CN101935946A - Method for preparing flame-retardant fibers - Google Patents
Method for preparing flame-retardant fibers Download PDFInfo
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- CN101935946A CN101935946A CN2010102735767A CN201010273576A CN101935946A CN 101935946 A CN101935946 A CN 101935946A CN 2010102735767 A CN2010102735767 A CN 2010102735767A CN 201010273576 A CN201010273576 A CN 201010273576A CN 101935946 A CN101935946 A CN 101935946A
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Abstract
The invention discloses a method for preparing flame-retardant fibers. The method comprises that: photosensitive polymer solution with flame retardant is uniformly coated on the surfaces of fibers by dipping or spraying, and the coating is solidified under the irradiation of an ultraviolet lamp so that the flame retardant is fixed on the surfaces of the fibers and the fibers are endowed with flame-retardant performance, wherein the temperature of a lamp box is controlled to be between 25 and 125 DEG C, the wavelength of an ultraviolet light source is controlled to be between 280 and 350 nanometers, the power is 150 to 250mW/cm<2>, and the irradiation time is 2 to 15 seconds. Compared with the prior art, the flame-retardant fibers have the advantages of difficult fall, durable flame-retardant property, soft handfeel, wearing comfortableness and the like; and the preparation method has simple process and low cost.
Description
Technical field
That the present invention relates to is a kind of preparation method of fire resistance fibre, belongs to the functional fibre technical field.
Background technology
Along with the development of society and the raising of living standards of the people, the people's fire-retardant consciousness constantly strengthens, and also more and more higher to the fire-retardant requirement of living environment simultaneously, the demand of flame retardant products increases day by day.The fire that is caused by fibre has simultaneously become one of great disaster in the society.As clothing dress ornament and household supplies, also must cause its flammable concern.At present countries in the world are all at the laws and rules of strictly formulating and improving aspect the relevant fire safety.Particularly indoor curtain, carpet and ornaments such as some important public building such as hospital, hotel, school all must possess certain fire protection flame retarding ability.Therefore, the development of fire resistance fibre and development have become an important topic of the development of functional fibre.The method for preparing at present fire resistance fibre mainly is divided into following several:
One, co-blended spinning method: promptly before melt spinning, in melt, add additive flame retardant, obtain fire resistance fibre through spinning technique.Flame-retardant modified method is added in blend, the patent documentation a lot (as CN200710034311.9) of preparation fire resistance fibre.But by this method, exist certain defective, as the spinning spinnability, the addition of fire retardant is many, and is bigger to other performance impact of fiber.Some halogen flame resistance to elevated temperatures is poor simultaneously, causes in the spinning process because the temperature height causes the fire retardant premature decomposition to influence flame retardant effect.
Two, copolymerization method: in the polymer reaction process, reactive flame retardant is added, the common participation reacted, and fire retardant is attached on the macromolecular chain the most at last.This kind method can obtain flame retardant effect preferably.But as the fire-resistant copolyesters monomer, except containing ignition-proof element, should have reactive group, and can stand long-time reaction and the high temperature action of macromolecule in course of reaction, also will consider simultaneously spinning technique, processability are reached other Effect on Performance degree of fiber.The patent that this kind method has been applied for a lot of as: CN200780047558.3, CN200810211851.5, CN200710020744.X, CN200710045376.4, CN200710045380.0.
Three, surface grafting copolymerization method: this method is to carry out the surface grafting copolymerization with reactive flame retardant on fiber.Its principle is to utilize the vinyl monomer of phosphorous or halogen to carry out polymerization on fiber surface, then, fixes (as GP2006899) or after fiber surface is with the styrene polymerization grafting, carries out bromination again with some resins again, can obtain flame retardant effect.This method complex process, polymerization is wayward, and the problems such as removal of reaction back monomer are difficult to solve.Be difficult for realizing suitability for industrialized production.
Four, surface-coated method: by the method for back arrangement, fiber or the surface-coated fire retardant, (as CN94104564.1, CN200680006506.7), this kind method is simple, easily row to give the fiber anti-flaming function with this.But because strong as polarity, the water-soluble inorganic combustion inhibitor of the fire retardant overwhelming majority that uses, therefore, poor durability descends obviously through the washing flame retardant effect.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, and a kind of anti-flaming function fiber preparation method that has is provided, the fire resistance fibre good flame resistance that this method is prepared, the intensity height, good endurance, applied range, and easily realize suitability for industrialized production.
The objective of the invention is to finish by following technical solution, this method is that fiber is the method by dipping or spraying, the photosensitive polymer solution that will have fire retardant is evenly coated in fiber surface, utilize under the UV-irradiation, the coating generation principle of solidification makes the fire retardant fiber surface that is fixed obtained; Described lamp box temperature is controlled at 25～125 ℃, and the ultraviolet source wavelength control is at 280-350nm; Power 150-250mW/cm
2Irradiation time 2-15s.
The described photosensitive polymer solution that has fire retardant is made as follows:
One, the preparation of photosensitive polymer:
(1) preparation of big molecule photosensitizer: with an amount of 2,4 dihydroxy benaophenonels (UV-0), and NaOH adds in the dry there-necked flask, behind the inflated with nitrogen 30 minutes, add glycidyl methacrylate (GMA), stir, heat up, react, obtain yellow thick liquid (BPMA), lucifuge is stand-by; Wherein the mol ratio of UV-0 and GMA is 1: 1～1: 2, and temperature is controlled between 60 ℃～90 ℃, and the reaction time is controlled at 3h～8h.
(2) preparation of photosensitive polymer: in there-necked flask, add polyvinyl monomer, BPMA, dodecyl sulphate, initator respectively, add proper amount of deionized water, logical nitrogen 30 minutes, the temperature reaction certain hour is purified.As select non-soluble polymer for use, after finishing, reaction needs the calcium chloride (CaCl of adding 5%
2) aqueous solution, purify by centrifuge.Obtain photosensitive polymer and can pass through oxolane (THF), one of dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) or its mixed solution dissolve.Above-mentioned described initator can be one of benzoyl peroxide (BPO), azodiisobutyronitrile (AIBN) or ammonium persulfate (APS); Described vinyl monomer and BMPA consumption mol ratio can be 10%～90%, and reaction temperature is controlled at 50 ℃～80 ℃, and the reaction time is controlled at 2h～5h.Non-soluble polymer adopts 5% calcium chloride (CaCl
2) aqueous solution purification.
Two, the configuration of flame retardant coating solution: photosensitive polymer is dissolved in the appropriate solvent, and fire retardant is poured in the photosensitive polymer solution, stir, be configured to the homogeneous polymer solution; In preparation flame retardant solution process, fire retardant accounts for 20%～80% of fire retardant and photosensitive polymer total amount, and all the other are photosensitive polymer; What the quantity of solvent of flame retardant coating solution accounted for gross weight is 50%～95%.
The big molecule photosensitizer of described synthetic BPMA is raw materials used to be UV-0 and GMA (or with the compound of GMA structural similarity, promptly contain the compound of epoxide group and two keys in the molecular structure simultaneously).
Described initator is one of benzoyl peroxide (BPO), azodiisobutyronitrile (AIBN) or ammonium persulfate (APS).
Described fire retardant can comprise any one of fire retardant that organic halogenated flame retardant, organic phosphorus flame retardant or inorganic flame retardant comprises; Wherein organic halogenated flame retardant comprises that chlorine system, bromine are two big classes, comprises chlorinated paraffin wax, perchloro-ring penta decane, deca-BDE, pentabromotoluene etc.; Organic phosphorus flame retardant comprises phosphate, phosphite ester, organophosphorated salt, phosphorous oxide, phosphorus-containing polyol; Inorganic system comprises that Phos is ammonium dihydrogen phosphate (ADP), boric acid, aluminium hydroxide, magnesium hydroxide, red phosphorus, antimony oxide, zinc oxide.
The present invention designs a kind of fire resistance fibre, this fire resistance fibre is the method by dipping or spraying, and the photosensitive polymer solution that will have fire retardant is evenly coated in fiber surface, utilizes under the UV-irradiation, the coating generation principle of solidification makes the fire retardant fiber surface that is fixed obtained.
Preparation method's technology of fire resistance fibre of the present invention is simple, and the configuration of the synthetic and solution of photosensitive polymer all just can be carried out under normal pressure, used reagent is conventional reagent, equipment mainly contains reactor, temperature control system etc., belong to the chemical plant the basic equipment that should possess.Need not to design in addition autonomous device; Need the flush coater or the equipment that oils, ultraviolet lamp box and heating path in the coating procedure, these equipment are chemical fibre factory's common equipment, therefore, do not need additionally to increase equipment, just can industrial continuously produce, so have characteristics such as industrializing implementation is easy.
The preparation method of fire resistance fibre compares with prior art products among the present invention, because flame-retardant composition effectively is fixed on fiber surface, anti-flammability is lasting and fire resistance is controlled, does not influence the characteristics such as proper property of fiber simultaneously.Therefore, prepared fire resistance fibre has good flame resistance, and is soft, takes comfortable advantage.In addition, compare with other preparation fire resistance fibre methods, the present invention has the simple and lower-cost advantage of technology.
The specific embodiment
The present invention is further illustrated below in conjunction with specific embodiment: the preparation method who the present invention relates to a kind of fire resistance fibre, this method is the method by dipping or spraying, the surface that the fire retardant for preparing and photosensitive polymer mixed solution are coated in fiber uniformly, under the irradiation of ultraviolet light, coating curing, fire retardant is fixed on fiber surface, difficult drop-off during the fire retardant washing, and fire-retardant persistence is strong.Its concrete steps are as follows:
One, the preparation of photosensitive polymer:
1, the preparation of big molecule photosensitizer:
With an amount of 2,4 dihydroxy benaophenonels (UV-0), reaching weight ratio is 0.8%～2%NaOH, adds in the dry there-necked flask, and inflated with nitrogen is after 30 minutes, add glycidyl methacrylate (GMA), (with the mol ratio of UV-0 be 1: 1～2: 1), stir and to be warmed up to 60 ℃～90 ℃, the reaction time is 3h～8h, obtain yellow thick liquid (BPMA), lucifuge is stand-by.
2, the preparation of photosensitive polymer:
In there-necked flask, add polymer monomer N-vinyl pyrrolidone (VP) and BPMA (wherein the consumption of VP and BPMA accounts for both total moles and all can be 10%～90%) respectively, add proper amount of deionized water, the adding weight ratio is 1%～10% lauryl sodium sulfate (SDS), the azo-bis-isobutyl cyanide (AIBN) of adding 1%～5% is as initator, logical nitrogen 30 minutes stirs, and refluxes, 50 ℃～80 ℃ of reaction temperatures, reaction time 2h～5h.After reaction finishes, filter small-molecule substance, keep in Dark Place by bag filter or filter membrane.Above-mentioned described polymer monomer can be vinyl monomers such as methacrylic acid, acrylic acid, esters of acrylic acid, methyl acrylic ester, acrylic amide and Methacrylamide.As select non-soluble polymer for use, after finishing, reaction needs the calcium chloride (CaCL of adding 5%
2) aqueous solution, purify by centrifuge.Obtain photosensitive polymer and can pass through oxolane (THF), one of dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) or its mixed solution dissolve.Above-mentioned described initator can be one of benzoyl peroxide (BPO), azodiisobutyronitrile (AIBN) or ammonium persulfate (APS).
Two, the configuration of flame retardant coating solution:
The configuration of flame retardant coating liquid: photosensitive polymer is dissolved in the appropriate solvent, and fire proofing is poured in the photosensitive polymer solution, stir, be configured to the homogeneous polymer solution.Wherein fire retardant accounts for 20%～80% of fire retardant and photosensitive polymer total amount, and all the other are photosensitive polymer; The quantity of solvent of flame retardant coating solution accounts for 50%～95% of gross weight.
Three, coating and curing:
The fiber that does not oil or the fiber that deoils are coated in flame retardant coating solution on the fiber surface uniformly by the method for dipping or the method for spraying, and are placed on irradiation under the ultraviolet light.25 ℃～125 ℃ of lamp box temperature controls, this temperature should can not damaged the physical property of fiber like this below the vitrification point Tg of fibrous material.Owing to contain the photosensitive polymer component in the coating solution,, realize the flame retardant coating of high tack so under the exciting of ultraviolet light, in the coating and between coating and polymer base coat covalent coupling can take place.Realize solvent evaporates and curing.In this solidification process, the ultraviolet source wavelength control is at 280-350nm; Power 150-250mW/cm
2Irradiation time 2-15s;
Though the preparation method of fire resistance fibre of the present invention has similarity with existing surface coating process, all be that retardant solution is coated onto fiber surface, but the principle of existing surface coating process belongs to bonding theory, easily comes off, and belongs to physical bond, fire-retardant persistence is poor, feel is poor.After key of the present invention was that the photosensitive polymer that disposed and fire retardant mixed liquor are coated onto fiber surface, under the irradiation of ultraviolet light, the H proton generation chemical reaction of photosensitive polymer and polymer and fiber surface formed firm chemical bond, and coating can not come off.Fire retardant is embedded in the coating firmly.Can regulate the ratio of fire retardant as required in preparation process, prepare the fiber of different fire resistances, therefore, anti-flammability is controlled.
The preparation method of fire resistance fibre of the present invention utilizes photosensitive polymer to issue biochemical reaction principle at ultra violet lamp, the preparation fire resistance fibre.Because the effect of chemical bond is that cured layer is durable, firm, difficult drop-off, therefore, only needs coating solution seldom, just can reach solidification effect.So just guaranteed the performance that fiber is intrinsic greatly.Overweight coating can not occur and cause the fiber hardening, the shortcoming of feel difference.
Among the preparation method of fire resistance fibre of the present invention, it is characterized in that the big molecule photosensitizer of described synthetic BPMA is raw materials used for UV-0 and GMA, wherein all to meet be to contain epoxide group and two keys in the molecular structure simultaneously to the compound that has a structural similarity with GMA.
Among the preparation method of fire resistance fibre of the present invention, it is characterized in that used polymer monomer should be vinyl monomer in the described synthetic photosensitive polymer process; The initator that uses is one of benzoyl peroxide (BPO), azodiisobutyronitrile (AIBN) or ammonium persulfate (APS); Solvent for use should be selected according to selected polymer.
The preparation method of fire resistance fibre of the present invention is characterized in that any one of fire retardant that fire retardant can comprise that organic halogenated flame retardant, organic phosphorus flame retardant or inorganic flame retardant comprises.Wherein organic halogenated flame retardant comprises that chlorine system, bromine are two big classes (as chlorinated paraffin wax, perchloro-ring penta decane, deca-BDE, pentabromotoluenes etc.); Organic phosphorus flame retardant (comprising phosphate, phosphite ester, organophosphorated salt, phosphorous oxide, phosphorus-containing polyol etc.); Inorganic system comprises Phos system (ammonium dihydrogen phosphate (ADP), boric acid etc.), aluminium hydroxide, magnesium hydroxide, red phosphorus, antimony oxide, zinc oxide etc.Because organic phosphorus flame retardant and inorganic flame retardant are non-volatile because of its Heat stability is good, do not produce corrosive gas, low toxin.Therefore, according to environmental requirement, preferably select organophosphor system or inorganic flame retardant for use.
In the preparation method of fire resistance fibre of the present invention, it is further characterized in that this method is applicable to that polyester fiber, polypropylene fibre, polyurethane fiber, polyvinyl alcohol etc. contain nytron fibres and fabric thereof.
Introduce specific embodiments of the invention below:
Embodiment 1
One, the preparation of photosensitive polymer:
1, the preparation of big molecule photosensitizer:
With 10.7g2,4 dihydroxy benaophenonels (UV-0), and 0.155gNaOH, adding in the dry there-necked flask, inflated with nitrogen is after 30 minutes, add 7.9g glycidyl methacrylate (GMA), (with the mol ratio of UV-0 be 1: 1), stir and to be warmed up to 80 ℃, the reaction time is 5h, obtain yellow thick liquid (BPMA), lucifuge is stand-by.
2, the preparation of photosensitive polymer:
Respectively in there-necked flask 33gN-vinyl pyrrolidone (VP) and 12gBPMA (wherein the consumption of VP and BPMA accounts for both total moles and is respectively 90%, 10%), add proper amount of deionized water, the adding weight ratio is the lauryl sodium sulfate (SDS) of 1.7g (4wt%), adds the azo-bis-isobutyl cyanide (AIBN) of 0.48g (2wt%), logical nitrogen 30 minutes, stir, reflux 80 ℃ of reaction temperatures, reaction time 3h.After reaction finishes, filter small-molecule substance, keep in Dark Place by bag filter.
Two, the configuration of flame retardant coating solution:
The configuration of flame retardant coating liquid: photosensitive polymer is dissolved in the appropriate solvent, and fire retardant (selecting aluminium hydroxide for use) is poured in the photosensitive polymer solution, stir, be configured to the homogeneous polymer solution.Wherein fire retardant accounts for 20% of fire retardant and photosensitive polymer total amount, and photosensitive polymer accounts for 80%; The quantity of solvent of flame retardant coating solution accounts for 70% of gross weight.
Three, coating and curing:
The method of polyester fiber by spraying that do not oil is sprayed on flame retardant coating solution on the fiber surface uniformly, and is placed on irradiation under the ultraviolet light.90 ℃ of lamp box temperature controls, the ultraviolet source wavelength control is at 300nm; Power 200mW/cm
2Irradiation time 8s; After tested, prepared polyester fire resistant fibre limited oxygen index (LOI) is 29%.
Embodiment 2
One, the preparation of photosensitive polymer:
1, the preparation of big molecule photosensitizer:
With 10.7g2,4 dihydroxy benaophenonels (UV-0), and 0.212gNaOH, adding in the dry there-necked flask, inflated with nitrogen is after 30 minutes, add 15.8g glycidyl methacrylate (GMA), (with the mol ratio of UV-0 be 2: 1), stir and to be warmed up to 60 ℃, the reaction time is 3h, obtain yellow thick liquid (BPMA), lucifuge is stand-by.
2, the preparation of photosensitive polymer:
Respectively in there-necked flask 3.7gN-vinyl pyrrolidone (VP) and 108gBPMA (wherein the consumption of VP and BPMA accounts for both total moles and is respectively 10%, 90%), add proper amount of deionized water, the adding weight ratio is the lauryl sodium sulfate (SDS) of 1.17g (1wt%), adds the ammonium persulfate (APS) of 1.17g (1wt%), logical nitrogen 30 minutes, stir, reflux 50 ℃ of reaction temperatures, reaction time 2h.After reaction finishes, filter small-molecule substance, keep in Dark Place by bag filter.
Two, the configuration of flame retardant coating solution:
The configuration of flame retardant coating liquid: photosensitive polymer is dissolved in the appropriate solvent, and fire retardant (selecting ammonium dihydrogen phosphate (ADP) for use) is poured in the photosensitive polymer solution, stir, be configured to the homogeneous polymer solution.Wherein fire retardant accounts for 50% of fire retardant and photosensitive polymer total amount amount, and photosensitive polymer accounts for 50%; The quantity of solvent of flame retardant coating solution accounts for 50% of gross weight.
Three, coating and curing:
The method of polyurethane fiber by spraying that do not oil is sprayed on flame retardant coating solution on the fiber surface uniformly, and is placed on irradiation under the ultraviolet light.125 ℃ of lamp box temperature controls, the ultraviolet source wavelength control is at 350nm; Power 250mW/cm
2Irradiation time 15s; After tested, prepared polyurethane flame-proof fiber limited oxygen index (LOI) is 31%.
Embodiment 3
One, the preparation of photosensitive polymer:
1, the preparation of big molecule photosensitizer:
With 10.7g2,4 dihydroxy benaophenonels (UV-0), and 0.372gNaOH, adding in the dry there-necked flask, inflated with nitrogen is after 30 minutes, add 7.9g glycidyl methacrylate (GMA), (with the mol ratio of UV-0 be 1: 1), stir and to be warmed up to 90 ℃, the reaction time is 8h, obtain yellow thick liquid (BPMA), lucifuge is stand-by.
2, the preparation of photosensitive polymer:
Respectively in there-necked flask 16gN-vinyl pyrrolidone (VP) and 36gBPMA (wherein the consumption of VP and BPMA accounts for both total moles and is respectively 60%, 40%), add proper amount of deionized water, the adding weight ratio is the lauryl sodium sulfate (SDS) of 4.5g (10wt%), adds the azo-bis-isobutyl cyanide (AIBN) of 2.25g (2wt%), logical nitrogen 30 minutes, stir, reflux 80 ℃ of reaction temperatures, reaction time 5h.After reaction finishes, filter small-molecule substance, keep in Dark Place by bag filter.
Two, the configuration of flame retardant coating solution:
The configuration of flame retardant coating liquid: photosensitive polymer is dissolved in the appropriate solvent, and fire retardant (phosphite ester) is poured in the photosensitive polymer solution, stir, be configured to the homogeneous polymer solution.Wherein fire retardant accounts for 80% of fire retardant and photosensitive polymer total amount, and photosensitive polymer accounts for 20%; The quantity of solvent of flame retardant coating solution accounts for 30% of gross weight.
Three, coating and curing:
The method of polypropylene fibre by spraying that do not oil is sprayed on flame retardant coating solution on the fiber surface uniformly, and is placed on irradiation under the ultraviolet light.90 ℃ of lamp box temperature controls, the ultraviolet source wavelength control is at 330nm; Power 200mW/cm
2Irradiation time 15s; After tested, prepared polypropylene flame-retardant fibre limited oxygen index (LOI) is 33%.
Embodiment 4
One, the preparation of photosensitive polymer:
1, the preparation of big molecule photosensitizer: with example 1
2, the preparation of photosensitive polymer:
Respectively in there-necked flask 21.6g acrylic acid (Ac) and 36gBPMA (wherein the consumption of VP and BPMA accounts for both total moles and is respectively 60%, 40%), add proper amount of deionized water, the adding weight ratio is the lauryl sodium sulfate (SDS) of 1.7g (4wt%), adds the azo-bis-isobutyl cyanide (AIBN) of 0.48g (2wt%), logical nitrogen 30 minutes, stir, reflux 80 ℃ of reaction temperatures, reaction time 3h.After reaction finishes, filter small-molecule substance, keep in Dark Place by bag filter.
Two, the configuration of flame retardant coating solution:
The configuration of flame retardant coating liquid: photosensitive polymer is dissolved in the dimethyl sulfoxide (DMSO), and fire retardant (selecting phosphate for use) is poured in the photosensitive polymer solution, stir, be configured to the homogeneous polymer solution.Wherein fire retardant accounts for 20% of fire retardant and photosensitive polymer total amount amount, and photosensitive polymer accounts for 80%; The quantity of solvent of flame retardant coating solution accounts for 30% of gross weight.
Three, coating and curing: with example 1.After tested, prepared polyester fire resistant fibre limited oxygen index (LOI) is 30%.
Embodiment 5
One, the preparation of photosensitive polymer:
1, the preparation of big molecule photosensitizer: with example 1
2, the preparation of photosensitive polymer:
Respectively in there-necked flask 25.8g methyl acrylate and 12gBPMA (wherein the consumption of methyl acrylate and BPMA accounts for both total moles and is respectively 90%, 10%), add proper amount of deionized water, the adding weight ratio is the lauryl sodium sulfate (SDS) of 1.7g (4wt%), adds the azo-bis-isobutyl cyanide (AIBN) of 0.48g (2wt%), logical nitrogen 30 minutes, stir, reflux 80 ℃ of reaction temperatures, reaction time 3h.After finishing, reaction needs the calcium chloride (CaCl of adding 5%
2) aqueous solution, centrifuge is purified.Keep in Dark Place.
Two, the configuration of flame retardant coating solution:
The configuration of flame retardant coating liquid: photosensitive polymer is dissolved in the oxolane, and fire retardant (phosphate) is poured in the photosensitive polymer solution, stir, be configured to the homogeneous polymer solution.Wherein fire retardant accounts for 20% of fire retardant and photosensitive polymer total amount amount, and photosensitive polymer accounts for 80%; The quantity of solvent of flame retardant coating solution accounts for 30% of gross weight.
Three, coating and curing: with example 1.After tested, prepared polyester fire resistant fibre limited oxygen index (LOI) is 30%.
Embodiment 6
One, the preparation of photosensitive polymer: with example 1
Two, the configuration of flame retardant coating solution: with example 1
Three, coating and curing:
The method of polyester fiber by spraying that do not oil is sprayed on flame retardant coating solution on the dacron fabric uniformly, and is placed on irradiation under the ultraviolet light.90 ℃ of lamp box temperature controls, the ultraviolet source wavelength control is at 300nm; Power 200mW/cm
2Irradiation time 8s; After tested, prepared polyester fire resistant fibre/fabric limited oxygen index (LOI) is 31%.
Claims (5)
1. the preparation method of a fire resistance fibre, this method is that fiber is the method by dipping or spraying, and the photosensitive polymer solution that will have fire retardant is evenly coated in fiber surface, utilizes under the UV-irradiation, the coating generation principle of solidification makes the fire retardant fiber surface that is fixed obtained; Described lamp box temperature is controlled at 25～125 ℃, and the ultraviolet source wavelength control is at 280-350nm; Power 150-250mW/cm
2Irradiation time 2-15s.
2. the preparation method of fire resistance fibre according to claim 1 is characterized in that the described photosensitive polymer solution that has fire retardant makes as follows:
One, the preparation of photosensitive polymer:
(1) preparation of big molecule photosensitizer: with an amount of 2,4 dihydroxy benaophenonels (UV-0), and NaOH adds in the dry there-necked flask, behind the inflated with nitrogen 30 minutes, add glycidyl methacrylate (GMA), stir, heat up, react, obtain yellow thick liquid (BPMA), lucifuge is stand-by; Wherein the mol ratio of UV-0 and GMA is 1: 1～1: 2, and temperature is controlled between 60 ℃～90 ℃, and the reaction time is controlled at 3h～8h.
(2) preparation of photosensitive polymer: in there-necked flask, add polyvinyl monomer, BPMA, dodecyl sulphate, initator respectively, add proper amount of deionized water, logical nitrogen 30 minutes, the temperature reaction certain hour is purified.As select non-soluble polymer for use, after finishing, reaction needs the calcium chloride (CaCl of adding 5%
2) aqueous solution, purify by centrifuge.Obtain photosensitive polymer and can pass through oxolane (THF), one of dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) or its mixed solution dissolve.Above-mentioned described initator can be one of benzoyl peroxide (BPO), azodiisobutyronitrile (AIBN) or ammonium persulfate (APS); Described vinyl monomer and BMPA consumption mol ratio can be 10%～90%, and reaction temperature is controlled at 50 ℃～80 ℃, and the reaction time is controlled at 2h～5h.Non-soluble polymer adopts 5% calcium chloride (CaCl
2) aqueous solution purification.
Two, the configuration of flame retardant coating solution: photosensitive polymer is dissolved in the appropriate solvent, and fire retardant is poured in the photosensitive polymer solution, stir, be configured to the homogeneous polymer solution; In preparation flame retardant solution process, fire retardant accounts for 20%～80% of fire retardant and photosensitive polymer total amount, and all the other are photosensitive polymer; What the quantity of solvent of flame retardant coating solution accounted for gross weight is 50%～95%.
3. according to the preparation method of the described fire resistance fibre of claim 2, it is characterized in that the big molecule photosensitizer of described synthetic BPMA is raw materials used for UV-0 and GMA, wherein all to meet be to contain epoxide group and two keys in the molecular structure simultaneously to the compound that has a structural similarity with GMA.
4. according to the preparation method of the described fire resistance fibre of claim 2, it is characterized in that described initator is one of benzoyl peroxide (BPO), azodiisobutyronitrile (AIBN) or ammonium persulfate (APS); Solvent for use should be selected according to selected polymer.
5. according to the preparation method of the described fire resistance fibre of claim 2, it is characterized in that any one of fire retardant that fire retardant can comprise that organic halogenated flame retardant, organic phosphorus flame retardant or inorganic flame retardant comprises; Wherein organic halogenated flame retardant comprises that chlorine system, bromine are two big classes, comprises chlorinated paraffin wax, perchloro-ring penta decane, deca-BDE, pentabromotoluene etc.; Organic phosphorus flame retardant comprises phosphate, phosphite ester, organophosphorated salt, phosphorous oxide, phosphorus-containing polyol; Inorganic system comprises that Phos is ammonium dihydrogen phosphate (ADP), boric acid, aluminium hydroxide, magnesium hydroxide, red phosphorus, antimony oxide, zinc oxide.
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| CN105369593A (en) * | 2015-12-16 | 2016-03-02 | 常熟绣珀纤维有限公司 | Preparation method of ultrahigh molecular weight polyethylene protofilament |
| CN106400235A (en) * | 2016-12-07 | 2017-02-15 | 北京赛欧兰阻燃纤维有限公司 | Blended yarn of organic silicon nitrogen system flame-retardant fiber and organophosphorus system flame-retardant fiber |
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| CN103774448A (en) * | 2013-05-03 | 2014-05-07 | 江南大学 | Method for flame-proof treatment of textiles based on light curing method |
| CN103361959A (en) * | 2013-07-05 | 2013-10-23 | 吴江龙纺纺织有限公司 | Preparation method of anti-bacterial flame-retardant fabric |
| CN104191751A (en) * | 2014-09-22 | 2014-12-10 | 丹阳市宇晟纺织新材料有限公司 | Fire resistant non-glue cotton and preparation method thereof |
| CN104594026A (en) * | 2015-02-02 | 2015-05-06 | 中国人民解放军总后勤部军需装备研究所 | Flame retardant fiber and preparation method thereof |
| CN105369593A (en) * | 2015-12-16 | 2016-03-02 | 常熟绣珀纤维有限公司 | Preparation method of ultrahigh molecular weight polyethylene protofilament |
| CN106400235A (en) * | 2016-12-07 | 2017-02-15 | 北京赛欧兰阻燃纤维有限公司 | Blended yarn of organic silicon nitrogen system flame-retardant fiber and organophosphorus system flame-retardant fiber |
| CN107956029A (en) * | 2017-12-02 | 2018-04-24 | 绍兴柯桥杰坝针纺科技有限公司 | A kind of production technology of Roman cloth |
| CN109267345A (en) * | 2018-09-17 | 2019-01-25 | 张家港市万能氨纶制品有限公司 | A kind of fire prevention spandex thread |
| CN118065004A (en) * | 2024-02-22 | 2024-05-24 | 广州市双雄化纤有限公司 | High-temperature-resistant flame-retardant chemical fiber material |
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