CN107936664A - One kind is without molten drop water stain-free halogen-free flameproof polyurethane resin and its application - Google Patents
One kind is without molten drop water stain-free halogen-free flameproof polyurethane resin and its application Download PDFInfo
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- CN107936664A CN107936664A CN201711174875.3A CN201711174875A CN107936664A CN 107936664 A CN107936664 A CN 107936664A CN 201711174875 A CN201711174875 A CN 201711174875A CN 107936664 A CN107936664 A CN 107936664A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2201/00—Chemical constitution of the fibres, threads or yarns
- D06N2201/02—Synthetic macromolecular fibres
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2203/00—Macromolecular materials of the coating layers
- D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06N2203/068—Polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
- D06N2209/067—Flame resistant, fire resistant
Abstract
The invention discloses one kind without molten drop water stain-free halogen-free flameproof polyurethane resin, by weight percentage, raw material composition includes：Polyurethane matrix material 65~90%；Diethyl hypo-aluminum orthophosphate 5~20%；Into carbon component 1~15%；Described is insoluble insoluble cross-linked polymer into charcoal component, and Crosslink structure such as following formula (I) is shown.The present invention develops one kind without molten drop water stain-free halogen-free flameproof polyurethane resin, the polyurethane resin material has the characteristics that high fire-retardance, without molten drop, water stain-free, resistance to migration, available for the preparation of halogen-free anti-inflaming polyurethane leather, so as to further apply the high flame-retardancy requirements field such as furniture, vehicles inside gadget.
Description
Technical field
The present invention relates to the technical field of halogen-free anti-inflaming polyurethane, and in particular to one kind is gathered without molten drop water stain-free halogen-free flameproof
Urethane resin and its application in halogen-free anti-inflaming polyurethane leather.
Background technology
Polyurethane is a kind of polymer of main chain constitutional repeating unit Han-NHCOO-, english abbreviation PU, by isocyanates
(monomer) is polymerized with hydroxy compounds.Due to containing highly polar carbamate groups, insoluble in nonpolar solvent, having good
Oil resistivity well, toughness, wearability, resistance to ag(e)ing etc., are widely used multi-field.Wherein, it is as synthetic leather
A kind of important application of polyurethane material, it have gloss it is soft, naturally, soft, the strong appearance of kishke feel, have and base
The excellent mechanical performances such as material adhesive property is excellent, wear-resistant, flex endurant, anti-aging, resistance to fungi is good, while be also equipped with resisting cold
Property it is good, ventilative, washable, easy to process, cheap the advantages that, be natural leather ideal substitute, extensively should
For industries such as clothes, shoemaking, luggage, furniture, internal decorative material for vehicle, aircraft interior material, ship interior materials.
Application for furniture and vehicles interior material, relevant standard propose it is higher to synthetic leather it is fire-retardant will
Ask.Synthetic Leather is typically that polyurethane is impregnated with or is layered on the fiber base materials such as non-woven fabrics, textile, knitwear and shape
Into, and it is different to form the combustion mechanism between the polyurethane resin of synthetic leather and fiber base material, therefore Synthetic Leather is hindered
Burning is extremely difficult.
At present, for the fire-retardant of Synthetic Leather, the basic flame-retardant system of two classes is included：Halogen system flame-retardant system and non-
Halogen flame-retardant system.Halogen system flame-retardant system is typically brominated flame-retardant collaboration antimony oxide, and numerous studies show, added with bromine system
The polyurethane material of fire retardant can produce thick smoke and the harmful substance such as hydrogen bromide in burning, human body can be caused to suffocate.Therefore, it is
The safe and environment-friendly, halogen-free flame-retardant system of polyurethane exploitation becomes the hot spot of research, occurs the new polyurethane that is applied in recent years
Halogen-free flame retardants.
According to the literature, the halogen-free flame retardants applied to polyurethane mainly includes two major class primary structures：One kind is inorganic
Hydroxide system, including magnesium hydroxide and aluminium hydroxide；Another kind of is phosphorus nitrogen system flame-retardant system.For inorganic hydroxide body
System, its fire retardation is limited, and in order to reach the requirement of various codes and standards, usual additive amount is very high, sometime up to entirely matches somebody with somebody
The 80% of cube system, due to inorganic hydroxide fire retardant and matrix resin and incompatible, is disperseed in a manner of a kind of filler
In matrix resin, therefore, high filler loading capacity will substantially reduce the mechanical property of material.Sometimes for reduction inorganic hydroxide
Additive amount, also by the way of red phosphorus collaboration, but the application of red phosphorus can have the appearance color of material, and the combustion of red phosphorus
Burn and easily produce toxic gas and the substantial amounts of smog such as hydrogen phosphide, therefore this is nor optimal solution.
For phosphorus nitrogen system flame-retardant system, this is a kind of efficient flame-retardant system, has high flame retarding efficiency, additive amount is significantly
Reduce and can realize high flame retardant, be the hot spot studied at present.Apply more at present, high polymerization degree APP
(APP) and organophosphorus compounds, high polymerization degree APP (APP) flame-retardant system, it belongs to a kind of Intumscent Flame Retardant System, by
Stronger in its anti-flammability, its additive amount will be substantially reduced compared to inorganic hydroxide system, but APP is due to its surface hydrophilic spy
Property, and have certain water solubility, it is still incompatible with basis material, therefore the mechanics of the fire-retardant polyurethane material of APP systems
Intensity is still very low, while easy migration precipitation, and the albinism separated out is produced in product surface.Further, since ammonium ion
In the presence of the easy moisture absorptions of APP, after polyurethane leather product surface is with the presence of droplet, or leather contact water after a period of time, after doing
Formed in product surface water stain, influence the appearance of product, while have tacky feel, reduce the sense of touch of polyurethane leather；And
Organophosphorus ester, some still have water solubility, although some are water-soluble small, overcome to form the problem of water stain, its fire-retardant machine
It is fire-retardant that reason belongs to condensed phase, belongs to non-expansion type, non-expansion type flame-retardant system is easily formed for polyurethane material when catching fire
Drippage, molten drop can influence flame retardant effect, be extremely difficult to the requirement of standard.
Generally speaking, it is applied to major defect existing for the flame-retardant system of polyurethane leather material at present：Poor fire,
Easy molten drop, the easy moisture absorption form the problems such as water stain and migration albefaction.Therefore, it is necessary to research and develop new to be applied to the new of polyurethane material
The halogen-free flame-retardant system of type.
The content of the invention
The present invention develops one kind has height without molten drop water stain-free halogen-free flameproof polyurethane resin, the polyurethane resin material
The features such as fire-retardant, without molten drop, water stain-free, resistance to migration, available for the preparation of halogen-free anti-inflaming polyurethane leather, so as to further apply
In the high flame-retardancy requirements field such as furniture, vehicles inside gadget.
Concrete technical scheme is as follows：
One kind is without molten drop water stain-free halogen-free flameproof polyurethane resin, and by weight percentage, raw material composition includes：
Polyurethane matrix material 65~90%；
Diethyl hypo-aluminum orthophosphate 5~20%；
Into carbon component 1~15%；
Described is insoluble insoluble cross-linked polymer into carbon component, and Crosslink structure such as following formula (I) is shown：
The present invention relates to the exploitation of halogen-free anti-inflaming polyurethane leather, using new low aqueous solubility diethyl hypo-aluminum orthophosphate,
Cooperateed with by special low aqueous solubility carbonific, form the expansion type flame-retarding mechanism for polyurethane material, solve existing resistance
The defects of combustion system additive amount is big, with polyurethane base material poor compatibility, the easy moisture absorption, precipitation easy to migrate and molten drop.By the diethyl
The novel flame-retardant system of hypo-aluminum orthophosphate and special carbonific composition can be well adapted for polyurethane material, and it is excellent to obtain performance
Different polyurethane resin of the halogen-free flameproof water stain-free without molten drop.
It will elaborate below to the present invention.
The present invention is to solve various defects existing for the existing halogen-free flame-retardant system being applied in polyurethane material as mesh
, inventor has made extensive and intensive studies.For existing flame-retardant system the flame retardant polyurethane material the problem of, investigate
New flame-retardant system, it turns out that the collaboration of diethyl hypo-aluminum orthophosphate is special to solve the problems, such as this well into carbon component.
Shown in the chemical constitution of diethyl hypo-aluminum orthophosphate such as following formula (II)：
Diethyl hypo-aluminum orthophosphate is characterized in phosphorus content height, and good flame resistance, has higher temperature of initial decomposition, water-soluble
Low, resistance to migration is nonhygroscopic, and more application is particularly the engineering plastics of fiberglass reinforced in the engineering plastics such as nylon, PBT at present
In.Applied to polyurethane material, due to water-soluble extremely low, be not in the moisture absorption and have the problem of water stain, but due to being condensed phase
Fire retardant mechanism so that polyurethane material easily drips again in burning, reduces fire resistance, can not pass through resistance as defined in standard
Combustion requires, if reaching flame-retardancy requirements by improving additive amount, can cause the reduction of material property.
Inventor is had found by studying, and in the presence of diethyl hypo-aluminum orthophosphate, is added suitably into carbon component, this
When expansion type flame-retarding is become to the fire retardant mechanism of polyurethane material, and under the action of carbon-coating is expanded, the molten drop of material is also
Control is arrived, it is shown that good anti-flammability.
As into charcoal component, being usually the compound of polyhydroxy, such as the compound such as pentaerythrite, but these compounds by
In the presence of hydroxyl, although have it is good into carbon effect, it is water-soluble higher, asking for the moisture absorption occurs after being applied to polyurethane
The problems such as inscribing, causing surfaces of tacky, water stain and insulating properties to reduce.
Study, found by two kinds of compounds of methylphosphonic acid and trihydroxyethyl isocyanuric ester in equivalent through inventor
Under the conditions of carry out polycondensation reaction, obtain heat cured carboxylate, when application is crushed to the carboxylate in the powder of certain particle size range
End is described into carbon component.This into carbon component had into carbon effect, the concertedness having had with diethyl hypo-aluminum orthophosphate,
There are phosphorus and nitrogen in molecular structure, the additive amount of diethyl hypo-aluminum orthophosphate can be reduced, with molecular configurational due to not depositing
It is nonhygroscopic in water suction group, it will not be formed water stain, surfaces of tacky will not be caused.
The preparation method into carbon component, is specially：
(1) trihydroxyethyl isocyanuric ester and methylphosphonic acid of equivalent, under phase transfer catalyst effect, 150~
4~8h is reacted at 220 DEG C esterification prepolymer is made；
(2) vacuumize and be warming up to 260~280 DEG C, the esterification prepolymer is obtained through condensation curing, then after crushed
Arrive.
In the preparation process of step (1) prepolymer, in order to accelerate reaction speed, it is necessary to using phase transfer catalyst.Make
To be preferred, the phase transfer catalyst is selected from quaternary ammonium salt, such as tetrabutylammonium bromide.
In step (2), high-temperature polycondensation curing is carried out to prepolymer, it is necessary to high vacuum, hot conditions.Preferably, take out true
Sky to vacuum is not higher than 50KPa.The reaction can carry out in an oven, can also use high-power with agitating function
Kneader.
It is block by being obtained after condensation curing into carbon component, in order to be added in basis material, it is also necessary to carry out
Pulverization process, using mechanical crushing equipment, controls into the average grain diameter D50 of carbon component<5μm.
Meanwhile also the water that esterification generates is drained in time.Prepolymer changes colour in order to prevent, and reaction can be in nitrogen
Atmosphere carries out.
Preferably, the diethyl hypo-aluminum orthophosphate is white powder, average grain diameter D50<5μm.
The polyurethane matrix material system includes polyurethane matrix material, solvent, curing agent and catalyst, as excellent
Choosing, the polyurethane matrix material is the linear polymer synthesized by polyalcohol, isocyanates and chain extender, selected from polyester
At least one of type polyurethane, polyether polyurethane, polycarbonate polyurethane, polycaprolactone-type urethane.
In the halogen-free flameproof polyurethane resin of the present invention, in the physical property and the premise of fire resistance for not influencing polyurethane
Under, other additives, such as anti-mildew agent, antistatic additive, lubricant, anti-UV agent, antioxidant can be added.
Further preferably, by weight percentage, the raw material group of the no molten drop water stain-free halogen-free flameproof polyurethane resin
Into including：
Polyurethane matrix material 75~85%；
Diethyl hypo-aluminum orthophosphate 10~20%；
Into carbon component 1~10%；
The diethyl hypo-aluminum orthophosphate is 1.25~8 with the mass ratio into carbon component：1.
Still further preferably, in the component into carbon, nitrogen content 10.4%, phosphorus content 11.5%.Through further
Application test finds that the content of nitrogen and phosphorous is being applied in polyurethane resin into carbon component after being compounded with diethyl hypo-aluminum orthophosphate,
More preferably flame retardant effect can be obtained.
The invention also discloses a kind of halogen-free anti-inflaming polyurethane leather, with the no poly- ammonia of molten drop water stain-free halogen-free flameproof
Ester resin is superficial layer, with the fibrous layer as base material it is compound after be prepared.
The method for preparing the halogen-free anti-inflaming polyurethane leather is not particularly limited, and can be known wet method or dry
Method.
The halogen-free anti-inflaming polyurethane leather being prepared can be applied to the interior material of automobile, train, aircraft, steamer etc.
Seat sheet material, ground cushion, ceiling tile materials etc., the tables and chairs of furniture, the attending a banquet of chair, curtain, blind, valance etc., outdoor
Tent, vehicle cover etc..
Compared with prior art, the invention has the advantages that：
The present invention provides one kind without molten drop water stain-free halogen-free flameproof polyurethane resin, comprising by diethyl hypo-aluminum orthophosphate with
The novel flame-retardant system of special carbonific composition, the polyurethane resin material have high fire-retardance, without molten drop, water stain-free, resistance to
The features such as migration.It can reach the mark of FMVSS (american car security legislation) using it as flame retardant polyurethane leather prepared by raw material
It is accurate.
Embodiment
Following performance is investigated to material：
(1) fire resistance
Inner decoration material for automobile combustion testing standard according to FMVSS (american car security legislation) No.302.
(2) water stain experiment
Flame retardant polyurethane leather sample is placed in polyurethane foam, 5ml water is placed on surface, is placed and is air-dried, and observes surface
Whether water stain formation is had.
(3) resistance to migration experiment
Flame retardant polyurethane leather is cut into the sample of 18 × 25cm, is put into climatic chamber, 85 DEG C of set temperature, phase
To humidity 85%, visual observations when 168 is small after specimen surface state.
Embodiment 1
Follow these steps to prepare and characterize polyurethane leather：
(1) by formula as below, flame retardant polyurethane resin composition is prepared (unless otherwise stated, after each raw material is blended
Proportioning in the present invention is weight percentage)：
Polyurethane system 82%；
Diethyl hypo-aluminum orthophosphate 13%；
Into carbon component 5%；
Wherein, by weight, the composition of polyurethane system is：
(2) the flame retardant polyurethane resin composition for preparing step (1), is coated on polyester warp knitting cloth, forms thickness
The coating of 250um, dry solidification 3 minutes in 120 DEG C of drying machine, and pricked with the cloth machine pressure of bundle, when progress 72 is small at 40 DEG C
Aging, obtains fire-retardant synthetic leather.
(3) correlated performance is tested.
It is as follows into the preparation process of carbon component in the present embodiment：
In the flask of 1L, 522 grams of (2 moles) trihydroxyethyl isocyanuric esters are added, leads to nitrogen protection, is heated to 150
DEG C so that trihydroxyethyl isocyanuric ester fusing, then adds 2.7 grams of tetrabutylammonium bromide and 288g (3 moles) methylphosphonic acid,
Strong stirring mixture, 6 it is small when within heating from 150 DEG C be raised to 210 DEG C, the water in reaction process is discharged, and condense metering,
When 210 DEG C of insulations 1 are small, 150 DEG C are cooled to, melt is discharged to a metal tray, a kind of faint yellow hair is obtained after melt cooling
Crisp solids, for melting range from 100~120 DEG C, residual acid value is 7 milligrams of KOH/g.
Prepolymer is placed into vacuum drying oven together with pallet, is vacuumized, vacuum keeps 50KPa, is heated to 270
DEG C, when holding 2 is small, complete to cure, cooling discharge.Crushing material to average grain diameter D50<5 microns stand-by.
Through analysis：
It is manufactured in the present embodiment to be into carbon component, content：10.5%, nitrogen content is：10.1% (phosphorus, nitrogen content are real
Calculated value in border measured value, slightly below specification), solubility<0.1%, 1% weightless decomposition temperature is 320 DEG C.
Unless otherwise instructed, in following embodiment product manufactured in the present embodiment is used into carbon component.
Each material and proportioning are shown in Table 1 in embodiment, and the performance test results of obtained material are shown in Table 1.
Embodiment 2
Implementation process is same as Example 1, except diethyl hypo-aluminum orthophosphate and outer, the raising diethyl into the proportioning adjustment of carbon component
The proportioning of base hypophosphorous acid, keeps flame-retardant system total amount constant.Other materials and proportioning are shown in Table 1, and obtained material the results are shown in Table
1。
Embodiment 3
Implementation process is same as Example 1, except diethyl hypo-aluminum orthophosphate and into carbon component proportioning adjustment in addition to, improve into carbon
The proportioning of component, keeps flame-retardant system total amount constant.Other materials and proportioning are shown in Table 1, and obtained material the results are shown in Table 1.
Embodiment 4
Implementation process is same as Example 1, in addition to the proportioning adjustment of formula, reduces flame-retardant system sum-rate.Other things
Material and proportioning are shown in Table 1, and obtained material the results are shown in Table 1.
Embodiment 5
Implementation process is same as Example 1, in addition to the proportioning adjustment of formula, improves flame-retardant system sum-rate.Other things
Material and proportioning are shown in Table 1, and obtained material the results are shown in Table 1.
Comparative example 1
Implementation process is same as Example 1, in addition to without using into carbon component.Other materials and proportioning are shown in Table 1, resulting
Material the results are shown in Table 1.
Comparative example 2
Implementation process is same as Example 1, in addition to without using diethyl hypo-aluminum orthophosphate.Other materials and proportioning are shown in Table 1,
Obtained material the results are shown in Table 1.
Comparative example 3
Implementation process is same as Example 1, in addition to only using ammonium polyphosphate, without using diethyl hypo-aluminum orthophosphate and into carbon
Component.Other materials and proportioning are shown in Table 1, and obtained material the results are shown in Table 1.
Comparative example 4
Implementation process is same as Example 1, except only use aromatic phosphoric acid ester in addition to, without using diethyl hypo-aluminum orthophosphate and into
Carbon component.Other materials and proportioning are shown in Table 1, and obtained material the results are shown in Table 1.Table 1
Claims (10)
1. one kind is without molten drop water stain-free halogen-free flameproof polyurethane resin, it is characterised in that by weight percentage, raw material composition bag
Include：
Polyurethane matrix material system 65~90%；
Diethyl hypo-aluminum orthophosphate 5~20%；
Into carbon component 1~15%；
Described is insoluble insoluble cross-linked polymer into carbon component, and Crosslink structure such as following formula (I) is shown：
2. no molten drop water stain-free halogen-free flameproof polyurethane resin according to claim 1, it is characterised in that the poly- ammonia
Ester group body material system includes polyurethane matrix material, solvent, curing agent and catalyst；The polyurethane matrix material is selected from
At least one of polyester polyurethane, polyether polyurethane, polycarbonate polyurethane, polycaprolactone-type urethane.
3. no molten drop water stain-free halogen-free flameproof polyurethane resin according to claim 1, it is characterised in that the diethyl
Base hypo-aluminum orthophosphate, average grain diameter D50<5μm.
4. no molten drop water stain-free halogen-free flameproof polyurethane resin according to claim 1, it is characterised in that described into carbon
Component is prepared using the trihydroxyethyl isocyanuric ester of equivalent and methylphosphonic acid as raw material after polycondensation reaction.
5. no molten drop water stain-free halogen-free flameproof polyurethane resin according to claim 4, it is characterised in that described into carbon group
The preparation method divided, is specially：
(1) trihydroxyethyl isocyanuric ester and methylphosphonic acid of equivalent, under phase transfer catalyst effect, at 150~220 DEG C
Esterification prepolymer is made in 4~8h of lower reaction；
(2) vacuumize and be warming up to 260~280 DEG C, the esterification prepolymer is obtained through condensation curing, then after crushed.
6. no molten drop water stain-free halogen-free flameproof polyurethane resin according to claim 5, it is characterised in that in step (1),
The phase transfer catalyst is selected from quaternary ammonium salt.
7. no molten drop water stain-free halogen-free flameproof polyurethane resin according to claim 5, it is characterised in that in step (2),
It is evacuated to vacuum and is not higher than 50KPa；It is crushed to average grain diameter D50<5μm.
It is 8. any described without molten drop water stain-free halogen-free flameproof polyurethane resin according to claim 1~7, it is characterised in that to press
Percentage by weight meter, raw material composition include：
Polyurethane matrix material system 75~85%；
Diethyl hypo-aluminum orthophosphate 10~20%；
Into carbon component 1~10%；
The diethyl hypo-aluminum orthophosphate is 1.25~8 with the mass ratio into carbon component：1.
9. no molten drop water stain-free halogen-free flameproof polyurethane resin according to claim 8, it is characterised in that described into carbon
In component, nitrogen content 10.4%, phosphorus content 11.5%.
A kind of 10. halogen-free anti-inflaming polyurethane leather, it is characterised in that with according to claim 1~9 it is any it is described without molten drop without
Water stain halogen-free flameproof polyurethane resin is superficial layer, with the fibrous layer as base material it is compound after be prepared.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711174875.3A CN107936664B (en) | 2017-11-22 | 2017-11-22 | A kind of no molten drop water stain-free halogen-free flameproof polyurethane resin and its application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711174875.3A CN107936664B (en) | 2017-11-22 | 2017-11-22 | A kind of no molten drop water stain-free halogen-free flameproof polyurethane resin and its application |
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| Publication Number | Publication Date |
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| CN107936664A true CN107936664A (en) | 2018-04-20 |
| CN107936664B CN107936664B (en) | 2019-08-06 |
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| CN201711174875.3A Active CN107936664B (en) | 2017-11-22 | 2017-11-22 | A kind of no molten drop water stain-free halogen-free flameproof polyurethane resin and its application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108797136A (en) * | 2018-06-28 | 2018-11-13 | 浙江大学 | A kind of no molten drop water stain-free is based on the fire-retardant polyurethane leather composition of the thio hypophosphites of dialkyl group list |
| CN109082900A (en) * | 2018-06-28 | 2018-12-25 | 浙江大学 | Without the molten drop water stain-free polyurethane leather composition fire-retardant based on dialkyl dithio hypophosphites |
| CN109400837A (en) * | 2018-09-30 | 2019-03-01 | 南通紫琅生物医药科技有限公司 | A kind of Halogen does not migrate flame retardant polyurethane resin and its application without molten drop |
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| CN103756546A (en) * | 2014-01-08 | 2014-04-30 | 株洲时代新材料科技股份有限公司 | Inflaming retarding coating and application thereof |
| CN105175735A (en) * | 2015-07-24 | 2015-12-23 | 常州大学 | Branched phosphorus-nitrogen type flame retardant and preparation method therefor |
| CN106827710A (en) * | 2015-12-07 | 2017-06-13 | 中国科学院宁波材料技术与工程研究所 | A kind of flexible fiber fabric enhancing compound polyurethane material and preparation method and application |
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| CN103756546A (en) * | 2014-01-08 | 2014-04-30 | 株洲时代新材料科技股份有限公司 | Inflaming retarding coating and application thereof |
| CN105175735A (en) * | 2015-07-24 | 2015-12-23 | 常州大学 | Branched phosphorus-nitrogen type flame retardant and preparation method therefor |
| CN106827710A (en) * | 2015-12-07 | 2017-06-13 | 中国科学院宁波材料技术与工程研究所 | A kind of flexible fiber fabric enhancing compound polyurethane material and preparation method and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108797136A (en) * | 2018-06-28 | 2018-11-13 | 浙江大学 | A kind of no molten drop water stain-free is based on the fire-retardant polyurethane leather composition of the thio hypophosphites of dialkyl group list |
| CN109082900A (en) * | 2018-06-28 | 2018-12-25 | 浙江大学 | Without the molten drop water stain-free polyurethane leather composition fire-retardant based on dialkyl dithio hypophosphites |
| CN108797136B (en) * | 2018-06-28 | 2019-10-01 | 浙江大学 | A kind of polyurethane leather composition that no molten drop water stain-free is fire-retardant based on the thio hypophosphites of dialkyl group list |
| CN109400837A (en) * | 2018-09-30 | 2019-03-01 | 南通紫琅生物医药科技有限公司 | A kind of Halogen does not migrate flame retardant polyurethane resin and its application without molten drop |
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| CN107936664B (en) | 2019-08-06 |
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