CN101962448B - Compound fire retardant containing hydroxymethylated melamine silicide, preparation method and application thereof - Google Patents
Compound fire retardant containing hydroxymethylated melamine silicide, preparation method and application thereof Download PDFInfo
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- CN101962448B CN101962448B CN2010102862940A CN201010286294A CN101962448B CN 101962448 B CN101962448 B CN 101962448B CN 2010102862940 A CN2010102862940 A CN 2010102862940A CN 201010286294 A CN201010286294 A CN 201010286294A CN 101962448 B CN101962448 B CN 101962448B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a compound fire retardant containing hydroxymethylated melamine silicide and application thereof. The compound fire retardant comprises the following components in parts by weight: 100 parts of hydroxymethylated melamine silicide, 5-100 parts of inorganic fire retardant and 0-100 parts of inorganic filler which are compounded. The compound fire retardant does not contain halogens, releases fewer toxic substances, is environmentally friendly and has smaller threat to the life safety of people. In addition, the compound fire retardant has the advantages of high heat stability, high limited oxygen index, strong fire resistance and better compatibility with polymer materials and can be used for effectively improving the heat resistance and the fire resistance of high polymer materials such as chloroethylene, epoxy resin, polypropylene, polyester, and the like. The development of the compound fire retardant successfully solves the problems of the traditional fire retardants of toxicity, environmental pollution, poor fire resistance, incompatibility with the high polymer materials, and the like.
Description
Technical field
The present invention relates to the flame retardant materials field, particularly a kind of composite flame-retardant agent that contains methylolation trimeric cyanamide silicide and preparation method thereof and application.
Background technology
At present, using more fire retardant in the polymer materials is halogen containing flame-retardant.The halogen containing polymers material discharges toxic substance easily in combustion processes, to people's life security existence threat.Therefore,, contain nitrogen combustion inhibitor as a kind of expansion type flame retardant from environmental protection, safe requirement, because of it has Halogen, low toxicity, advantages such as low cigarette, and receive publicity gradually.
Contain at present nitrogen combustion inhibitor research more be the fire retardant that contains triazine ring structure, be main with trimeric cyanamide and verivate thereof again wherein.Yet the consistency of trimeric cyanamide and macromolecular material is relatively poor, is difficult to be used for direct modified polymer material.In order to improve compatibility problem, Chinese scholars is with trimeric cyanamide and verivate methylolation thereof or pass through the reaction formation condenses between hydroxyl, be incorporated in the polymer materials then, thus the flame retardant properties of raising material.But single use contains nitrogen combustion inhibitor, and the flame retardant effect of polymer materials is unsatisfactory.Therefore, have the scholar respectively hydroxylated trimeric cyanamide and silicon-containing compound to be reacted in the polymkeric substance (like epoxy resin), the flame retardant resistance of the polymer materials after the modification is improved significantly.But this method only is the effect that has utilized silicon/nitrogen cooperative flame retardant, and trimeric cyanamide and silicon-containing compound are reacted to respectively in the polymkeric substance, both reactions is not become a kind of fire retardant that contains silicon/nitrogen element.
Summary of the invention
Primary and foremost purpose of the present invention is to overcome the shortcoming of prior art with not enough, a kind of environmental friendliness is provided, thermostability is high, flame retardant resistance is strong, contain the composite flame-retardant agent of methylolation trimeric cyanamide silicide preferably with the polymer materials consistency.
Another object of the present invention is to provide the said preparation method who contains the composite flame-retardant agent of methylolation trimeric cyanamide silicide.
A purpose more of the present invention is to provide the said application that contains the composite flame-retardant agent of methylolation trimeric cyanamide silicide.
The object of the invention is realized through following technical proposals:
A kind of composite flame-retardant agent that contains methylolation trimeric cyanamide silicide is to be composited by the methylolation trimeric cyanamide silicide of 100 weight parts, the inorganic combustion inhibitor of 5～100 weight parts and the mineral filler of 0～100 weight part.
Said methylolation trimeric cyanamide silicide, adopt following method to prepare:
(1) be that 20%～37% formaldehyde solution is mixed with 100 weight part trimeric cyanamides and 100～400 weight part massfractions; Regulate pH value to 7～9 with 0.5～8 weight part catalyst I; 60～90 ℃ were reacted 20～90 minutes down; Remove remaining formaldehyde then, obtain methylolation trimeric cyanamide (suc as formula I);
(2) in the reaction system of step (1), add 50～500 weight part organoalkoxysilanes (suc as formula II), 100～1000 weight parts waters, 1～15 weight part catalyst I I; 70～100 ℃ are reacted after 0.5～5 hour down; Filtering-depositing, will precipitate the oven dry after obtain methylolation trimeric cyanamide silicide.
Among the formula I, R
1, R
2, R
3, R
4, R
5, R
6For hydrogen or-CH
2OH, and R
1, R
2, R
3, R
4, R
5, R
6Can not be hydrogen simultaneously.
Among the formula II, M
1Be methyl, ethyl, n-propyl, sec.-propyl or butyl; M
2, M
3, M
4For C1～5 straight chains or contain alkyl, benzyl, phenyl, the C1～4 alkoxyl groups of side chain.
Said organoalkoxysilane is one or more mixtures in benzyl triethoxyl silane, methyldiethoxysilane, methyl silicate, dimethyldiethoxysilane, ethyl triethoxysilane, phenyltrimethoxysila,e, Union carbide A-162 and the tetraethoxy.
Preferred triethylamine of said catalyst I or sodium hydroxide.
Preferred dibutyl tin dilaurate of said catalyst I I or aluminum chloride.
Said inorganic combustion inhibitor is one or more mixtures in white lake, Antimony Trioxide: 99.5Min, zinc borate and the Marinco H;
Said mineral filler is one or more mixtures in lime carbonate, calcined kaolin, silicon powder, mica powder and the talcum powder
Above-mentioned a kind of preparation method who contains the composite flame-retardant agent of methylolation trimeric cyanamide silicide is to be composited by the methylolation trimeric cyanamide silicide of 100 weight parts, the inorganic combustion inhibitor of 5～100 weight parts and the mineral filler of 0～100 weight part.
Above-mentioned a kind of composite flame-retardant agent that contains methylolation trimeric cyanamide silicide is used with vinylchlorid, epoxy resin, Vestolen PP 7052, polyester etc., can improve the thermotolerance and the flame retardant resistance of these macromolecular materials.
The present invention has following advantage and effect with respect to prior art:
(1) composite flame-retardant agent of the present invention is not halogen-containing, and the toxic substance that discharges during burning is less, and is environmentally friendly, and is less to people's life security threat.
(2) composite flame-retardant agent thermostability of the present invention is high, limiting oxygen index(LOI) (LOI) is high, flame retardant resistance is strong.
(3) consistency of composite flame-retardant agent of the present invention and polymer materials is better, can effectively improve the thermotolerance and the flame retardant resistance of macromolecular materials such as vinylchlorid, epoxy resin, Vestolen PP 7052, polyester.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
Embodiment 1
The preparation of methylolation trimeric cyanamide silicide:
(1) be that 37% formaldehyde solution is mixed with 100 weight part trimeric cyanamides and 100 weight part massfractions; Behind 1 weight part triethylamine adjusting pH=7, under 90 ℃, hydroxymethylation 20 minutes; Rotary evaporation is removed remaining formaldehyde then, obtains the methylolation trimeric cyanamide;
(2) in the reaction system of step (1), add 300 weight part tetraethoxys, 200 weight part Union carbide A-162s, 1000 weight parts waters, 15 weight part dibutyl tin dilaurates; Adjust the temperature to 90 ℃; React after 5 hours; Filtering-depositing, will precipitate the oven dry after obtain Powdered methylolation trimeric cyanamide silicide.
Contain the preparation of the composite flame-retardant agent of methylolation trimeric cyanamide silicide: the methylolation trimeric cyanamide silicide of getting the preparation of 100 weight part present embodiments; 1 weight part zinc borate; 1 weight part Antimony Trioxide: 99.5Min; 2 weight part Marinco Hs, the compound composite flame-retardant agent that obtains containing methylolation trimeric cyanamide silicide of 1 weight part white lake.
Get composite flame-retardant agent 30 weight parts of polyvinyl chloride resin 100 weight parts, present embodiment preparation; Calcium stearate 1 weight part, DOP (DOP) 40 weight parts, vinyltriethoxysilane (coupling agent) 1 weight part; Organotin stabilizer 3 weight parts mix; At 180 ℃ of following mixing 15min, move into dull and stereotyped pressing machine with mixing roll, hot pressing 10min under 180 ℃, 240MPa pressure.The flexible PVC limiting oxygen index(LOI) (LOI) that gained contains the composite flame-retardant agent of nitrogenated silicon hybrid is 28.7.
Embodiment 2
The preparation of methylolation trimeric cyanamide silicide:
(1) be that 30% formaldehyde solution is mixed with 100 weight part trimeric cyanamides and 200 weight part massfractions, 6 weight part triethylamines are regulated pH=9, under 85 ℃, and hydroxymethylation 20 minutes, rotary evaporation is removed remaining formaldehyde then, obtains the hydroxylation trimeric cyanamide;
(2) in the reaction system of step (1), add 130 weight part tetraethoxys, 70 weight part Union carbide A-162s, 10 weight part phenyltrimethoxysila,e; 850 weight parts waters; 8 weight part dibutyl tin dilaurates adjust the temperature to 90 ℃, react after 5 hours; Filtering-depositing, will precipitate the oven dry after obtain Powdered methylolation trimeric cyanamide silicide.
Contain the preparation of the composite flame-retardant agent of methylolation trimeric cyanamide silicide: the methylolation trimeric cyanamide silicide of getting the preparation of 100 weight part present embodiments; 30 weight part white lakes; 40 weight part Antimony Trioxide: 99.5Mins; 30 weight part zinc borates, the compound composite flame-retardant agent that contains methylolation trimeric cyanamide silicide that makes of 10 weight part silicon powders, 20 weight part mica powders and 40 weight part lime carbonate.
Get the composite flame-retardant agent of 100 weight part polyvinyl chloride resins, the preparation of 5 weight part present embodiments; 50 weight part DOPs (DOP), 4.5 weight part organotin stabilizers, 0.5 parts by weight of ethylene ethyl triethoxy silicane alkane (coupling agent); 0.5 the weight part calcium stearate mixes; At 175 ℃ of following mixing 12min, move into dull and stereotyped pressing machine with mixing roll, hot pressing 10min under 180 ℃, 260MPa pressure.The flexible PVC limiting oxygen index(LOI) (LOI) that gained contains nitrogenated silicon hydridization type fire retardant is 26.1.
Embodiment 3
The preparation of methylolation trimeric cyanamide silicide:
(1) be that 20% formaldehyde solution is mixed with 100 weight part trimeric cyanamides and 400 weight part massfractions; 0.5 weight part sodium hydroxide is regulated pH=7.5, under 80 ℃, and hydroxymethylation 40 minutes; Rotary evaporation is removed remaining formaldehyde then, obtains the methylolation trimeric cyanamide;
(2) in the reaction system of step (1), add 25 weight part Union carbide A-162s, 25 weight part dimethyl-diethoxy silicon; 0.25 weight part aluminum chloride; 100 weight parts waters adjust the temperature to 85 ℃, react after 2 hours; Filtering-depositing, will precipitate the oven dry after obtain Powdered methylolation trimeric cyanamide silicide.
Contain the preparation of the composite flame-retardant agent of methylolation trimeric cyanamide silicide: the methylolation trimeric cyanamide silicide of getting the preparation of 100 weight part present embodiments; 30 weight part white lakes; 30 weight part zinc borates and 30 weight part mica powders; 10 weight part calcined kaolins are compound, make the composite flame-retardant agent that contains methylolation trimeric cyanamide silicide.
After the composite flame-retardant agent of 100 weight part Vestolen PP 7052 and 50 weight part present embodiments preparation mixed; (forcing machine I district--IV district temperature is respectively 160 ℃, 170 ℃, 190 ℃, 200 ℃ to join twin screw extruder; Screw speed is 50r/min) extrude, granulation, the oven dry; Then in the I district--process the batten of standard-required under 160 ℃, 170 ℃, 190 ℃, 200 ℃ conditions of IV district temperature with plastic-injection moulding machine.The limiting oxygen index(LOI) (LOI) of gained polypropylene fire retardant matrix material is 23.
Embodiment 4
The preparation of methylolation trimeric cyanamide silicide:
(1) be that 30% formaldehyde solution is mixed with 100 weight part trimeric cyanamides and 350 weight part massfractions; After 8 weight part triethylamines are regulated pH=9, under 72 ℃, hydroxymethylation 40 minutes; Rotary evaporation is removed remaining formaldehyde then, obtains the methylolation trimeric cyanamide;
(2) in the reaction system of step (1), add 25 weight part Union carbide A-162s, 25 weight part dimethyl-diethoxy silicon; 100 weight part methyl silicates; 100 weight parts waters, 2 weight part dibutyl tin dilaurates adjust the temperature to 70 ℃, react after 0.5 hour; Filtering-depositing, will precipitate the oven dry after obtain Powdered methylolation trimeric cyanamide silicide.
Contain the preparation of the composite flame-retardant agent of methylolation trimeric cyanamide silicide: methylolation trimeric cyanamide silicide, 10 weight part zinc borates and the 10 weight part Antimony Trioxide: 99.5Mins of getting the preparation of 100 weight part present embodiments are compound, make the composite flame-retardant agent that contains methylolation trimeric cyanamide silicide.
With 80 weight part polycarbonates (PC); 20 parts by weight of acrylonitrile/Butadiene (ABS); Composite flame-retardant agent 210 ℃ of following blend 6min in Haake torque rheometer of 10 weight part present embodiments preparations are pressed into mixture the sample strip of standard-required then in vulcanizing press.The limiting oxygen index(LOI) of gained PC/ABS fire retardant material is 26.4.
Embodiment 5
The preparation of methylolation trimeric cyanamide silicide:
(1) be that 25% formaldehyde solution is mixed with 100 weight part trimeric cyanamides and 180 weight part massfractions; After 3 weight part triethylamines are regulated pH=8, under 75 ℃, hydroxymethylation 30 minutes; Rotary evaporation is removed remaining formaldehyde then, obtains the methylolation trimeric cyanamide;
(2) in the reaction system of step (1), add 220 weight part methyl silicates, 80 weight part Union carbide A-162s, 50 weight part dimethyldiethoxysilanes; 50 weight part diethylammonium, two TMOSs, 600 weight parts waters, 3 weight part aluminum chlorides; Adjust the temperature to 80 ℃; React after 3 hours, filtering-depositing, will precipitate the oven dry after obtain Powdered methylolation trimeric cyanamide silicide.
Contain the preparation of the composite flame-retardant agent of methylolation trimeric cyanamide silicide: methylolation trimeric cyanamide silicide, 20 weight part white lakes, 10 weight part zinc borates and 24 weight parts, 600 order silicon powders, 16 weight part lime carbonate, 30 weight part mica powders, the 30 weight part talcum powder of getting the preparation of 100 weight part present embodiments are compound, make the composite flame-retardant agent that contains methylolation trimeric cyanamide silicide.
With 70 weight part polycarbonates (PC); 30 parts by weight of acrylonitrile/Butadiene (ABS); Composite flame-retardant agent 210 ℃ of following blend 6min in Haake torque rheometer of 20 weight part present embodiments preparations are pressed into mixture the sample strip of standard-required then in vulcanizing press.The limiting oxygen index(LOI) of gained PC/ABS fire retardant material is 27.8.
Embodiment 6
The preparation of methylolation trimeric cyanamide silicide:
(1) be that 37% formaldehyde solution is mixed with 100 weight part trimeric cyanamides and 200 weight part massfractions; After 5 weight part sodium hydroxide are regulated pH=8, under 70 ℃, hydroxymethylation 45 minutes; Rotary evaporation is removed remaining formaldehyde then, obtains the methylolation trimeric cyanamide;
(2) in the reaction system of step (1), add 10 weight part trimethylethoxysilanes, 20 weight part methyldiethoxysilane, 70 weight part methyl silicates; 100 weight parts waters, 1 weight part dibutyl tin dilaurate adjusts the temperature to 75 ℃; Regulating pH is 8; React after 2 hours, filtering-depositing, will precipitate the oven dry after obtain Powdered methylolation trimeric cyanamide silicide.
Contain the preparation of the composite flame-retardant agent of methylolation trimeric cyanamide silicide: methylolation trimeric cyanamide silicide and the 10 weight part zinc borates of getting the preparation of 100 weight part present embodiments; The inorganic combustion inhibitor that 15 weight part Antimony Trioxide: 99.5Mins and 30 weight parts, 300 order silicon powders are formed is compound, makes the composite flame-retardant agent that contains methylolation trimeric cyanamide silicide structural.
Get the phenolic aldehyde epoxy that 100 weight part oxirane values are 0.48mol/g; The composite flame-retardant agent of 30 weight part present embodiments preparation, 63 weight part linear phenolic resins, 2 weight part triphenyl phosphorus; Stir the back in vacuum drying oven 60 ℃ be evacuated to and do not produce bubble; Inject mould then, keeping under the vacuum state, be cured according to 90 ℃/1h+150 ℃/2h+200 ℃/3h curing process.Gained epoxy resin limiting oxygen index(LOI) (LOI) is 28.3.
Embodiment 7
The preparation of methylolation trimeric cyanamide silicide:
(1) be that 37% formaldehyde solution is mixed with 100 weight part trimeric cyanamides and 400 weight part massfractions, 7 weight part triethylamines are behind the adjusting pH=9; Under 60 ℃; Hydroxymethylation 90 minutes, rotary evaporation is removed remaining formaldehyde then, obtains the methylolation trimeric cyanamide;
(2) in the reaction system of step (1), add 50 weight part ethyl triethoxysilanes, 150 weight part tetraethoxys, 40 weight part phenyltrimethoxysila,e; 2 weight part dibutyl tin dilaurates; 1000 weight parts waters adjust the temperature to 100 ℃, react after 2 hours; Filtering-depositing, will precipitate the oven dry after obtain Powdered methylolation trimeric cyanamide silicide.
Contain the preparation of the composite flame-retardant agent of methylolation trimeric cyanamide silicide: methylolation trimeric cyanamide silicide and the 20 weight part Marinco Hs of getting the preparation of 100 weight part present embodiments; 20 weight part zinc borates and 30 weight part Antimony Trioxide: 99.5Mins are compound, make the composite flame-retardant agent that contains methylolation trimeric cyanamide silicide.
Get composite flame-retardant agent 15 weight parts, MDA 25.4 weight parts of the bisphenol A epoxide resin that oxirane value is 0.51mol/g (E51) 100 weight parts, present embodiment preparation; Stir the back in vacuum drying oven 90 ℃ vacuumize 30min; Inject mould then; Under vacuum state, be cured according to 90 ℃/3h+150 ℃/2h+180 ℃/2h curing process.Gained epoxy resin composite curing thing limiting oxygen index(LOI) (LOI) is 29.1.
The performance test example
Table 1 flexible PVC adds the flame retardant properties (each composition is all in weight part) behind the composite flame-retardant agent of the present invention
The preparation method of composite flame-retardant agent 1# is following in the table 1:
(1) be that 37% formaldehyde solution is mixed with 100 weight part trimeric cyanamides and 150 weight part massfractions; 2 weight part triethylamines are regulated pH=8, under 80 ℃, and hydroxymethylation 30 minutes; Rotary evaporation is removed remaining formaldehyde then, obtains the methylolation trimeric cyanamide;
(2) in the reaction system of step (1), add 150 weight part tetraethoxys, 60 weight part Union carbide A-162s, 40 weight part dimethyldiethoxysilanes; 500 weight parts waters, 5 weight part aluminum chlorides are regulated pH=8; Adjust the temperature to 90 ℃; React after 5 hours, filtering-depositing, will precipitate the oven dry after obtain Powdered methylolation trimeric cyanamide silicide.
(3) get the Powdered methylolation trimeric cyanamide of 100 weight parts silicide, 5 weight parts, 300 order silicon powders, 15 weight part Antimony Trioxide: 99.5Mins, the compound composite flame-retardant agent 1# that contains methylolation trimeric cyanamide silicide that makes of 20 weight part Marinco Hs.
The preparation technology of flexible PVC who has added composite flame-retardant agent in the table 1 is following: with fire retardant 1#; Polyvinyl chloride resin, DOP (DOP), organotin stabilizer, vinyltriethoxysilane (coupling agent); Calcium stearate carries out compound according to the consumption of table 1; At 180 ℃ of following mixing 10min, move into dull and stereotyped pressing machine with mixing roll, hot pressing 10min takes out to cold pressing again and processes sample or standard test specimen under 190 ℃, 250MPa pressure.
The limiting oxygen index(LOI) of flexible PVC of composite flame-retardant agent that contains methylolation trimeric cyanamide silicide in the table 1 adopts the LOI determinator of U.S. DYNISCO company to measure according to ASTM D2863 standard step operation.
Visible by table 1; With respect to the soft pvc that does not add fire retardant, the limiting oxygen index(LOI) that has added the soft pvc of fire retardant of the present invention raises, and flame retardant properties is better; And, proved absolutely the marked improvement of the present invention's technology along with its limiting oxygen index(LOI) of increase of flame retardant agent content significantly raises.
Table 2 epoxy resin composite curing thing adds the flame retardant properties (each composition is all in weight part) behind the composite flame-retardant agent of the present invention
The preparation method of composite flame-retardant agent 2# is following in the table 2:
(1) be that 37% formaldehyde solution is mixed with 100 weight part trimeric cyanamides and 200 weight part massfractions, 2 weight part triethylamines are regulated pH=9; Under 78 ℃; Hydroxymethylation 40 minutes, rotary evaporation is removed remaining formaldehyde then, obtains the methylolation trimeric cyanamide;
(2) in the reaction system of step (1), add 50 weight part ethyl triethoxysilanes; 100 weight part tetraethoxys, 400 weight parts waters, 1 weight part dibutyl tin dilaurate; Adjust the temperature to 85 ℃; React after 2 hours, filtering-depositing, will precipitate the oven dry after obtain Powdered methylolation trimeric cyanamide silicide.
(3) it is compound to get 100 weight part methylolation trimeric cyanamide silicides, 10 weight part talcum powder, 10 weight part zinc borates and 25 weight part Antimony Trioxide: 99.5Mins, makes the composite flame-retardant agent 2# that contains methylolation trimeric cyanamide silicide.
The curing process of epoxy resin composite curing thing that has added composite flame-retardant agent in the table 2 is following: with oxirane value is the bisphenol A type epoxy resin of 0.51mol/g; Diaminodiphenyl-methane (solidifying agent); Fire retardant 2# is according to the consumption mixing stirring in the table 2, stir the back in vacuum drying oven 80 ℃ be evacuated to and do not produce bubble, inject mould then; Keeping under the vacuum state, adopting 90 ℃/1h+150 ℃/3h+180 ℃/3h curing process to be cured.
The limiting oxygen index(LOI) of epoxy resin composite curing thing of composite flame-retardant agent that contains methylolation trimeric cyanamide silicide in the table 2 adopts the LOI determinator of U.S. DYNISCO company to measure according to ASTM D2863 standard step operation.
Visible by table 2; With respect to the epoxy resin composite curing thing that does not add fire retardant; The limiting oxygen index(LOI) that has added the epoxy resin composite curing thing of fire retardant of the present invention raises; Flame retardant properties is better, and along with its limiting oxygen index(LOI) of increase of flame retardant agent content significantly raises, has proved absolutely the marked improvement of the present invention's technology.
Table 3 epoxy resin composite curing thing PC/ABS adds the flame retardant properties (each composition is all in weight part) behind the composite flame-retardant agent of the present invention
The preparation method of composite flame-retardant agent 3# is following in the table 3:
(1) be that 37% formaldehyde solution is mixed with 100 weight part trimeric cyanamides and 240 weight part massfractions, 3.5 weight part triethylamines are regulated pH=9; Under 82 ℃; Hydroxymethylation 40 minutes, rotary evaporation is removed remaining formaldehyde then, obtains the methylolation trimeric cyanamide;
(2) in the reaction system of step (1), add 100 weight part methyl silicates, 50 weight part Union carbide A-162s, 50 weight part dimethyldiethoxysilanes; 50 weight part phenyl triethoxysilanes, 700 weight parts waters, 10 weight part aluminum chlorides; Adjust the temperature to 80 ℃; React after 2.5 hours, filtering-depositing, will precipitate the oven dry after obtain Powdered methylolation trimeric cyanamide silicide.
(3) get 100 weight part methylolation trimeric cyanamide silicides, 25 weight part white lakes, 10 weight part zinc borates and 30 weight part lime carbonate, 30 weight part talcum powder are compound, make the composite flame-retardant agent 3# that contains methylolation trimeric cyanamide silicide.
The preparation technology of PC/ABS composite flame-proof material who has added composite flame-retardant agent in the table 3 is following: with polycarbonate (PC); Acrylonitrile/butadiene/styrene (ABS); Fire retardant 3# is according to the consumption mixing stirring in the table 3; 210 ℃ of following blend 6min in Haake torque rheometer are pressed into mixture the sample strip of standard-required then in vulcanizing press.
The limiting oxygen index(LOI) of PC/ABS composite flame-proof material of composite flame-retardant agent that contains methylolation trimeric cyanamide silicide in the table 3 adopts the LOI determinator of U.S. DYNISCO company to measure according to ASTM D2863 standard step operation.
Visible by table 3; With respect to the PC/ABS composite flame-proof material that does not add fire retardant; The limiting oxygen index(LOI) that has added the PC/ABS composite flame-proof material of fire retardant of the present invention raises; Flame retardant properties is better, and along with its limiting oxygen index(LOI) of increase of flame retardant agent content significantly raises, has proved absolutely the marked improvement of the present invention's technology.
Table 4 PP composite material adds the flame retardant properties (each composition is all in weight part) behind the composite flame-retardant agent of the present invention
The preparation method of composite flame-retardant agent 4# is following in the table 4:
(1) be that 20% formaldehyde solution is mixed with 100 weight part trimeric cyanamides and 300 weight part massfractions; Behind 2 weight part sodium hydroxide adjusting pH=9, under 80 ℃, hydroxymethylation 40 minutes; Rotary evaporation is removed remaining formaldehyde then, obtains the methylolation trimeric cyanamide;
(2) in the reaction system of step (1), add 60 weight part Union carbide A-162s, 80 weight part dimethyl-diethoxy silicon; 60 weight part tetraethoxys, 100 weight parts waters, 3 weight part aluminum chlorides; Adjust the temperature to 100 ℃; React after 3 hours, filtering-depositing, will precipitate the oven dry after obtain Powdered methylolation trimeric cyanamide silicide.
(3) get 100 weight part methylolation trimeric cyanamide silicides, 10 weight part Marinco Hs, 10 weight part Antimony Trioxide: 99.5Mins and 30 weight part mica powders, 20 weight part talcum powder are compound, make the composite flame-retardant agent 4# that contains methylolation trimeric cyanamide silicide.
The preparation technology of PP composite material who has added composite flame-retardant agent in the table 4 is following: after Vestolen PP 7052, fire retardant 4# are mixed according to the consumption in the table 4; (forcing machine I district--IV district temperature is respectively 170 ℃, 180 ℃, 200 ℃, 210 ℃ to join twin screw extruder; Screw speed is 50r/min) extrude, granulation, the oven dry; Then in the I district--process the batten of standard-required under 170 ℃, 180 ℃, 200 ℃, 210 ℃ conditions of IV district temperature with plastic-injection moulding machine.
The limiting oxygen index(LOI) of Vestolen PP 7052 composite flame-proof material of composite flame-retardant agent that contains methylolation trimeric cyanamide silicide in the table 4 adopts the LOI determinator of U.S. DYNISCO company to measure by ASTM D2863 standard step operation.
Visible by table 4; With respect to the Vestolen PP 7052 composite flame-proof material that does not add fire retardant; The limiting oxygen index(LOI) that has added the Vestolen PP 7052 composite flame-proof material of fire retardant of the present invention raises; Flame retardant properties is better, and along with its limiting oxygen index(LOI) of increase of flame retardant agent content significantly raises, has proved absolutely the marked improvement of the present invention's technology.
Table 5 novolac epoxy composite curing thing adds the flame retardant properties (each composition is all in weight part) behind the composite flame-retardant agent of the present invention
The preparation method of composite flame-retardant agent 5# is following in the table 5:
(1) be that 20% formaldehyde solution is mixed with 100 weight part trimeric cyanamides and 350 weight part massfractions, 0.5 weight part sodium hydroxide is regulated pH=9; Under 78 ℃; Hydroxymethylation 50 minutes, rotary evaporation is removed remaining formaldehyde then, obtains the methylolation trimeric cyanamide;
(2) in the reaction system of step (1), add 50 weight part diethylammonium diethoxy silanes, 50 weight part methyldiethoxysilane, 100 weight part methyl silicates; 100 weight parts waters; 2 weight part dibutyl tin dilaurates adjust the temperature to 80 ℃, react after 2 hours; Filtering-depositing, will precipitate the oven dry after obtain Powdered methylolation trimeric cyanamide silicide.
(3) get 100 weight part methylolation trimeric cyanamide silicides, 10 weight part Antimony Trioxide: 99.5Mins and 5 weight part polynites, 5 weight parts, 325 order silicon powders are compound, make the composite flame-retardant agent 5# that contains methylolation trimeric cyanamide silicide.
The preparation technology of novolac epoxy cured article who has added composite flame-retardant agent in the table 5 is following: the novolac epoxy of 0.48mol/g; Solidifying agent is after triphenyl phosphorus, fire retardant 5# stir according to the consumption in the table 5; 80 ℃ are evacuated to and do not produce bubble in vacuum drying oven; Inject mould then, keeping under the vacuum state, be cured according to 90 ℃/1h+150 ℃/2h+200 ℃/3h curing process.
The limiting oxygen index(LOI) of epoxy resin composite curing thing of composite flame-retardant agent that contains methylolation trimeric cyanamide silicide in the table 5 adopts the LOI determinator of U.S. DYNISCO company to measure by ASTM D2863 standard step operation.
Visible by table 5; With respect to the novolac epoxy composite curing thing that does not add fire retardant; The limiting oxygen index(LOI) that has added the novolac epoxy composite curing thing of fire retardant of the present invention raises; Flame retardant properties is better, and along with its limiting oxygen index(LOI) of increase of flame retardant agent content significantly raises, has proved absolutely the marked improvement of the present invention's technology.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. a composite flame-retardant agent that contains methylolation trimeric cyanamide silicide is to be composited by the methylolation trimeric cyanamide silicide of 100 weight parts, the inorganic combustion inhibitor of 5～100 weight parts and the mineral filler of 0～100 weight part;
Said methylolation trimeric cyanamide silicide adopts following method to prepare:
(1) be that 20%～37% formaldehyde solution is mixed with 100 weight part trimeric cyanamides and 100～400 weight part massfractions; Regulate pH value to 7～9 with 0.5～8 weight part catalyst I; 60～90 ℃ were reacted 20～90 minutes down; Remove remaining formaldehyde then, obtain suc as formula the trimeric cyanamide of methylolation shown in the I;
(2) in the reaction system of step (1), add 50～500 weight parts suc as formula organoalkoxysilane shown in the II, 100～1000 weight parts waters, 1～15 weight part catalyst I I; 70～100 ℃ are reacted after 0.5～5 hour down; Filtering-depositing, will precipitate the oven dry after obtain Powdered methylolation trimeric cyanamide silicide;
Among the formula I, R
1, R
2, R
3, R
4, R
5, R
6For hydrogen or-CH
2OH, and R
1, R
2, R
3, R
4, R
5, R
6Can not be hydrogen simultaneously;
Among the formula II, M
1Be methyl, ethyl, n-propyl, sec.-propyl or butyl; M
2, M
3, M
4For C1～5 straight chains or contain alkyl, benzyl, phenyl, the C1～4 alkoxyl groups of side chain;
Said catalyst I is triethylamine or sodium hydroxide;
Said catalyst I I is dibutyl tin dilaurate or aluminum chloride.
2. the composite flame-retardant agent that contains methylolation trimeric cyanamide silicide according to claim 1 is characterized in that: said organoalkoxysilane is one or more mixtures in benzyl triethoxyl silane, methyldiethoxysilane, methyl silicate, dimethyldiethoxysilane, ethyl triethoxysilane, phenyltrimethoxysila,e, Union carbide A-162 and the tetraethoxy.
3. the composite flame-retardant agent that contains methylolation trimeric cyanamide silicide according to claim 1 is characterized in that: said inorganic combustion inhibitor is one or more mixtures in white lake, Antimony Trioxide: 99.5Min, zinc borate and the Marinco H.
4. the composite flame-retardant agent that contains methylolation trimeric cyanamide silicide according to claim 1 is characterized in that: said mineral filler is one or more mixtures in lime carbonate, calcined kaolin, silicon powder, mica powder and the talcum powder.
5. the described preparation method who contains the composite flame-retardant agent of methylolation trimeric cyanamide silicide of claim 1 is characterized in that: be to be composited by the methylolation trimeric cyanamide silicide of 100 weight parts, the inorganic combustion inhibitor of 5～100 weight parts and the mineral filler of 0～100 weight part.
6. the described application that contains the composite flame-retardant agent of methylolation trimeric cyanamide silicide of claim 1, it is characterized in that: said composite flame-retardant agent and vinylchlorid, epoxy resin, Vestolen PP 7052, polyester are used.
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| CN2010102862940A CN101962448B (en) | 2010-09-16 | 2010-09-16 | Compound fire retardant containing hydroxymethylated melamine silicide, preparation method and application thereof |
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