CN1847362A - Expansion type fireproof moisture-resisting phosphorus-nitrogen material and its prepn - Google Patents
Expansion type fireproof moisture-resisting phosphorus-nitrogen material and its prepn Download PDFInfo
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Abstract
The present invention discloses one kind of expansion type fireproof moisture-resisting phosphorus-nitrogen material and its preparation process. The fireproof material consists of expansion type phosphorus-nitrogen fire retardant and organosilicon with hydroxyl radical in polyol, amino radical in amino phosphate or amino radical in melamine. The present invention processes expansion type phosphorus-nitrogen material through encapsulating and reaction to combine so as to form compact outer capsule layer on high dispersed fire retardant to isolate the amine salt and phosphorus oxide from outside and improve the compatibility of the fire retardant in organic polymer. The present invention has high fire retardant performance, high moisture resistance, less smoke, no toxicity, no corrosion and environment friendship.
Description
Technical field
The present invention relates to a kind of moisture-resistant method of organic fire-resisting material, relate in particular to the phosphorus nitrogen series expansion type anti-flaming material.
Background technology
Phosphorus nitrogen series expansion type anti-flaming material (IFR) is a main component with phosphorus, nitrogen, and is not halogen-containing, and it is as a kind of novel flame redundant material that grows up on the basis of anti-flaming dope, is the disclosed fire retardant material of CN1446844A as publication number.When the poly-material of height that contains IFR was heated burning, the surface generated one deck carbonaceous foam layer, can be heat insulation, oxygen barrier, press down cigarette, and can prevent the molten drop behavior, long-time or repeated exposure are had good resistivity in flame.
IFR is a kind of very rising BACN, more and more is subject to people's attention.As the material of tetramethylolmethane kind phosphate ester, dipentaerythritol phosphoric acid ester and tripentaerythritol phosphoric acid ester, Pentaerythritols phosphorous acid ester and corresponding melamine salt thereof, phosphoric acid amine, organic melamine Ammonia etc.
But the described IFR also fire retardant material with other is the same, exist with polyolefinic consistency be not fine, defective such as water absorbability is big has influenced the use properties and the processing characteristics of material.
Therefore, how described material is carried out surface treatment, as the micro encapsulation of such material, top coat etc., be the relevant personnel the problem very paid close attention to.
At present, relate to the technology that the phosphorus nitrogen series expansion type anti-flaming material surface handles and mainly contain following a few class:
(1) US6444315 has selected for use and has contained the alkoxyl group organosilicon and wrap up to the phosphoric acid amine with by the melamine salt fire retardant powder of oxalic acid, phthalic acid, isocyanic acid, boron phosphoric acid; Its parcel mode adopts under the condition of heating, directly drips, sprays or injection;
(2) JP-A 3-131 508 has selected for use and has contained the alkoxyl group organosilicon polyphosphoric acid amine fire retardant powder is wrapped up; Its parcel mode adopts in the presence of organic solvent, the suspension parcel;
(3) CN1379078A has adopted a kind of unsaturated polyester resin that expansion-type N-P flame-retarding agent has been carried out micro encapsulation.
The method of mentioning among above-mentioned US6444315, the JP-A 3-131 is only applicable to the material of phosphoric acid amine, organic melamine Ammonia; The method complex process that CN1379078A mentions influences the flame retardant properties of material.
For flame retardant resistance than the material of phosphoric acid amine, organic melamine Ammonia better, contain poly-hydroxy alcohol phosphate and melamine salt fire retardant thereof, as tetramethylolmethane kind phosphate ester, dipentaerythritol phosphoric acid ester and tripentaerythritol phosphoric acid ester, Pentaerythritols phosphorous acid ester and corresponding melamine salt thereof also exist with polyolefinic consistency be not fine, water absorbability is big, influences problems such as the use properties of material and processing characteristics.This based flame retardant is because the introducing of polyhydroxy-alcohol, generate ester compound with phosphate compound, mention among the surface of this class material and above-mentioned US6444315, the JP-A 3-131 that the alkyl alkoxy organic silicone oil can not interact, and can not play effective package action.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of expansion type fireproof moisture-resisting phosphorus-nitrogen material and preparation method thereof, to overcome the problem that prior art exists.
Expansion type fireproof moisture-resisting phosphorus-nitrogen material of the present invention is the phosphorus nitrogen expansion type combustion inhibitor of micro encapsulation, be made of phosphorus nitrogen expansion type combustion inhibitor and the organosilicon that links to each other with hydroxyl, amido on the phosphamide or the amido on the melamine salt on its polyvalent alcohol, phosphorus nitrogen expansion type combustion inhibitor and organosilyl weight ratio are:
Organosilicon: phosphorus nitrogen expansion type combustion inhibitor=1: 10～1000;
Preferred mass ratio is 1: 50～100;
Organosilicon parcel amount can not be wrapped up fire retardant very little fully; Organosilicon content is too many, and the cost of fire retardant rises, and the performance of fire retardant changes.
Said phosphorus nitrogen expansion type combustion inhibitor comprises the melamine salt of many tetramethylolmethanes kind phosphate ester melamine salt, phosphoric acid amine or oxalic acid, phthalic acid, isocyanic acid or boron phosphoric acid, said many tetramethylolmethanes kind phosphate ester melamine salt has had detailed description in Chinese patent CN 1446844A, can adopt patent CN1446844A disclosed method to be prepared.
The melamine salt of phosphoric acid amine or oxalic acid, phthalic acid, isocyanic acid or boron phosphoric acid can adopt the commercially available prod.
Said organosilicon is various containing hydrogen silicone oils, and its structural formula is suc as formula shown in I or the formula II:
Wherein: R represents alkyl, aryl, thiazolinyl, n=30～35;
Preferred alkyl, aryl, thiazolinyl;
OR wherein is various alkoxyl groups, preferable methyl alkoxyl group, ethyl alkoxyl group, allyloxy alkoxyl group, n=30～35.
Said organosilicon can adopt the commercially available prod, and the trade mark of producing as Japan XINYUE is that the trade mark that KF-99 containing hydrogen silicone oil, Wuxi all one's effort chemical industry company limited produce is the QLS-202 containing hydrogen silicone oil.
The preparation method of expansion type fireproof moisture-resisting phosphorus-nitrogen material of the present invention comprises the steps:
With organosilicon, organic solvent and phosphorus nitrogen expansion type combustion inhibitor, low whipping speed is 1000～5000rmin
-1Under stir 3～10h, then stir speed (S.S.) is reduced to 100～500r min
-1Be heated to reflux temperature, microcapsule are handled 10～24h, be cooled to 20～35 ℃ then, filter, with under the filter cake vacuum at 30～50 ℃ of drying 10～24h, again the exsiccant solid is warmed up to 150～200 ℃ in air, continue reaction 5～24h, obtain the phosphorus nitrogen expansion type combustion inhibitor of micro encapsulation, be expansion type fireproof moisture-resisting phosphorus-nitrogen material of the present invention.
In the preferred scheme of the present invention, the temperature that microcapsule are handled is 30～200 ℃;
In the preferred scheme of the present invention, solvent is the organic solvent immiscible with water, preferred benzene,toluene,xylene, acetonitrile or dioxane;
The particle size of phosphorus-nitrogen expanding fire retardant is 10～50 μ m;
This technology is to phosphorus-nitrogen expanding fire retardant, carries out micro encapsulation as many tetramethylolmethanes kind phosphate ester melamine salt or polyphosphoric acid amine and handles, and under the effect of fire retardant neutral and alkali group, utilizes alcoholic extract hydroxyl group superfluous on reactive hydrogen and the fire retardant on the hydrogeneous organosilicon to react; Utilize alkoxyl group in the organosilicon and the amine in the fire retardant or ammonium salt partly to interact simultaneously, on the fire retardant powder of high dispersing, produce fine and close outer capsule layer, make be easy to the moisture absorption originally or water miscible amine salt, phosphorus oxidation compound be hedged off from the outer world; Because there are a large amount of organosilicon molecule non-polar groups in capsular skin, improved the consistency of phosphate ester melamine salt fire retardant in organic polymer greatly simultaneously.The fire retardant polyolefin good mechanical property that obtains, the flame retardant resistance height, humidity resistance is good, and low cigarette, nontoxic, non-corrosiveness are environmentally friendly.
Description of drawings
Fig. 1 is a tripentaerythritol melamine salt fire retardant thermogravimetric curve.
Fig. 2 is containing hydrogen silicone oil parcel back tripentaerythritol melamine salt fire retardant thermogravimetric curve.
Fig. 3 is a tripentaerythritol melamine salt fire retardant infared spectrum.
Fig. 4 is containing hydrogen silicone oil parcel back tripentaerythritol melamine salt fire retardant infared spectrum.
Fig. 5 is the thermogravimetric curve of polypropylene flame redardant before and after the tripentaerythritol melamine salt fire retardant parcel.
Fig. 6 is the thermal weight loss rate curve of polypropylene flame redardant before and after the tripentaerythritol melamine salt fire retardant parcel.
Embodiment
Prepare tripentaerythritol phosphate ester melamine salt powder that the 200g particle mean size is 30 μ m (Fig. 1 is seen in the thermogravimetric test) and 500mL toluene by the method for mentioning among the Chinese invention patent CN 1446844A, be added in the there-necked flask of 1000mL, use agitator, mix, rotating speed is 5000r min
-1, add 4g then suc as formula the containing hydrogen silicone oil shown in (I), wherein, R is a methyl, the mean value of n is 33;
Heating makes system be in reflux state, and maintains reaction 5h, suction filtration then under the reflux state, the product of gained at 50 ℃ of vacuum-drying 24h, is taken out and moves in the retort furnace, be heated to 180 ℃, continue reaction 5h, last grinding powder, particle mean size is 35 μ m.
The weight that containing hydrogen silicone oil is handled back tripentaerythritol phosphate ester melamine salt is 203.6g, and the amount of containing hydrogen silicone oil is approximately 2wt%.
Tripentaerythritol phosphate ester melamine salt and be expressed as follows with the structural general formula of containing hydrogen silicone oil:
Fig. 2 is the thermogravimetric curve of fire retardant after 2% organosilicon parcel, and wherein 3 is thermogravimetric curve; 4 is the rate of weight loss curve, and as shown in Figure 2, after organic silicone oil was handled, under same thermal weight loss, decomposition temperature slightly increased, and illustrates that the thermostability of fire retardant increases.Table 1 is tripentaerythritol melamine salt fire retardant ir data and counter structure thereof, and table 2 is containing hydrogen silicone oil parcel back tripentaerythritol melamine salt fire retardant ir data and counter structure thereof.
Table 1. tripentaerythritol melamine salt fire retardant ir data and counter structure thereof
| Produce absorption peak position (wave number/cm -1) | Characteristic group |
| 3374cm -1 3172cm -1 2940cm -1，2900cm -1 1226cm -1 1444，1045cm -1 1055cm -1 759cm -1 | The N-H structure O-H structural fatty C-H of family structure P=O structure dicyclo P=O structure dicyclo P-O-C structure |
Table 2. containing hydrogen silicone oil parcel back tripentaerythritol melamine salt fire retardant ir data and counter structure thereof
| Produce absorption peak position (wave number/cm -1) | Characteristic group |
| 3387 3232 2159 1203 1447，1048，830 981 837，758 | The N-H structure O-H structural fatty C-H of family structure P=O structure dicyclo P=O structure Si-O Si (CH3) 3 |
Fig. 3 and Fig. 4 are respectively the infrared spectras before and after the tripentaerythritol melamine salt fire retardant parcel.After handling through containing hydrogen silicone oil, in infrared spectrum, there be the dicyclo P=O structure and the dicyclo P-O-C structure of feature equally, also have the N-H structure that causes by melamine salt simultaneously, can infer that this fire retardant still has ring texture.But also as can be seen owing to the introducing of containing hydrogen silicone oil, also brought the characteristic group peak of containing hydrogen silicone oil into simultaneously.2159cm
-1Belong to the Si-H absorption peak, 837cm
-1, 758cm
-1Belong to Si (CH
3)
3Absorption peak, 981cm
-1Belong to the Si-O stretching vibration peak, do not have the Si-O key in the raw material containing hydrogen silicone oil, illustrate that reactive hydrogen and alcoholic extract hydroxyl group reaction that this key results from the silicone oil generate.
Embodiment 2
As embodiment 1, the add-on of containing hydrogen silicone oil (I) is changed into 8g, making coating levels is 4% parcel back tripentaerythritol phosphate ester melamine salt.
Embodiment 3
As embodiment 1, the add-on of containing hydrogen silicone oil (I) is changed into 12g, making coating levels is 6% parcel back tripentaerythritol phosphate ester melamine salt.
Embodiment 4
As embodiment 1, the add-on of containing hydrogen silicone oil (I) is changed into 20g, making coating levels is 10% parcel back tripentaerythritol phosphate ester melamine salt.
The comparative example 1
As embodiment 1, the add-on of containing hydrogen silicone oil (I) is changed into 1g, making coating levels is 0.5% parcel back tripentaerythritol phosphate ester melamine salt.
Embodiment 5
At height is in the glass cylinder of 5cm for the 20cm diameter, add deionized water to full scale, add the tripentaerythritol phosphate ester melamine salt of the above-mentioned three kinds of containing hydrogen silicone oils parcel of 2g and the sample that does not wrap up respectively, immediately use manual time-keeping, according to not sedimentation powder object oven dry weighing, calculate the amount of different residence time system sedimentation powder.
The test result of this experiment will show the hydrolytic resistance or the wet fastness of powder.By the data of table 3 as can be known, parcel can not all wrap fire retardant very little, can not play the effect isolated with water, still hydrolysis can take place in water, and submerged.Table 3 is water resistance test data before and after the tripentaerythritol phosphate ester melamine salt parcel.
Water resistance test before and after the table 3. tripentaerythritol phosphate ester melamine salt parcel
| Sample | Use sample size (g) | 15min | 60min | 90min |
| Comparative example 1 sample | 2 | 50％ | 80％ | 95％ |
| The sample of | 2 | 35％ | 68％ | 76％ |
| The sample of embodiment 2 | 2 | 15％ | 39％ | 58％ |
| The sample of embodiment 3 | 2 | 0％ | 0％ | 0％ |
| The sample of embodiment 4 | 2 | 0％ | 0％ | 0％ |
| Do not wrap up sample | 2 | 85％ | 90％ | 100％ |
Embodiment 6～8
(application number: the 150g particle of the method preparation of mentioning 200410067525.3) is added in the there-necked flask of 1000mL at dipentaerythritol phosphorous acid ester powder and the 600mL dioxane (chemical pure) of 10～50 μ m by Chinese invention patent, use agitator, mix, rotating speed is 5000r min
-1, add 3g containing hydrogen silicone oil (II) then, wherein: OR is a methoxyl group, the mean value of n is 31;
The system of being heated to is in reflux state, and maintains reaction 5h, suction filtration then under the reflux state, the product of gained at 50 ℃ of vacuum-drying 24h, is taken out and moves in the retort furnace, be heated to 180 ℃, continue reaction 5h, last grinding powder, particle size is 10～60 μ m.The weight of containing hydrogen silicone oil parcel back dipentaerythritol phosphorous acid ester is 152.8g, and the amount of coating is approximately 2%.
Keep under the constant condition of dioxane quantity of solvent and other processing condition, improve the add-on of containing hydrogen silicone oil, be incorporated as 4.5g, 6g respectively, make coating levels respectively and be dipentaerythritol phosphorous acid ester behind 3% and 4% the parcel.
Amount according to embodiment 1 test system sedimentation powder in the formulation time.Its result is as shown in table 4.
Water resistance test before and after the table 4. dipentaerythritol phosphorous acid ester parcel
| Sample | Use sample size (g) | 15min | 60min | 90min |
| Embodiment 6 samples | 2 | 15％ | 26％ | 36％ |
| Embodiment 7 parcel samples | 2 | 8％ | 13％ | 19％ |
| Embodiment 8 parcel samples | 2 | 0％ | 0％ | 0％ |
| Do not wrap up sample | 2 | 18％ | 39％ | 60％ |
Embodiment 9
With parcel coating amount among the embodiment 2 is 4% fire retardant and the fire retardant that do not wrap up, adopt the twin-roll plasticator that it is added in the polypropylene, add-on is 20%, (weight), 185 ℃ of mixing 10min mix it, 185 ℃ of shaped by fluid pressures on vulcanizer, omnipotent sampling machine sample preparation, sample size are 100 * 100 * 3mm.Adopt taper calorimeter FTT, according to the ASTME-1354 standard, sample placement positioning horizontal direction is measured the flame retardant properties and the mechanical property of material.
Fig. 5 is the thermogravimetric curve of polypropylene flame redardant before and after the tripentaerythritol melamine salt fire retardant parcel, among Fig. 5,5 lines are that its addition of 6% containing hydrogen silicone oil parcel fire retardant is that polypropylene specimen, 6 lines of 25wt% are that its addition of 4% containing hydrogen silicone oil parcel fire retardant is that polypropylene specimen, 7 lines of 20wt% are that its addition of 4% containing hydrogen silicone oil parcel fire retardant is that polypropylene specimen, 8 lines of 25wt% are that its addition of 6% containing hydrogen silicone oil parcel fire retardant is that the polypropylene specimen, 9 lines of 20wt% is polypropylene specimen in the interpolation not in the example 3 in the example 2 in the example 2 in the example 3.As shown in Figure 5, the temperature of initial decomposition of all fire retardant materials all is much the same, it is 321 ℃, the weight loss rate difference of 321 ℃ of fire retardant materials between 500 ℃ the time, the material weight loss rate of 20%-6%Si is maximum, thermostability is the poorest, secondly is the fire retardant material of 20%-4%Si and 25%-6%Si, and what thermostability was best is the fire retardant material of 25%-4%Si.After 500 ℃, material does not substantially all have weightless again, and the carbon residue amount of various materials is more or less the same, and the neat coal amout of the fire retardant material of 25% content is some more a little, increases relevant with the content of fire retardant in the fire retardant material.Compare with the fire retardant material that does not wrap up, big variation does not take place in the TG curve, and the variation of the thermostability of organosilicon modification not causing material is described.
Fig. 6 is the thermal weight loss rate curve of polypropylene flame redardant before and after the tripentaerythritol melamine salt fire retardant parcel, among Fig. 6,10 lines are that its addition of 4% containing hydrogen silicone oil parcel fire retardant is that polypropylene specimen, 11 lines of 20wt% are that its addition of 4% containing hydrogen silicone oil parcel fire retardant is that polypropylene specimen, 12 lines of 25wt% are that its addition of 6% containing hydrogen silicone oil parcel fire retardant is that polypropylene specimen, 13 lines of 20wt% are that its addition of 6% containing hydrogen silicone oil parcel fire retardant is that the polypropylene specimen, 14 lines of 25wt% is polypropylene specimen in the interpolation not in the example 3 in the example 3 in the example 2 in the example 2.
As shown in Figure 6, when coating flame retardant agent content when all being 20%, the fire retardant material that contains 6% silicone oil is lower than the thermostability that contains 4% silicone oil.The temperature that maximum weightless peak appears in the fire retardant material that contains 6% silicone oil be 394 ℃ of peak values be 1.27%/℃, and the temperature at maximum weightless peak appears in the fire retardant material that contains 4% silicone oil is 433 ℃, peak value is 0.92%/℃, not Bao Guo fire retardant material occur the temperature at maximum weightless peak be 418 ℃ of peak values be 1.11%/℃, the thermostability of this explanation fire retardant material is along with the variation of containing hydrogen silicone oil has complicated relation, and suitable silicone content can improve the thermostability of material.Equally, when the content that coats fire retardant increased to 25%, the temperature that maximum weightless peak appears in the fire retardant material that contains 4% silicone oil was 473 ℃, the peak value size is 0.9%/℃, and the temperature of the maximum weightless peak of the material that contains 6% silicone oil when occurring is 431 ℃, peak value is 0.82%/℃.This shows when the content of containing hydrogen silicone oil increases, and can reduce the thermostability of material a little.Table 5 is handled the polyacrylic performance of front and back fire retardant for containing hydrogen silicone oil.
The polyacrylic performance of fire retardant before and after table 5. containing hydrogen silicone oil is handled
By table 5 as seen, after fire retardant is handled through containing hydrogen silicone oil (I), with the polypropene blended polypropylene flame redardant that is processed into, the mechanical property of this polypropylene flame redardant has obtained improvement to a certain degree, especially unit elongation, unnotched impact strength and has obtained corresponding raising again.And flame retardant properties changes not quite, and oxygen index still maintains 28.2, still can reach the HB rank by the horizontal firing test, and vertical combustion also can be tested by UL94V-0
Fire retardant before and after containing hydrogen silicone oil with 4% is handled is added in the polypropylene with 20% addition, makes batten respectively, and wherein one is the fire retardant polypropylene that containing hydrogen silicone oil was handled, and another piece is the fire retardant polypropylene that is untreated.Drip deionized water on the surface of two block of material, make surface wettability, cross 5min afterwards with the test of PH test paper.The result shows, latter surface PH test paper presents redness rapidly, and the surface presents acidity, illustrate that the acid source in the fire retardant moved to the surface of material, also is that the phosphorus oxidation compound in the fire retardant fails to be wrapped up by polypropylene, and chance water is hydrolyzed into phosphoric acid; And latter PH test paper and nondiscoloration, the surface presents neutrality, and the phosphorus oxidation compound of fire retardant is not separated out.The above results shows that containing hydrogen silicone oil has good hydrophobic effect, can prevent the fire retardant material moisture absorption effectively, makes material have flame retardant properties preferably for a long time.
The 150g particle size is that (App-1101 is commercially available, and model is that LCS-G * JLSA) and 600mL acetonitrile (chemical pure) are added in the there-necked flask of 1000mL, uses agitator, mixes, and rotating speed is 5000r min for the polyphosphoric acid amine powder of 50～150 μ m
-1, add 3g containing hydrogen silicone oil (I) then, wherein: R is an ethyl, n mean value is 33;
The system of being heated to is in reflux state, and maintains under the reflux state reaction 5h, and suction filtration then at 50 ℃ of vacuum-drying 24h, takes out the product of gained to move in the retort furnace, is heated to 180 ℃, continues reaction 5h, last grinding powder, and particle is 80 μ m.The weight of containing hydrogen silicone oil parcel back polyphosphoric acid amine is 152.8g, and the amount of coating is approximately 2%.
Keep under the constant condition of acetonitrile solvent amount and other processing condition, improve the add-on of containing hydrogen silicone oil (I), be incorporated as 4.5g, 6g respectively, make coating levels and be polyphosphoric acid amine behind 3% and 4% the parcel, be respectively embodiment 11, embodiment 12.
Amount according to embodiment 1 test system sedimentation powder in the formulation time.Its result is as shown in table 6.
Water resistance test before and after the table 6. polyphosphoric acid amine parcel
| Sample | Use sample size (g) | 15sec | 60sec | 90sec |
| | 2 | 15％ | 26％ | 38％ |
| Embodiment 11 samples | 2 | 0％ | 13％ | 27 |
| Embodiment | ||||
| 12 samples | 2 | 0％ | 0％ | 0％ |
| Do not wrap up sample | 2 | 95％ | 100％ | 100％ |
The 250g particle size is that melamine phosphate powder and the 600mL tetrahydrofuran (THF) (chemical pure) of 10～100 μ m is added in the there-necked flask of 1000mL, uses agitator, mixes, and rotating speed is 5000r min
-1, add the containing hydrogen silicone oil of 1.25g formula (II) then, wherein, R is an oxyethyl group, and the mean value of n is 35, and the system of being heated to is in reflux state, and maintain under the reflux state reaction 5h, suction filtration then at 50 ℃ of vacuum-drying 24h, takes out the product of gained to move in the retort furnace, be heated to 200 ℃, continue reaction 7h, last grinding powder, particle is 75 μ m.The phosphatic weight of containing hydrogen silicone oil parcel back melamine is 254.8g, and the amount of coating is approximately 2%.
Keep under the constant condition of tetrahydrofuran solvent amount and other processing condition, improve the add-on of containing hydrogen silicone oil (II), be incorporated as 7.5g, 15g respectively, make coating levels and be polyphosphoric acid amine behind 3% and 6% the parcel, be respectively embodiment 14 and embodiment 15.
Amount according to embodiment 1 test system sedimentation powder in the formulation time.Its result is as shown in table 7.
Water resistance test before and after the table 7. polyphosphoric acid amine parcel
| Sample | Use sample size (g) | 15sec | 60sec | 90sec |
| | 2 | 5％ | 16％ | 38 |
| Embodiment | ||||
| 14 samples | 2 | 0％ | 5％ | 20％ |
| Embodiment 15 samples | 2 | 0％ | 0％ | 0％ |
| Do not wrap up sample | 2 | 81％ | 95％ | 100％ |
Claims (9)
1. expansion type fireproof moisture-resisting phosphorus-nitrogen material, it is characterized in that, be made of phosphorus nitrogen expansion type combustion inhibitor and the organosilicon that links to each other with hydroxyl, amido on the phosphamide or the amido on the melamine salt on its polyvalent alcohol, the weight ratio of organosilicon and phosphorus nitrogen expansion type combustion inhibitor is: organosilicon: phosphorus nitrogen expansion type combustion inhibitor=1: 10～1000.
2. expansion type fireproof moisture-resisting phosphorus-nitrogen material according to claim 1 is characterized in that, mass ratio is organosilicon: phosphorus nitrogen expansion type combustion inhibitor=1: 50～100.
3. expansion type fireproof moisture-resisting phosphorus-nitrogen material according to claim 1, it is characterized in that the phosphorus nitrogen expansion type combustion inhibitor comprises the melamine salt of many tetramethylolmethanes kind phosphate ester melamine salt, phosphoric acid amine or oxalic acid, phthalic acid, isocyanic acid or boron phosphoric acid.
4. expansion type fireproof moisture-resisting phosphorus-nitrogen material according to claim 3 is characterized in that, the phosphorus nitrogen expansion type combustion inhibitor, and said organosilicon structural formula is suc as formula shown in I or the formula II:
Wherein :-R represents alkyl, aryl, thiazolinyl, n=30～35;
Wherein-OR is an alkoxyl group, n=30～35.
5. expansion type fireproof moisture-resisting phosphorus-nitrogen material according to claim 4 is characterized in that, R is methyl, ethyl or phenyl, and OR is methyl alkoxy, ethyl alkoxyl group, allyloxy alkoxyl group.
6. prepare the method for each described expansion type fireproof moisture-resisting phosphorus-nitrogen material of claim 1～5, it is characterized in that, comprise the steps: that with organosilicon, organic solvent and phosphorus nitrogen expansion type combustion inhibitor, low whipping speed is 1000～5000r min
-1Under stir 3～10h, then stir speed (S.S.) is reduced to 100～500r min
-1, being heated to reflux temperature, microcapsule are handled 10～24h, be cooled to 20～35 ℃ then, filter, with filter cake at 30～50 ℃ of following vacuum-drying 10～24h, again the exsiccant solid is warmed up to 150～200 ℃ in air, continues reaction 5～24h, be expansion type fireproof moisture-resisting phosphorus-nitrogen material.
7. method according to claim 6 is characterized in that, the temperature that microcapsule are handled is 30～200 ℃.
8. method according to claim 6 is characterized in that, solvent is benzene,toluene,xylene, acetonitrile or dioxane.
9. method according to claim 6 is characterized in that, the particle size of phosphorus-nitrogen expanding fire retardant is 10～50 μ m.
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| CN102634017B (en) * | 2012-04-13 | 2013-09-25 | 浙江华亿工程设计有限公司 | Organosilicone-containing nitrogen phosphorus flame retardant and preparation method thereof |
| CN110483898A (en) * | 2019-09-29 | 2019-11-22 | 上海化工研究院有限公司 | A kind of resistance to precipitation halogen-free flame retardants of high fluidity and its preparation method and application |
| CN115536924A (en) * | 2022-09-26 | 2022-12-30 | 广东祥利科技有限公司 | High-flame-retardant polyethylene cable material and preparation method thereof |
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