CN105178006B - A kind of reactive flame retardant of phosphorus-nitrogen containing silicon and preparation method and application - Google Patents
A kind of reactive flame retardant of phosphorus-nitrogen containing silicon and preparation method and application Download PDFInfo
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- CN105178006B CN105178006B CN201510662808.0A CN201510662808A CN105178006B CN 105178006 B CN105178006 B CN 105178006B CN 201510662808 A CN201510662808 A CN 201510662808A CN 105178006 B CN105178006 B CN 105178006B
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Abstract
A kind of reactive flame retardant of phosphorus-nitrogen containing silicon and preparation method thereof, comprises the following steps that：Diethyl chloro-phosphate is dissolved in organic solvent, 05 DEG C are cooled to, γ aminopropyl triethoxysilanes and triethylamine is added dropwise over, 60 100 DEG C are gradually heating to after completion of dropping, be sufficiently stirred for reacting 8 12h；After question response terminates, precipitation is filtered to remove, solvent, unreacted raw material in clarified solution vacuum distillation removal reaction mixture are dried, and obtain the reactive flame retardant of phosphorus-nitrogen containing silicon.The inventive method reaction condition is gentle, process is simple, raw material are cheap and easy to get, and the reactive flame retardant good water solubility of the phosphorus-nitrogen containing silicon synthesized by the method, product yield is higher, and safety non-toxic can prepare the flame retardant textiles with excellent fire-retardancy.
Description
Technical field
The present invention relates to textile production technical field, more particularly, to a kind of reactive flame retardant containing phosphorus nitrogen silicon and
The application of its preparation method and the fire retardant in Fire-proof Finishing Agents for Textile arrangement.
Background technology
There is statistics to show, 20% fire incident is caused or expanded due to textile combustion in the world, especially
It is that house catches fire, because textile catches fire or the fire incident ratio that spreading and leading to is bigger, therefore, the anti-flaming function of textile
To eliminating disaster hidden-trouble, delay fire spreading, reduce people life property loss particularly important.Fabric fire-retardant finishing is by changing
The effects such as bonding, chemical adhesion, absorption deposition and nonpolar Van der Waals force combination are learned, fire retardant is anchored at fiber and fabric
On, so that fabric obtains the process of fire resistance.In numerous textiles, wollen fabrics because its good hygroscopicity with
Gas permeability, without electrostatic, it is comfortable and easy to wear the advantages of and turn into the dress material being loved by people.But compared with other textiles,
Bafta is easier burning, therefore, develop the textile with excellent flame retardant performance particularly important.
Conventional organic fire-retardant has phosphorus system, halogen system and nitrogen system etc., but halogenated flame retardant due to containing in its catabolite
Hydracid, smog is big, the shortcomings of harmful, just progressively by other flame retardant insteads.Wherein phosphorus flame retardant is efficient, low because of its
The advantages of cigarette, low toxic and environment-friendly and be widely used in the flame-proof treatment of fabric, but phosphorus flame retardant is because its poor heat resistance, volatility
It is big and require the problems such as could forming charring layer containing a large amount of H, O elements in flame retarding construction and be restricted.Nitrogenated flame retardant
Halogen, low toxicity, low cigarette, all stablize to heat and ultraviolet, and organic silicon fibre retardant is efficient, ecological friendly, and anti-molten drop simultaneously presses down cigarette.
In consideration of it, the reactive flame retardant of phosphorus-nitrogen containing silicon is worked out, and it is strong with excellent flame retardant performance and good fracture
The anti-flaming function textile of power, tool is of great significance.
The content of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provide a kind of phosphorus-nitrogen containing silicon reactive flame retardant and
Its preparation method and application.The inventive method reaction condition is gentle, process is simple, raw material are cheap and easy to get, by containing that the method synthesizes
The reactive flame retardant good water solubility of phosphorus nitrogen silicon, product yield is higher, and safety non-toxic can be prepared with excellent fire-retardancy
Flame retardant textiles.
Technical scheme is as follows：
The invention provides a kind of reactive flame retardant of phosphorus-nitrogen containing silicon, the fire retardant is the change of structure shown in formula (I)
Compound：
Present invention also offers the preparation method of the reactive flame retardant of the phosphorus-nitrogen containing silicon, comprise the following steps that：
Diethyl chloro-phosphate is dissolved in organic solvent, 0-5 DEG C is cooled to, gamma-aminopropyl-triethoxy silicon is added dropwise over
Alkane and triethylamine, are gradually heating to 60-100 DEG C after completion of dropping, be sufficiently stirred for reacting 8-12h；After question response terminates, cross and filter
Precipitation is gone, solvent, unreacted raw material in clarified solution vacuum distillation removal reaction mixture are dried, and obtain the anti-of phosphorus-nitrogen containing silicon
Answer sex flame retardant.
The mol ratio of the diethyl chloro-phosphate, gamma-aminopropyl-triethoxy-silane and triethylamine is 1:1:1~1:1.3:
1.The organic solvent is that ethyl acetate or tetrahydrofuran are THF.
Present invention also offers the application of the reactive flame retardant in fire proofing is prepared of the phosphorus-nitrogen containing silicon, specific side
Method is：
The fire retardant of formula (I) described structure is configured to the dressing liquid that mass percentage concentration is 10-35%；Will be pending
Bafta impregnated in 12~24h in dressing liquid, and two leachings two are rolled, and then 100 DEG C of drying 5min bake in 140-170 DEG C of high temperature
5min, taking-up is soaped, washes and dried, and fire proofing is obtained.
6th, application according to claim 5, it is characterised in that：The dressing liquid is 30wt% ethanol solutions.
7th, application according to claim 5, it is characterised in that：The Cotton Fabric pick-up is 100%.
The present invention is beneficial to be had technical effect that：
The reactive flame retardant of phosphorus-nitrogen containing silicon of the present invention is cheap and easy to get, greatly reduces production cost；The inventive method is anti-
Answer mild condition, one-step method that product is obtained, the reaction time is short, and energy consumption is low, and technical process is simple；Phosphorus-nitrogen containing in the inventive method
The reactive flame retardant of silicon is water solubility, and organic solvent hydrotropy need not be added during dressing liquid is prepared, and reduces
Flame-proof treatment cost and treatment cost of waste liquor.There is excellent anti-flammability by flame retardant textiles obtained in technique for applying of the present invention
Can, flame retarding efficiency is high, and limited oxygen index rises to 31% by the 18.4% of raw cotton, and vertical combustion fabric char length is
11.4cm。
In summary described, the inventive method technological operation is simple, and the time is short, and power consumption is few；Obtained flame-proof cotton fabric
Have excellent lasting fire resistance and wearability concurrently.
Brief description of the drawings
Fig. 1 is the vertical burn test schematic diagram of the reactive flame retardant of phosphorus-nitrogen containing silicon of the present invention.
Specific embodiment
With reference to embodiment, the present invention is specifically described.
First, the reactive flame retardant of phosphorus-nitrogen containing silicon and its synthetic method embodiment：
Embodiment 1
7.08g diethyl chloro-phosphates are weighed in 250ml round-bottomed flasks, 100ml ethyl acetate is added, 0 DEG C is cooled to, so
After be added dropwise over 8.85g gamma-aminopropyl-triethoxy-silanes and 4.04g triethylamines, be warming up to 80 DEG C reaction 12h；Reaction terminates
Afterwards, suction filtration removes precipitation, and clarified solution is removed ethyl acetate and unreacted raw material in reaction mixture by vacuum distillation, obtained
Water-soluble faint yellow oily reactive flame retardant, yield is 77%.
Embodiment 2
7.08g diethyl chloro-phosphates are weighed in 250ml round-bottomed flasks, 100ml ethyl acetate is added, 5 DEG C is cooled to, so
After be added dropwise over 11.48g gamma-aminopropyl-triethoxy-silanes and 4.04g triethylamines, be warming up to 100 DEG C reaction 10h；Reaction knot
Shu Hou, suction filtration removes precipitation, and clarified solution is removed ethyl acetate and unreacted raw material in reaction mixture by vacuum distillation, obtained
To water-soluble faint yellow oily reactive flame retardant, yield is 81%.
2nd, the reactive flame retardant Application Example of phosphorus-nitrogen containing silicon：
Application Example 1
By embodiment it is 2-in-1 into the reactive flame retardant of phosphorus-nitrogen containing silicon be configured to the dressing liquid that mass percentage concentration is 10%
(30wt% ethanol solutions)；Pending bafta (being purchased from Zhejiang Guandong Dyeing and Garment Co., Ltd.) be impregnated in into above-mentioned arrangement
In liquid whole night, take out the leaching of pure cotton fabric two two to roll, pick-up 100% dries 5min, then in 140 DEG C of bakers in 100 DEG C
Bake 5min；The pure cotton fabric after baking is taken out, soaped, wash, dried, fire-retardant pure cotton fabric is obtained.Determination limit oxygen index (OI)
It is 23%.
Application Example 2
By embodiment it is 2-in-1 into the reactive flame retardant of phosphorus-nitrogen containing silicon be configured to the dressing liquid that mass percentage concentration is 25%
(30wt% ethanol solutions)；Pending bafta (being purchased from Zhejiang Guandong Dyeing and Garment Co., Ltd.) be impregnated in into above-mentioned arrangement
In liquid whole night, take out the leaching of pure cotton fabric two two to roll, pick-up 100% dries 5min, then in 150 DEG C of bakers in 100 DEG C
Bake 5min；The pure cotton fabric after baking is taken out, soaped, wash, dried, fire-retardant pure cotton fabric is obtained.Determination limit oxygen index (OI)
It is 27%.
Application Example 3
By embodiment it is 2-in-1 into the reactive flame retardant of phosphorus-nitrogen containing silicon be configured to the dressing liquid that mass percentage concentration is 35%
(30wt% ethanol solutions)；Pending bafta (being purchased from Zhejiang Guandong Dyeing and Garment Co., Ltd.) be impregnated in into above-mentioned arrangement
In liquid whole night, take out the leaching of pure cotton fabric two two to roll, pick-up 100% dries 5min, then in 160 DEG C of bakers in 100 DEG C
Bake 5min；The pure cotton fabric after baking is taken out, soaped, wash, dried, fire-retardant pure cotton fabric is obtained.Determination limit oxygen index (OI)
It is 31%.
3rd, performance test
1st, bafta fire resistance test after arranging：
According to GB/T 5455-1997《Textile combustion performance test normal beam technique》With GB/T 5454-1997《Textile fires
Burn performance test oxygen index method》, flame-proof treatment is carried out according to the methods described of Application Example 3, test result is referring to Fig. 1 and Biao 1.
The flame retardant test result of table 1
Table 1 and Fig. 1 show that the flame-proof cotton fabric obtained by the present invention has excellent fire resistance, and flame retarding efficiency is high；With
The fabric limited oxygen index that 35% dressing liquid is arranged reaches 31%, and char length is 10.1cm.
2nd, fabric strength test after arranging：
The test of bafta tensile break strength is with reference to GB/T 3923-1997《Fabric tension performance ultimate strength and fracture are stretched
The measure galley proof method of rate long》.Fabric cuts according to testing standard, and the length direction of sample should be parallel to the warp-wise of fabric and latitude
3 pieces of samples are respectively cut to, fabric warp-wise and broadwise, every piece of specimen length about 25cm, width is 6cm, pulls yarn side and makes
5cm, test result is referring to table 2.
The tension failure of the fabric of table 2 is strongly
| Fabric | Warp-wise (N) | Broadwise (N) |
| Raw cotton fabric | 710 | 477 |
| 10% concentration finish fabric | 681 | 448 |
| 15% concentration finish fabric | 675 | 433 |
| 20% concentration finish fabric | 651 | 390 |
| 25% concentration finish fabric | 642 | 354 |
| 30% concentration finish fabric | 608 | 345 |
| 35% concentration finish fabric | 585 | 325 |
The test data of table 2 shows, compared with raw cotton fabric, the warp direction stretching ultimate strength of 30% concentration finishing of cotton textiles loses
About 14% or so, broadwise tension failure strength loss is about 27%, and this is in reduced levels in Fire-proof Finishing Agents for Textile arrangement, it is seen that
This kind of technique has no effect on the normal of fabric and uses.
Claims (3)
1. a kind of reactive flame retardant of phosphorus-nitrogen containing silicon, it is characterised in that the fire retardant is the compound of structure shown in formula (I)：
The preparation method of the reactive flame retardant of the phosphorus-nitrogen containing silicon is comprised the following steps that：
Diethyl chloro-phosphate is dissolved in organic solvent, 0-5 DEG C is cooled to, be added dropwise over gamma-aminopropyl-triethoxy-silane and
Triethylamine, is gradually heating to 60-100 DEG C after completion of dropping, be sufficiently stirred for reacting 8-12h；After question response terminates, it is heavy to be filtered to remove
Form sediment, solvent, unreacted raw material in clarified solution vacuum distillation removal reaction mixture are dried, and obtain the reactivity of phosphorus-nitrogen containing silicon
Fire retardant；
The mol ratio of the diethyl chloro-phosphate, gamma-aminopropyl-triethoxy-silane and triethylamine is 1:1:1~1:1.3:1；
The organic solvent is that ethyl acetate or tetrahydrofuran are THF.
2. application of the reactive flame retardant of phosphorus-nitrogen containing silicon in fire proofing is prepared described in claim 1, it is characterised in that：
The fire retardant of formula (I) described structure is configured to the dressing liquid that mass percentage concentration is 10-35%；Pending cotton is knitted
Thing impregnated in 12~24h in dressing liquid, and two leachings two are rolled, and then 100 DEG C of drying 5min bake 5min in 140-170 DEG C of high temperature, take
Go out to soap, wash and dry, fire proofing is obtained.
3. application according to claim 2, it is characterised in that：The Cotton Fabric pick-up is 100%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107383102A (en) * | 2017-07-18 | 2017-11-24 | 江南大学 | A kind of siliceous phosphamide and preparation method thereof |
| CN110563954B (en) * | 2019-09-11 | 2022-03-15 | 西北工业大学 | Phosphorus-silicon-nitrogen ternary synergistic flame retardant and preparation method thereof |
| CN112876508A (en) * | 2020-10-29 | 2021-06-01 | 广东广山新材料股份有限公司 | Reactive phosphorus-silicon synergistic flame retardant, polymeric phosphorus-silicon synergistic flame retardant, and preparation method and application thereof |
| CN112521660B (en) * | 2020-11-11 | 2021-08-06 | 厦门大学 | Titanium dioxide hybrid nano particle flame retardant containing phosphorus, nitrogen and silicon and preparation method and application thereof |
| CN113308888B (en) * | 2021-06-08 | 2023-02-21 | 上海化工研究院有限公司 | Method for preparing hydrophobic flame-retardant textile by soaking method |
| CN113429435A (en) * | 2021-06-30 | 2021-09-24 | 成都硅宝科技股份有限公司 | Silane coupling agent containing phosphorus and nitrogen and preparation method thereof |
| CN115491899B (en) * | 2022-10-26 | 2024-03-15 | 安徽深呼吸纺织科技有限公司 | Biodegradable flame-retardant protective fabric and production process thereof |
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