing DOPO derivative is promoted; the concentration of the ammonia water is controlled to be 15-20 wt%, the reduction of hydrolysis degree caused by thermal decomposition due to overhigh concentration of the ammonia water is avoided, the reduction of production efficiency caused by prolonging hydrolysis time due to overlow concentration of the ammonia water is avoided, and the DOPO silicon-containing hydrolysate obtained by the step (S2) by adopting the scheme is light brown liquid.
Preferably, the aromatic vinyl monomer is at least one of styrene, methyl styrene, ethyl styrene and butyl styrene.
By adopting the technical scheme, the DOPO silicon-containing hydrolysate is further polymerized with the aromatic vinyl monomer emulsion, so that the compatibility of the PC/ABS alloy material and the high heat-resistant phosphorus-silicon flame retardant is improved, the phenyl content of the high heat-resistant phosphorus-silicon flame retardant is increased, and the heat resistance of the high heat-resistant phosphorus-silicon flame retardant is improved. More preferably, the aromatic vinyl monomer is styrene, and the content of phenyl groups is higher.
Preferably, the emulsifier-water solution is prepared by mixing an emulsifier and water in a weight ratio of 0.1-0.5: 5-8, and mixing.
By adopting the technical scheme, the added emulsifier has less dosage, and the step (S3) of adding the pre-prepared emulsifier-water solution effectively controls the dosage of the emulsifier added system, reduces errors, avoids a large amount of side reactions, and improves the yield of the high-heat-resistance phosphorus-silicon flame retardant. Further, the emulsifier is an anionic emulsifier and a nonionic emulsifier in a weight ratio of 3-6: 1-2, wherein the anionic emulsifier is fatty alcohol sulfate and/or alkyl sulfonate, the fatty alcohol sulfate is fatty alcohol sodium sulfate, the alkyl sulfonate is petroleum sodium sulfonate, sodium alkyl benzene sulfonate or sodium lignosulfonate, and the nonionic emulsifier is at least one of linear fatty alcohol polyoxyethylene ether, isomeric fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether and polyol ester polyoxyethylene ether. The emulsifier is prepared by compounding an anionic emulsifier and a nonionic emulsifier, so that a synergistic effect is generated, the chemical stability of the emulsion is improved, and the solid content is improved.
Preferably, the step (S3) further includes: before mixing the aromatic vinyl monomer, the DOPO silicon-containing hydrolyzate and the emulsifier-water solution, 10 to 15 parts by weight of the acrylonitrile monomer is added and mixed with the aromatic vinyl monomer.
By adopting the technical scheme, the DOPO silicon-containing hydrolysate, the aromatic vinyl monomer and the acrylonitrile monomer are subjected to emulsion polymerization together, so that nitrogen is introduced into the high-heat-resistance phosphorus-silicon flame retardant for synergetic flame retardance, and the heat resistance and the flame retardance of the high-heat-resistance phosphorus-silicon flame retardant are greatly improved.
Preferably, the acrylonitrile-based monomer is acrylonitrile and/or methacrylonitrile.
The second purpose of the invention is realized by the following technical scheme: the phosphorus-silicon flame retardant with high heat resistance is prepared by the preparation method of the phosphorus-silicon flame retardant with high heat resistance.
The third purpose of the invention is realized by the following technical scheme: the application of the high heat-resistant phosphorus-silicon flame retardant is to PC/ABS alloy materials.
The invention has the beneficial effects that: according to the preparation method of the high heat-resistant phosphorus-silicon flame retardant, the DOPO and the vinyl silane coupling agent are initiated to react to obtain the DOPO silicon-containing derivative, so that silicon is introduced into the DOPO silicon-containing derivative, and the heat resistance and the flame retardance of the high heat-resistant phosphorus-silicon flame retardant are greatly improved; adding ammonia water into the DOPO silicon-containing derivative for hydrolysis to obtain a DOPO silicon-containing hydrolysate, so that the DOPO silicon-containing hydrolysate can obtain-OH active groups, and can conveniently react with aromatic vinyl monomers; finally, the DOPO silicon-containing hydrolysate and the aromatic vinyl monomer are subjected to emulsion polymerization to obtain the high heat-resistant phosphorus-silicon flame retardant, so that the compatibility of the high heat-resistant phosphorus-silicon flame retardant and the PC/ABS alloy is improved, and the heat resistance of the high heat-resistant phosphorus-silicon flame retardant is improved by introducing phenyl. The preparation method has the advantages of simple operation, convenient control, high production efficiency and low production cost, and can be used for large-scale production.
The high heat-resistant phosphorus-silicon flame retardant disclosed by the invention is high in heat resistance, good in flame retardant stability and good in compatibility with a PC/ABS alloy material.
The application of the high heat-resistant phosphorus-silicon flame retardant disclosed by the invention applies the high heat-resistant phosphorus-silicon flame retardant to a PC/ABS alloy material, so that the compatibility of the high heat-resistant phosphorus-silicon flame retardant and the PC/ABS alloy material is improved, and the flame retardance of the high heat-resistant phosphorus-silicon flame retardant is also improved.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A preparation method of a high-heat-resistance phosphorus-silicon flame retardant comprises the following steps:
(S1), mixing 25 parts by weight of vinyl silane coupling agent, 13 parts by weight of DOPO and 1.3 parts by weight of initiator A, and reacting at 78 ℃ for 25 hours to obtain the silicon-containing DOPO derivative;
(S2) adding water into the DOPO silicon-containing derivative prepared in the step (S1) for dilution, then adding ammonia water to adjust the pH value to 10, and then carrying out hydrolysis reaction for 6 hours at the temperature of 40-60 ℃ to obtain a DOPO silicon-containing hydrolysate;
(S3) mixing 23 parts by weight of aromatic vinyl monomer, 40 parts by weight of DOPO silicon-containing hydrolysate prepared in the step (S2) and 65 parts by weight of emulsifier-water solution, adding an initiator B, heating to 90 ℃ under the condition of continuous stirring, reacting for 8 hours, demulsifying, filtering and drying to prepare the high-heat-resistance phosphorus-silicon flame retardant.
The vinyl silane coupling agent is prepared by mixing vinyl trimethoxy silane, p-vinyl phenyl methyl ethoxy silane and 3- (p-vinyl benzoyloxy) propyl methyl diethoxy silane in a weight ratio of 3: 2:1, in a mixture of the components.
The initiator A is a mixture of benzoyl peroxide and azobisisobutyronitrile in a weight ratio of 2: 2; the initiator B is a mixture of di-tert-butyl peroxide, dicumyl peroxide and azobisisobutyronitrile in a weight ratio of 1:1: 2.
In the step (S2), the ratio of the weight of the DOPO silicon-containing derivative to the weight of water is 1: 8; the concentration of the ammonia water is 18 wt%.
The aromatic vinyl monomer is styrene.
The emulsifier-water solution is prepared from an emulsifier and water in a weight ratio of 0.3: 6.5 mixing.
The emulsifier is an anionic emulsifier and a nonionic emulsifier according to a weight ratio of 4.5: 1.5, and the anionic emulsifier is fatty alcohol sulfate and alkyl sulfonate according to a weight ratio of 3: 1, the fatty alcohol sulfate is fatty alcohol sodium sulfate, the alkyl sulfonate is petroleum sodium sulfonate, and the nonionic emulsifier is linear fatty alcohol-polyoxyethylene ether and heterogeneous fatty alcohol-polyoxyethylene ether in a weight ratio of 5: 8, and mixing.
The high-heat-resistance phosphorus-silicon flame retardant is prepared by the preparation method of the high-heat-resistance phosphorus-silicon flame retardant.
Example 2
A preparation method of a high-heat-resistance phosphorus-silicon flame retardant comprises the following steps:
(S1), mixing 20 parts by weight of vinyl silane coupling agent, 10 parts by weight of DOPO and 1 part by weight of initiator A, and reacting at 70 ℃ for 30 hours to obtain the DOPO silicon-containing derivative;
(S2) adding water into the DOPO silicon-containing derivative prepared in the step (S1) for dilution, then adding ammonia water to adjust the pH value to 9, and then carrying out hydrolysis reaction for 7 hours at the temperature of 40 ℃ to obtain a DOPO silicon-containing hydrolysate;
(S3) mixing 15 parts by weight of aromatic vinyl monomer, 30 parts by weight of DOPO silicon-containing hydrolysate prepared in the step (S2) and 50 parts by weight of emulsifier-water solution, adding an initiator B, heating to 85 ℃ under the condition of continuous stirring, reacting for 9 hours, demulsifying, filtering and drying to prepare the high-heat-resistance phosphorus-silicon flame retardant.
The vinyl silane coupling agent is prepared by mixing vinyl trimethoxy silane, p-vinyl phenyl methyl ethoxy silane and 3- (p-vinyl benzoyloxy) propyl methyl diethoxy silane in a weight ratio of (2): 1.5:1, in a mixture of the components.
The initiator A is a mixture of benzoyl peroxide and azobisisobutyronitrile in a weight ratio of 2: 1.5; the initiator B is a mixture of di-tert-butyl peroxide, dicumyl peroxide and azobisisobutyronitrile in a weight ratio of 1:0.5: 1.5.
In the step (S2), the ratio of the weight of the DOPO silicon-containing derivative to the weight of water is 1: 5; the concentration of the ammonia water is 15 wt%.
The aromatic vinyl monomer is butyl styrene.
The emulsifier-water solution is prepared from an emulsifier and water in a weight ratio of 0.1: 8, and mixing.
The emulsifier is an anionic emulsifier and a nonionic emulsifier according to the weight ratio of 3: 1, the anionic emulsifier is alkyl sulfonate, the alkyl sulfonate is sodium alkyl benzene sulfonate, and the nonionic emulsifier is nonylphenol polyoxyethylene ether.
The high-heat-resistance phosphorus-silicon flame retardant is prepared by the preparation method of the high-heat-resistance phosphorus-silicon flame retardant.
Example 3
A preparation method of a high-heat-resistance phosphorus-silicon flame retardant comprises the following steps:
(S1), mixing 30 parts by weight of vinyl silane coupling agent, 15 parts by weight of DOPO and 1.5 parts by weight of initiator A, and reacting at 85 ℃ for 20 hours to obtain the silicon-containing DOPO derivative;
(S2) adding water into the DOPO silicon-containing derivative prepared in the step (S1) for dilution, then adding ammonia water to adjust the pH value to 11, and then carrying out hydrolysis reaction for 5 hours at the temperature of 60 ℃ to obtain a DOPO silicon-containing hydrolysate;
(S3) mixing 30 parts by weight of aromatic vinyl monomer, 50 parts by weight of DOPO silicon-containing hydrolysate prepared in the step (S2) and 80 parts by weight of emulsifier-water solution, adding an initiator B, heating to 98 ℃ under the condition of continuous stirring, reacting for 7 hours, demulsifying, filtering and drying to prepare the high-heat-resistance phosphorus-silicon flame retardant.
The vinyl silane coupling agent is prepared by mixing vinyl trimethoxy silane, p-vinyl phenyl methyl ethoxy silane and 3- (p-vinyl benzoyloxy) propyl methyl diethoxy silane in a weight ratio of 4: 2.5: 1, in a mixture of the components.
The initiator A is a mixture of benzoyl peroxide and azobisisobutyronitrile in a weight ratio of 2: 2.5; the initiator B is a mixture of di-tert-butyl peroxide, dicumyl peroxide and azobisisobutyronitrile in a weight ratio of 1:1.5: 2.5.
In the step (S2), the ratio of the weight of the DOPO silicon-containing derivative to the weight of water is 1: 10; the concentration of the ammonia water is 20 wt%.
The aromatic vinyl monomer is styrene and ethyl styrene according to the weight ratio of 3: 1 are mixed.
The emulsifier-water solution is prepared from an emulsifier and water in a weight ratio of 0.5: 5, mixing the components.
The emulsifier is an anionic emulsifier and a nonionic emulsifier in a weight ratio of 6: 2, the anionic emulsifier is fatty alcohol sodium sulfate, and the nonionic emulsifier is linear fatty alcohol-polyoxyethylene ether and isomeric fatty alcohol-polyoxyethylene ether in a weight ratio of 2:1 are mixed.
The high-heat-resistance phosphorus-silicon flame retardant is prepared by the preparation method of the high-heat-resistance phosphorus-silicon flame retardant.
Example 4
A preparation method of a high-heat-resistance phosphorus-silicon flame retardant comprises the following steps:
(S1), mixing 22 parts by weight of vinyl silane coupling agent, 14 parts by weight of DOPO and 1.4 parts by weight of initiator A, and reacting at 72 ℃ for 27h to obtain the silicon-containing DOPO derivative;
(S2) adding water into the DOPO silicon-containing derivative prepared in the step (S1) for dilution, then adding ammonia water to adjust the pH value to 10, and then carrying out hydrolysis reaction at the temperature of 58 ℃ for 5.5h to obtain a DOPO silicon-containing hydrolysate;
(S3) mixing 18 parts by weight of aromatic vinyl monomer, 32 parts by weight of DOPO silicon-containing hydrolysate prepared in the step (S2) and 73 parts by weight of emulsifier-water solution, adding an initiator B, heating to 95 ℃ under the condition of continuous stirring, reacting for 7.2 hours, demulsifying, filtering and drying to prepare the high-heat-resistance phosphorus-silicon flame retardant.
The vinyl silane coupling agent is vinyl trimethoxy silane.
The initiator A is azobisisobutyronitrile.
In the step (S2), the ratio of the weight of the DOPO silicon-containing derivative to the weight of water is 1: 6; the concentration of the ammonia water is 16 wt%.
The aromatic vinyl monomer is styrene.
The emulsifier-water solution is prepared from an emulsifier and water in a weight ratio of 0.2: 6, mixing the components.
The emulsifier is an anionic emulsifier and a nonionic emulsifier according to the weight ratio of 5: 1.8, the anionic emulsifier is alkyl sulfonate, and the alkyl sulfonate is petroleum sodium sulfonate and sodium alkyl benzene sulfonate according to the weight ratio of 1: 5, and the nonionic emulsifier is linear fatty alcohol-polyoxyethylene ether.
The high-heat-resistance phosphorus-silicon flame retardant is prepared by the preparation method of the high-heat-resistance phosphorus-silicon flame retardant.
Example 5
This example differs from example 1 in that:
the step (S3) further includes: 13 parts by weight of acrylonitrile was added and mixed with the aromatic vinyl monomer before mixing the aromatic vinyl monomer, the DOPO silicon-containing hydrolyzate and the emulsifier-water solution.
The acrylonitrile monomer is
Example 6
This example differs from example 1 in that:
the step (S3) further includes: before mixing the aromatic vinyl monomer, DOPO silicon-containing hydrolyzate and emulsifier-water solution, 10 parts by weight of methacrylonitrile was added and mixed with the aromatic vinyl monomer.
Example 7
This example differs from example 1 in that:
the step (S3) further includes: before mixing the aromatic vinyl monomer, the DOPO silicon-containing hydrolyzate, and the emulsifier-water solution, 15 parts by weight of the acrylonitrile-based monomer was added and mixed with the aromatic vinyl monomer.
The acrylonitrile monomer is acrylonitrile and methacrylonitrile according to a weight ratio of 5:1 are mixed.
Example 8 Performance testing
1. Main raw materials
PC resin (shanghai jingle industries ltd); ABS resin (shanghai jingle industries ltd); antioxidant PEPQ (Hangzhou Baise chemical technology Co., Ltd.); anti-dripping agent PTFE (shanghai jingle industries ltd); examples 1 to 7 were each prepared as a high heat-resistant phosphorus-silicon flame retardant; flame retardant RDP (shanghai dary fine chemicals, ltd); the compatibilizer SAG-001 (Hipport molecular materials science Co., Ltd., Nantong Ri.).
2. Formula of PC/ABS alloy material
The PC/ABS alloy material comprises the following raw materials in parts by weight:
TABLE 1
Wherein the high heat-resistant phosphorus-silicon flame retardants of examples 1 to 7 correspond one-to-one to the high heat-resistant phosphorus-silicon flame retardants prepared in examples 1 to 7, respectively.
3. Preparation of PC/ABS alloy material
The PC/ABS alloy material is prepared by the following steps: uniformly mixing the raw materials in parts by weight corresponding to each sample, and then feeding the mixture into a double-screw granulator for melting, extruding and granulating to obtain the PC/ABS alloy material, wherein the temperature of each area of the double-screw granulator is set as follows: the temperature of the first zone is 195 ℃, the temperature of the second zone is 205 ℃, the temperature of the third zone is 215 ℃, the temperature of the fourth zone is 215 ℃, the temperature of the fifth zone is 215 ℃, the temperature of the sixth zone is 215 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 205 ℃ and the temperature of a machine head is 225 ℃, the retention time of the raw materials in the double-screw granulator is 6min, and the rotating speed of a screw of the double-screw granulator is 360 r/.
4. And (3) flame retardant test:
the test is carried out by adopting the test method B-the provision of the vertical combustion test in GB/T2408-2008 determination of the combustion performance of the plastic, and the thickness of the test sample is 3.2 mm; the test results are shown in table 2 below:
TABLE 2
Note: t is t1Indicating that the test sample is applied with flame for 10s +/-0.5 s for the first time, and then measuring the test afterflame time; t is t2Indicating that the specimen is immediately renewed after the after-flame of the first applied flame has been extinguishedMeasuring the test afterflame time after applying the flame for 10s +/-0.5 s; t is t1+t2Represents the individual test afterflame time in s. If the test results do not meet the specified criteria, the material cannot be rated using the test method.
As is apparent from tables 1 and 2 above, the flame retardants used in the comparative examples and examples 1 to 7 were 14 parts by weight, but the flame holding times and the anti-dripping effects in the individual tests were different. Compared with the implementation group 1, the comparison group has longer flame time and poorer flame-retardant effect, which shows that the implementation group 1 can play a better flame-retardant role at lower use level; compared with the embodiment 1, the embodiment 5 has shorter remaining flame time and better flame retardant effect, and the possible reason is that the high heat-resistant phosphorus-silicon flame retardant used in the embodiment 5 introduces nitrogen element, and the N/P/Si synergistic effect ensures that the flame retardant effect is better.
5. Thermogravimetric testing
The test is carried out according to the regulation of GB _ T33047.1-2016 plastic polymer thermogravimetry, and the weight of each sample is 10 mg; the test results are shown in table 3 below:
TABLE 3
As can be seen from the above tables 1 and 3, the Vicat softening point of the PC/ABS alloy material added with the high heat-resistant phosphorus-silicon flame retardant can reach more than 120 ℃, which is higher than that of the comparison group and the blank comparison group, and the PC/ABS alloy materials of the implementation groups 1 to 7 have better thermal stability. According to thermogravimetric result analysis of Table 3, the PC/ABS alloy material is decomposed earlier by adding the flame retardant, and carbon formation is accelerated; the carbon residue rates of the implementing groups 1 to 7 using the high heat-resistant phosphorus-silicon flame retardant are higher than those of the comparison group, because the high heat-resistant phosphorus-silicon flame retardant contains silicon elements, phosphorus can promote carbon formation at high temperature, and silicon can increase the stability of a carbon layer, so that the synergistic flame retardant effect of phosphorus and silicon is exerted; phosphorus forms free radicals on combustion to quench the combustion chain reactions in the gas phase, and silicon promotes more residue concentration to form a coke layer. Among them, embodiment 5 has a lower vicat softening point than embodiment 1, and it is faster in thermal decomposition due to the introduction of nitrogen element, and although the flame retardant effect can be improved, the thermal stability is lowered.
6. Mechanical Property test
The tensile strength of the alloy material is measured by GB/T1040.2-2006, and the test speed is as follows: 50mm/min in MPa; the bending strength of the alloy material is determined by GB/T9341-2008, and the unit is MPa; the notch impact strength of the alloy material is measured by GB/T1043.1-2008, and the sample strip size is as follows: (80X 10X 4) mm, notch type: type A, the test environment is 23 +/-2 ℃, and the unit is kJ/m2(ii) a The test results are shown in table 4 below:
TABLE 4
As can be seen from the above Table 1 and Table 4, the PC/ABS alloy materials of the embodiments 1-7 have higher tensile strength, bending strength and notched impact strength than those of the comparative group, which shows that the high heat-resistant phosphorus-silicon flame retardant of the present invention can improve the compatibility of the PC/ABS alloy materials, thereby improving the tensile strength, bending strength and notched impact strength thereof, and fully exerting the respective advantages of the obtained polymer alloys.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. A preparation method of a high heat resistance phosphorus-silicon flame retardant is characterized by comprising the following steps: the method comprises the following steps:
(S1) mixing 20-30 parts by weight of vinyl silane coupling agent, 10-15 parts by weight of DOPO and 1-1.5 parts by weight of initiator A, and reacting at 70-85 ℃ for 20-30h to obtain the silicon-containing DOPO derivative;
(S2) adding water into the DOPO silicon-containing derivative prepared in the step (S1) for dilution, then adding ammonia water to adjust the pH value to 9-11, and then carrying out hydrolysis reaction at the temperature of 40-60 ℃ for 5-7h to obtain a DOPO silicon-containing hydrolysate;
(S3) mixing 15-30 parts by weight of aromatic vinyl monomer, 30-50 parts by weight of DOPO silicon-containing hydrolysate prepared in the step (S2) and 50-80 parts by weight of emulsifier-water solution, adding an initiator B, heating to 85-98 ℃ under the condition of continuous stirring, reacting for 7-9h, demulsifying, filtering and drying to prepare the high-heat-resistance phosphorus-silicon flame retardant.
2. The method for preparing a phosphorus-silicon flame retardant with high heat resistance according to claim 1, wherein: the vinyl silane coupling agent is vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tris (beta-methoxyethoxy) silane, vinyl phenyl dimethoxysilane, vinyl diphenyl methoxysilane, divinyl phenyl methoxysilane, vinyl phenyl diethoxysilane, vinyl diphenyl ethoxysilane, divinyl phenyl ethoxysilane, divinyl dimethoxysilane, divinyl diethoxysilane, vinyl methyl dimethoxysilane, vinyl methyl diethoxysilane, vinyl ethyl dimethoxysilane, vinyl ethyl diethoxysilane, vinyl propyl dimethoxysilane, vinyl propyl diethoxysilane, p-vinyl phenyl methyl methoxysilane, p-vinyl phenyl methyl ethoxysilane, p-vinyl phenyl ethyl methoxysilane, vinyl ethyl dimethoxysilane, vinyl methyl diethoxysilane, vinyl ethyl dimethoxysilane, vinyl propyl diethoxysilane, p-vinyl phenyl methyl methoxysilane, vinyl methyl ethoxysilane, p-vinyl phenyl ethyl methoxysilane, vinyl methyl ethoxy, P-vinylphenylethylethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldiethoxysilane, 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane, 3- (p-vinylbenzoyloxy) propylmethyldiethoxysilane.
3. The method for preparing a phosphorus-silicon flame retardant with high heat resistance according to claim 1, wherein: the initiator A is at least one of benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate; the initiator B is at least one of benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.
4. The method for preparing a phosphorus-silicon flame retardant with high heat resistance according to claim 1, wherein: in the step (S2), the ratio of the weight of the DOPO silicon-containing derivative to the weight of water is 1: 5-10; the concentration of the ammonia water is 15-20 wt%.
5. The method for preparing a phosphorus-silicon flame retardant with high heat resistance according to claim 1, wherein: the aromatic vinyl monomer is at least one of styrene, methyl styrene, ethyl styrene and butyl styrene.
6. The method for preparing a phosphorus-silicon flame retardant with high heat resistance according to claim 1, wherein: the emulsifier-water solution is prepared from an emulsifier and water according to the weight ratio of 0.1-0.5: 5-8, and mixing.
7. The method for preparing a phosphorus-silicon flame retardant with high heat resistance according to claim 1, wherein: the step (S3) further includes: before mixing the aromatic vinyl monomer, the DOPO silicon-containing hydrolyzate and the emulsifier-water solution, 10 to 15 parts by weight of the acrylonitrile monomer is added and mixed with the aromatic vinyl monomer.
8. The method for preparing a phosphorus-silicon flame retardant with high heat resistance according to claim 7, wherein: the acrylonitrile monomer is acrylonitrile and/or methacrylonitrile.
9. A high heat-resistant phosphorus-silicon flame retardant is characterized in that: the phosphorus-silicon flame retardant with high heat resistance is prepared by adopting the preparation method of the phosphorus-silicon flame retardant with high heat resistance as claimed in any one of claims 1 to 8.
10. Use of the highly heat-resistant phosphorus-silicon flame retardant according to claim 9, wherein: the high heat-resistant phosphorus-silicon flame retardant is applied to PC/ABS alloy materials.
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