CN107936664B - A kind of no molten drop water stain-free halogen-free flameproof polyurethane resin and its application - Google Patents
A kind of no molten drop water stain-free halogen-free flameproof polyurethane resin and its application Download PDFInfo
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- CN107936664B CN107936664B CN201711174875.3A CN201711174875A CN107936664B CN 107936664 B CN107936664 B CN 107936664B CN 201711174875 A CN201711174875 A CN 201711174875A CN 107936664 B CN107936664 B CN 107936664B
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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
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Fireproofing Substances (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a kind of no molten drop water stain-free halogen-free flameproof polyurethane resins, and by weight percentage, raw material composition includes: polyurethane matrix material 65~90%；Diethyl hypo-aluminum orthophosphate 5~20%；At carbon component 1~15%；Described is divided into insoluble insoluble cross-linked polymer at charcoal group, shown in Crosslink structure such as following formula (I).The present invention develops a kind of no 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, it can be used for the preparation of halogen-free anti-inflaming polyurethane leather, 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 fields of halogen-free anti-inflaming polyurethane, and in particular to a kind of no molten drop water stain-free halogen-free flameproof is poly-
Urethane resin and its application in halogen-free anti-inflaming polyurethane leather.
Background technique
Polyurethane is a quasi polymer of main chain constitutional repeating unit Han-NHCOO-, english abbreviation PU, by isocyanates
(monomer) is polymerized with hydroxy compounds.Due to not dissolving in nonpolar solvent containing highly polar carbamate groups, have good
Good oil resistivity, toughness, wearability, resistance to ag(e)ing etc., is widely used multi-field.Wherein, it is as synthetic leather
A kind of important application of polyurethane material, it has soft glossy, naturally, soft, the strong appearance of kishke feel, has 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 being also equipped with cold-resistant
The advantages that property is good, ventilative, washable, easy to process, cheap, is the ideal substitute of natural leather, answers extensively
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 fire-retardant want higher to synthetic leather
It asks.Synthetic Leather is usually that polyurethane is impregnated with or is layered on the fiber base materials such as non-woven fabrics, textile, knitwear and shape
At, and it is different to constitute the combustion mechanism between the polyurethane resin of synthetic leather and fiber base material, therefore hinders Synthetic Leather
Burning is extremely difficult.
Currently, including the basic flame-retardant system of two classes for the fire-retardant of Synthetic Leather: halogen system flame-retardant system and non-
Halogen flame-retardant system.Halogen system flame-retardant system is usually brominated flame-retardant collaboration antimony oxide, a large number of studies show that, it is added with bromine system
The polyurethane material of fire retardant can produce thick smoke and the harmful substances 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 has become a hot topic of research, and occurs the novel polyurethane that is applied in recent years
Halogen-free flame retardants.
According to the literature, mainly include two major classes primary structure applied to the halogen-free flame retardants of polyurethane: 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, 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
The 80% of cube system due to inorganic hydroxide fire retardant and matrix resin and incompatible is dispersed 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
Burning is easy to produce the toxic gases such as hydrogen phosphide and a large amount of smog, therefore this is also not 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 substantially
It reduces and is able to achieve 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, 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 system
Intensity is still very low, while being easy migration precipitation, and the albinism being precipitated is generated in product surface.Further, since ammonium ion
In the presence of APP is easy the moisture absorption, after polyurethane leather product surface is with the presence of droplet or leather contact water after a period of time, after doing
It is formed in product surface water stain, influences the appearance of product, while having 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 water stain problem, its fire-retardant machine
It is fire-retardant that reason belongs to condensed phase, belongs to non-expansion type, and non-expansion type flame-retardant system is easy to form in kindling for polyurethane material
Drippage, molten drop will affect 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 novel to be applied to the new of polyurethane material
The halogen-free flame-retardant system of type.
Summary of the invention
The present invention develops a kind of no molten drop water stain-free halogen-free flameproof polyurethane resin, which has height
The features such as fire-retardant, without molten drop, water stain-free, resistance to migration, it can be used for the preparation of halogen-free anti-inflaming polyurethane leather, to further apply
In the high flame-retardancy requirements field such as furniture, vehicles inside gadget.
Specific technical solution is as follows:
A kind of no 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%；
At carbon component 1~15%；
Described is divided into insoluble insoluble cross-linked polymer at carbon group, shown in Crosslink structure such as following formula (I):
The present invention relates to the exploitation of halogen-free anti-inflaming polyurethane leather, using novel low aqueous solubility diethyl hypo-aluminum orthophosphate,
It is cooperateed with by special low aqueous solubility carbonific, forms the expansion type flame-retarding mechanism for being directed to polyurethane material, solve existing resistance
Combustion system additive amount is big, with polyurethane base material poor compatibility, the easy moisture absorption, the defect of precipitation and molten drop easy to migrate.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 applied in polyurethane material as mesh
, inventor has made extensive and intensive studies.Existing flame-retardant system aiming at the problem that flame retardant polyurethane material, investigate
New flame-retardant system, as a result, it has been found that diethyl hypo-aluminum orthophosphate cooperates with and special can be well solved this problem at carbon component.
Shown in the chemical structure of diethyl hypo-aluminum orthophosphate such as following formula (II):
Diethyl hypo-aluminum orthophosphate is characterized in phosphorus content height, good flame resistance, temperature of initial decomposition with higher, water solubility
Low, resistance to migration is nonhygroscopic, and more application is in the engineering plastics such as nylon, PBT at present, especially engineering plastics of fiberglass reinforced
In.Applied to polyurethane material, due to water-soluble extremely low, be not in the moisture absorption and have water stain problem, but due to being condensed phase
Fire retardant mechanism reduces flame retardant property so that polyurethane material is easy drippage in burning again, can not be by hindering as defined in standard
Combustion requires, if reaching flame-retardancy requirements by improving additive amount, can cause the reduction of material property.
Inventors discovered through research that in the presence of diethyl hypo-aluminum orthophosphate, it 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 expanding carbon-coating, the molten drop of material is also
Control is arrived, it is shown that good anti-flammability.
As at charcoal component, the usually compounds such as compound of polyhydroxy, such as pentaerythrite, but these compounds by
In the presence of hydroxyl, although have it is good at carbon effect, it is water-soluble higher, will appear asking for the moisture absorption after being applied to polyurethane
The problems such as inscribing, surfaces of tacky, water stain and insulating properties caused to reduce.
It is studied through inventor, discovery is by two kinds of compounds of methylphosphonic acid and trihydroxyethyl isocyanuric ester in equivalent
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, it is as described at carbon component.This at carbon component had at carbon effect, the concertedness having had with diethyl hypo-aluminum orthophosphate,
There are phosphorus and nitrogen in molecular structure, can reduce the additive amount of diethyl hypo-aluminum orthophosphate, in molecular configurational due to not depositing
It is nonhygroscopic in water suction group, it not will form water stain, surfaces of tacky will not be caused.
The preparation method at carbon component, specifically:
(1) trihydroxyethyl isocyanuric ester and methylphosphonic acid of equivalent, under phase transfer catalyst effect, 150~
4~8h is reacted at 220 DEG C, and esterification prepolymer is made；
(2) it vacuumizes and is warming up to 260~280 DEG C, the esterification prepolymer is obtained through condensation curing, then after crushed
It arrives.
In the preparation process of step (1) prepolymer, in order to accelerate reaction speed, need 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 solidification is carried out to prepolymer, needs high vacuum, hot conditions.Preferably, taking out true
Sky to vacuum degree is not higher than 50KPa.The reaction can carry out in an oven, also can be used with the high-power of agitating function
Kneader.
It is block at carbon component by what is obtained after condensation curing, in order to be added in basis material, it is also necessary to carry out
Pulverization process controls average grain diameter D50 < 5 μm at carbon component using mechanical crushing equipment.
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 < 5 μm.
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, is selected from polyester
At least one of type polyurethane, polyether polyurethane, polycarbonate polyurethane, polycaprolactone-type urethane.
In halogen-free flameproof polyurethane resin of the invention, in the premise for the physical property and flame retardant property for not influencing polyurethane
Under, other additives, such as anti-mildew agent, antistatic agent, 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
At including:
Polyurethane matrix material 75~85%；
Diethyl hypo-aluminum orthophosphate 10~20%；
At carbon component 1~10%；
The diethyl hypo-aluminum orthophosphate is 1.25~8:1 with the mass ratio at carbon component.
Still further preferably, described in carbon component, nitrogen content 10.4%, phosphorus content 11.5%.Through further
Application test discovery, the content of nitrogen and phosphorous are applied in polyurethane resin after compounding with diethyl hypo-aluminum orthophosphate at carbon component,
More preferably flame retardant effect can be obtained.
The invention also discloses a kind of halogen-free anti-inflaming polyurethane leathers, with the no poly- ammonia of molten drop water stain-free halogen-free flameproof
Ester resin be superficial layer, with the fibrous layer as substrate it is compound after be prepared.
The method of the preparation halogen-free anti-inflaming polyurethane leather is not particularly limited, and can be well known wet process 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, venetian blind, valance etc., outdoor
Tent, vehicle cover etc..
Compared with prior art, the present invention has the advantage that
The present invention provides a kind of no 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 the flame retardant polyurethane leather of raw material preparation
It is quasi-.
Specific embodiment
Following performance is investigated to material:
(1) flame retardant property
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 surface is observed
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, is arranged 85 DEG C of temperature, phase
To humidity 85%, the state of specimen surface of the visual observations after 168 hours.
Embodiment 1
It follows these steps to prepare and characterizes polyurethane leather:
(1) by formula as below, flame retardant polyurethane resin composition is prepared (unless otherwise stated, after each raw material is blended
Proportion in the present invention is weight percentage):
Polyurethane system 82%；
Diethyl hypo-aluminum orthophosphate 13%；
At carbon component 5%；
Wherein, by weight, the composition of polyurethane system are as follows:
(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, it is carried out 72 hours at 40 DEG C
Aging obtains fire-retardant synthetic leather.
(3) correlated performance is tested.
Preparation process in the present embodiment at carbon component is as follows:
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 trihydroxyethyl isocyanuric ester is melted, 2.7 grams of tetrabutylammonium bromide and 288g (3 moles) methylphosphonic acid is then added,
Strong stirring mixture, heating is raised to 210 DEG C from 150 DEG C within 6 hours, the water in reaction process is discharged, and condense metering,
210 DEG C keep the temperature 1 hour, are cooled to 150 DEG C, and melt is discharged to a metal tray, obtains a kind of faint yellow hair after melt is 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 degree keeps 50KPa, is heated to 270
DEG C, it is kept for 2 hours, completes solidification, cooling discharge.Crushing material is stand-by to average grain diameter D50 < 5 micron.
Through analyzing:
It is manufactured in the present embodiment at carbon component, content are as follows: 10.5%, nitrogen content are as follows: 10.1% (phosphorus, nitrogen content are real
Border measured value, the slightly below calculated value in specification), solubility < 0.1%, 1% weightlessness decomposition temperature is 320 DEG C.
Unless otherwise instructed, product manufactured in the present embodiment is all made of at carbon component in following embodiment.
Each material and proportion 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, in addition to diethyl hypo-aluminum orthophosphate and at the proportion adjustment of carbon component, improves diethyl
The proportion of base hypophosphorous acid keeps flame-retardant system total amount constant.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table
1。
Embodiment 3
Implementation process is same as Example 1, in addition to diethyl hypo-aluminum orthophosphate and at the proportion adjustment of carbon component, improves into carbon
The proportion of component keeps flame-retardant system total amount constant.Other materials and proportion 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 adjustment of the proportion of formula, reduces flame-retardant system sum-rate.Other objects
Material and proportion 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 adjustment of the proportion of formula, improves flame-retardant system sum-rate.Other objects
Material and proportion 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 not using into carbon group exceptionally.Other materials and proportion are shown in Table 1, acquired
Material the results are shown in Table 1.
Comparative example 2
Implementation process is same as Example 1, other than without using diethyl hypo-aluminum orthophosphate.Other materials and proportion are shown in Table 1,
Obtained material the results are shown in Table 1.
Comparative example 3
Implementation process is same as Example 1, other than only using ammonium polyphosphate, without using diethyl hypo-aluminum orthophosphate and at carbon
Component.Other materials and proportion 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, other than only using aromatic phosphoric acid ester, without using diethyl hypo-aluminum orthophosphate and at
Carbon component.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table 1.Table 1
Claims (10)
1. a kind of no molten drop water stain-free halogen-free flameproof polyurethane resin, which is characterized in that by weight percentage, raw material composition packet
It includes:
Polyurethane matrix material system 65~90%；
Diethyl hypo-aluminum orthophosphate 5~20%；
At carbon component 1~15%；
Described is divided into insoluble insoluble cross-linked polymer at carbon group, shown in Crosslink structure such as following formula (I):
2. no molten drop water stain-free halogen-free flameproof polyurethane resin according to claim 1, which is characterized 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, which is characterized in that the diethyl
Base hypo-aluminum orthophosphate, average grain diameter D50 < 5 μm.
4. no molten drop water stain-free halogen-free flameproof polyurethane resin according to claim 1, which is characterized in that described at carbon
Component is prepared after polycondensation reaction using the trihydroxyethyl isocyanuric ester of equivalent and methylphosphonic acid as raw material.
5. no molten drop water stain-free halogen-free flameproof polyurethane resin according to claim 4, which is characterized in that described at carbon group
The preparation method divided, specifically:
(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) it vacuumizes and is 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, which is characterized 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, which is characterized in that in step (2),
Vacuum degree is evacuated to not higher than 50KPa；It is crushed to average grain diameter D50 < 5 μm.
8. any described without molten drop water stain-free halogen-free flameproof polyurethane resin according to claim 1~7, which is characterized in that press
Weight percent meter, raw material composition include:
Polyurethane matrix material system 75~85%；
Diethyl hypo-aluminum orthophosphate 10~20%；
At carbon component 1~10%；
The diethyl hypo-aluminum orthophosphate is 1.25~8:1 with the mass ratio at carbon component.
9. no molten drop water stain-free halogen-free flameproof polyurethane resin according to claim 8, which is characterized in that described at carbon
In component, nitrogen content 10.4%, phosphorus content 11.5%.
10. a kind of halogen-free anti-inflaming polyurethane leather, which is characterized 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 be superficial layer, with the fibrous layer as substrate it is compound after be prepared.
Priority Applications (1)
| 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 |
Applications Claiming Priority (1)
| 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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| 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 |
| CN109082900B (en) * | 2018-06-28 | 2020-06-19 | 浙江大学 | Flame-retardant polyurethane leather composition based on dialkyl dithiophosphate and free of molten drops and water stains |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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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