CN109824861A - A kind of modified fluorinated polyurethane resin of polyphenylene sulfide - Google Patents
A kind of modified fluorinated polyurethane resin of polyphenylene sulfide Download PDFInfo
- Publication number
- CN109824861A CN109824861A CN201910049676.2A CN201910049676A CN109824861A CN 109824861 A CN109824861 A CN 109824861A CN 201910049676 A CN201910049676 A CN 201910049676A CN 109824861 A CN109824861 A CN 109824861A
- Authority
- CN
- China
- Prior art keywords
- polyphenylene sulfide
- added
- parts
- polyurethane resin
- reaction
- 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
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a kind of modified fluorinated polyurethane resins of polyphenylene sulfide, are made by following steps: a. synthesizes the methyl diphenylene diisocyanate that side chain end group is fluorine-containing functional group's segment；B. polytetrahydrofuran ether glycol is added, synthesizes fluorochemical urethane performed polymer；C. chain extension, cross-linking reaction are carried out using small molecule chain extender, last stage reaction is added end-capping reagent and carries out sealing end to introduce hydrophobic grouping, completes the preparation of fluorochemical urethane/polyphenylene sulfide；D. fluorochemical urethane/polyphenylene sulfide is subjected to ultrasonic wave mixing, glycerine and N-Methyl pyrrolidone is added, polyphenylene sulfide modified hydrophobic polyurethane resin is obtained by filtration in purifying reaction.The present invention gives full play to the oxidative resistance of polyphenylene sulfide, high adhesion force, the electronegativity of fluorine atom is big, and the bond energy of C-F key is big, can make the surface tension of water significantly reduces, the material of surface enrichment C-F group has the features such as excellent performance possessed by the big hardness of preferable hydrophobic, oleophobic property and polyurethane resin, wearability, flexibility, adhesion and micro phase separation structure.
Description
Technical field
The present invention relates to a kind of modified fluorinated polyurethane resins of polyphenylene sulfide, belong to synthetic resin technical field.
Background technique
Polyurethane resin full name is polyurethane formate resin abbreviation PU, and polyurethane resin is usually by containing more than two different
Cyanic acid ester group (i.e.-NCO) compound and compound (such as chemical combination of hydroxyl, carboxyl, amino containing more than two active hydrogens
Object) react high-molecular compound obtained.It is obtained because containing a large amount of ammonia ester bond in the molecular structure of high-molecular compound composition
Name.Polyurethane (PU) coating, which removes, has excellent wearability, also has adhesive force strong outside excellent chemical-resistant and oil resistivity,
Low temperature curing properties and high-decoration can wait, performance multiplicity and adjustable, both high temperature resistant or low temperature resistant, nontoxic after curing of coating
Property, it is the ep-type material of low VOC.After the 1970s, polyurethane coating auto industry, aviation, ocean, building,
The fields such as plastics, electromechanics, petrochemical industry are widely used.With the development of science and technology people propose the performance of polyurethane coating
Go out higher requirement, such as requires film that there is better hydrophobicity and lower table using it as the low-surface-energy material of base exploitation
Face energy.The material requirements used in harsh environments has superior under superior mechanical property and specific condition
Electrical property etc..In order to meet requirement of the industrial application to polyurethane coating different performance, to the study on the modification of polyurethane at
For the hot spot of Recent study.
Summary of the invention
The present invention provides a kind of preparation method of polyphenylene sulfide modified hydrophobic polyurethane coating, and the present invention is first in poly- ammonia
Fluorine element is introduced in ester molecule, then it is modified using polyphenylene sulfide, so that the polyurethane coating of preparation is with excellent
Oxidative resistance, hydrophobicity, corrosion resistance, high adhesion force, resistance toization moral character and resistance to ag(e)ing；It is changed using polyphenylene sulfide
Property, good stability of the dimension is obtained, to UV stable, radiation resistance, the polyurethane resin of high temperature resistance.
The object of the present invention is achieved in the following manner:
A kind of modified fluorinated polyurethane resin of polyphenylene sulfide, is made by following steps:
A. synthesis side chain end group is the methyl diphenylene diisocyanate of fluorine-containing functional group's segment；
B. polytetrahydrofuran ether glycol is added, synthesizes fluorochemical urethane performed polymer；
C. chain extension, cross-linking reaction are carried out using small molecule chain extender, end-capping reagent (methanol, ethylene glycol, third is added in last stage reaction
Triol etc.) sealing end is carried out to introduce hydrophobic grouping, complete the preparation of fluorochemical urethane/polyphenylene sulfide；
D. fluorochemical urethane/polyphenylene sulfide is subjected to ultrasonic wave mixing, glycerine and N-Methyl pyrrolidone, purifying is added
Reaction, is obtained by filtration polyphenylene sulfide modified hydrophobic polyurethane resin.
Further, a preferred embodiment of the present invention are as follows:
The step a specifically: in parts by weight, sequentially add 2.0~5.0 parts of polyalcohol, oligomer polyol 4.0
1.0~8.0 parts of polyphenylene sulfide after~15.0 parts, 2.0~8.0 parts of fluorine vinyl monomer and dehydration, it is heated to 65 DEG C
~80 DEG C, 1.0~1.5h of vacuum dehydration；40 DEG C~45 DEG C are cooled to, is added dropwise 10.0~25.0 parts of polyisocyanates, with drop speed 2
~4d/s is added dropwise, and 0.5h is stirred to react, make the mass fraction 0.40wt% of-NCO of free state in reactant~
0.45wt%, while keeping 20r/min mixing speed excessive to avoid local reaction region perfluoroalkyl determining alcohol, then it is added dropwise
0.01~0.1 part of catalyst, 50 DEG C of 2.5~3.0h of reaction are warming up to, 0.01~0.02 part of compensation system viscosity of butanone, drop is added
It adds the reaction was continued 0.5h after finishing diphenyl methane two is made and lead cyanate.
Further, a preferred embodiment of the present invention are as follows: the step b is that polytetrahydrofuran ether glycol 7.0~9.0 is added
Part, it is stirred to react 0.8~1.2h, has synthesized the fluorochemical urethane performed polymer using polytetrahydrofuran ether glycol as soft chain segment.
Further, a preferred embodiment of the present invention are as follows: the step c's comprises the concrete steps that: by small molecule chain extender three
Ethylene glycol 0.5~2.0 part of progress chain extension, cross-linking reaction, 1.5~3.5 parts of methanol of addition block drawing after reacting 0.5h
Into hydrophobic grouping；Then it is added in fluorochemical urethane performed polymer, and is warming up to 70 DEG C~80 DEG C 1.5~2.5h of reaction, make to react
The side end of strand is terminated afterwards with-NCO, obtains fluorochemical urethane/polyphenylene sulfide.
Further, a preferred embodiment of the present invention are as follows: the step d is specially to add fluorochemical urethane/polyphenylene sulfide
Enter progress ultrasonic wave mixing 0.5-1.0h in reactor, is warming up to 78~80 DEG C, drops evenly scarvenger glycerine 4.0~20.0
Part and 3.0~5.0 parts of N-Methyl pyrrolidone, be added dropwise and be continuously heating to 80 DEG C~85 DEG C, 0.5~2.0h of insulation reaction,
30 DEG C~40 DEG C are cooled to, filtering obtains the modified fluorinated polyurethane resin of polyphenylene sulfide.
Further, a preferred embodiment of the present invention are as follows: the polyisocyanates be methyl diphenylene diisocyanate,
Hexamethylene diisocyanate, isophorone diisocyanate, toluene di-isocyanate(TDI), dicyclohexyl methyl hydride diisocyanate,
Diphenyl methane -4,4,-diisocyanate, benzene dimethylene diisocyanate, naphthalene -1,5- diisocyanate, to two isocyanide of benzene
The combination of one or more of acid esters, tetramethylxylylene diisocyanate.
Further, a preferred embodiment of the present invention are as follows: the polyalcohol be ethylene glycol, propylene glycol, butanediol, oneself two
One of alcohol, neopentyl glycol, polyester polyol, polyether polyol, acrylic acid, castor oil polyhydric alcohol, sorbierite, xylitol or
Several combinations.
Further, a preferred embodiment of the present invention are as follows: the oligomer polyol is polytetrahydrofuran polyol, gathers
One of carbonate polyol, polyethylene oxide polyol, polycaprolactone polyol, polyether Glycols, polyethylene glycol are several
The combination of kind, the oligomer polyol molecular weight is between 1000~4000.
Further, a preferred embodiment of the present invention are as follows: the dilute class monomer of the fluorine is Hexafluorobutyl mathacrylate, first
Base acrylic acid octafluoro pentyl ester, methacrylic acid hexafluoro isopropyl ester, hexafluorobutyl acrylate, perfluor base ethyl methacrylate
One of ester, perfluorooctylethyl group acrylate, perfluorooctylethyl group methacrylate, perfluoroalkyl acrylate are several
The combination of kind.
Further, a preferred embodiment of the present invention are as follows: the catalyst is dibutyl tin dilaurate.
Beneficial effects of the present invention:
The modified fluorinated polyurethane resin performance test experiment of polyphenylene sulfide of the invention: (1) composite material and substrate are mechanical
Cohesive force is up to 22.58MPa (> 20MPa), and dense structure, uniformly；(2) the cavitation corrosion amount of coating is by 2.38 × 10- 3Kg drop
As low as 0.78 × 10- 3kg；(3) oxidative resistance is tested, salt fog resistance (500g 1000N): >=2800h, anti-ultraviolet ageing
(h): 2200；(4) hydrophobic performance is tested, and contact angle is by 56.8 ° of polyurethane resin as the addition of polyphenylene sulfide, fluorine element increases
123.1 ° are added to, water absorption rate drops to 0.0102 by 0.0413, and hydrophobic effect is obvious.
The experimental results showed that present invention incorporates the characteristics of polyphenylene sulfide, fluorine element and polyurethane resin.It gives full play to poly-
The oxidative resistance of diphenyl sulfide.The electronegativity of fluorine atom is big, and the bond energy of C-F key is big, the surface tension of water can be made to significantly reduce, table
The material that face is enriched with C-F group has a preferable hydrophobic, oleophobic property, and the fluorocarbon chain (- CF2CF3) of low-surface-energy is to material surface
It migrates and forms the hydrophobicity that micro/nano level raised structures have on surface.And the hardness of polyurethane resin is big, wearability,
The features such as excellent performance possessed by flexibility, adhesion and micro phase separation structure.
Specific embodiment
Technical solution of the present invention is clearly and completely described in specific embodiment below, it is clear that described reality
Applying example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff every other embodiment obtained without creative efforts belongs to what the present invention protected
Range.
A kind of modified fluorinated polyurethane resin of polyphenylene sulfide, is made by following steps:
A. synthesis side chain end group is the methyl diphenylene diisocyanate of fluorine-containing functional group's segment；
B. polytetrahydrofuran ether glycol is added, synthesizes fluorochemical urethane performed polymer；
C. chain extension, cross-linking reaction are carried out using small molecule chain extender, end-capping reagent (methanol, ethylene glycol, third is added in last stage reaction
Triol etc.) sealing end is carried out to introduce hydrophobic grouping, complete the preparation of fluorochemical urethane/polyphenylene sulfide；
D. fluorochemical urethane/polyphenylene sulfide is added in reactor and carries out ultrasonic wave mixing, glycerine and N- methyl is added
Pyrrolidones, purifying reaction, is obtained by filtration polyphenylene sulfide modified hydrophobic polyurethane resin, specific embodiment is as follows:
Embodiment 1-4
A kind of modified fluorinated polyurethane resin of polyphenylene sulfide, is made by following steps:
A. equipped with thermometer, blender, constant pressure funnel and nitrogen protection four-hole boiling flask in, according to weight ratio, according to
The secondary polyphenylene sulfide 1 being added after 2 parts of polyalcohol, 2.0~3.5 parts of oligomer polyol, 2.5 parts of fluorine vinyl monomer, dehydration
Part, 65 DEG C are heated to, vacuum dehydration 1.0h；50 parts of deionized water are added under the conditions of being cooled to 40 DEG C, to drip 2~4d/s of speed
Be added dropwise 10 parts of polyisocyanates, be stirred to react 0.5h, make the mass fraction 0.40wt% of-NCO of free state in reactant~
0.45wt%；It keeps 20r/min mixing speed excessive to avoid local reaction region perfluoroalkyl determining alcohol simultaneously, is then added dropwise
0.01 part of the dibutyl tin dilaurate of proportional quantity is warming up to 50 DEG C of reaction 2.5h, and 0.01 part of compensation system viscosity of butanone is added,
50 DEG C of the reaction was continued 2h after being added dropwise.
B. after the reaction of upper step, reaction system is warming up to 60 DEG C, 7 parts of polytetrahydrofuran ether glycol is added at one time, stirs
Mix reaction 1h, dehydration.This process has synthesized the fluorochemical urethane performed polymer using polytetrahydrofuran ether glycol as soft chain segment.
C. small molecule chain extender triethylene glycol 1.0 parts of progress chain extensions, cross-linking reaction are used, are added first after reaction 0.5h, 2 parts
It carries out sealing end to walk in performed polymer in addition to introduce hydrophobic grouping (- COOCH3 hydrophobic group), and is warming up to 75 DEG C of reactions
2h terminates the side end of strand after reacting with-NCO, obtains fluorochemical urethane/polyphenylene sulfide；
Fluorochemical urethane/polyphenylene sulfide is added in reactor and carries out ultrasonic wave mixing 0.5h by d, is warming up to 79 DEG C, uniformly
Scarvenger glycerine 4.0 and 5.0 parts of N-Methyl pyrrolidone are dripped, is added dropwise and is continuously heating to 85 DEG C, insulation reaction 0.5h, drop
For temperature to 40 DEG C, filtering obtains the modified fluorinated polyurethane of polyphenylene sulfide.
Poly-p-phenylene sulfide ether is purified and is carried out dehydrating, purification process agent be glycerine and N-Methyl pyrrolidone,
Proportional quantity is the proportion of polyphenylene sulfide and glycerine, N-Methyl pyrrolidone are as follows: polyphenylene sulfide quality (g): N- crassitude
The volume (ml) of ketone: volume (ml)=2:3:40 of glycerine.A certain amount of polyphenylene sulfide is added to reaction vessel, and then the third three
Pure and mild N-Methyl pyrrolidone mixing, heat rise under 180 DEG C of normal pressures and handle 3 hours, finally obtain purifying polyphenylene sulfide resin cosmetics
End.
Embodiment 5-8
A kind of modified fluorinated polyurethane resin of polyphenylene sulfide, is made by following steps:
A. in the four-hole boiling flask equipped with thermometer, blender, constant pressure funnel and nitrogen protection, in parts by weight,
6 parts of polyphenylene sulfide after sequentially adding 3 parts of polyalcohol, 10 parts of oligomer polyol, 2 parts of fluorine vinyl monomer and dehydration, add
Heat is warming up to 70 DEG C, vacuum dehydration 1.5h；50 parts of deionized water are added under the conditions of being cooled to 40 DEG C, is added dropwise with dripping 2~4d/s of speed
18 parts of polyisocyanates, be stirred to react 0.5h, make the mass fraction 0.40wt% of-NCO of free state in reactant~
0.45wt%；It keeps 20r/min mixing speed excessive to avoid local reaction region perfluoroalkyl determining alcohol simultaneously, is then added dropwise
0.06 part of the dibutyl tin dilaurate of proportional quantity is warming up to 50 DEG C of reaction 3.0h, 0.01 part of compensation body of addition butanone appropriate
It is viscosity, 50 DEG C of the reaction was continued 2h after being added dropwise.
B. after the reaction of upper step, reaction system is warming up to 60 DEG C, 8 parts of polytetrahydrofuran ether glycol is added at one time, stirs
Mix reaction 0.8h, dehydration.This process has synthesized the fluorochemical urethane pre-polymerization using polytetrahydrofuran ether glycol as soft chain segment
Body.
C. small molecule chain extender triethylene glycol 0.5 part of progress chain extension, cross-linking reaction are used, methanol is added after reacting 0.5h
1.5 parts carry out sealing end and walk in performed polymer in addition to introduce hydrophobic grouping (- COOCH3 hydrophobic group), and are warming up to 80 DEG C
2.5h is reacted, terminates the side end of strand after reacting with-NCO, obtains fluorochemical urethane/polyphenylene sulfide；
Fluorochemical urethane/polyphenylene sulfide is added in reactor and carries out ultrasonic wave mixing 1h by d, is warming up to 80 DEG C, uniformly drips
It 20.0 parts and 4.0 parts of N-Methyl pyrrolidone of scarvenger glycerine, is added dropwise and is continuously heating to 80 DEG C, insulation reaction 2h, drop
For temperature to 30 DEG C, filtering obtains the modified fluorinated polyurethane of polyphenylene sulfide.
Poly-p-phenylene sulfide ether is purified and is carried out dehydrating, purification process agent be glycerine and N-Methyl pyrrolidone,
Proportional quantity is the proportion of polyphenylene sulfide and glycerine, N-Methyl pyrrolidone are as follows: polyphenylene sulfide quality (g): N- crassitude
The volume (ml) of ketone: volume (ml)=2:3:40 of glycerine.A certain amount of polyphenylene sulfide is added to reaction vessel, and then the third three
Pure and mild N-Methyl pyrrolidone mixing, heat rise under 180 DEG C of normal pressures and handle 3 hours, finally obtain purifying polyphenylene sulfide resin cosmetics
End.
Embodiment 9-12
A kind of modified fluorinated polyurethane resin of polyphenylene sulfide, is made by following steps:
A. in the four-hole boiling flask equipped with thermometer, blender, constant pressure funnel and nitrogen protection, successively according to recipe ratio
8 parts of polyphenylene sulfide after 5 parts of polyalcohol, 15 parts of oligomer polyol, 8 parts of fluorine vinyl monomer and dehydration is added, heating rises
Temperature is to 80 DEG C, vacuum dehydration 1.5h；50 parts of deionized water are added under the conditions of being cooled to 45 DEG C, polyisocyanate is added dropwise to drip 2~4d/s of speed
25 parts of cyanate, it is stirred to react 0.5h, makes the mass fraction 0.40wt%~0.45wt% of-NCO of free state in reactant；
It keeps 20r/min mixing speed excessive to avoid local reaction region perfluoroalkyl determining alcohol simultaneously, proportional quantity is then added dropwise
0.1 part of dibutyl tin dilaurate, 50 DEG C of reaction 3.0h are warming up to, 0.02 part of compensation system viscosity of butanone is added, is added dropwise
50 DEG C of the reaction was continued 2h afterwards.
B. after the reaction of upper step, reaction system is warming up to 60 DEG C, 9 parts of polytetrahydrofuran ether glycol is added at one time, stirs
Reaction 1.2h, dehydration are mixed, this process has synthesized the fluorochemical urethane pre-polymerization using polytetrahydrofuran ether glycol as soft chain segment
Body.
C. small molecule chain extender triethylene glycol 2.0 parts of progress chain extensions, cross-linking reaction are used, methanol is added after reacting 0.5h
3.5 parts carry out sealing end and walk in performed polymer in addition to introduce hydrophobic grouping (- COOCH3 hydrophobic group), and are warming up to 70 DEG C
1.5h is reacted, terminates the side end of strand after reacting with-NCO, obtains fluorochemical urethane/polyphenylene sulfide；
Fluorochemical urethane/polyphenylene sulfide is added in reactor and carries out ultrasonic wave mixing 0.8h by d, is warming up to 78 DEG C, uniformly
10 parts and 3.0 parts of N-Methyl pyrrolidone of scarvenger glycerine are dripped, is added dropwise and is continuously heating to 82 DEG C, insulation reaction 1h, drop
For temperature to 35 DEG C, filtering obtains the modified fluorinated polyurethane of polyphenylene sulfide.
Poly-p-phenylene sulfide ether is purified and is carried out dehydrating, purification process agent be glycerine and N-Methyl pyrrolidone,
Proportional quantity is the proportion of polyphenylene sulfide and glycerine, N-Methyl pyrrolidone are as follows: polyphenylene sulfide quality (g): N- crassitude
The volume (ml) of ketone: volume (ml)=2:3:40 of glycerine.A certain amount of polyphenylene sulfide is added to reaction vessel, and then the third three
Pure and mild N-Methyl pyrrolidone mixing, heat rise under 180 DEG C of normal pressures and handle 3 hours, finally obtain purifying polyphenylene sulfide resin cosmetics
End.
Polyalcohol, oligomer polyol, fluorine vinyl monomer and the polyisocyanates that each embodiment is added see the table below.
The physicochemical property of the modified fluorinated polyurethane of polyphenylene sulfide prepared by each embodiment is measured, specific data are seen below
Table.
(1) composite material and substrate are mechanically bonded power, measuring method: PosiTest AT Pulling escape adhesion-force tester, right
Sample carries out cohesive force test, and multiple groups test respectively takes 3 test points, test result is averaged.
(2) measuring method: the cavitation corrosion amount of coating uses MCF-30 type rotating disc type tester for testing scouring wear to quality for m1Examination
Sample carries out continuous erosion experiment, sample (coating+bottom plate) having a size of 100mm × 100mm × (2+1) mm, setting test linear velocity
It is 45 ° for 16m/s, erosion angle, mortar solution PH=6.7, concentration are 40% (quartz sand of 1.5L tap water addition 1L), quartz
0.1~0.5mm of fineness of sand；Each erosion test 480h replaces mortar solution every 48h；Examination is cleaned with acetone after experiment
Sample, drying, it is m that the electronic balance that precision is 0.1mg, which weighs quality,2, using the cavitation polishing machine of cavitation corrosion amount evaluation material
(ε), i.e., as the practical cavitation corrosion amount C of material, less than by the cavitation corrosion guaranteed discharge Cn (C≤Cn) after real time conversion, then the material
Cavitation corrosion amount think qualified.
Calculating formula according to the cavitation corrosion guaranteed discharge of actual run time conversion is as follows:
Cn=Cr(tr/tr)n
Cr=KmD2
In formula:
CnThe cavitation corrosion guaranteed discharge that-conversion obtains, kg
Cr- cavitation corrosion guaranteed discharge, kg
Tn-actual run time, 480h
Tr-benchmark runing time, standard are defined as 8000h
N-exponential conversion: tn less than 10000 when, n=1.0
Km-quality assurance coefficient, Km=0.8
D-sample rotation nominal diameter, 100 × 10-3m
(3) resistance to artificial circulation burn-in test: this item test is executed according to ISO20340:2003, specific test job are as follows: examination
Plate by circulation exposure (168 hours) one week for a cycle period, point or less three:
The exposure of (1) 72 hour ultraviolet light and water, ultraviolet light irradiation (60 ± 2 DEG C) in 6 hours and condensation (50 ± 2 in 6 hours
DEG C) intersect progress.And pay attention to starting with ultraviolet light irradiation, terminated with condensation.
Low temperature exposure test (- 20 ± 2) DEG C in (2) 24 hours
(3) 72 hours salt spray tests.After the 3rd salt spray test is complete, test plate (panel) can be cleaned with deionized water, but is not had to dry
It is dry.
One week above (168 hours) are a cycle period, and total recycles test plate (panel) exposure for 15, i.e., 2520 hours.
Resistance to ag(e)ing, salt fog resistance measuring method；Sample is put on the aid plate of salt spray test chamber, and pays attention to tested surface
Placement location.Adjusting salt fog discharge rate is 6mm/ (minmm2), after operation 48 hours, sample is taken out.Observe specimen surface
Variation, if be corroded, photographed to record.And sample is put into artificial ultraviolet aging test chamber and carries out next follow
Ring.
Anti-ultraviolet ageing measuring method: the QUV ageing oven of use is divided into three ultraviolet lighting (UV), spray, condensation steps
Suddenly.Ancillary equipment: water purification machine.Test concrete operations: whether the route of pretest inspection machine and connected ancillary equipment can
It works normally
(1) it opens and the connected water route of ageing machine；
(2) observation specimen surface is photographed to record whether there is or not stomata, bubble, hole caused by artificial ageing；
(3) sample is put on the panel of ageing machine, tested surface is made to face quartz burner, setting panel has prevented purple
Outward leakage；
(4) ancillary test equipment supplies enough deionized waters；
(5) operating parameter of the program set according to test requirements document starts chamber.
Experimental observation: after 72 hours, sample is taken out from QUV chamber, observes the variation of specimen surface, whether is epidermis
Whether cracking is changed with scanning electron microscopic observation interior tissue, and is recorded.
The extent of corrosion of specimen surface is observed, when necessary by surface clean, observation, and is recorded.
(4) hydrophobic performance is tested, measuring method: hydrophobic angle test is surveyed using OCA20 video contact angle tester
Examination, experiment before syringe, dosage pipe, injection needle are thoroughly soaked with deionized water, and ensure to fill in syringe deionized water,
Without any blistering；Water droplet drop is observed after the 1min of fluorochemical urethane surface, and each sample takes 3 test points, is averaged.
Water absorption rate test is measured using EMS-10 magnetic-mixing constant temperature water bath boiler, and weighing quality is m1Sample simultaneously
The area of sample 2/3 is soaked in a tepid bath；Be arranged coolant-temperature gage be 25 DEG C, magnetic stirring speed 180r/min, impregnate 1200h
After time, the water on surface is quickly blotted in taking-up with filter paper, and the quality for sample of weighing is m2, then the water absorption rate (η) of sample is available
Following formula calculates:
η=[(m2-m1)/m1] × 100%
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of modified fluorinated polyurethane resin of polyphenylene sulfide, which is characterized in that be made by following steps:
A. synthesis side chain end group is the methyl diphenylene diisocyanate of fluorine-containing functional group's segment；
B. polytetrahydrofuran ether glycol is added, synthesizes fluorochemical urethane performed polymer；
C. chain extension, cross-linking reaction are carried out using small molecule chain extender, last stage reaction is added end-capping reagent and carries out blocking to introduce and dredge
Water base group completes the preparation of fluorochemical urethane/polyphenylene sulfide；
D. fluorochemical urethane/polyphenylene sulfide is subjected to ultrasonic wave mixing, glycerine and N-Methyl pyrrolidone is added, purifying is anti-
It answers, polyphenylene sulfide modified hydrophobic polyurethane resin is obtained by filtration.
2. the modified fluorinated polyurethane resin of a kind of polyphenylene sulfide according to claim 1, it is characterised in that:
The step a specifically: in parts by weight, sequentially add 2.0~5.0 parts of polyalcohol, oligomer polyol 4.0~
1.0~8.0 parts of polyphenylene sulfide after 15.0 parts, 2.0~8.0 parts of fluorine vinyl monomer and dehydration, be heated to 65 DEG C~
80 DEG C, 1.0~1.5h of vacuum dehydration；Be cooled to 40 DEG C~45 DEG C, be added dropwise 10.0~25.0 parts of polyisocyanates, with drop speed 2~
4d/s is added dropwise, and 0.5h is stirred to react, and makes the mass fraction 0.40wt%~0.45wt% of-NCO of free state in reactant,
It keeps 20r/min mixing speed excessive to avoid local reaction region perfluoroalkyl determining alcohol simultaneously, catalyst is then added dropwise
0.01~0.1 part, 50 DEG C of 2.5~3.0h of reaction are warming up to, 0.01~0.02 part of compensation system viscosity of butanone is added, is added dropwise
The reaction was continued afterwards, and the obtained diphenyl methane two of 0.5h leads cyanate.
3. the modified fluorinated polyurethane resin of a kind of polyphenylene sulfide according to claim 2, it is characterised in that: the step b
It is to be added 7.0~9.0 parts of polytetrahydrofuran ether glycol, is stirred to react 0.8~1.2h, has synthesized and be with polytetrahydrofuran ether glycol
The fluorochemical urethane performed polymer of soft chain segment.
4. the modified fluorinated polyurethane resin of a kind of polyphenylene sulfide according to claim 3, it is characterised in that: the step c
Comprise the concrete steps that: small molecule chain extender triethylene glycol 0.5~2.0 part of progress chain extension, cross-linking reaction are added after reacting 0.5h
1.5~3.5 parts of methanol carry out sealing end to introduce hydrophobic grouping；Then it is added in fluorochemical urethane performed polymer, and is warming up to 70
DEG C~80 DEG C of reaction 1.5-2.5h, terminate the side end of strand after reacting with-NCO, obtains fluorochemical urethane/polyphenylene sulfide
Ether.
5. the modified fluorinated polyurethane resin of a kind of polyphenylene sulfide according to claim 4, it is characterised in that: the step d
Specially fluorochemical urethane/polyphenylene sulfide is added in reactor and carries out ultrasonic wave 0.5~1.0h of mixing, is warming up to 78~80
DEG C, 4.0-20.0 parts and 3.0~5.0 parts of N-Methyl pyrrolidone of scarvenger glycerine are dropped evenly, is added dropwise and continues to heat up
To 80 DEG C~85 DEG C, 0.5~2.0h of insulation reaction, 30 DEG C -40 DEG C are cooled to, filtering obtains the modified fluorinated poly- ammonia of polyphenylene sulfide
Ester resin.
6. the modified fluorinated polyurethane resin of a kind of polyphenylene sulfide according to claim 2, it is characterised in that:
The polyisocyanates is methyl diphenylene diisocyanate, hexamethylene diisocyanate, two isocyanide of isophorone
Acid esters, toluene di-isocyanate(TDI), dicyclohexyl methyl hydride diisocyanate, diphenyl methane -4,4,-diisocyanate, benzene two are sub-
Methyl diisocyanate, naphthalene -1,5- diisocyanate, paraphenylene diisocyanate, in tetramethylxylylene diisocyanate
One or more of combinations.
7. the modified fluorinated polyurethane resin of a kind of polyphenylene sulfide according to claim 2, it is characterised in that:
The polyalcohol be ethylene glycol, propylene glycol, butanediol, hexylene glycol, neopentyl glycol, polyester polyol, polyether polyol,
The combination of one or more of acrylic acid, castor oil polyhydric alcohol, sorbierite, xylitol.
8. the modified fluorinated polyurethane resin of a kind of polyphenylene sulfide according to claim 2, it is characterised in that: described is oligomeric
Object polyalcohol is polytetrahydrofuran polyol, polycarbonate polyol, polyethylene oxide polyol, polycaprolactone polyol, gathers
The combination of one or more of ether dihydric alcohol, polyethylene glycol, the oligomer polyol molecular weight is between 1000~4000.
9. the preparation method of polyphenylene sulfide modified hydrophobic polyurethane coating according to claim 2, it is characterised in that: institute
The dilute class monomer of the fluorine stated is Hexafluorobutyl mathacrylate, methacrylic acid octafluoro pentyl ester, methacrylic acid hexafluoro isopropyl ester, third
Olefin(e) acid hexafluoro butyl ester, perfluor base ethylmethyl acrylate, perfluorooctylethyl group acrylate, perfluorooctylethyl group methyl-prop
The combination of one or more of olefin(e) acid ester, perfluoroalkyl acrylate.
10. the preparation method of polyphenylene sulfide modified hydrophobic polyurethane coating according to claim 2, it is characterised in that:
The catalyst is dibutyl tin dilaurate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910049676.2A CN109824861A (en) | 2019-01-18 | 2019-01-18 | A kind of modified fluorinated polyurethane resin of polyphenylene sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910049676.2A CN109824861A (en) | 2019-01-18 | 2019-01-18 | A kind of modified fluorinated polyurethane resin of polyphenylene sulfide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109824861A true CN109824861A (en) | 2019-05-31 |
Family
ID=66860502
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910049676.2A Pending CN109824861A (en) | 2019-01-18 | 2019-01-18 | A kind of modified fluorinated polyurethane resin of polyphenylene sulfide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109824861A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112662296A (en) * | 2020-12-18 | 2021-04-16 | 合众（佛山）化工有限公司 | Polyphenylene sulfide ketone modified polyurethane resin water-based paint |
| CN112724771A (en) * | 2020-12-26 | 2021-04-30 | 安徽酉阳防水科技有限公司 | Quick-drying waterproof exposed waterproof coating |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995087A (en) * | 2006-12-27 | 2007-07-11 | 武汉工程大学 | High solid share fluorine-containing polyurethane preparation method |
| CN104046026A (en) * | 2014-07-02 | 2014-09-17 | 广州高八二塑料有限公司 | Polyurethane co-mixed modified polyphenylene sulfide composite material and preparation method thereof |
| CN104829809A (en) * | 2014-02-11 | 2015-08-12 | 王祖文 | High-molecular foam material |
| CN104892850A (en) * | 2015-05-27 | 2015-09-09 | 华侨大学 | Preparation method of side-chain fluorine-containing water-based polyurethane |
| CN105482680A (en) * | 2016-01-06 | 2016-04-13 | 天津科技大学 | Ultraviolet light polymerization hyperbranched perfluoropolyether urethane acrylate coating |
| CN106256861A (en) * | 2016-08-23 | 2016-12-28 | 华北水利水电大学 | A kind of hydrophobicity fluorochemical urethane coating and preparation method thereof |
| CN107880266A (en) * | 2017-11-30 | 2018-04-06 | 珠海长先新材料科技股份有限公司 | A kind of ultrasonic wave cleaning of polyphenylene sulfide and purification process |
-
2019
- 2019-01-18 CN CN201910049676.2A patent/CN109824861A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995087A (en) * | 2006-12-27 | 2007-07-11 | 武汉工程大学 | High solid share fluorine-containing polyurethane preparation method |
| CN104829809A (en) * | 2014-02-11 | 2015-08-12 | 王祖文 | High-molecular foam material |
| CN104046026A (en) * | 2014-07-02 | 2014-09-17 | 广州高八二塑料有限公司 | Polyurethane co-mixed modified polyphenylene sulfide composite material and preparation method thereof |
| CN104892850A (en) * | 2015-05-27 | 2015-09-09 | 华侨大学 | Preparation method of side-chain fluorine-containing water-based polyurethane |
| CN105482680A (en) * | 2016-01-06 | 2016-04-13 | 天津科技大学 | Ultraviolet light polymerization hyperbranched perfluoropolyether urethane acrylate coating |
| CN106256861A (en) * | 2016-08-23 | 2016-12-28 | 华北水利水电大学 | A kind of hydrophobicity fluorochemical urethane coating and preparation method thereof |
| CN107880266A (en) * | 2017-11-30 | 2018-04-06 | 珠海长先新材料科技股份有限公司 | A kind of ultrasonic wave cleaning of polyphenylene sulfide and purification process |
Non-Patent Citations (1)
| Title |
|---|
| 李子东等编著: "《实用胶粘剂原材料手册》", 31 July 1999, 国防工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112662296A (en) * | 2020-12-18 | 2021-04-16 | 合众（佛山）化工有限公司 | Polyphenylene sulfide ketone modified polyurethane resin water-based paint |
| CN112724771A (en) * | 2020-12-26 | 2021-04-30 | 安徽酉阳防水科技有限公司 | Quick-drying waterproof exposed waterproof coating |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5637772A (en) | Fluorinated diamines and polymers formed therefrom | |
| CN106256861B (en) | Hydrophobic fluorine-containing polyurethane coating and preparation method thereof | |
| CA3032309A1 (en) | Actinic radiation-curable urethane/urea-containing aerospace coatings and sealants | |
| CN104893539B (en) | Preparation method of hydrophobic and flame-retardant PU (polyurethane) coating | |
| CN104974656B (en) | Moisturecuring one-component polyacrylate modified polyurethane water-repellent paint and its preparation | |
| CN109824861A (en) | A kind of modified fluorinated polyurethane resin of polyphenylene sulfide | |
| AU2005287543A1 (en) | Fluorine-modified reactive resin systems, method for producing them and their use | |
| CA2648153A1 (en) | Dual component (aqueous) hybrid reactive resin system, method for production and use thereof | |
| CN108912870A (en) | A kind of selfreparing anti-corrosion outdoor building graphene coating and preparation method | |
| CN110028885A (en) | A kind of not solvent-laden high tenacity anticorrosive paint and preparation method thereof | |
| JPS63199724A (en) | Epoxy resin produced by co-curing of fluorinated epoxy prepolymer and non-fluorinated epoxy prepolymer | |
| CN107531871A (en) | Fluorochemical, Photocurable composition, coating fluid, hard coat formation composition and article | |
| CN111410732B (en) | Water-based UV resin and preparation method thereof | |
| Koochaki et al. | A highly responsive healing agent for the autonomous repair of anti-corrosion coatings on wet surfaces. In operando assessment of the self-healing process | |
| RU2717688C2 (en) | System for forming elastomeric compositions for deposition on metal | |
| JPH0129389B2 (en) | ||
| CN102516489A (en) | Preparation method and application of wear resistant hydroxyl terminated polyurethane resin used for protection coating of silica key | |
| CN104877523A (en) | Solvent-free organosilicone modified epoxy sealing prime paint and preparing method thereof | |
| KR101402013B1 (en) | Environment-friendly steel pipe coated with vegetable paint and its manufacturing method | |
| CN1955237A (en) | Polyurea anti-corrosion coating | |
| CN109852320A (en) | Graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive and preparation method thereof | |
| JP5319454B2 (en) | Mixed polyalicyclic amines (MPCA) and MPCA alkylates | |
| Liu et al. | Toughened polybenzoxazine coating matrix with improved comprehensive performance through hydrogen bond tuning with new polyurethanes | |
| CN113831830B (en) | High-barrier polyurethane self-repairing composition and preparation method thereof | |
| CN103589297A (en) | Photocuring composite paint containing vinyl-terminated fluorosilicone graft copolymer and preparation method thereof |
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: 20190531 |
|
| RJ01 | Rejection of invention patent application after publication |