CN102516785A - Core-shell urea formaldehyde modified lignin intumescent flame-retardant charring agent and preparation method thereof - Google Patents
Core-shell urea formaldehyde modified lignin intumescent flame-retardant charring agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a core-shell urea formaldehyde modified lignin intumescent flame-retardant charring agent. The charring agent is a powdery solid formed by using lignin as a core and wrapping urea formaldehyde resin obtained by polymerizing urea and formaldehyde and serving as a shell layer on the surface of the lignin. The invention also relates to a preparation method for the charring agent. The method comprises the following steps of: polymerizing the urea and the formaldehyde to form an aqueous solution of a urea formaldehyde resin prepolymer under an alkali condition, adding the lignin in an amount which is 2 to 9 times total weight of the urea and the formaldehyde and a surfactant in an amount which is 0.5 to 10 percent of the weight of the lignin into the aqueous solution, and thus obtaining the charring agent product at the temperature of between 65 and 85 DEG C under an acidic condition. The preparation method is simple and easy to implement; the obtained charring agent has good water resistance; and when an intumescent flame retardant formed by compounding the charring agent and an acid source is applied to a polylactic acid matrix, the flame-retardant stability and the flame-retardant efficiency can be improved; and because the flame retardant has good compatibility with the polymer matrix, the influence of the flame retardant on the physical properties of a material can be reduced.
Description
Technical field
The invention belongs to the fire retardant preparing technical field, be specifically related to a kind of core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent and preparation method thereof, this char-forming agent can with the new expansion type flame retardant of the composite formation of acid source
Background technology
along with the progress of science and technology and the raising of living standards of the people, the application of macromolecular material has more and more widely also driven simultaneously the fast development of fire retardant material, and fire retardant has become the second largest auxiliary agent in the present additives for plastics.But existing halogen containing flame-retardant is because burning the time can produce a large amount of toxic smogs; It is used and is just receiving increasing restriction; Inorganic combustion inhibitor such as metal hydroxides then flame retarding efficiency are low, and be bigger to the influences such as mechanical property of material, also makes it be difficult to meet the demands in a lot of fields.
expansion type flame retardant (IFR) is a kind of halogen-free flame retardants that receives extensive concern in recent years, and it is made up of charcoal source, acid source and source of the gas three parts.Because the surface can form the expansion charcoal layer of outer fine and close, loose and porous inner surface during the fire-retardant polymer combustion of IFR, this expansion charcoal layer is heat insulation because of having, the effect of oxygen barrier, thereby can give polymkeric substance high flame retardant, advantages such as anti-drippage property.Char-forming agent that uses in traditional expansion type flame-retarding system such as tetramethylolmethane (PER), N.F,USP MANNITOL (mannitol) and sorbyl alcohol (or being referred to as first-generation char-forming agent) such as (sorbitol); Its drawback is that these char-forming agents all derive from expensive oil; Therefore it is high not meet environmental requirement and cost, need find surrogate.Xylogen is exactly that a kind of common alternative tetramethylolmethane serves as the natural polymer in charcoal source.But, because this type of xylogen char-forming agent generally all is rich in hydroxyl, thus still exist when being applied to plastic substrate in the time poor with the consistency of plastics, be prone to ooze out, shortcomings such as the easy moisture absorption, poor water resistance
Summary of the invention
technical problem to be solved by this invention is the deficiency that overcomes prior art, and a kind of core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent is provided.
the present invention also will provide a kind of preparation method of above-mentioned core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent.
For solving above technical problem, the present invention takes following technical scheme:
a kind of core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent, the urea-formaldehyde resin that it is is nuclear with the xylogen, obtain with urea and oxymethylene polymerization is that shell is coated on the pulverulent solids that the xylogen surface forms.
preferably, the weight ratio of xylogen and urea-formaldehyde resin is 1.5 ~ 9:1 (can pass through the x-ray photoelectron power spectrum, i.e. XPS measure) in the said core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent.
A kind of preparation method of core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent comprises the steps:
(1), with urea and formaldehyde in molar ratio 1:1 be dissolved in the water that weight is 4 ~ 20 times of urea and formaldehyde gross weights; Between regulator solution pH value to 8 ~ 12; Be warming up to 65 ℃-85 ℃ under the agitation condition, continue reaction 15 ~ 45 minutes, obtain the transparent urea aldehyde performed polymer aqueous solution;
(2), to add weight in the urea aldehyde performed polymer aqueous solution of step (1) gained be that the xylogen and the weight of 2 ~ 9 times of urea and formaldehyde gross weights is the tensio-active agent of xylogen weight 0.5% ~ 10%; And regulation system pH value to 1 ~ 5; Be warming up to 65 ℃-85 ℃ under the agitation condition, continue reaction 2 ~ 5 hours, then cooling, suction filtration; Suction filtration gained solid product through washing, drying, promptly gets said core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent again.
preferably, the weight ratio of water and xylogen is between 4 ~ 5:1 among the above-mentioned preparation method.
Preferably in the step (1), stir between pH value to 9 ~ 11 of heat up preceding adjusting urea and formalin
; In the step (2), add behind xylogen and the tensio-active agent between regulation system pH value to 2 ~ 4.
preferably, the add-on of xylogen is urea and formaldehyde gross weight 3 ~ 8 times in the step (2).If the consumption of urea and formaldehyde is low excessively, xylogen can not exclusively cause the part particle exposed because of coating, and not only can influence flame retardant effect, and the moisture absorption can take place easily; And urea and formaldehyde is if consumption is too much, then can make the xylogen surface coating layer blocked up and make cost improve.
preferably, the add-on of said tensio-active agent is 1% ~ 5% of an xylogen weight.Amount of surfactant can not be too low, and xylogen is dispersed to descend otherwise can make, and forms and reunites, and influences final covered effect.
preferably, said tensio-active agent is the aliphatics ionic compound of aliphatics polyoxy ethylene compounds or 4-20 carbon atom.
further, said aliphatics polyoxy ethylene compounds comprises TX10 (like OP-10), aliphatic acid polyethenoxy ether (like peregal), carboxylic acid polyoxyethylene ester or T 46155-polyoxypropylene multipolymer; Said aliphatics ionic compound comprises DTAC, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, OTAC, trioctylphosphine trimethyl ammonium chloride, three nonyl ammonio methacrylates, two ten alkyl-dimethyl ammonium chlorides, two dodecyl dimethyl ammonium chloride, two tetradecyl alkyl dimethyl ammonium chloride, Varisoft 432PPG, distearyl dimethyl ammonium chloride or Sodium palmityl sulfate.
the prepared core-shell type namely urea-formaldehyde modified lignin of the inventive method expandable flame retardant char-forming agent is compared with the xylogen that did not coat; Median size does not obviously increase; But particle surface is fine and close, evenly, do not find the phenomenon that single xylogen particle is exposed, and the water-soluble greatly reduction of the xylogen particle after coating; Water tolerance is significantly improved, and does not have moisture absorption phenomenon.
above-mentioned preparation and core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent can be applied in the expansion type flame-retarding system as the charcoal source.A kind of concrete application is that above-mentioned core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent and acid source are applied in the POLYACTIC ACID matrix by mass ratio 1:1 ~ 5 formation expansion type flame retardants; Wherein acid source is phosphoric acid salt, SULPHOSUCCINIC ACID ESTER or 9, the 10-dihydro-9-oxy is assorted-and in 10-phospho hetero phenanthrene-10-oxide compound (commercial name DOPO) and the verivate thereof any.
Because the enforcement of above technical scheme, the present invention compared with prior art has following advantage:
The chemical property that
the present invention can be used as source of the gas according to the cooperative flame retardant principle and the urea-formaldehyde resin itself of expanding fire retardant; Adopt the method for in-situ polymerization, in the process of urea and the synthetic urea-formaldehyde resin of formaldehyde, add xylogen, be coated on the xylogen particle surface as cyst material (being shell) with urea-formaldehyde resin; Preparation technology is simple; Implement easily, can in a big way, regulate the mass ratio between shell and stratum nucleare, obtain water tolerance and the good char-forming agent of flame retardant resistance.Xylogen expandable flame retardant char-forming agent of the present invention can constitute expansion type flame retardant jointly with acid source; Improve the stability and the flame retarding efficiency of expansion type flame retardant; And the consistency of xylogen char-forming agent of the present invention and polymkeric substance is good, can reduce the influence to the polymeric matrix physicals.
Embodiment
are done further detailed explanation below in conjunction with concrete embodiment to the present invention, but are not limited to these embodiment.
Embodiment 1
add 20g urea and 10g formaldehyde in the reaction kettle that stirring and reflux are housed, be dissolved in 300 ml waters, and using sodium hydroxide solution to regulate the pH value is 9 ~ 11.Be warming up to 80 ℃, insulation reaction is 30 minutes under stirring, and obtains the transparent urea aldehyde performed polymer aqueous solution.In this urea aldehyde performed polymer aqueous solution, add 100 gram xylogen and 2.5 gram OP-10 again, use hydrochloric acid soln to regulate the pH value and be 2-4; Slowly be heated to 80 ℃, and under this temperature, continued insulation reaction 4 hours.Stir cooling, suction filtration then, suction filtration gained solid product promptly obtains core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent 125 grams again through washing, drying.
The solubleness of products therefrom in the time of 50 ℃ is 0.023g/100mlH
2
O.
Embodiment 2
add 30g urea and 15g formaldehyde in the reaction kettle that stirring and reflux are housed, be dissolved in 200 ml waters, and using sodium hydroxide solution to regulate the pH value is 9 ~ 11.Be warming up to 80 ℃, insulation reaction is 30 minutes under stirring, and obtains the transparent urea aldehyde performed polymer aqueous solution.In this urea aldehyde performed polymer aqueous solution, add 100 gram xylogen and 2.5 gram OP-10 again, using hydrochloric acid soln to regulate the pH value is 2 ~ 4; Slowly be heated to 80 ℃, and under this temperature, continued insulation reaction 3 hours.Stir cooling, suction filtration then, suction filtration gained solid product promptly obtains core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent 140 grams again through washing, drying.
The solubleness of products therefrom in the time of 50 ℃ is 0.012g/100mlH
2
O.
Embodiment 3
add 20g urea and 10g formaldehyde in the reaction kettle that stirring and reflux are housed, be dissolved in 500 ml waters, and using sodium hydroxide solution to regulate the pH value is 9 ~ 11.Be warming up to 80 ℃, insulation reaction is 30 minutes under stirring, and obtains the transparent urea aldehyde performed polymer aqueous solution.In this urea aldehyde performed polymer aqueous solution, add 100 gram xylogen and 2.5 gram OP-10 again, use hydrochloric acid soln to regulate the pH value and be 2-4; Slowly be heated to 85 ℃, and under this temperature, continued insulation reaction 4 hours.Stir cooling, suction filtration then, suction filtration gained solid product promptly obtains core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent 123 grams again through washing, drying.
The solubleness of products therefrom in the time of 50 ℃ is 0.025g/100mlH
2
O.
if the mass ratio of water in the foregoing description and xylogen is remained between 3 ~ 6:1, all can obtain 123g left and right sides core-shell type namely urea-formaldehyde modified lignin of the present invention expandable flame retardant char-forming agent under the constant situation of other conditions.
Embodiment 4
add 20g urea and 10g formaldehyde in the reaction kettle that stirring and reflux are housed, be dissolved in 400 ml waters, and using sodium hydroxide solution to regulate the pH value is 9 ~ 11.Be warming up to 70 ℃, insulation reaction is 30 minutes under stirring, and obtains the transparent urea aldehyde performed polymer aqueous solution.In this urea aldehyde performed polymer aqueous solution, add 100 gram xylogen and 3.5 gram OP-10 again, use hydrochloric acid soln to regulate the pH value and be 3-4; Slowly be heated to 85 ℃, and under this temperature, continued insulation reaction 3 hours.Stir cooling, suction filtration then, suction filtration gained solid product promptly obtains core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent 126 grams again through washing, drying.
The solubleness of products therefrom in the time of 50 ℃ is 0.027g/100mlH
2
O.
are under the constant situation of other conditions; Adopt sulphuric acid soln, phosphoric acid solution, perchloric acid solution, solution chlorate, hydrogen bromide solution, oxalic acid solution, acetum to replace if will appeal the hydrochloric acid soln that is used to regulate pH among the embodiment; Regulating the pH value is 2 ~ 5; Or preferably regulate the pH value to preferable 2 ~ 4, and can obtain core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent of the present invention, its performance and pattern almost do not change.
Embodiment 5
add 20g urea and 10g formaldehyde in the reaction kettle that stirring and reflux are housed, be dissolved in 400 ml waters, and using sodium hydroxide solution to regulate the pH value is 11 ~ 12.Be warming up to 80 ℃, insulation reaction is 45 minutes under stirring, and obtains the transparent urea aldehyde performed polymer aqueous solution.In this urea aldehyde performed polymer aqueous solution, add 150 gram xylogen and 4 gram OP-10 again, use hydrochloric acid soln to regulate the pH value and be 3-4; Slowly be heated to 80 ℃, and under this temperature, continued insulation reaction 5 hours.Stir cooling, suction filtration then, suction filtration gained solid product promptly obtains core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent 175 grams again through washing, drying.
The solubleness of products therefrom in the time of 50 ℃ is 0.043g/100mlH
2
O.
are under the constant situation of other conditions; Adopt ammoniacal liquor, potassium hydroxide solution, sodium carbonate solution, sodium sulfide solution, aqua calcis, sodium radio-phosphate,P-32 solution to replace if will appeal the sodium hydroxide solution that is used to regulate pH among the embodiment; The conditioned reaction system pH is in 8 ~ 12 scope; Or preferably regulate the pH value to 9 ~ 11 preferable scopes; Can obtain core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent of the present invention, its performance and pattern almost do not change.
Embodiment 6
add 20g urea and 10g formaldehyde in the reaction kettle that stirring and reflux are housed, be dissolved in 300 ml waters, and using sodium hydroxide solution to regulate the pH value is 10 ~ 11.Be warming up to 70 ℃, insulation reaction is 45 minutes under stirring, and obtains the transparent urea aldehyde performed polymer aqueous solution.In this urea aldehyde performed polymer aqueous solution, add 100 gram xylogen and 1.5 gram OP-10 again, use hydrochloric acid soln to regulate the pH value and be 2-4; Slowly be heated to 70 ℃, and under this temperature, continued insulation reaction 5 hours.Stir cooling, suction filtration then, suction filtration gained solid product promptly obtains core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent 122 grams again through washing, drying.
The solubleness of products therefrom in the time of 50 ℃ is 0.033g/100mlH
2
O.
Embodiment 7
add 20g urea and 10g formaldehyde in the reaction kettle that stirring and reflux are housed, be dissolved in 300 ml waters, and using sodium hydroxide solution to regulate the pH value is 10 ~ 11.Be warming up to 80 ℃, insulation reaction is 30 minutes under stirring, and obtains the transparent urea aldehyde performed polymer aqueous solution.In this urea aldehyde performed polymer aqueous solution, add 120 gram xylogen and 5 gram OP-10 again, use hydrochloric acid soln to regulate the pH value and be 2-4; Slowly be heated to 80 ℃, and under this temperature, continued insulation reaction 3 hours.Stir cooling, suction filtration then, suction filtration gained solid product promptly obtains core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent 146 grams again through washing, drying.
The solubleness of products therefrom in the time of 50 ℃ is 0.029g/100mlH
2
O.
Embodiment 8
add 20g urea and 10g formaldehyde in the reaction kettle that stirring and reflux are housed, be dissolved in 400 ml waters, and using sodium hydroxide solution to regulate the pH value is 9 ~ 11.Be warming up to 80 ℃, insulation reaction is 30 minutes under stirring, and obtains the transparent urea aldehyde performed polymer aqueous solution.In this urea aldehyde performed polymer aqueous solution, add 150 gram xylogen and 4 gram OP-10 again, using hydrochloric acid soln to regulate the pH value is 2 ~ 4; Slowly be heated to 80 ℃, and under this temperature, continued insulation reaction 3 hours.Stir cooling, suction filtration then, suction filtration gained solid product promptly obtains core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent 175 grams again through washing, drying.
The solubleness of products therefrom in the time of 50 ℃ is 0.043g/100mlH
2
O.
are under the constant situation of other conditions; If the tensio-active agent OP-10 in the foregoing description is replaced with the nonionogenic tenside that comprises peregal, carboxylic acid polyoxyethylene ester or T 46155-polyoxypropylene multipolymer, lower molecular weight polypyrrole alkane ketone; Or replace with DTAC, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, OTAC, trioctylphosphine trimethyl ammonium chloride, three nonyl ammonio methacrylates, two ten alkyl-dimethyl ammonium chlorides, two dodecyl dimethyl ammonium chloride, two tetradecyl alkyl dimethyl ammonium chloride, Varisoft 432PPG, distearyl dimethyl ammonium chloride or Sodium palmityl sulfate at interior ionogenic surfactant, all can access core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent of the present invention.
The solubility test method of product is among
above-mentioned each embodiment: in 15 gram products suspensions and 100 ml deionized water; Stirred 5 hours down at 50 ℃; Disperse deposition 20 minutes with whizzer then, surperficial clear liquid is pipetted in 10 milliliters to one watch-glasss of having weighed, put into loft drier;, calculate in the solubleness of product in water to constant weight 100 ℃ of following evaporation dryings according to the amount of evaporation residue.
Embodiment 9 ~ 11
obtain multiple expansion type flame retardant system with embodiment 1 ~ 8 prepared core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent and ammonium polyphosphate (APP) by the proportioning of table 1 is composite; And it is the multiple expansion type flame retardant system of gained is even with POLYACTIC ACID (PLA) blend in high-speed mixer respectively; Then under 80 ℃ in vacuum drying oven dry 8-10h; Melt extrude through twin screw extruder, cooling and dicing makes the halogen-free flame-proof polylactic acid matrix material again.Gained halogen-free flame-proof polylactic acid matrix material and pure poly-lactic acid material are demarcated limiting oxygen index(LOI) (LOI) according to GB/T2406-93, and batten is of a size of 100mm * 6.5mm * 3.0m.Adopt the vertical combustion method (UL-94) of 94V-0,94V-1,94V-2, press ASTM-63S working sample flame retardant resistance, batten is of a size of 130mm * 13mm * 3.0mm, and the flame retardant test result sees table 1.Press the tensile property of GBIT 1040-92 standard testing batten, draw speed is 30mm/min, and the result sees table 2.
The preparation of the comparison sample 1 ~ 3 in
table 1 and the table 2 is identical with embodiment 9 ~ 11 with testing method, and difference is: the xylogen that adopts non-modified in the comparison sample 1 ~ 3 is as char-forming agent.
Table 1
Table 2
can be found out from table 1 and table 2; Adopt core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent to compare as the fire retardant in charcoal source with adopting unmodified xylogen char-forming agent, POLYACTIC ACID is had better flame retardant effect and mechanical property as the fire retardant in charcoal source.
More than the present invention has been done detailed description; Its purpose is to let the personage that is familiar with this art can understand content of the present invention and implements; Can not limit protection scope of the present invention with this; All equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention
Claims (10)
1. core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent is characterized in that: the urea-formaldehyde resin that said core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent is is nuclear with the xylogen, obtain with urea and oxymethylene polymerization is that shell is coated on the pulverulent solids that the xylogen surface forms.
2. core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent according to claim 1 is characterized in that: the weight ratio of xylogen and urea-formaldehyde resin is 1.5 ~ 9:1 in the said core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent.
3. the preparation method of a core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent is characterized in that: comprise the steps:
(1), with urea and formaldehyde in molar ratio 1:1 be dissolved in the water that weight is 4 ~ 20 times of urea and formaldehyde gross weights; Between regulator solution pH value to 8 ~ 12; Be warming up to 65 ℃-85 ℃ under the agitation condition, continue reaction 15 ~ 45 minutes, obtain the transparent urea aldehyde performed polymer aqueous solution;
(2), adding weight in the urea aldehyde performed polymer aqueous solution of step (1) gained is that the xylogen and the weight of 2 ~ 9 times of urea and formaldehyde gross weights is the tensio-active agent of xylogen weight 0.5% ~ 10%; And regulation system pH value to 1 ~ 5; Be warming up to 65 ℃-85 ℃ under the agitation condition, continue reaction 2 ~ 5 hours, then cooling, suction filtration; Suction filtration gained solid product through washing, drying, promptly gets said core-shell type namely urea-formaldehyde modified lignin expandable flame retardant char-forming agent again.
4. preparation method according to claim 3 is characterized in that: the weight ratio of water and xylogen is 4 ~ 5:1.
5. preparation method according to claim 3 is characterized in that: in the step (1), stir between pH value to 9 ~ 11 of heat up preceding adjusting urea and formalin; In the step (2), add behind xylogen and the tensio-active agent between regulation system pH value to 2 ~ 4.
6. preparation method according to claim 3 is characterized in that: the add-on of the middle xylogen of step (2) is urea and formaldehyde gross weight 3 ~ 8 times.
7. preparation method according to claim 3 is characterized in that: the add-on of said tensio-active agent is 1% ~ 5% of an xylogen weight.
8. preparation method according to claim 3 is characterized in that: said tensio-active agent is the aliphatics ionic compound of aliphatics polyoxy ethylene compounds or 4-20 carbon atom.
9. preparation method according to claim 8 is characterized in that: said aliphatics polyoxy ethylene compounds comprises TX10, aliphatic acid polyethenoxy ether, carboxylic acid polyoxyethylene ester or T 46155-polyoxypropylene multipolymer; Said aliphatics ionic compound comprises DTAC, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, OTAC, trioctylphosphine trimethyl ammonium chloride, three nonyl ammonio methacrylates, two ten alkyl-dimethyl ammonium chlorides, two dodecyl dimethyl ammonium chloride, two tetradecyl alkyl dimethyl ammonium chloride, Varisoft 432PPG, distearyl dimethyl ammonium chloride or Sodium palmityl sulfate.
10. the prepared core-shell type namely urea-formaldehyde modified lignin of each preparation method expandable flame retardant char-forming agent and acid source in the claim 3 ~ 9 being constituted expansion type flame retardant by mass ratio 1:1 ~ 5 is applied in the POLYACTIC ACID matrix; Wherein acid source is phosphoric acid salt, SULPHOSUCCINIC ACID ESTER or 9, the 10-dihydro-9-oxy is assorted-and in 10-phospho hetero phenanthrene-10-oxide compound and the verivate thereof any.
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| CN105696100A (en) * | 2016-02-25 | 2016-06-22 | 东华大学 | Green carbon source copolymerized anti-flaming polylactic acid fiber and preparation method thereof |
| CN106957513A (en) * | 2017-05-22 | 2017-07-18 | 安徽三义和能源科技有限公司 | A kind of preparation method of Green Flammability sheet material |
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| CN105696100A (en) * | 2016-02-25 | 2016-06-22 | 东华大学 | Green carbon source copolymerized anti-flaming polylactic acid fiber and preparation method thereof |
| CN106957513A (en) * | 2017-05-22 | 2017-07-18 | 安徽三义和能源科技有限公司 | A kind of preparation method of Green Flammability sheet material |
| CN108638262A (en) * | 2018-06-11 | 2018-10-12 | 阜南县永兴工艺品有限公司 | A method of improving high intensity herba fibraureae recisae material toughness |
| CN109081974A (en) * | 2018-08-16 | 2018-12-25 | 杭州卓能密封科技有限公司 | A kind of expansion fire-proof sealing material and preparation method thereof |
| CN114133586A (en) * | 2021-10-27 | 2022-03-04 | 浙大宁波理工学院 | Core-shell intumescent flame retardant and preparation method and application thereof |
| CN115637055A (en) * | 2022-11-01 | 2023-01-24 | 苏州博大永旺新材股份有限公司 | Waterproof rice hull/polylactic acid tableware and preparation method thereof |
| CN115637055B (en) * | 2022-11-01 | 2023-09-26 | 苏州博大永旺新材股份有限公司 | Waterproof rice hull/polylactic acid tableware and preparation method thereof |
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