CN105862415B - One kind is containing boron fire retardant preservative and its preparation method and application - Google Patents
One kind is containing boron fire retardant preservative and its preparation method and application Download PDFInfo
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- CN105862415B CN105862415B CN201610409195.4A CN201610409195A CN105862415B CN 105862415 B CN105862415 B CN 105862415B CN 201610409195 A CN201610409195 A CN 201610409195A CN 105862415 B CN105862415 B CN 105862415B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 101
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 24
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000003755 preservative agent Substances 0.000 title claims abstract description 16
- 230000002335 preservative effect Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004202 carbamide Substances 0.000 claims abstract description 30
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims abstract description 22
- RDBMUARQWLPMNW-UHFFFAOYSA-N phosphanylmethanol Chemical compound OCP RDBMUARQWLPMNW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004327 boric acid Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 239000012467 final product Substances 0.000 claims abstract description 4
- ZIPYUYXAPBPJIG-UHFFFAOYSA-N OB(O)O.OCP Chemical compound OB(O)O.OCP ZIPYUYXAPBPJIG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000009467 reduction Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 238000004079 fireproofing Methods 0.000 claims description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 43
- 230000000694 effects Effects 0.000 abstract description 23
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 235000019504 cigarettes Nutrition 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 33
- 239000004744 fabric Substances 0.000 description 30
- RZJRJXONCZWCBN-UHFFFAOYSA-N alpha-octadecene Natural products CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 19
- -1 n-octadecane amine Chemical class 0.000 description 18
- 238000012360 testing method Methods 0.000 description 15
- 239000003431 cross linking reagent Substances 0.000 description 14
- 238000002485 combustion reaction Methods 0.000 description 11
- 229920000742 Cotton Polymers 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229940038384 octadecane Drugs 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000009988 textile finishing Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- QZHCWVOOQUPXGE-UHFFFAOYSA-N OC[P] Chemical compound OC[P] QZHCWVOOQUPXGE-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses one kind containing boron fire retardant preservative and its preparation method and application, and the preparation method comprises the following steps：Boric acid, tetrakis hydroxymetyl phosphonium sulfuric, the concentrated sulfuric acid and water mixing are taken, 16 18h are heated to reflux, stops heating after the reaction was complete, obtains tetra methylol phosphorus borate；PH value is adjusted after temperature reduction, add urea, octadecylamine, continue to be heated to reflux 8 10h, be added to the water reaction product after the completion of reaction, be made into 60% solution to obtain the final product.Technical scheme of the present invention, raw material resources are abundant, cheap, technological operation simple possible, overcome the defect of previous single-element fire retardant, it completes B, N, P new flame retardant effectively combined and significant effect, there is very considerable economic benefit and social benefit.Fire retardant prepared by the present invention meets nontoxic, Halogen, low cigarette, to this minimum global evolution new trend of environmental impact, possesses huge market development potential.
Description
Technical field
The invention belongs to fireproof material technology fields, specifically, be related to it is a kind of containing boron fire retardant preservative and preparation method thereof and
Using.
Background technology
Fire retardant, as the term suggests it is exactly the chemical reagent for preventing object from burning, or reducing burning degree, also known as incombustible agent
Or fire-proofing chemical, using the distinctive absorption calory burning of fire retardant, reaction-ure surface protective mulch, inhibit chain reaction, every
Anoxybiotic vapour lock, which only burns away, waits fire retardant mechanisms to reach fire-retardant purpose.Wood furniture in our daily lifes, plastic product are spun
Textured fiber etc. all has combustibility.Chemically the origin of fire-retardant high polymer will trace back to early 20th century, G.A.Engelard
Equal scientists obtain fire-retardant chlorinated rubber using natural rubber and chlorine reaction, substantially increase the flame retardant property of fire retardant, will
Flame retardant area is promoted to new height.
The appearance of fire retardant reduces fire and threatens the life harm of people and property.Recent years usage amount most
Almost 90% ratio is mostly occupied in fire retardant consumer field in some flourishing industrial countries in West Europe, such as the U.S., Japan
Weight, it is contemplated that can also improve 4% or so in several years in the future.Although the fire retardant development starting evening in China, in synthetic technology and consumption figure
Aspect is all not as good as developed country, but due to development scientific and technological in recent years, the increasing of the consumption such as PVC, rubber, textile, construction material
It is more, also significantly go up to the usage amount of fire retardant, fire retardant yield increases considerably, the extent of supply of manufacturer towards the whole world,
Therefore the competition of flame retardant area also can be relatively fierce, and development prospect is quite optimistic.In this context, fire retardant is fire-retardant
Performance is more exposed to the extensive concern of people.
Since global environment gradually deteriorates, earth home for the survival of mankind is seriously threatened, country promulgates many laws
Problem of environmental pollution is controlled, is pushed out come specification fire retardant for the environmental protection relevant laws and regulations of this topic.This requires
While with higher flame retardant property, more focus on protection of the product to environment.Some big companies in West Europe are for environmental protection
Center of production is switched to the small halogen-free flame retardants of pollution by the considerations of problem by Br flame retardants.In order to adapt to the need in market
It asks, the compounding of fire retardant also occurs therewith, instead of the single situation of previous synthesized element.Such as in order to reduce the corruption of equipment
Erosion can add master batch etc. in fire retardant and carry out anti-corrosion.Small toxicity is developed, smog is few, and clean new flame retardant has become fire-retardant
The new trend in agent field.
China's boron is resourceful, and required cost of material is cheap, of low cost, and boron is applied can improve resistance in fire retardant
Fire the application efficiency of agent.Boron flame retardant has many advantages, such as that toxicity is low, smoke amount is small and superior flame retardant property and increasingly by people
Be widely used in life.Previous boron flame retardant synthesized element is single, and method is complicated, has higher want to reaction condition
It asks, is badly in need of finding a kind of easy to operate, the synthesis technology of the cheap health environment-friendly again of raw material.
Invention content
In view of this, the present invention to be solved, existing boron flame retardant synthesized element is single, and method is complicated, to reaction condition
More demanding problem provides a kind of containing boron fire retardant preservative and its preparation method and application.
In order to solve the above-mentioned technical problem, the invention discloses a kind of preparation methods containing boron fire retardant preservative, including following step
Suddenly：Boric acid, tetrakis hydroxymetyl phosphonium sulfuric, the concentrated sulfuric acid and water mixing are taken, 16-18h is heated to reflux, stops heating after the reaction was complete, obtains
To tetra methylol phosphorus borate；PH value is adjusted after temperature reduction, urea and octadecylamine is added, continues to be heated to reflux 8-
Reaction product is added to the water by 10h after the completion of reaction, is made into 60% solution to obtain the final product.
Further, with molar ratio computing, the boric acid：Tetrakis hydroxymetyl phosphonium sulfuric：The concentrated sulfuric acid：Water=1:2:0.1:20.
Further, the mass fraction of the concentrated sulfuric acid is 98%.
Further, it is 110-113 DEG C to be heated to reflux temperature twice.
Further, the pH value is adjusted to 6.0.
Further, the mass concentration of the NaOH is 50%.
Further, with molar ratio computing, the tetrakis hydroxymetyl phosphonium sulfuric：Urea：Octadecylamine=4:0.85:0.15.
Further, the octadecylamine includes n-octadecane amine (C18H37NH2)。
The invention also discloses one kind containing boron fire retardant preservative, is prepared by the above method.
The present invention discloses the above-mentioned application containing boron fire retardant preservative in preparing fire proofing material again.
Compared with prior art, the present invention can be obtained including following technique effect：
1) technical scheme of the present invention, raw material resources are abundant, cheap, technological operation simple possible, overcome previous
The defect of single-element fire retardant completes B, N, P new flame retardant effectively combined and significant effect, has very considerable
Economic benefit and social benefit.
2) fire retardant for preparing of the present invention meets nontoxic, Halogen, low cigarette, new to this minimum global evolution of environmental impact
Trend possesses huge market development potential.
Certainly, implementing any of the products of the present invention must be not necessarily required to reach all the above technique effect simultaneously.
Specific implementation mode
Carry out the embodiment that the present invention will be described in detail below in conjunction with embodiment, thereby to the present invention how application technology hand
Section solves technical problem and reaches the realization process of technical effect to fully understand and implement.
Embodiment
One, preparation method containing boron fire retardant preservative
1.1 weigh boric acid (6.18g, 0.1mol) with electronic balance, and the graduated cylinder wash clean that a range is 20ml is weighed
Tetrakis hydroxymetyl phosphonium sulfuric (81.2g, 0.2mol), 98% concentrated sulfuric acid (0.98g, 0.01mol) and water (36g, 2mol), wherein dense sulphur
Acid is used as catalyst, water as solvent that above-mentioned substance is put into 250ml three-necked flasks, condensation reflux unit is installed, puts together
Enter in heated at constant temperature magnetic stirrer, gradually rises temperature until flow back, optimum temperature (the about 110-113 as reacted
℃).Kept for 16-18 hour of thermotonus, with the progress of reaction, the color of reactant becomes clear oil from colourless liquid
Liquid, TLC trace detections determine that the reaction was complete.
The upper intermediate product obtained suddenly is adjusted PH to 6.0 by 1.2 with 50% NaOH, by urea and n-octadecane amine press than
Example is put into reaction kettle, is increased temperature to reflux (about 110-113 DEG C), is kept thermotonus 8-10 hours, tested with PH test paper
Display acidity can determine whether that amine disappears, so far target product tetra methylol phosphorus borate-urea preshrunk thing synthesis.By reaction product plus
Enter in water, be made into 60% solution to obtain the final product.
Two, reaction condition optimization
Influence of 2.1 tetrakis hydroxymetyl phosphonium sulfurics to flame retardant effect
2.1.1 prepared by fire retardant
Assuming that urea and n-octadecane amine proportion are fixed, change tetrakis hydroxymetyl phosphonium sulfuric and (urea+n-octadecane amine)
Ratio, according to the method described in 1.2, intermediate product, urea and the n-octadecane for selecting proper amount of 1.1 step to be prepared
Amine continues that different fire retardants is prepared.The addition of intermediate product, urea and n-octadecane amine that 1.1 steps are prepared
Amount is calculated according to shown in table 1.
1 tetrakis hydroxymetyl phosphonium sulfuric of table：Urea：The molar ratio of n-octadecane amine
| Tetrakis hydroxymetyl phosphonium sulfuric (mol) | Urea (mol) | N-octadecane amine (mol) | |
| 1 | 5.5 | 0.95 | 0.05 |
| 2 | 5.0 | 0.95 | 0.05 |
| 3 | 4.5 | 0.95 | 0.05 |
| 4 | 4.0 | 0.95 | 0.05 |
| 5 | 3.5 | 0.95 | 0.05 |
| 6 | 3.0 | 0.95 | 0.05 |
| 7 | 2.5 | 0.95 | 0.05 |
| 8 | 2.0 | 0.95 | 0.05 |
| 9 | 1.5 | 0.95 | 0.05 |
| 10 | 1.0 | 0.95 | 0.05 |
2.1.2 textile finishing
Cotton fabric sample is got out, is cleaned with suds and is once dried, flame retardant property may may be influenced on cloth by washing away
Substance.Sample is put into heating plate rising high-temperature and is restored to homogeneous liquid phase to it, cotton, which is immersed different each groups, respectively hinders
2~3min is uniformly impregnated in combustion agent treatment fluid, extra solution is rolled in taking-up on laboratory mangle, and repetition is padded primary.Pick-up
100%.5min is baked in 100 DEG C of drying box.So far the fabric treating for completing combustion testing gives over to flame retardant property test and uses.
2.1.3 flame retardant property is tested
The purpose of combustion test be by measure the char area and char length of sample, smoldering time and after flame time come
Determine the performance of fire retardant.Combustion experiment is divided into normal beam technique, gradient method and Horizontal Bridgman Method.The flame retardant property test of pure cotton fabric is usual
Use normal beam technique.
Will by different flame retardant, treated that cloth specimen is put into the specimen holder of flame retardant property tester, cloth specimen lower end and frame
Lower end alignment is pressed from both sides, burning chamber door is opened, is put into the centre of babinet frame, close the door.Air source to be connected, is pressed " igniting ", igniter is ignited,
It allows flame stabilization 10 seconds or so, presses " startup " button, igniter moves on under sample, and sample is ignited, and igniter automatically restores to
It is in situ to start timing, when no flame afterflame is recorded there is no " timing of glowing " is pressed when red Mars by " afterflame timing "
Time and smoldering time.Power supply is closed, specimen holder is taken out, unloads sample, char area is measured with graduated scale.According to fabric weight
Counterweight appropriate is selected, that end is being burnt far from counterweight is hung up at the 6mm of side, is keeping sample hanging with the other end of portable sample, put down
Sample measures char length with graduated scale, is as a result accurate to 1mm.
This operation is 20 DEG C or so in temperature, and humidity carries out between 30% to 80%.
2.1.4 result
Under the same reaction conditions, compare tetrakis hydroxymetyl phosphonium sulfuric：The variation of (urea+n-octadecane amine) molar ratio is to production
The influence of object flame retardant effect, the results are shown in Table 2.
Influence of 2 tetrakis hydroxymetyl phosphonium sulfuric of table to flame retardant effect
A is tetrakis hydroxymetyl phosphonium sulfuric；B is urea；C is n-octadecane amine.
Table 2 statistics indicate that, when urea and octadecylamine proportion assume fixed, molar ratio is 4:0.95:When burning when 0.05
Between it is most short, the damage degree of fabric is minimum, therefore tetrakis hydroxymetyl phosphonium sulfuric：(urea+n-octadecane amine) ≈ 4:Flame retardant effect when 1
It is best.
The influence of 2.2 urea and octadecylamine to flame retardant effect
2.2.1 prepared by fire retardant
In order to preferably determine urea and influence of the octadecylamine to anti-flammability, it is assumed that the proportion of tetrakis hydroxymetyl phosphonium sulfuric is solid
It is fixed, change the ratio of urea and n-octadecane amine, according to the method described in 1.2, proper amount of 1.1 step is selected to be prepared
Intermediate product, urea and n-octadecane amine continue that different fire retardants is prepared.Intermediate product that 1.1 steps are prepared,
The addition of urea and n-octadecane amine is calculated according to shown in table 3.
3 tetrakis hydroxymetyl phosphonium sulfuric of table：Urea：The molar ratio of n-octadecane amine
| Tetrakis hydroxymetyl phosphonium sulfuric (mol) | Urea (mol) | N-octadecane amine (mol) | |
| 1 | 4.0 | 0.95 | 0.05 |
| 2 | 4.0 | 0.90 | 0.10 |
| 3 | 4.0 | 0.85 | 0.15 |
| 4 | 4.0 | 0.80 | 0.20 |
| 5 | 4.0 | 0.75 | 0.25 |
| 6 | 4.0 | 0.70 | 0.30 |
| 7 | 4.0 | 0.65 | 0.35 |
| 8 | 4.0 | 0.60 | 0.40 |
| 9 | 4.0 | 0.55 | 0.45 |
| 10 | 4.0 | 0.50 | 0.50 |
2.2.2 textile finishing
Cotton fabric sample is got out, is cleaned with suds and is once dried, flame retardant property may may be influenced on cloth by washing away
Substance.Sample is put into heating plate rising high-temperature and is restored to homogeneous liquid phase to it, cotton, which is immersed different each groups, respectively hinders
2~3min is uniformly impregnated in combustion agent treatment fluid, extra solution is rolled in taking-up on laboratory mangle, and repetition is padded primary.Pick-up
100%.5min is baked in 100 DEG C of drying box.So far the fabric treating for completing combustion testing gives over to flame retardant property test and uses.
2.2.3 flame retardant property is tested
The purpose of combustion test be by measure the char area and char length of sample, smoldering time and after flame time come
Determine the performance of fire retardant.Combustion experiment is divided into normal beam technique, gradient method and Horizontal Bridgman Method.The flame retardant property test of pure cotton fabric is usual
Use normal beam technique.
Will by different flame retardant, treated that cloth specimen is put into the specimen holder of flame retardant property tester, cloth specimen lower end and frame
Lower end alignment is pressed from both sides, burning chamber door is opened, is put into the centre of babinet frame, close the door.Air source to be connected, is pressed " igniting ", igniter is ignited,
It allows flame stabilization 10 seconds or so, presses " startup " button, igniter moves on under sample, and sample is ignited, and igniter automatically restores to
It is in situ to start timing, when no flame afterflame is recorded there is no " timing of glowing " is pressed when red Mars by " afterflame timing "
Time and smoldering time.Power supply is closed, specimen holder is taken out, unloads sample, char area is measured with graduated scale.According to fabric weight
Counterweight appropriate is selected, that end is being burnt far from counterweight is hung up at the 6mm of side, is keeping sample hanging with the other end of portable sample, put down
Sample measures char length with graduated scale, is as a result accurate to 1mm.
This operation is 20 DEG C or so in temperature, and humidity carries out between 30% to 80%.
2.2.4 result
Under the same reaction conditions, compare urea：N-octadecane amine molar ratio changes the influence to product flame retardant effect,
The results are shown in Table 4.
The influence of 4 urea of table and n-octadecane amine to flame retardant effect
A is tetrakis hydroxymetyl phosphonium sulfuric；B is urea；C is n-octadecane amine.
It can be seen from Table 4 that when tetrakis hydroxymetyl phosphonium sulfuric molal quantity is fixed, urea is with n-octadecane amine according to 0.85:
0.15 ratio reaction, the flame retardant effect of product are best, the smoldering time of fire retardant at this time, after flame time, char length
It is minimum.Conclusive table 2 and table 4, it may be determined that synthesis tetra methylol phosphorus borate-this fire retardant of urea preshrunk thing most preferably rubbing
You are than being 4:0.85:0.15.
Three, influence of the crosslinking agent to flame retardant effect
It is prepared by 3.1 fire retardants
1.1 intermediate products being prepared are taken, by tetrakis hydroxymetyl phosphonium sulfuric：Urea：N-octadecane amine=4:0.85:
0.15, urea and n-octadecane amine is added, fire retardant is prepared according to 1.2 the methods.
3.2 textile finishing
The fire retardant that 3.1 are prepared is divided into two parts, a portion is marked as 1；Another part is into fire retardant
The butanediol glycidol ether that addition mass fraction is 5% matches resulting mixture, marked as 1+ as crosslinking agent.
Cotton fabric sample is got out, is cleaned with suds and is once dried, flame retardant property may may be influenced on cloth by washing away
Substance.Cotton is immersed in different each group fire retardant treatment fluids respectively and uniformly impregnates 2~3min, taking-up is rolled on laboratory mangle
Extra solution, repetition are padded primary.Pick-up 100%.5min is baked in 100 DEG C of drying box.So far combustion testing is completed
Fabric treating, give over to flame retardant property test use.
3.3 flame retardant properties are tested
The purpose of combustion test be by measure the char area and char length of sample, smoldering time and after flame time come
Determine the performance of fire retardant.Combustion experiment is divided into normal beam technique, gradient method and Horizontal Bridgman Method.The flame retardant property test of pure cotton fabric is usual
Use normal beam technique.
Will by different flame retardant, treated that cloth specimen is put into the specimen holder of flame retardant property tester, cloth specimen lower end and frame
Lower end alignment is pressed from both sides, burning chamber door is opened, is put into the centre of babinet frame, close the door.Air source to be connected, is pressed " igniting ", igniter is ignited,
It allows flame stabilization 10 seconds or so, presses " startup " button, igniter moves on under sample, and sample is ignited, and igniter automatically restores to
It is in situ to start timing, when no flame afterflame is recorded there is no " timing of glowing " is pressed when red Mars by " afterflame timing "
Time and smoldering time.Power supply is closed, specimen holder is taken out, unloads sample, char area is measured with graduated scale.According to fabric weight
Counterweight appropriate is selected, that end is being burnt far from counterweight is hung up at the 6mm of side, is keeping sample hanging with the other end of portable sample, put down
Sample measures char length with graduated scale, is as a result accurate to 1mm.
This operation is 20 DEG C or so in temperature, and humidity carries out between 30% to 80%.
Influence of the crosslinking agent to flame retardant effect is shown in Table 5.In table 5, the cloth specimen after flame time of crosslinking agent is added to be higher than not plus be crosslinked
The cloth specimen of agent, while the cloth specimen damage degree of crosslinking agent being added to be more than the cloth specimen not added.By comparison it could be assumed that：Addition crosslinking
Agent is in the method to flame retardant effect without too big help.
Influence of 5 crosslinking agent of table to flame retardant effect
| Serial number | After flame time (s) | Smoldering time (s) | Char length (mm) |
| 1 | 0 | 0 | 2.9 |
| 1+ | 0 | 0 | 4.5 |
3.4 antistatic properties are tested
Fabric surface is rubbed to will produce electrostatic, not only causes difficulty to technique processing, and absorbing dust makes the people of dress feel
To discomfort, the serious Mars that also will produce causes fire to order generation threat to life.Good fire retardant is while preventing to burn
Also good antistatic property.
Instrument switch is opened, 10-30min is first being preheated before.In the state of standby, before test sample, mix up with
Lower default value：Motor elimination run time 15s, method are set as voltage method, set spray point with examination between-sample distance d as 2, discharge end
Son is 20mm with sample spacing, and electrostatic probe is 15mm, high input voltage 10000v, attenuation ratio 0.5 with sample spacing.
It waits for that the above numerical value is adjusted to finish, by ready cloth specimen, is put into position as defined in folder sample dish, presses " RUN " button, machine is opened
Dynamic test is started from, after stopping, replacing sample, is completed until all samples detect.Influence of the crosslinking agent to flame retardant effect is shown in Table 6.
Since this synthetic product has more hydrophilic radical, wettability power is stronger, being capable of shape during triboelectrification
At conductive film, rapidly by electric charge transfer.By table 6 it is apparent that treated cloth specimen is compared with as former state, peak value electricity
Pressing to have with damped cycle significantly reduces, and antistatic effect is preferable.Addition crosslinking agent and the cloth specimen phase for being not added with crosslinking agent
Than, be not added with the damped cycle of crosslinking agent less than plus crosslinking agent, therefore it is concluded that this substance have it is good anti-quiet
Electric energy power, and adding crosslinking agent can not be such that antistatic effect improves.
Influence of 6 crosslinking agent of table to antistatic effect
| Serial number | Crest voltage (v) | Damped cycle (s) | End point voltage (v) |
| As former state | 1279 | 0.88 | 633 |
| 1 | 282 | 0.61 | 139 |
| 1+ | 282 | 0.72 | 134 |
Technical scheme of the present invention, raw material resources are abundant, cheap, and technological operation simple possible overcomes previous list
The defect of one element fire retardant completes B, N, P new flame retardant effectively combined and significant effect, has very considerable
Economic benefit and social benefit.Fire retardant prepared by the present invention, meets that nontoxic, Halogen, low cigarette, minimum to environmental impact this is complete
Ball new development trend possesses huge market development potential.
Some vocabulary has such as been used to censure special component or method in specification and claim.Art technology
Personnel are, it is to be appreciated that different regions may call the same ingredient with different nouns.This specification and claims are not
In such a way that the difference of title is used as and distinguishes ingredient.As the "comprising" of the specification in the whole text and claim mentioned in is
One open language, therefore should be construed to " including but not limited to "." substantially " refer to this field in receivable error range
Technical staff can solve the technical problem within a certain error range, basically reach the technique effect.Specification is follow-up
It is described as implementing the better embodiment of the present invention, so description is for the purpose of the rule for illustrating the present invention, not
To limit the scope of the present invention.Protection scope of the present invention is when subject to appended claims institute defender.
It should also be noted that, the terms "include", "comprise" or its any other variant are intended to nonexcludability
Including so that commodity or system including a series of elements include not only those elements, but also include not clear
The other element listed, or further include for this commodity or the intrinsic element of system.In the feelings not limited more
Under condition, the element that is limited by sentence "including a ...", it is not excluded that including the element commodity or system in also
There are other identical elements.
Several preferred embodiments of the present invention have shown and described in above description, but as previously described, it should be understood that the present invention
Be not limited to form disclosed herein, be not to be taken as excluding other embodiments, and can be used for various other combinations,
Modification and environment, and the above teachings or related fields of technology or knowledge can be passed through in the scope of the invention is set forth herein
It is modified.And changes and modifications made by those skilled in the art do not depart from the spirit and scope of the present invention, then it all should be in this hair
In the protection domain of bright appended claims.
Claims (7)
1. a kind of preparation method containing boron fire retardant preservative, which is characterized in that include the following steps：Take boric acid, tetrakis hydroxymetyl phosphonium sulfuric,
The concentrated sulfuric acid and water mixing, are heated to reflux 16-18h, stop heating after the reaction was complete, obtain tetra methylol phosphorus borate；Wait for temperature
PH value is adjusted after reduction, adds urea and octadecylamine, is continued to be heated to reflux 8-10h, is added reaction product after the completion of reaction
Enter in water, be made into 60% solution to obtain the final product；
With molar ratio computing, the boric acid：Tetrakis hydroxymetyl phosphonium sulfuric：The concentrated sulfuric acid：Water=1:2:0.1:20；
The mass fraction of the concentrated sulfuric acid is 98%；
With molar ratio computing, the tetrakis hydroxymetyl phosphonium sulfuric：Urea：Octadecylamine=4:0.85:0.15.
2. the preparation method containing boron fire retardant preservative as described in claim 1, which is characterized in that the octadecylamine includes positive 18
Alkanamine.
3. the preparation method containing boron fire retardant preservative as claimed in claim 2, which is characterized in that the pH value is adjusted to 6.0.
4. the preparation method containing boron fire retardant preservative as claimed in claim 3, which is characterized in that the pH value is with mass concentration
50% NaOH is adjusted.
5. the preparation method containing boron fire retardant preservative as claimed in claim 4, which is characterized in that being heated to reflux temperature twice is
110-113℃。
6. one kind containing boron fire retardant preservative, which is characterized in that be prepared by method as described in any one in claim 1-5.
7. the application containing boron fire retardant preservative in preparing fire proofing material as claimed in claim 6.
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