CN106958143A - A kind of preparation method of antiflaming finishing agent and its fire-retardant Lyocell fiber fabric - Google Patents
A kind of preparation method of antiflaming finishing agent and its fire-retardant Lyocell fiber fabric Download PDFInfo
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- CN106958143A CN106958143A CN201710222336.6A CN201710222336A CN106958143A CN 106958143 A CN106958143 A CN 106958143A CN 201710222336 A CN201710222336 A CN 201710222336A CN 106958143 A CN106958143 A CN 106958143A
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- Prior art keywords
- diamine
- methylenephosphonic acid
- retardant
- fire
- lyocell fiber
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 52
- 229920000433 Lyocell Polymers 0.000 title claims abstract description 51
- 239000004744 fabric Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 55
- 150000004985 diamines Chemical class 0.000 claims abstract description 53
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 19
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 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 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000000979 retarding effect Effects 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000012153 distilled water Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 230000002459 sustained effect Effects 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 238000005096 rolling process Methods 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000004753 textile Substances 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229920003043 Cellulose fiber Polymers 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 229920000297 Rayon Polymers 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- BSBSDQUZDZXGFN-UHFFFAOYSA-N cythioate Chemical compound COP(=S)(OC)OC1=CC=C(S(N)(=O)=O)C=C1 BSBSDQUZDZXGFN-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 230000001473 noxious effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- MCONGYNHPPCHSD-UHFFFAOYSA-N 3-dimethoxyphosphoryl-n-(hydroxymethyl)propanamide Chemical compound COP(=O)(OC)CCC(=O)NCO MCONGYNHPPCHSD-UHFFFAOYSA-N 0.000 description 1
- JJIXKNZGIUPHIL-UHFFFAOYSA-N OC=1C=C(C=CC=1)[P] Chemical compound OC=1C=C(C=CC=1)[P] JJIXKNZGIUPHIL-UHFFFAOYSA-N 0.000 description 1
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- ZNSDNJGLCKLLQW-UHFFFAOYSA-N [O].C1(=CC=CC=C1)[P] Chemical compound [O].C1(=CC=CC=C1)[P] ZNSDNJGLCKLLQW-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- AKXUUJCMWZFYMV-UHFFFAOYSA-M tetrakis(hydroxymethyl)phosphanium;chloride Chemical compound [Cl-].OC[P+](CO)(CO)CO AKXUUJCMWZFYMV-UHFFFAOYSA-M 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 238000009941 weaving Methods 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
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/44—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing nitrogen and phosphorus
- D06M13/447—Phosphonates or phosphinates containing nitrogen atoms
-
- 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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
-
- 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
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
-
- 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)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a kind of preparation method of antiflaming finishing agent and its fire-retardant Lyocell fiber fabric, it is related to organic synthesis and textile engineering technical field.The preparation process of antiflaming finishing agent is：First using hydrazine hydrate, phosphorous acid and formaldehyde as the methylenephosphonic acid of Material synthesis diamine four, the methylenephosphonic acid of diamine four and urea reaction are secondly generated into the fire retardant：The methylenephosphonic acid ammonium of diamine four, the methylenephosphonic acid ammonium of diamine four is soluble in water, solution is configured to, and a certain amount of dicyandiamide formation mixed solution is added, produce fire retarding treating liquid；The antiflaming finishing agent is applied to the fire-retardant of Lyocell fiber fabric using compregnate, baking.Fire retardant preparation technology of the present invention is simple, low cost, yield are high, and environmental protection on the basis of the good durable flame-retardant of Lyocell fiber fabric is ensured, its dyeability is not influenceed, with great market prospects.
Description
Technical field
The present invention relates to organic synthesis and textile engineering technical field, and in particular to a kind of preparation of antiflaming finishing agent
Method and its fire-retardant Lyocell fiber fabric.
Background technology
Cellulose fibre, such as cotton fiber, flaxen fiber are the most maximum natural fibers of extensive, storage level of originating in the world,
Have the advantages that excellent hygroscopicity, easy dyeing, with skin compatibility is good, environmental protection, be widely used in clothes, drapery
Deng field, significant role has been played in national economy.Viscose rayon is as regenerated celulose fibre, with smooth nice and cool, saturating
Gas is good, antistatic, comfortable and easy to wear, dyes the characteristic such as gorgeous, pure can both spin, can also with other textile fabric blending, suitably
In manufacturing underwear, coat and various adornments.However, cotton fiber belongs to flammable fiber with viscose rayon, the weaving being made from it
Grade easy firing and trigger fire, therefore, be directed to the fire-retardant research of cellulose fibre always both at home and abroad.
So far, the flame-proof cotton fabric of industrialization is more based on halogenated flame retardant and phosphorus flame retardant, such as Proban ammonia
Smoked technique, preshrunk body is generated using tetra methylol phosphonium chloride and urea reaction, and the subsequent preshrunk body is oozed in the way of padding drying
Enter into the amorphous area and gap of cellulose fibre, then by ammonia cure processing, the methylol and ammonia for making preshrunk body are crosslinked, in fabric
It is internally formed after non-soluble polymer and obtains rock-steady structure through hydrogen peroxide oxidation, obtains excellent flame-proof cotton fabric.Through the resistance
Though combustion finishing technique can obtain excellent fire-retardant durable fabric, it can be discharged during arranging after formaldehyde gas, and arrangement
Fabric feeling is poor, limits the extensive use of this technique.Another flame-proof finishing process is Pyrovatex CP techniques, is utilized
N- methylols -3- (dimethoxy phosphono) propionamides crosslink reaction under acid catalysis with crosslinking agent with cellulose, are formed
Durable flame-retardant bafta, but the finishing agent contains free formaldehyde, can be discharged during storage and use after textile finishing
Free formaldehyde, equally limits its extensive use.Crosslinking agent is made using polyacid, is knitted though the fire-retardant of low formaldehyde emission can be obtained
Thing, but still growing environmental requirement can not be met.
Lyocell fiber is a kind of new regenerated celulose fibre, compared with cellulose viscose manufacturing technique, with technique
The features such as relatively easy, environmental protection, prepared Lyocell fiber has high-strength good characteristic, as falling over each other both at home and abroad
The green fiber of exploitation.However, the fiber is as other native cellulose fibres and regenerated celulose fibre, with inflammable
Defect, therefore, the fire-retardant research to Lyocell fiber both at home and abroad are done a lot of work.Chinese invention patent application number is CN
A kind of method for preparing flame-retardant Lyocell fiber disclosed in 1133617A, i.e., will in conventional Lyocell fiber production process
Proban and Pyrovatex fire retarding treating liquids are penetrated into the non-dry fibers before fiber is dried for the first time, are prepared fire-retardant
Lyocell fiber, but the feel decline of fiber；Chinese invention patent application number is disclosed 3- hydroxyls for CN 103541034A
Phenyl phosphorus oxygen base propionic acid is blended in Lyocell fiber spinning solution, spinning flame-retardant Lyocell fiber, but 3- hydroxy phenyl phosphorus
Epoxide propionic acid has certain water solubility, have impact on the durability of fire-retardant of the flame-retardant Lyocell fiber.
The content of the invention
For deficiency present on prior art, the present invention seeks to be to provide a kind of preparation method of antiflaming finishing agent
And its fire-retardant Lyocell fiber fabric, simply, yield is high by preparation technology, and environmental protection, fire-retardant Lyocell fiber is knitted
Thing fire resistance is good, good endurance.
To achieve these goals, the present invention is to realize by the following technical solutions：A kind of antiflaming finishing agent, its is same
Shi Hanyou phosphorus nitrogen flame-retardant compositions, its structural formula is
A kind of preparation method of antiflaming finishing agent, its preparation process is：(1) first using hydrazine hydrate, phosphorous acid and formaldehyde as
The methylenephosphonic acid of Material synthesis diamine four, wherein, n (hydrazine hydrate)：N (formaldehyde)：N (phosphorous acid)=1：4：4；
(2) secondly, the methylenephosphonic acid of diamine four and urea reaction are generated into the fire retardant：The methylenephosphonic acid ammonium of diamine four.Its
In, n (methylenephosphonic acid of diamine four)：N (urea)=1：2~1：4；
(3) it is the methylenephosphonic acid ammonium of diamine four is soluble in water, it is configured to concentration and is 50g/L~300g/L solution, and adds
A certain amount of dicyandiamide formation mixed solution, produces fire retarding treating liquid.
The specific preparation process of antiflaming finishing agent is：(1) weigh 80% hydrazine hydrate 200g (5mol), be poured into and be equipped with
In the 5L reactors of constant pressure funnel, mechanical agitator and thermometer, add 240g distilled water and be diluted to 80% hydrazine hydrate
40%, agitator is started, automatically controlled heating, when temperature rises to 30~40 DEG C, adds 20mol (1640g, 993.3ml) phosphorous acid,
Be continuously heating to 40~50 DEG C, then by constant pressure funnel be added dropwise 36% formalin 1666.7g (20mol,
2032.5ml), formalin completion of dropping is treated, reaction system 100~110 DEG C are warming up to, 2~3h of sustained response produces connection
The methylenephosphonic acid crude product of amine four, is 1 with volume ratio：1 absolute ethyl alcohol and acetone is recrystallized to crude product, obtains refined
The methylenephosphonic acid of diamine four；
(2) methylenephosphonic acid of a certain amount of diamine four obtained in step (1) is dissolved in distilled water, and with urea according to rubbing
You compare 1：2~1：4 react 1~2h in 100~105 DEG C, that is, obtain fire retardant：The methylenephosphonic acid ammonium of diamine four；
(3) it is 50g/L~300g/L the methylenephosphonic acid ammonium of diamine four obtained in step (2) to be configured into concentration with distilled water
Solution, and add the methylenephosphonic acid ammonium mass fraction of diamine four be 1~10% dicyandiamide, that is, obtain antiflaming finishing agent.
A kind of fire-retardant Lyocell fiber fabric of application antiflaming finishing agent, its preparation process is：Lyocell fiber is knitted
Thing be impregnated in concentration be 50g/L~300g/L fire retarding treating liquid, dipping temperature scope room temperature~100 DEG C, dip time be 5~
30min, is suppressed Lyocell fiber fabric with double roll press, the pick-up rate of Lyocell fiber fabric is maintained at 50% afterwards
Between~120%, then in 100~120 DEG C of dry 5~30min, 30s~5min is baked then at 160~200 DEG C, that is, is hindered
Fire Lyocell fiber fabric.
Beneficial effects of the present invention：This fire retardant preparation technology is simple, and yield is high, environmental protection, fire-retardant Lyocell
Fabric fire resistance is good, good endurance, and its mechanical property is good, preparation method environmental protection, and technique is simple, finisher
Without using noxious material in skill, and also discharged during its use without noxious material, meet environmental requirement.
Embodiment
To be easy to understand technological means, creation characteristic, reached purpose and effect of the invention realized, with reference to
Embodiment, is expanded on further the present invention.
Present embodiment uses following technical scheme：A kind of antiflaming finishing agent, it contains phosphorus nitrogen flame-retardant composition simultaneously,
Its structural formula is
A kind of preparation method of antiflaming finishing agent, its preparation process is：(1) first using hydrazine hydrate, phosphorous acid and formaldehyde as
The methylenephosphonic acid of Material synthesis diamine four, wherein, n (hydrazine hydrate)：N (formaldehyde)：N (phosphorous acid)=1：4：4；
(2) secondly, the methylenephosphonic acid of diamine four and urea reaction are generated into the fire retardant：The methylenephosphonic acid ammonium of diamine four.Its
In, n (methylenephosphonic acid of diamine four)：N (urea)=1：2~1：4；
(3) it is the methylenephosphonic acid ammonium of diamine four is soluble in water, it is configured to concentration and is 50g/L~300g/L solution, and adds
A certain amount of dicyandiamide formation mixed solution, produces fire retarding treating liquid.
The specific preparation process of the antiflaming finishing agent is：(1) weigh 80% hydrazine hydrate 200g (5mol), be poured into dress
Have in the 5L reactors of constant pressure funnel, mechanical agitator and thermometer, add 240g distilled water and dilute 80% hydrazine hydrate
To 40%, agitator is started, automatically controlled heating, when temperature rises to 30~40 DEG C, adds 20mol (1640g, 993.3ml) phosphorous
Acid, is continuously heating to 40~50 DEG C, then by constant pressure funnel be added dropwise 36% formalin 1666.7g (20mol,
2032.5ml), formalin completion of dropping is treated, reaction system 100~110 DEG C are warming up to, 2~3h of sustained response produces connection
The methylenephosphonic acid crude product of amine four, is 1 with volume ratio：1 absolute ethyl alcohol and acetone is recrystallized to crude product, obtains refined
The methylenephosphonic acid of diamine four；
(2) methylenephosphonic acid of a certain amount of diamine four obtained in step (1) is dissolved in distilled water, and with urea according to rubbing
You compare 1：2~1：4 react 1~2h in 100~105 DEG C, that is, obtain fire retardant：The methylenephosphonic acid ammonium of diamine four；
(3) it is 50g/L~300g/L the methylenephosphonic acid ammonium of diamine four obtained in step (2) to be configured into concentration with distilled water
Solution, and add the methylenephosphonic acid ammonium mass fraction of diamine four be 1~10% dicyandiamide, that is, obtain antiflaming finishing agent.
A kind of fire-retardant Lyocell fiber fabric of application antiflaming finishing agent, its preparation process is：Lyocell fiber is knitted
Thing be impregnated in concentration be 50g/L~300g/L fire retarding treating liquid, dipping temperature scope room temperature~100 DEG C, dip time be 5~
30min, is suppressed Lyocell fiber fabric with double roll press, the pick-up rate of Lyocell fiber fabric is maintained at 50% afterwards
Between~120%, then in 100~120 DEG C of dry 5~30min, 30s~5min is baked then at 160~200 DEG C, that is, is hindered
Fire Lyocell fiber fabric.
Present embodiment fire retardant phosphorus, nitrogen content are of a relatively high, and fire retardant can be with the shape of chemical bond during arrangement
Formula is combined with cellulosic molecule, improves the durability of fire-retardant of Lyocell fiber fabric；It is fire-retardant process environmental protection, fire-retardant
The brill function admirable of Lyocell fiber fabric, limited oxygen index value is up to more than 30%；This fire retardant preparation method is simple, into
This low, environmental protection, on the basis of the good durable flame-retardant of Lyocell fiber fabric is ensured, its dyeability is not influenceed,
With wide market application foreground.
Embodiment 1：Prepared by fire retardant and the specific preparation process of flame-proof treatment of Lyocell fiber fabric is：(1) weigh
80% hydrazine hydrate 50g (1.25mol), is poured into the 2L reactions equipped with constant pressure funnel, mechanical agitator and thermometer
In kettle, add 60g distilled water and 80% hydrazine hydrate is diluted to 40%, start agitator, automatically controlled heating, when temperature rises to 30 DEG C
When, 5mol (410g, 248.3ml) phosphorous acid is added, 50 DEG C are continuously heating to, then 36% is added dropwise by constant pressure funnel
Formalin 416.7g (5mol, 508ml), treats formalin completion of dropping, and reaction system is warming up into 105 DEG C, sustained response
2h, produces the methylenephosphonic acid crude product of diamine four, is 1 with volume ratio：1 absolute ethyl alcohol and acetone is recrystallized to crude product,
Obtain the refined methylenephosphonic acid of diamine four；
(2) methylenephosphonic acid of a certain amount of diamine four obtained in step (1) is dissolved in distilled water, and with urea according to rubbing
You compare 1：2 react 1.5h in 100 DEG C, that is, obtain fire retardant：The methylenephosphonic acid ammonium of diamine four；
(3) the methylenephosphonic acid ammonium of diamine four obtained in step (2) is configured to the solution that concentration is 60g/L with distilled water,
And add the dicyandiamide that the methylenephosphonic acid ammonium mass fraction of diamine four is 5%, that is, obtain antiflaming finishing agent.
In the fire retarding treating liquid that Lyocell fiber fabric is impregnated in above-mentioned concentration, 50 DEG C of dipping temperature, dip time is
20min, is suppressed Lyocell fiber fabric with double roll press afterwards, and the pick-up rate for making Lyocell fiber fabric is 50%, so
After 105 DEG C of dry 10min, 30s is baked then at 200 DEG C, that is, obtains flame-retardant Lyocell fiber fabric.
Embodiment 2：Prepared by fire retardant and the specific preparation process of flame-proof treatment of Lyocell fiber fabric is：(1) weigh
80% hydrazine hydrate 50g (1.25mol), is poured into the 2L reactions equipped with constant pressure funnel, mechanical agitator and thermometer
In kettle, add 60g distilled water and 80% hydrazine hydrate is diluted to 40%, start agitator, automatically controlled heating, when temperature rises to 40 DEG C
When, 5mol (410g, 248.3ml) phosphorous acid is added, 40 DEG C are continuously heating to, then 36% is added dropwise by constant pressure funnel
Formalin 416.7g (5mol, 508ml), treats formalin completion of dropping, and reaction system is warming up into 110 DEG C, sustained response
3h, produces the methylenephosphonic acid crude product of diamine four, is 1 with volume ratio：1 absolute ethyl alcohol and acetone is recrystallized to crude product,
Obtain the refined methylenephosphonic acid of diamine four；
(2) methylenephosphonic acid of a certain amount of diamine four obtained in step (1) is dissolved in distilled water, and with urea according to rubbing
You compare 1：4 react 1h in 105 DEG C, that is, obtain fire retardant：The methylenephosphonic acid ammonium of diamine four；
(3) the methylenephosphonic acid ammonium of diamine four obtained in step (2) is configured to the solution that concentration is 50g/L with distilled water,
And add the dicyandiamide that the methylenephosphonic acid ammonium mass fraction of diamine four is 1%, that is, obtain antiflaming finishing agent.
In the fire retarding treating liquid that Lyocell fiber fabric is impregnated in above-mentioned concentration, 50 DEG C of dipping temperature, dip time is
20min, is suppressed Lyocell fiber fabric with double roll press afterwards, and the pick-up rate for making Lyocell fiber fabric is 100%, so
After 120 DEG C of dry 5min, 3min is baked then at 160 DEG C, that is, obtains flame-retardant Lyocell fiber fabric.
Embodiment 3：Prepared by fire retardant and the specific preparation process of flame-proof treatment of Lyocell fiber fabric is：(1) weigh
80% hydrazine hydrate 50g (1.25mol), is poured into the 2L reactions equipped with constant pressure funnel, mechanical agitator and thermometer
In kettle, add 60g distilled water and 80% hydrazine hydrate is diluted to 40%, start agitator, automatically controlled heating, when temperature rises to 40 DEG C
When, 5mol (410g, 248.3ml) phosphorous acid is added, 45 DEG C are continuously heating to, then 36% is added dropwise by constant pressure funnel
Formalin 416.7g (5mol, 508ml), treats formalin completion of dropping, and reaction system is warming up into 100 DEG C, sustained response
2h, produces the methylenephosphonic acid crude product of diamine four, is 1 with volume ratio：1 absolute ethyl alcohol and acetone is recrystallized to crude product,
Obtain the refined methylenephosphonic acid of diamine four；
(2) methylenephosphonic acid of a certain amount of diamine four obtained in step (1) is dissolved in distilled water, and with urea according to rubbing
You compare 1：3 react 1.5h in 100 DEG C, that is, obtain fire retardant：The methylenephosphonic acid ammonium of diamine four；
(3) the methylenephosphonic acid ammonium of diamine four obtained in step (2) is configured to the solution that concentration is 300g/L with distilled water,
And add the dicyandiamide that the methylenephosphonic acid ammonium mass fraction of diamine four is 10%, that is, obtain antiflaming finishing agent.
In the fire retarding treating liquid that Lyocell fiber fabric is impregnated in above-mentioned concentration, 30min, Zhi Houyong are impregnated at room temperature
Double roll press is suppressed Lyocell fiber fabric, and the pick-up rate for making Lyocell fiber fabric is 120%, then dry in 100 DEG C
Dry 30min, 30min is baked then at 1600 DEG C, that is, obtains flame-retardant Lyocell fiber fabric.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appending claims and its
Equivalent thereof.
Claims (4)
1. a kind of antiflaming finishing agent, it is characterised in that it contains phosphorus nitrogen flame-retardant composition simultaneously, its structural formula is
2. a kind of preparation method of antiflaming finishing agent, it is characterised in that its preparation process is：
(1) first using hydrazine hydrate, phosphorous acid and formaldehyde as the methylenephosphonic acid of Material synthesis diamine four, wherein, n (hydrazine hydrate)：N (first
Aldehyde)：N (phosphorous acid)=1：4：4；
(2) secondly, the methylenephosphonic acid of diamine four and urea reaction are generated into the fire retardant：The methylenephosphonic acid ammonium of diamine four.Wherein, n
(methylenephosphonic acid of diamine four)：N (urea)=1：2~1：4；
(3) it is the methylenephosphonic acid ammonium of diamine four is soluble in water, the solution that concentration is 50g/L~300g/L is configured to, and add certain
The dicyandiamide formation mixed solution of amount, produces fire retarding treating liquid.
3. a kind of fire-retardant Lyocell fiber fabric of application antiflaming finishing agent, it is characterised in that its preparation process is：Will
Lyocell fiber fabric be impregnated in concentration be 50g/L~300g/L fire retarding treating liquid, dipping temperature scope room temperature~100 DEG C,
Dip time is 5~30min, and Lyocell fiber fabric is suppressed with double roll press afterwards, makes rolling for Lyocell fiber fabric
Liquid rate is maintained between 50%~120%, and then in 100~120 DEG C of dry 5~30min, 30s is baked then at 160~200 DEG C
~5min, that is, obtain flame-retardant Lyocell fiber fabric.
4. a kind of preparation method of antiflaming finishing agent according to claim 2, it is characterised in that its specific preparation process
For：(1) weigh 80% hydrazine hydrate 200g (5mol), be poured into equipped with constant pressure funnel, mechanical agitator and thermometer
5L reactors in, add 240g distilled water 80% hydrazine hydrate is diluted to 40%, start agitator, temperature is worked as in automatically controlled heating
When rising to 30~40 DEG C, 20mol (1640g, 993.3ml) phosphorous acid is added, 40~50 DEG C is continuously heating to, then passes through constant pressure
36% formalin 1666.7g (20mol, 2032.5ml) is added dropwise in dropping funel, formalin completion of dropping is treated, by reactant
System is warming up to 100~110 DEG C, and 2~3h of sustained response produces the methylenephosphonic acid crude product of diamine four, is 1 with volume ratio：1 it is anhydrous
Ethanol and acetone are recrystallized to crude product, obtain the refined methylenephosphonic acid of diamine four；
(2) methylenephosphonic acid of a certain amount of diamine four obtained in step (1) is dissolved in distilled water, and with urea according to mol ratio
1：2~1：4 react 1~2h in 100~105 DEG C, that is, obtain fire retardant：The methylenephosphonic acid ammonium of diamine four；
(3) it is the molten of 50g/L~300g/L the methylenephosphonic acid ammonium of diamine four obtained in step (2) to be configured into concentration with distilled water
Liquid, and add the dicyandiamide that the methylenephosphonic acid ammonium mass fraction of diamine four is 1~10%, that is, obtain antiflaming finishing agent.
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| CN107353437A (en) * | 2017-08-08 | 2017-11-17 | 青岛长荣化工科技有限公司 | A kind of expansion type flame retardant and preparation method thereof |
| CN107903286A (en) * | 2017-10-17 | 2018-04-13 | 山东泰和水处理科技股份有限公司 | A kind of two methylenephosphonic acid of fire retardant cyclohexylamine and preparation method thereof |
| CN108018715A (en) * | 2017-12-08 | 2018-05-11 | 天津工业大学 | A kind of preparation method of antiflaming finishing agent and fire-retardant regenerated cellulose fiber |
| CN109180724A (en) * | 2018-10-22 | 2019-01-11 | 长江大学 | A kind of environment-friendly type calcium scale is drawn up agent and preparation method thereof |
| CN109576809A (en) * | 2018-12-10 | 2019-04-05 | 天津工业大学 | Compound phosphorous-nitrogen system bittern-free fire retardant and its preparation method and application |
| CN112680963A (en) * | 2020-12-15 | 2021-04-20 | 南京金羚生物基纤维有限公司 | Preparation method of novel flame-retardant Lyocell fiber |
| CN114197222A (en) * | 2021-12-24 | 2022-03-18 | 山东龙港硅业科技有限公司 | Flame-retardant anti-dripping polyester fiber and preparation method and application thereof |
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| CN107353437A (en) * | 2017-08-08 | 2017-11-17 | 青岛长荣化工科技有限公司 | A kind of expansion type flame retardant and preparation method thereof |
| CN107903286A (en) * | 2017-10-17 | 2018-04-13 | 山东泰和水处理科技股份有限公司 | A kind of two methylenephosphonic acid of fire retardant cyclohexylamine and preparation method thereof |
| CN108018715A (en) * | 2017-12-08 | 2018-05-11 | 天津工业大学 | A kind of preparation method of antiflaming finishing agent and fire-retardant regenerated cellulose fiber |
| CN109180724A (en) * | 2018-10-22 | 2019-01-11 | 长江大学 | A kind of environment-friendly type calcium scale is drawn up agent and preparation method thereof |
| CN109576809A (en) * | 2018-12-10 | 2019-04-05 | 天津工业大学 | Compound phosphorous-nitrogen system bittern-free fire retardant and its preparation method and application |
| CN109576809B (en) * | 2018-12-10 | 2021-09-14 | 天津工业大学 | Composite phosphorus-nitrogen halogen-free flame retardant and preparation method and application thereof |
| CN112680963A (en) * | 2020-12-15 | 2021-04-20 | 南京金羚生物基纤维有限公司 | Preparation method of novel flame-retardant Lyocell fiber |
| CN114197222A (en) * | 2021-12-24 | 2022-03-18 | 山东龙港硅业科技有限公司 | Flame-retardant anti-dripping polyester fiber and preparation method and application thereof |
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