CN107057331A - A kind of preparation method of aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material - Google Patents
A kind of preparation method of aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material Download PDFInfo
- Publication number
- CN107057331A CN107057331A CN201611208718.5A CN201611208718A CN107057331A CN 107057331 A CN107057331 A CN 107057331A CN 201611208718 A CN201611208718 A CN 201611208718A CN 107057331 A CN107057331 A CN 107057331A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- aqueous polyurethane
- composite material
- fiber composite
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/025—Polyphosphazenes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a kind of preparation method of aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material.It is by hexachlorocyclotriph,sphazene and 4, 4'(hexafluoroisopropyli,enes) bis-phenol is dissolved in toluene/acetone composite solution, triethylamine is added dropwise dropwise and nucleophilic substitution is carried out under magnetic stirring, it is post-treated to obtain fluorine-containing polyphosphazene nanofiber, during the nanofiber is added in polypropylene glycol, add IPDI, catalyst, 2, 2 dihydromethyl propionic acids to reaction terminates, triethylamine is added to neutralize after dropping to, it is scattered in deionized water and obtains aqueous polyurethane emulsion, aqueous polyurethane emulsion is poured into the spontaneous curing in tensile bars mould and obtains aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material.The present invention is reacted and is added in aqueous polyurethane matrix by using chemistry polymerizing in situ method, Waterborne PU Composite prepared by success, with excellent heat endurance, tensile property and friction and wear behavior.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, and in particular to a kind of aqueous polyurethane/polyphosphazene nanofiber
The preparation method of composite.
Background technology
Aqueous polyurethane(WPU)It is to be introduced on strand after hydrophilic group, stably can be dissolved or dispersed in water
One birdss of the same feather flock together compound.WPU can be divided into two stage synthesis.Be first it is pre- progressively polymerize, i.e., by oligomer dihydric alcohol, two isocyanic acids
Ester, hydrophilic monomer and chain extender are progressively polymerized to the larger Waterborne Polyurethane Prepolymer of relative molecular mass;Secondly neutralize, with
And rear performed polymer is scattered in water.The aqueous polyurethane organic volatile synthesized by this method is low, relatively environmentally friendly, leads to
After research in recent years, also it is widely used, such as adhesive, surface conditioning agent, fabric coating, coating and arrangement
Agent.
Volatile organic matter is not present in aqueous polyurethane during synthesis and use(VOC), it is to avoid dirt is caused to environment
Dye, meets development green industry resource, the energy, free of contamination three premises and four E principles.Its is nontoxic, non-ignitable, VOC values are low, soft
Section hard section can adjust.Because aqueous polyurethane heat endurance is low, poor mechanical property limits aqueous polyurethane the features such as not wear-resisting
The development of industry.To expand its application, high-performance water-based polyurethane composite is prepared, it is necessary to be modified research to it.
The nanomaterial-filled modifying agent reported has nano-calcium carbonate, nano titanium oxide, nano silicon, carbon to receive
Mitron, organo montmorillonite etc..But during physics is filling-modified, easily occur the reunion of nano-particle, so as to cause filler
It is scattered uneven and poor with matrix resin interface compatibility, and then trigger the drawbacks of composite material combination property is remarkably decreased.In addition,
Due to the inactive point in most inorganic nano-particle surface, it is filling-modified before it must be surface-treated, and this process need
To be made troubles by complicated multi-step chemical reaction to production technology.Complicated modification also can be to the knot of nano-particle
Structure and pattern produce destruction, it is lost part functionalities.Therefore, using chemistry polymerizing in situ method, nano-particle is passed through
Chemical bond is introduced into aqueous polyurethane, can be avoided physics lack of fill, be significantly increased Waterborne PU Composite comprehensive
Energy.
The content of the invention
The present invention is directed to deficiencies of the prior art, it is therefore an objective to provide a kind of system of Waterborne PU Composite
Preparation Method, adds the preparation technology of the Waterborne PU Composite of fluorine-containing polyphosphazene nanofiber modification prepared by design, system
Standby obtained Waterborne PU Composite has excellent heat endurance, tensile property and friction and wear behavior.
A kind of preparation method of described aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material, it is characterised in that
Comprise the following steps:
1)By hexachlorocyclotriph,sphazene and 4,4'- (hexafluoroisopropyli,ene) bis-phenol is completely dissolved in toluene/acetone composite solution, dropwise
Triethylamine is added dropwise and normal temperature nucleophilic substitution is carried out under magnetic stirring, after reaction terminates, is distinguished with deionized water and ethanol
Cleaning 3 times is simultaneously centrifuged, and fluorine-containing polyphosphazene nanofiber is obtained after vacuum drying;
12)Under nitrogen protection, by step 1)Obtained fluorine-containing polyphosphazene nanofiber is added in polypropylene glycol and dispersed with stirring
Uniformly, under nitrogen charging gas shielded, IPDI and catalyst are added, 1.5-2.5 h are reacted at 90-100 DEG C
Afterwards, 2,2- dihydromethyl propionic acids are added and continue to react 2.5-3.5 h, temperature of reaction system is dropped to 30 DEG C by reaction after terminating, plus
It is 7 to enter triethylamine to be neutralized to pH value, obtains base polyurethane prepolymer for use as after constant temperature stirring, base polyurethane prepolymer for use as is divided under high velocity agitation
Dissipate in deionized water, stir 1.5-2.5h, obtain aqueous polyurethane emulsion, aqueous polyurethane emulsion is poured in tensile bars mould
In tool, the solidification demoulding, produces aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material under field conditions (factors).
A kind of preparation method of described aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material, it is characterised in that
Step 1)In hexachlorocyclotriph,sphazene, the molar ratio of 4,4'- (hexafluoroisopropyli,ene) bis-phenols and triethylamine be 1:2.5-3.5:
5-8, preferably 1:3:6.
A kind of preparation method of described aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material, it is characterised in that
Step 1)In hexachlorocyclotriph,sphazene quality and tetrahydrofuran volume ratio be 1:0.2-0.8, its unit is g/L;Described first
The volume ratio of toluene and acetone is 6-8 in propiophenone solution:1, preferably 7:1.
A kind of preparation method of described aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material, it is characterised in that
Step 1)In constant temperature nucleophilic substitution temperature be 20-30 DEG C, preferably 25 DEG C, the reaction time be 10-15 hours, preferably
For 12 hours.
A kind of preparation method of described aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material, it is characterised in that step
1)In centrifuge speed be 3500-4500 r/min, preferably 4000 r/min.
A kind of preparation method of described aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material, it is characterised in that
Step 1)In magnetic agitation rotating speed be 1000-1400 r/min, preferably 1200 r/min.
A kind of preparation method of described aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material, it is characterised in that
Step 2)Described in polypropylene glycols amount be 1000 ~ 10000.
A kind of preparation method of described aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material, it is characterised in that
Step 2)Described in polypropylene glycol, IPDI, 2,2- dihydromethyl propionic acids, triethylamine pass through before the reaction
Cross vacuum dehydration processing.
A kind of preparation method of described aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material, it is characterised in that
Step 2)Described in catalyst be dibutyl tin laurate;
A kind of preparation method of described aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material, it is characterised in that step
2)Described in base polyurethane prepolymer for use as high-speed stirred rotating speed be 1800-2200r/min, preferably 2000 r/min.
Fluorine-containing polyphosphazene nanofiber synthetic route is as follows:
。
The present invention has following beneficial effect compared with prior art:Fluorine-containing polyphosphazene Nanowire prepared by the present invention
Dimension table face has a large amount of active hydroxy groups, can be obtained by single step reaction, and preparation method is simple, yield is higher.Using chemical former
Position polymerization, is reacted and is added in aqueous polyurethane matrix, and Waterborne PU Composite prepared by success has excellent
Different heat endurance, tensile property and friction and wear behavior.The aqueous polyurethane composite wood of filled fluoropolymer polyphosphazene nanofiber
Expect that heat endurance is good compared with blank batten, with the increase for the fibre weight being mixed into batten, the thermal stability of batten is lifted therewith.
In the course of the polymerization process, chemically reacted between polyphosphazene nanofiber and IPDI, generate covalent linkage, play one kind
The effect of crosslinking agent, therefore, significantly improves batten thermal stability.When filling quality percentage composition is 2.0 wt.%, polyphosphazene
Nanofiber is uniformly dispersed in aqueous polyurethane matrix, and the tensile strength of composite brings up to 3.24 MPa, extension at break
Rate brings up to 752.16%.Fluorine-containing polyphosphazene nanofiber improves the anti-friction wear-resistant characteristic of aqueous polyurethane, polyphosphazene fiber content
It is 1.1836 for 2.0 wt.% sample coefficient of friction, wear extent is 0.0087g, polyphosphazene nanofiber is dispersed in aqueous
In polyurethane matrix, fiber plays self-lubricating function, at the same in fiber P, N, F element presence, can be in surface of friction pair shape
Into chemical transfer membrane, comprehensive anti-friction wear-resistant effect is played.
Brief description of the drawings
Fig. 1 is fluorine-containing polyphosphazene nanofiber FTIR spectrograms prepared by embodiment 1;
Fig. 2 is fluorine-containing polyphosphazene nanofiber EDS spectrograms prepared by embodiment 1;
Fig. 3 is fluorine-containing polyphosphazene nanofiber SEM photograph prepared by embodiment 1.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.Step one in following examples is carried out specifically by synthetic route of Fig. 1
It is bright.
Embodiment 1:
Step one:Under 1200 r/min magnetic agitations, in the single-necked flask for filling 50 mL toluene acetone solution, 0.1 is added
G hexachlorocyclotriph,sphazene and 0.28 g 4,4'- (hexafluoroisopropyli,ene) bis-phenol, are slowly added to 0.24 mL triethylamines, in room temperature
Lower reaction 12 hours, is respectively washed 3 times by deionized water and ethanol, the centrifugation of 4000 r/min rotating speeds, 40 DEG C of vacuum drying 24
H, obtains fluorine-containing polyphosphazene nanofiber, and yield is 80%.
Step 2:30 g PPG-2000 are placed in three-neck flask, nitrogen charging gas shielded(Not fibre-bearing).In 100 DEG C of oil
Continuously stirred in bath 0.5 hour, add the drop dibutyltin dilaurate catalysts of 11.67 g IPDI and 5, it is anti-at 95 DEG C
Answer 2 hours.It vacuum drying 2.01 g DMPA will add in advance in three-neck flask, and continue to react 3 hours.System temperature is dropped
To 30 DEG C, it is 7 to add TEA and be neutralized to pH value, and constant temperature stirs 0.5 h and obtains PU performed polymers.Performed polymer is divided under high velocity agitation
Dissipate in deionized water, stir 2 h, obtain WPU emulsions.Emulsion is poured in tensile bars mould, solidified under field conditions (factors)
The demoulding.
Embodiment 2:
Step one:Under 1200 r/min magnetic agitations, in the single-necked flask for filling 100mL toluene acetone solution, 0.2 is added
G hexachlorocyclotriph,sphazene and 0.38 g 4,4'- (hexafluoroisopropyli,ene) bis-phenol, are slowly added to 0.48 mL triethylamines, in room temperature
Lower reaction 12 hours, is respectively washed 3 times by deionized water and ethanol, the centrifugation of 4000 r/min rotating speeds, 40 DEG C of vacuum drying 24
H, obtains fluorine-containing polyphosphazene nanofiber, and yield is 81%.
Step 2:30 g PPG-2000 are placed in three-neck flask, while plus 0.2552 g(0.5 wt.% )It is fluorine-containing poly-
Phosphonitrile fiber, nitrogen charging gas shielded.Continuously stirred in 100 DEG C of oil bath pan 0.5 hour, add the drops of 11.67 g IPDI and 5 two
Dibutyl tin laurate catalyst, reacts 2 hours at 95 DEG C.Three necks burning will be added by vacuum drying 2.01 g DMPA in advance
In bottle, continue to react 3 hours.System temperature is dropped to 30 DEG C, it is 7 to add TEA and be neutralized to pH value, and constant temperature stirs 0.5 h and obtained
PU performed polymers.Performed polymer is scattered in deionized water under high velocity agitation, 2h is stirred, obtains WPU emulsions.Emulsion is poured in drawing
Stretch in batten mould, under field conditions (factors) the solidification demoulding.
Embodiment 3:
Step one:Under 1200 r/min magnetic agitations, in the single-necked flask for filling 200 mL toluene acetone solution, add
0.4 g hexachlorocyclotriph,sphazene and 1.0 g 4,4'- (hexafluoroisopropyli,ene) bis-phenol, are slowly added to 0.96mL triethylamines, in room
The lower reaction of temperature 12 hours, is respectively washed 3 times, the centrifugation of 4000 r/min rotating speeds, 40 DEG C of vacuum drying by deionized water and ethanol
24 h, obtain fluorine-containing polyphosphazene nanofiber, and yield is 83%.
Step 2:30 g PPG-2000 are placed in three-neck flask, while adding 0.5104 g(1.0 wt.%)It is fluorine-containing poly-
Phosphonitrile fiber, nitrogen charging gas shielded.Continuously stirred in 100 DEG C of oil bath pan 0.5 hour, add the drops of 11.67 g IPDI and 5 two
Dibutyl tin laurate catalyst, reacts 2 hours at 95 DEG C.Three necks burning will be added by vacuum drying 2.01 g DMPA in advance
In bottle, continue to react 3 hours.System temperature is dropped to 30 DEG C, it is 7 to add TEA and be neutralized to pH value, and constant temperature stirs 0.5 h and obtained
PU performed polymers.Performed polymer is scattered in deionized water under high velocity agitation, 2 h is stirred, obtains WPU emulsions.By emulsion pour in
In tensile bars mould, the solidification demoulding under field conditions (factors).
Embodiment 4:
Step one:Under 1200 r/min magnetic agitations, in the single-necked flask for filling 400mL toluene acetone solution, 0.8 is added
G hexachlorocyclotriph,sphazene and 2.22 g 4,4'- (hexafluoroisopropyli,ene) bis-phenol, are slowly added to 1.92 mL triethylamines, in room temperature
Lower reaction 12 hours, is respectively washed 3 times by deionized water and ethanol, the centrifugation of 4000 r/min rotating speeds, 40 DEG C of vacuum drying
24h, obtains fluorine-containing polyphosphazene nanofiber, and yield is 83%.
Step 2:30 gPPG-2000 are placed in three-neck flask, while adding 1.0209 g(2.0 wt.%)It is fluorine-containing poly-
Phosphonitrile fiber, nitrogen charging gas shielded.Continuously stirred in 100 DEG C of oil bath pan 0.5 hour, add the drops of 11.67 g IPDI and 5 two
Dibutyl tin laurate catalyst, reacts 2 hours at 95 DEG C.Three necks burning will be added by vacuum drying 2.01 g DMPA in advance
In bottle, continue to react 3 hours.System temperature is dropped to 30 DEG C, it is 7 to add TEA and be neutralized to pH value, and constant temperature stirs 0.5 h and obtained
PU performed polymers.Performed polymer is scattered in deionized water under high velocity agitation, 2h is stirred, obtains WPU emulsions.Emulsion is poured in drawing
Stretch in batten mould, under field conditions (factors) the solidification demoulding.
Embodiment 5:
Step one:Under 1200 r/min magnetic agitations, in the single-necked flask for filling 500 mL toluene acetone solution, add
1.0 g hexachlorocyclotriph,sphazene and 2.8 g 4,4'- (hexafluoroisopropyli,ene) bis-phenol, are slowly added to 2.4 mL triethylamines, in room
The lower reaction of temperature 12 hours, is respectively washed 3 times, the centrifugation of 4000 r/min rotating speeds, 40 DEG C of vacuum drying by deionized water and ethanol
24 h, obtain fluorine-containing polyphosphazene nanofiber, and yield is 85%.
Step 2:30 g PPG-2000 are placed in three-neck flask, while adding 2.0418 g(4.0 wt.%)It is fluorine-containing poly-
Phosphonitrile fiber, nitrogen charging gas shielded.Continuously stirred in 100 DEG C of oil bath pan 0.5 hour, add the drops of 11.67 g IPDI and 5 two
Dibutyl tin laurate catalyst, reacts 2 hours at 95 DEG C.Three necks burning will be added by vacuum drying 2.01 g DMPA in advance
In bottle, continue to react 3 hours.System temperature is dropped to 30 DEG C, it is 7 to add TEA and be neutralized to pH value, and constant temperature stirs 0.5 h and obtained
PU performed polymers.Performed polymer is scattered in deionized water under high velocity agitation, 2 h is stirred, obtains WPU emulsions.By emulsion pour in
In tensile bars mould, the solidification demoulding under field conditions (factors).
The test effect of embodiment:
Tested by Fourier transform infrared spectroscopy, elementary analysis, scanning electron microscope test, thermogravimetric test, extension test
The fluorine-containing polyphosphazene nanofiber and Waterborne PU Composite of the present invention are characterized with friction and wear test, tested
As a result Fig. 1, Fig. 2, Fig. 3 are referred to.
The structure of polyphosphazene nanofiber is characterized by Fourier's infrared transform infrared spectroscopy instrument, test result
Curve is as shown in Figure 1.Wave number is in 1608 cm-1(a)With 1511 cm-1(b)The absworption peak at place is the feature of the phenyl ring in bisphenol AF
Peak, wave number is in 1209 cm-1(c)With 1174 cm-1(d)The absworption peak at place is-CF3 characteristic peak, and wave number is in 880 cm-1(f)Place
Absworption peak be hexachlorocyclotriph,sphazene P-N characteristic peak, may determine that accordingly in polyphosphazene nanofiber containing bisphenol AF and
The structure of hexachlorocyclotriph,sphazene;Simultaneously(e)Place's wave number is 940 cm-1Absworption peak be P-O- (Ph) characteristic peak.
Fig. 2 is fluorine-containing polyphosphazene nanofiber EDS spectrograms, is understood according to spectrogram and its report, rich in substantial amounts of in fiber
Fluorine and oxygen element, both of which come from bisphenol AF, and O is about 1 with F ratio:3, also further to prove, bisphenol AF is certain
It, with HCCP reactions, is corresponding with infrared result to be;The analysis result also supports the structure containing HCCP in fiber.
What Fig. 3 was represented is fluorine-containing polyphosphazene nanofiber SEM pictures.As can be seen from the figure fluorine-containing polyphosphazene nanofiber
Diameter is about 40-60nm, and length is 5-10 μm.
The thermogravimetric test of Waterborne PU Composite obtained by embodiment 1-5(Utilize TA companies of U.S. Q5000IR types heat
Analyzer is analyzed.Test scope be room temperature to 800 DEG C, programming rate is 10 DEG C/min, nitrogen atmosphere)As a result it is as follows:
The Waterborne PU Composite thermal weight loss of table 1
Shown in the result table 1 of the aqueous polyurethane of preparation/polyphosphazene nano-fiber composite material thermogravimetric analysis.Wherein TonRepresent
Initial solution temperature, T5%Represent temperature during degraded 5%, T50%Represent temperature during degraded half.With fluorine-containing polyphosphazene Nanowire
The increase of dimension hplc, temperature of initial decomposition, 5% decomposition temperature, 50% decomposition temperature have a certain amount of lifting, and heat endurance has been carried
It is high.This be due to polyphosphazene nanofiber heat endurance it is relatively good, with the increase of the amount for the fiber being mixed into batten, batten
Thermal stability lifted therewith, and in the course of the polymerization process, chemically reacted, generated between fiber and aqueous polyurethane
Covalent bond improves batten thermal stability.
The extension test of Waterborne PU Composite obtained by embodiment 1-5(Utilize U.S.'s instron5966 types height
Warm double column testing machines are tested.Batten stretched portion width and thickness are inserted in advance, draw speed is 50 mm/min.)
As a result it is as follows:
The Waterborne PU Composite tensile property of table 2
As shown in Table 2, the tensile strength of composite batten rises as fiber content increases, and it is 2.0 to reach content
During wt.% embodiment 4, ultimate tensile strength is after 3.24 MPa, tensile strength is as content continues to rise and declines.It is multiple
The elongation at break of condensation material batten rises as fiber content increases, and reaches the embodiment 4 that content is 2.0 wt.%
When, maximum elongation at break be 752.16% after, elongation at break with content continue rise and decline.The quality of fiber point
When number is smaller, nanofiber is can be distributed to than more uniform among the system of aqueous polyurethane, can be improved aqueous
The mechanical property of polyurethane;As the fiber content in system is excessive, fiber is easily reunited together, can reduce aqueous polyurethane
Mechanical property.
The friction and wear test of Waterborne PU Composite obtained by embodiment 1-5(Prepare long 30 mm, wide 10 mm,
3 mm of thickness sample, is tested under the N of load 10, the r/min of rotating speed 200, the min of test period 10 DRY SLIDING.)
As a result it is as follows:
The Waterborne PU Composite coefficient of friction of table 3, wear extent
As shown in Table 3, the coefficient of friction and wear extent of Waterborne PU Composite are compared to blank sample and declined,
I.e. the modification of polyphosphazene nanofiber is improved to the friction and wear behavior of aqueous polyurethane.Fiber content is 2.0 wt.% implementation
The sample of example 4 is most wear-resisting, and polyphosphazene nanofiber is dispersed in aqueous polyurethane matrix, and nanofiber plays self-lubricating work
With, at the same in fiber P, N, F element presence, chemical transfer membrane can be formed in surface of friction pair, comprehensive anti-friction wear-resistant is played
Effect.
Claims (10)
1. the preparation method of a kind of aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material, it is characterised in that including following
Step:
1)By hexachlorocyclotriph,sphazene and 4,4'- (hexafluoroisopropyli,ene) bis-phenol is completely dissolved in toluene/acetone composite solution, dropwise
Triethylamine is added dropwise and normal temperature nucleophilic substitution is carried out under magnetic stirring, after reaction terminates, is distinguished with deionized water and ethanol
Cleaning 3 times is simultaneously centrifuged, and fluorine-containing polyphosphazene nanofiber is obtained after vacuum drying;
12)Under nitrogen protection, by step 1)Obtained fluorine-containing polyphosphazene nanofiber is added in polypropylene glycol and dispersed with stirring
Uniformly, under nitrogen charging gas shielded, IPDI and catalyst are added, 1.5-2.5 h are reacted at 90-100 DEG C
Afterwards, 2,2- dihydromethyl propionic acids are added and continue to react 2.5-3.5 h, temperature of reaction system is dropped to 30 DEG C by reaction after terminating, plus
It is 7 to enter triethylamine to be neutralized to pH value, obtains base polyurethane prepolymer for use as after constant temperature stirring, base polyurethane prepolymer for use as is divided under high velocity agitation
Dissipate in deionized water, stir 1.5-2.5h, obtain aqueous polyurethane emulsion, aqueous polyurethane emulsion is poured in tensile bars mould
In tool, the solidification demoulding, produces aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material under field conditions (factors).
2. a kind of preparation method of aqueous polyurethane according to claim 1/fluorine-containing polyphosphazene nano-fiber composite material,
It is characterized in that step 1)In hexachlorocyclotriph,sphazene, the molar ratio of 4,4'- (hexafluoroisopropyli,ene) bis-phenols and triethylamine be
1:2.5-3.5:5-8, preferably 1:3:6.
3. a kind of preparation method of aqueous polyurethane according to claim 1/fluorine-containing polyphosphazene nano-fiber composite material,
It is characterized in that step 1)In hexachlorocyclotriph,sphazene quality and tetrahydrofuran volume ratio be 1:0.2-0.8, its unit is g/
L;The volume ratio of toluene and acetone is 6-8 in described toluene acetone solution:1, preferably 7:1.
4. a kind of preparation method of aqueous polyurethane according to claim 1/fluorine-containing polyphosphazene nano-fiber composite material,
It is characterized in that step 1)In constant temperature nucleophilic substitution temperature be 20-30 DEG C, preferably 25 DEG C, the reaction time is 10-
15 hours, preferably 12 hours.
5. a kind of preparation method of aqueous polyurethane according to claim 1/fluorine-containing polyphosphazene nano-fiber composite material,
It is characterized in that step 1)In centrifuge speed be 3500-4500 r/min, preferably 4000 r/min.
6. a kind of preparation method of aqueous polyurethane according to claim 1/fluorine-containing polyphosphazene nano-fiber composite material,
It is characterized in that step 1)In magnetic agitation rotating speed be 1000-1400 r/min, preferably 1200 r/min.
7. a kind of preparation method of aqueous polyurethane according to claim 1/fluorine-containing polyphosphazene nano-fiber composite material,
It is characterized in that step 2)Described in polypropylene glycols amount be 1000 ~ 10000.
8. a kind of preparation method of aqueous polyurethane according to claim 1/fluorine-containing polyphosphazene nano-fiber composite material,
It is characterized in that step 2)Described in polypropylene glycol, IPDI, 2,2- dihydromethyl propionic acids, triethylamine exist
Handled before reaction by vacuum dehydration.
9. a kind of preparation method of aqueous polyurethane according to claim 1/fluorine-containing polyphosphazene nano-fiber composite material,
It is characterized in that step 2)Described in catalyst be dibutyl tin laurate.
10. a kind of preparation side of aqueous polyurethane according to claim 1/fluorine-containing polyphosphazene nano-fiber composite material
Method, it is characterised in that step 2)Described in base polyurethane prepolymer for use as high-speed stirred rotating speed be 1800-2200r/min, preferably
For 2000 r/min.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611208718.5A CN107057331A (en) | 2016-12-23 | 2016-12-23 | A kind of preparation method of aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611208718.5A CN107057331A (en) | 2016-12-23 | 2016-12-23 | A kind of preparation method of aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107057331A true CN107057331A (en) | 2017-08-18 |
Family
ID=59623164
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611208718.5A Pending CN107057331A (en) | 2016-12-23 | 2016-12-23 | A kind of preparation method of aqueous polyurethane/fluorine-containing polyphosphazene nano-fiber composite material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107057331A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108587113A (en) * | 2018-03-20 | 2018-09-28 | 浙江工业大学 | A kind of preparation method of self-cleaning polyurethane elastomer film |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA911100A (en) * | 1972-09-26 | Szewczyk Stanislas | Derivative of phospho-nitrile chloride | |
CN103694632A (en) * | 2013-11-27 | 2014-04-02 | 浙江工业大学之江学院工业研究院 | Preparation method of epoxy resin composite material |
CN104403548A (en) * | 2014-12-29 | 2015-03-11 | 中科院广州化学有限公司 | Water-based polyurethane paint containing polyether glycol/nano TiO2 hybrid material |
CN105523541A (en) * | 2016-01-29 | 2016-04-27 | 上海交通大学 | Heteroatom doped hollow porous carbon microspheres and preparation method thereof |
-
2016
- 2016-12-23 CN CN201611208718.5A patent/CN107057331A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA911100A (en) * | 1972-09-26 | Szewczyk Stanislas | Derivative of phospho-nitrile chloride | |
CN103694632A (en) * | 2013-11-27 | 2014-04-02 | 浙江工业大学之江学院工业研究院 | Preparation method of epoxy resin composite material |
CN104403548A (en) * | 2014-12-29 | 2015-03-11 | 中科院广州化学有限公司 | Water-based polyurethane paint containing polyether glycol/nano TiO2 hybrid material |
CN105523541A (en) * | 2016-01-29 | 2016-04-27 | 上海交通大学 | Heteroatom doped hollow porous carbon microspheres and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
WEI WEI等: "A rapid and efficient strategy for preparation of super-hydrophobic surface with cross-linked cyclotriphosphazene/6F-bisphenol A copolymer microspheres", 《CHEMICAL COMMUNICATIONS》 * |
YAN ZHU等: "Morphology control between microspheres and nanofibers by solvent-induced approach based on crosslinked phosphazene-containing materials", 《MATERIALS SCIENCE AND ENGINEERING B》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108587113A (en) * | 2018-03-20 | 2018-09-28 | 浙江工业大学 | A kind of preparation method of self-cleaning polyurethane elastomer film |
CN108587113B (en) * | 2018-03-20 | 2020-11-24 | 浙江工业大学 | Preparation method of self-cleaning polyurethane elastomer film |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Andideh et al. | Effect of surface modification of electrochemically oxidized carbon fibers by grafting hydroxyl and amine functionalized hyperbranched polyurethanes on interlaminar shear strength of epoxy composites | |
Yu et al. | Crosslinked waterborne polyurethane with high waterproof performance | |
Bao et al. | Recent advances in the modification of polyacrylate latexes | |
US8664298B1 (en) | Self-healing polymer nanocomposite coatings for use on surfaces made of wood | |
Ma et al. | Synthesis of a novel silica modified environmentally friendly waterborne polyurethane matting coating | |
US8987352B1 (en) | Phase separated self-healing polymer coatings | |
CN109415643A (en) | Lubriation material and SRT material | |
Yuan et al. | Preparation and characterization of a polyimide coating on the surface of carbon fibers | |
Mülazim et al. | Preparation of photo curable highly hydrophobic coatings using a modified castor oil derivative as a sol–gel component | |
Yin et al. | Synthesis and properties of octadecylamine-graphene oxide modified highly hydrophobic waterborne polyurethane emulsion | |
Ding et al. | Preparation of waterborne polyurethane-silica nanocomposites by a click chemistry method | |
Zhao et al. | Synthesis and investigation of well-defined silane terminated and segmented waterborne hybrid polyurethanes | |
EP1837424A1 (en) | Oil agent for carbon fiber precursor fiber, carbon fiber and method for producing carbon fiber | |
CN104452453B (en) | A kind of speciality paper water base water and oil repellent agent and preparation method thereof | |
Zhou et al. | Design and development of HMS@ ZIF-8/fluorinated polybenzoxazole composite films with excellent low-k performance, mechanical properties and thermal stability | |
CN105860120A (en) | Super-hydrophobic polypropylene film and preparation method thereof | |
CN106750155A (en) | A kind of preparation method of aqueous polyurethane/fluorine-containing polyphosphazene microspheres composite | |
Jiang et al. | Effect of carbon fiber‐graphene oxide multiscale reinforcements on the thermo‐mechanical properties of polyurethane elastomer | |
Song et al. | Interfacial and interlayer enhancement of highly hydrophilic dual-affinity waterborne polyurethane sizing agent acting on carbon fiber/epoxy resin composites | |
Li et al. | Two-step method to realize continuous multi-wall carbon nanotube grafted on the fibers to improve the interface of carbon fibers/epoxy resin composites based on the Diels-Alder reaction | |
Yuan et al. | Aqueous PUA emulsion prepared by dispersing polyurethane prepolymer in polyacrylate emulsion | |
Xu et al. | Facile preparation of superhydrophobic polyester surfaces with fluoropolymer/SiO2 nanocomposites based on vinyl nanosilica hydrosols | |
Song et al. | Poly (methyl dihydroxybenzoate) modified waterborne polyurethane sizing coatings with chemical and hydrogen-bonded complex cross-linking structures for improving the surface wettability and mechanical properties of carbon fiber | |
Zhou et al. | Synthesis and properties of fluorine–silicon modified polyacrylate hybrid latex particles with core–shell structure obtained via emulsifier‐free emulsion polymerization | |
Ma et al. | Facile fabrication of self-roughened surfaces for superhydrophobic coatings via polarity-induced phase separation strategy |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170818 |
|
RJ01 | Rejection of invention patent application after publication |