阅读说明：本技术 一种防火填充制品 (A kind of fire prevention filled articles ) 是由 李金娣 于 2019-08-26 设计创作，主要内容包括：本发明涉及防火材料制备技术领域,具体涉及到一种防火填充制品。所述防火填充制品,其是由防火复合纳米纤维制成；所述防火复合纳米纤维由以下重量份的原料组成：改性聚酰亚胺75-85份、高硅氧玻璃纤维65-85份、聚磷酸铵12-18份、偶联剂8-12份、多孔炭材料1-5份、改性分子筛2-4份。本发明制得的防火填充制品具有显著的防火性能和抗静电性能,同时其具有轻质、韧性好的优良特性。(The present invention relates to fire proofing material preparation technical fields, and in particular to arrives a kind of fire prevention filled articles.The fire prevention filled articles, are made of fire prevention composite nano fiber；The fire prevention composite nano fiber is made of the raw material of following parts by weight: 75-85 parts of modified polyimide, 65-85 parts of resurrection glass fibre, 12-18 parts of ammonium polyphosphate, 8-12 parts of coupling agent, 1-5 parts of porous carbon material, 2-4 parts of modified molecular screen.Fire prevention filled articles produced by the present invention have significant fire protecting performance and antistatic property, while its good characteristic with lightweight, good toughness.)

1. a kind of fire prevention filled articles, which is characterized in that it is made of fire prevention composite nano fiber；The fire prevention composite Nano Fiber is made of the raw material of following parts by weight: 75-85 parts of modified polyimide, 65-85 parts of resurrection glass fibre, ammonium polyphosphate 12-18 parts, 8-12 parts of coupling agent, 1-5 parts of porous carbon material, 2-4 parts of modified molecular screen.

2. filled articles of preventing fires according to claim 1, which is characterized in that the modified polyimide is that sulfonation polyamides is sub- Amine.

3. filled articles of preventing fires according to claim 1, which is characterized in that it is 10-20 that the ammonium polyphosphate, which is by the degree of polymerization, Ammonium polyphosphate and the degree of polymerization be 1000-2000 ammonium polyphosphate form.

4. filled articles of preventing fires according to claim 3, which is characterized in that the degree of polymerization be 10-20 ammonium polyphosphate and The mass ratio for the ammonium polyphosphate that the degree of polymerization is 1000-2000 is 1:(1-2).

5. filled articles of preventing fires according to claim 1, which is characterized in that the coupling agent is silane coupling agent, metatitanic acid idol Join one of agent, zirconium aluminium profiles coupling agent, phosphate coupling agent or multiple combinations.

6. filled articles of preventing fires according to claim 1, which is characterized in that the porous carbon material is sulfonation charcoal.

7. filled articles of preventing fires according to claim 1, which is characterized in that the raw material for preparing of the modified molecular screen includes point Sub- sieve, water, 2- aminoisonicotinic acid, 4- pyridine phosphoric acid.

8. filled articles of preventing fires according to claim 7, which is characterized in that the molecular sieve, water, 2- aminoisonicotinic acid, 4- The mass ratio of pyridine phosphoric acid is 1:(20-50): (0.1-0.3): (0.05-0.15).

9. according to the fire prevention filled articles of claim 7 or 8, which is characterized in that the modified molecular screen the preparation method comprises the following steps: Molecular sieve is added to the water, is then added 2- aminoisonicotinic acid and 4- pyridine phosphoric acid, room temperature ultrasonic disperse, washing, it is dry to get Modified molecular screen.

10. a kind of preparation method of any one of -9 fire prevention filled articles according to claim 1, which is characterized in that will be above-mentioned Fire prevention composite nano fiber is woven into yarn, is woven into fire prevention filled articles according to conventional weft-knitted technique.

Technical field

The invention belongs to fire-proof fabric technical fields, more particularly it relates to a kind of fire prevention filled articles.

Background technique

In daily life, fire is on very close terms with people, needless to say the benefit that fire is brought, warms oneself, cooks Etc. all too busy to get away fire, but fire can similarly cause greatly to lose to the mankind or even threat to life, will occur every year More fire incidents, caused by casualties and economic loss it is inestimable, in order to protect the safety of the public, caused by reducing fire Loss, it is necessary to also have certain fire-proof function with people's closely related cloth of living, when fire or the intensity of a fire occurs to the person When safety and property safety generate threat, certain protective action can be played, is raced against time for fire fighter, by injures and deaths and loss It reduces.

Summary of the invention

To solve the above-mentioned problems, first aspect of the present invention provides a kind of fire prevention filled articles, is multiple by preventing fires It closes nanofiber to be made, the fire prevention composite nano fiber is made of the raw material of following parts by weight: modified polyimide 75-85 Part, 65-85 parts of resurrection glass fibre, 12-18 parts of ammonium polyphosphate, 8-12 parts of coupling agent, 1-5 parts of porous carbon material, modified point 2-4 parts of son sieve.

As a kind of perferred technical scheme, the modified polyimide is sulfonated polyimide.

As a kind of perferred technical scheme, the ammonium polyphosphate is the ammonium polyphosphate and polymerization for being 10-20 by the degree of polymerization The ammonium polyphosphate that degree is 1000-2000 forms.

As a kind of perferred technical scheme, the ammonium polyphosphate and the degree of polymerization that the degree of polymerization is 10-20 are 1000-2000 Ammonium polyphosphate mass ratio be 1:(1-2).

As a kind of perferred technical scheme, the coupling agent is silane coupling agent, metatitanic acid coupling agent, the coupling of zirconium aluminium profiles One of agent, phosphate coupling agent or multiple combinations.

As a kind of perferred technical scheme, the porous carbon material is sulfonation charcoal.

As a kind of perferred technical scheme, the raw material for preparing of the modified molecular screen includes molecular sieve, deionized water, 2- Aminoisonicotinic acid, 4- pyridine phosphoric acid.

As a kind of perferred technical scheme, the molecular sieve, deionized water, 2- aminoisonicotinic acid, 4- pyridine phosphoric acid Mass ratio is 1:(20-50): (0.1-0.3): (0.05-0.15).

As a kind of perferred technical scheme, the modified molecular screen the preparation method comprises the following steps: deionization is added in molecular sieve In water, 2- aminoisonicotinic acid and 4- pyridine phosphoric acid is added, room temperature ultrasonic disperse, washing, drying is to get modified molecular screen.

As a kind of perferred technical scheme, it is described fire prevention composite nano fiber the preparation method comprises the following steps: material modification is gathered Acid imide and resurrection glass fibre are uniformly mixed to obtain mixture；Mixture is made by conventional fabrication process can spin high gather Object solution；Sulfonation charcoal and modified molecules are added addition ammonium polyphosphate and coupling agent, heating stirring in high polymeric solution can be spun Sieve, thermostatic ultrasonic dispersion and constant temperature swelling, form spinning solution；Spinning solution is prepared into compound receive of preventing fires according to electrostatic spinning technique Rice fiber.

The second aspect of the present invention provide as described above fire prevention filled articles preparation method, include the following steps: by Above-mentioned fire prevention composite nano fiber is woven into yarn, is woven into fire prevention filled articles according to conventional weft-knitted technique.

The utility model has the advantages that being made the present invention provides a kind of fire prevention filled articles of fire prevention composite nano fiber.It is described anti- Fiery composite nano fiber by by modified polyimide, resurrection glass fibre, ammonium polyphosphate, coupling agent, porous carbon material, change Property molecular sieve mixing be prepared again through electrostatic spinning technique.The fire prevention filled articles have significant fire protecting performance and antistatic Performance, while its good characteristic with lightweight, good toughness.

Specific embodiment

The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily to understand Bright content.Unless otherwise defined, all technologies used herein and scientific term have common with fields of the present invention The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.

As used herein term " by ... preparation " it is synonymous with " comprising ".Term " includes " used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.E.g., including the combination of listed elements Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or Such composition, step, method, product or the intrinsic element of device.

Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this Phrase will make claim closed, make it not and include the material in addition to materials of those descriptions, but it is relative often Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body, It is only limited to element described in the clause；Other elements are not excluded except the claim as a whole.

Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end Value and all integers and score in the range.

Singular includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or it is " any It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and The situation that event does not occur.

Approximate term in specification and claims is used to modify quantity, and it is specific to indicate that the present invention is not limited to this Quantity further includes the acceptable modified part without will lead to the change of dependency basis this function close with the quantity.Phase It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate Term likely corresponds to the precision of the instrument of measurement numerical value.In present specification and claims, range limits can be with Combination and/or exchange, these ranges if not stated otherwise include all subranges contained therebetween.

In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component (i.e. frequency of occurrence) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number The element or component of form also include plural form, unless the obvious purport of the quantity refers to singular.

In view of the above technical problems, first aspect of the present invention provides a kind of fire prevention filled articles, is multiple by preventing fires Nanofiber is closed to be made；The fire prevention composite nano fiber is made of the raw material of following parts by weight: modified polyimide 75-85 Part, 65-85 parts of resurrection glass fibre, 12-18 parts of ammonium polyphosphate, 8-12 parts of coupling agent, 1-5 parts of porous carbon material, modified point 2-4 parts of son sieve.

In view of the above technical problems, first aspect of the present invention provides a kind of fire prevention filled articles, is multiple by preventing fires It closes nanofiber to be made, the fire prevention composite nano fiber is made of the raw material of following parts by weight: 80 parts of modified polyimide, height 75 parts of silica glass, 15 parts of ammonium polyphosphate, 10 parts of coupling agent, 3 parts of porous carbon material, 3 parts of modified molecular screen.

[fire prevention composite nano fiber]

In one embodiment, it is described fire prevention composite nano fiber the preparation method comprises the following steps: by material modification polyimides And resurrection glass fibre, it is uniformly mixed and obtains mixture；Mixture is made by conventional fabrication process to can to spin high polymer molten Liquid；Porous carbon material and modified molecules are added addition ammonium polyphosphate and coupling agent, heating stirring in high polymeric solution can be spun Sieve, thermostatic ultrasonic dispersion and constant temperature swelling, form spinning solution；Spinning solution is prepared into compound receive of preventing fires according to electrostatic spinning technique Rice fiber.

In one embodiment, the preparation method of the fire prevention composite nano fiber:

(1) modified polyimide and resurrection glass fibre are weighed according to parts by weight, is uniformly mixed, obtains mixture；

(2) using conventional fabrication process by mixture through dipping, squeezing, crushing, experienced, yellow, dissolution, maturation, deaeration, Filtering, which is made, can spin high polymeric solution；

(3) it is spun what ammonium polyphosphate and coupling agent were added to that step (2) obtains in high polymeric solution, at 200-300 DEG C Simultaneously magnetic agitation is aged to obtain spinnable solution for middle heating；

(4) porous carbon material and modified molecular screen are added in the spinnable solution that step (3) obtains, at 130-170 DEG C Middle holding constant temperature carries out ultrasonic wave dispersion and constant temperature swelling, forms spinning solution；

(5) spinning solution is prepared into fire prevention composite nano fiber according to electrostatic spinning technique.

In a preferred embodiment, the preparation method of the fire prevention composite nano fiber:

(1) modified polyimide and resurrection glass fibre are weighed according to parts by weight, is uniformly mixed, obtains mixture；

(2) using conventional fabrication process by mixture through dipping, squeezing, crushing, experienced, yellow, dissolution, maturation, deaeration, Filtering, which is made, can spin high polymeric solution；

(3) spun what ammonium polyphosphate and coupling agent were added to that step (2) obtains in high polymeric solution, in 250 DEG C plus Simultaneously magnetic agitation is aged to obtain spinnable solution heat；

(4) porous carbon material and modified molecular screen are added in the spinnable solution that step (3) obtains, are protected in 150 DEG C Constant temperature is held, ultrasonic wave dispersion and constant temperature swelling is carried out, forms spinning solution；

(5) spinning solution is prepared into fire prevention composite nano fiber according to electrostatic spinning technique.

[modified polyimide]

In one embodiment, the modified polyimide is sulfonated polyimide.

In one embodiment, the sulfonated polyimide the preparation method is as follows:

Bis- aminobenzidine -2, the 2'- disulfonic acid of 4, the 4'- of 2.6-3.0mmol are placed in three neck round bottom flask, are added 10-20mL metacresol standard solution, is then added excessive triethylamine.Lead to nitrogen protection, is risen after stirring 20-40min under room temperature Temperature persistently stirs 2-6h to 60-100 DEG C, adds 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids and 5.5- of 3.5-4.5mmol The benzoic acid of 6.5mmol is then heated to 100-140 DEG C of reaction 1-3h, then is warming up to 160-200 DEG C of reaction 20-28h with imines Change.After the reaction was completed, it is cooled to 60-100 DEG C, 10-30mL metacresol agitation and dilution is added, slowly pours into ethyl acetate, is used The multiple soaking and washing of ethyl acetate, then at 130-170 DEG C dry 22-26h to get.

In a preferred embodiment, the sulfonated polyimide the preparation method is as follows:

Bis- aminobenzidine -2, the 2'- disulfonic acid of 4, the 4'- of 2.8mmol are placed in dry three neck round bottom flask, dosage Cylinder measures 15mL metacresol standard solution and is added in three-necked flask, excessive triethylamine is then added, to be converted into triethylamine Salt form increases amino activity.Logical nitrogen protection, is warming up to 80 DEG C after mechanical stirring at least 30min at normal temperature, lasting to stir 4h adds 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids of 4.0mmol and the benzoic acid of 6mmol, is then heated to 120 DEG C instead 20h is answered, then is warming up to 180 DEG C of reactions for 24 hours with imidization.After the reaction was completed, 80 DEG C are cooled to, it is dilute that the stirring of 20mL metacresol is added Sticky polymer solution is released, the polymer solution after above-mentioned dilution is slowly poured into ethyl acetate solution and is reeled off raw silk from cocoons, is obtained white Color fibre shaped polymer product is sufficiently stirred to remove remaining metacresol solvent, then again with fresh ethyl acetate solution After multiple soaking and washing, be placed in 150 DEG C of baking ovens dry for 24 hours to get.