CN109852320A - Graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive and preparation method thereof - Google Patents
Graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive and preparation method thereof, feature is the polyether Glycols for including 1~30 part, 1~45 part of liquid polyesters dihydric alcohol, 1~50 part of flame retardant polyether polyol, 1~45 part of crystalline polyester dihydric alcohol, 1~50 part of hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer, 5~50 parts of isocyanates, 0.1~1 part of catalyst, 0.1~2 part of antioxidant, 0.1~5 part of silane coupling agent and 20~80 parts of graphene oxide.Elder generation's synthesis of hydroxy of the present invention sealing end is poly- (acrylic acid trifluoro ethyl ester-is random-ethyl methacrylate-is random-random -2- methyl -2- 2-hydroxyethyl acrylate phosphate of isodecyl methacrylate -), it is added in base polyurethane prepolymer for use as, high efficiency dispersion graphene oxide, fluoro-acrylate copolymer segment and reactive flame retardant are introduced in base polyurethane prepolymer for use as simultaneously, further promote the chemical resistance and flame retardant property of polyurethane gel.Graphene oxide reduces the cure shrinkage of polyurethane hot melt, improves adhesive strength and comprehensive mechanical property to substrate.
Description
Technical field
The invention belongs to structure glue technical fields, and in particular to a kind of graphene oxide modified fluoride-containing flame retardant polyurethane hot melt
Glue and preparation method thereof, which are mainly applied to electronics and appliance industry, automobile industry, weaving and shoe industry, food packing industry, timber
Material processing and furniture industry isostructuralism are bonded field.
Background technique
Polyurethane hot melt be a new generation can provide superior adhesion can structure glue, it is to be with polyurethane prepolymer
Material of main part is equipped with a hot melt adhesive prepared by various auxiliary agents.Polyurethane hot melt is easy to use, environmentally friendly, and performance again can be with
Solvent-based thermal melten gel compares favourably.Nearly ten years, polyurethane hot melt is obtained in the high-end fields such as electronics and appliance industry, automobile industry
It is fast-developing and be widely used.Polyurethane hot melt can be divided into thermoplastic polyurethane elastomer hot melt adhesive by cured form difference
And reactive polyurethane hot melt, reactive polyurethane hot melt can be divided into wet-cured type and closing by its principle of solidification difference
Type；Research of Moisture-curable Polyurethane Hot-melt Adhesive PUR is a kind of one pack system hot melt adhesive, is melted after heating, and flows scatter coated in substrate
Surface cools down after adherend bonding and forms excellent first adhesive property, then due to substrate surface contain micro-moisture or its
His compound containing active hydrogen reacts with isocyano (- NCO) and chemical crosslink reaction occurs, thus generate have it is highly cross-linked
A kind of structural bonding hot melt adhesive of network and cohesive force greatly.
Research of Moisture-curable Polyurethane Hot-melt Adhesive has technically obtained unprecedented development at present, low mainly around high-adhesive-strength
Melt viscosity, open hour reprocess and the progress performances such as cured form are optimized and revised.Chinese patent discloses a kind of entitled
The application for a patent for invention of " a kind of reactive hot melt adhesive ", application number are 201480080313.0, prepare it is a kind of have return
The removable polyurethane-hot melt adhesive repaired, more suitable for high-end electronic product scope application.Chinese patent also discloses one
The application for a patent for invention of kind entitled " solvent-free damp solidifying polyurethane hot-melt adhesive composition ", application number are
201180047316.0, prepare a kind of quick polyurethane-hot melt for establishing adhesive property polyacrylate and polyester preparation of low toxicity
Viscose binder.In order to improve the cured form of Research of Moisture-curable Polyurethane Hot-melt Adhesive, it is " a kind of that Chinese patent, which discloses a kind of title,
The application for a patent for invention of organic silicon modified polyurethane sealant ", application number are 201710271725.8, prepare a kind of organosilicon
Modified polyurethane sealant replaces isocyano (- NCO) with silane coupling agent, is more suitable for applying under high humidity environment.Currently, wet
The research and development technology of curable polyurethane hot-melt glue meets different type high-end electronic product scope application in fast development.It is wet solid
Although highly cross-linked network can be formed after hardening by changing type polyurethane hot melt adhesive, resistance to there is also waterproof performance, solvent resistant
Ageing properties and heat resistance deficiency problem.This main cause is most of Research of Moisture-curable Polyurethane Hot-melt Adhesive at the beginning of in order to improve it
Sticky energy joined a large amount of non-reacted thermoplasticity thickening resin or polynary acrylic copolymer.These non-reaction systems increase
Viscous resin can not participate in solidification and generate cross-linked network, to easily reduce the chemical resistance, heat-resisting of polyurethane hot melt adhesive coating
Performance and ageing-resistant performance etc..In addition, Research of Moisture-curable Polyurethane Hot-melt Adhesive in the curing process, is also easy to produce contraction, reduce to base
Material bonding.
Graphene (Graphene) is stripped out from graphite material, with excellent heating conduction and mechanical property
Energy.Graphene will cause adhesive field dramatic change, become gluing agent prescription design studies hot spot.But graphene specific surface area
It is higher, it is difficult high efficiency dispersion in adhesive, often needs to add dispersing agent and be effectively disperseed.This was using adhesive
Easily there is dispersing agent and surface layer phenomenon are precipitated, pollutes the surface structure of coating in Cheng Zhong, the decline of adhesive adhesive force.
Summary of the invention
A kind of fire-retardant poly- ammonia of graphene oxide modified fluoride-containing is provided the purpose of the present invention is overcome the deficiencies in the prior art
Ester hot melt adhesive and preparation method thereof, since graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive passes through containing fluorine richness, introducing
Reactive flame retardant and graphene oxide improve chemical resistance, flame retardant property, heat resistance of polyurethane coating etc.,
It further reduced the shrinking percentage of solidification process simultaneously.
In order to achieve the above object, the technical solution of graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive of the invention
It is achieved in that it is characterized by comprising 1~30 part of polyether Glycols, 1~45 part of liquid polyesters dihydric alcohol, 1~50
The flame retardant polyether polyol, 1~45 part of crystalline polyester dihydric alcohol, 1~50 part of hydroxy-end capped phosphor-containing flame-proof of part are fluorine-containing total
Polymers, 5~50 parts of isocyanates, 0.1~1 part of catalyst, 0.1~2 part of antioxidant, 0.1~5 part of silane coupling agent
It is above mass fraction with 20~80 parts of graphene oxide；The chemistry of the hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer
Structure is: it is hydroxy-end capped it is poly- (acrylic acid trifluoro ethyl ester-is random-ethyl methacrylate-is random-isodecyl methacrylate-nothing
Rule -2- methyl -2- 2-hydroxyethyl acrylate phosphate) i.e. P(TFDMA-r-EDMA-r-DMA-r-HMP), hydroxy-end capped to contain
1~2 hydroxy functional group is contained in average each macromolecular chain end in the fire-retardant fluorinated copolymer of phosphorus, and hydroxy-end capped phosphor-containing flame-proof is fluorine-containing
The number-average molecular weight of copolymer is 1000~50000.
In the technical scheme, the polyether Glycols are polyoxypropyleneglycol of the number-average molecular weight 500~4000
One or two kinds of any combination of PPG or polytetrahydrofuran ether glycol PTMG；
The liquid polyesters dihydric alcohol be number-average molecular weight 200~2000 polyethylene glycol adipate glycol PEA, gather oneself two
Acid -1,6- hexylene glycol esterdiol PHA or polyadipate -1,4-butanediol esterdiol PBA one or more any combination；
The flame retardant polyether polyol is WANOL FR-130, the WANOL of Wanhua Chemical Group Co., Ltd.'s production
One or two kinds of any combination of FR-212 or WANOL FR-312；
The crystalline polyester dihydric alcohol is to win 7380 one or more of wound Degussa model 7320, model 7360 and model
Any combination；
The isocyanates is modified diphenylmethane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer)；
The catalyst is one or more kinds of any groups of triethanolamine, 2,2- dimorpholine base Anaesthetie Ether and phosphoric acid
It closes；
The antioxidant is one or both of 168 and 1010 any combination；
The silane coupling agent is anilinomethyl triethoxysilane ND-42；
The graphene oxide is with a thickness of 0.55 ~ 1.2nm, and diameter is 0.5 ~ 3 μm and the number of plies is 1 ~ 5 layer.
In order to achieve the above object, graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive preparation method of the invention is
It is achieved, it is characterised in that preparation step is as follows:
Step 1: synthesis of hydroxy blocks phosphor-containing flame-proof fluorinated copolymer
By 1~30 part of acrylic acid trifluoro ethyl ester TFDMA, 1~40 part of ethyl methacrylate EDMA, 1~40 part of methyl
Isodecyl acrylate DMA and 1~30 part of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP are dissolved in 50~300 parts
Toluene in, be controlled in 40~100 DEG C, under nitrogen protection, 0.1~5 part of thermal initiator 4, bis- (the 4- cyanogen of 4'- azo be added
Base amylalcohol), polymerization reaction 1~40 hour, after rotary evaporation removes toluene, hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer is obtained,
The number-average molecular weight of hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer is 1000~50000；
Step 2: synthesis graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive
1~30 part of polyether Glycols, 1~45 part of liquid polyesters dihydric alcohol, 1~50 part of flame retardant polyether polyol, 1~45
The hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer of one synthesis of the step of crystalline polyester dihydric alcohol of part, 1~50 part, 0.1~1 part
Catalyst, 20~80 parts of graphene oxide and 0.1~2 part antioxidant mixing after, calorify 120~150 DEG C, carry out machine
Tool is dispersed with stirring 1~5 hour, vacuumize water removal about 1~3 hour, until mixture water content be lower than 280ppm, cooling in
70~100 DEG C, under nitrogen protection, 5~50 parts of isocyanates is added, carries out polymerization reaction 1~5 hour, sampling analysis is poly-
It closes product NCO% content and reaches 1%~3%, tested viscosity reaches 5000~50000 mPa.s at 100 DEG C, is added 0.1~5 part
Silane coupling agent obtains graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive, is above mass fraction.
In the technical scheme, with Brookfield DV-C digital viscometer viscosity.
Compared with prior art, the present invention have following advantages and effects
1, hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer can play the effect of dispersing agent, promote graphene oxide and disperse in colloid
Ability reduces the synthesis viscosity of colloid, further reduced the shrinking percentage of polyurethane hot melt solidification process；
2, the present invention improves polyurethane gel by introducing fluorine-containing groups and reactive flame retardant in base polyurethane prepolymer for use as
Chemicals-resistant, fire-retardant, heat resistance etc.；
3, thickening resin acrylic copolymer random polycondensation is introduced base polyurethane prepolymer for use as by the present invention, is improved thickening resin and is gathered
The compatibility of urethane further solves Research of Moisture-curable Polyurethane Hot-melt Adhesive solvent resistance；
4, the present invention solves the problems, such as that traditional Research of Moisture-curable Polyurethane Hot-melt Adhesive is poor to substrate wet performance, improves hot melt adhesive
The flow leveling of sizing, packaging and Process of Applying Glue are not likely to produce bubble.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Number involved in following embodiment is mass fraction.
Embodiment one
It is a kind of graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis of hydroxy blocks phosphor-containing flame-proof fluorinated copolymer
By 5 parts of acrylic acid trifluoro ethyl ester TFDMA, 20 parts of ethyl methacrylate EDMA), 10 parts of isodecyl
Ester DMA and 5 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP are dissolved in 80 parts of toluene, are controlled in 70 DEG C,
Under nitrogen protection, 4 parts of thermal initiator 4 is added, 4'- azo is bis- (4- cyano amylalcohol), and polymerization reaction 10 hours, rotary evaporation
After removing toluene, hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer is obtained, the number of hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer is divided equally
Son amount is 5000, and 1~2 hydroxyl-functional is contained in average each macromolecular chain end in hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer
Group, chemical structure is: it is hydroxy-end capped it is poly- (acrylic acid trifluoro ethyl ester-is random-ethyl methacrylate-is random-methacrylic acid
Random -2- methyl -2- 2-hydroxyethyl acrylate the phosphate of isodecyl ester -) i.e. P(TFDMA-r-EDMA-r-DMA-r-HMP).
Step 2: synthesis graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive
10 parts of polyoxypropyleneglycol PPG, 20 parts of polyethylene glycol adipate glycol PEA, 15 parts of flame retarding polyether are polynary
The hydroxy-end capped phosphor-containing flame-proof that alcohol WANOL FR-130,20 parts of 7360,20 parts of step 1 of crystalline polyester dihydric alcohol synthesize contains
After fluo-copolymer, 0.2 part of phosphoric acid, 10 parts of graphene oxide and the mixing of 0.4 part of irgasfos 168,120 DEG C are calorified, into
Row mechanical stirring is dispersed 2 hours, and water removal 2 hours is vacuumized, until the water content of mixture is lower than 280ppm, is cooled down in 80
DEG C, under nitrogen protection, 25 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI pre-polymerization of modified diphenylmethane-is added
Body), it carries out polymerization reaction 2 hours, sampling analysis polymerizate NCO% content reaches 1.6%, and viscosity reaches 8000 mPa.s, add
Enter 2 parts of silane coupling agent ND-42, obtains graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive, be above mass parts
Number.The number-average molecular weight of polyoxypropyleneglycol PPG is 1000, and the number-average molecular weight of polyethylene glycol adipate glycol PEA is
500, with Brookfield DV-C digital viscometer viscosity, test setting temperature is 100 DEG C.
Embodiment two
It is a kind of graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis of hydroxy blocks phosphor-containing flame-proof fluorinated copolymer
By 10 parts of acrylic acid trifluoro ethyl ester TFDMA, 10 parts of ethyl methacrylate EDMA, 30 parts of isodecyl
Ester DMA and 10 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP are dissolved in 100 parts of toluene, are controlled in 75
DEG C, under nitrogen protection, 3.3 parts of thermal initiator 4 being added, 4'- azo is bis- (4- cyano amylalcohol), and polymerization reaction 20 hours, rotation
After turning evaporation removing toluene, hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer is obtained, hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer
Number-average molecular weight is 12500, and 1~2 hydroxyl is contained in average each macromolecular chain end in hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer
Base functional group, chemical structure are: it is hydroxy-end capped it is poly- (acrylic acid trifluoro ethyl ester-is random-ethyl methacrylate-is random-methyl
Random -2- methyl -2- 2-hydroxyethyl acrylate the phosphate of isodecyl acrylate -) i.e. P(TFDMA-r-EDMA-r-DMA-r-
HMP).
Step 2: synthesis graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive
15 parts of polytetrahydrofuran ether glycol PTMG, 20 parts of polyadipate -1,6- hexylene glycol esterdiol PHA, 25 parts fire-retardant
Polyether polyol WANOL FR-130,20 parts of crystalline polyester dihydric alcohol 7380,30 parts of step 1 synthesis hydroxy-end capped containing
After the fire-retardant fluorinated copolymer of phosphorus, 0.6 part of triethanolamine, 20 parts of graphene oxide and the mixing of 0.9 part of irgasfos 168, add
Heat carries out mechanical stirring and disperses 3 hours, vacuumize water removal 3 hours in 130 DEG C, until the water content of mixture is lower than
280ppm cools down in 70 DEG C, under nitrogen protection, 35 parts of 4,4 '-diisocyanate of modified diphenylmethane-is added
Desmodur CD-C(MDI performed polymer), it carries out polymerization reaction 4 hours, sampling analysis polymerizate NCO% content reaches 1.5%,
Viscosity reaches 14000 mPa.s, and 2 parts of silane coupling agent ND-42 is added, and obtains graphene oxide modified fluoride-containing flame retardant polyurethane
Hot melt adhesive is mass fraction above.The number-average molecular weight of polytetrahydrofuran ether glycol PTMG is 2000, polyadipate -1,6-
The number-average molecular weight of hexylene glycol esterdiol PHA is 1000, and test setting temperature is 100 DEG C.
Embodiment three
It is a kind of graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis of hydroxy blocks phosphor-containing flame-proof fluorinated copolymer
By 15 parts of acrylic acid trifluoro ethyl ester TFDMA, 30 parts of ethyl methacrylate EDMA, 20 parts of isodecyl
Ester DMA and 20 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP are dissolved in 150 parts of toluene, are controlled in 70
DEG C, under nitrogen protection, 2 parts of thermal initiator 4 being added, 4'- azo is bis- (4- cyano amylalcohol), and polymerization reaction 12 hours, rotation
After evaporation removes toluene, hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer, the number of hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer are obtained
Average molecular weight is 18500, and 1~2 hydroxyl is contained in average each macromolecular chain end in hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer
Functional group, chemical structure are: it is hydroxy-end capped it is poly- (acrylic acid trifluoro ethyl ester-is random-ethyl methacrylate-is random-methyl-prop
Random -2- methyl -2- 2-hydroxyethyl acrylate the phosphate of olefin(e) acid isodecyl ester -) i.e. P(TFDMA-r-EDMA-r-DMA-r-
HMP).
Step 2: synthesis graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive
10 parts of polyoxypropyleneglycol PPG, 20 parts of polyethylene glycol adipate glycol PEA, 30 parts of flame retarding polyether are polynary
The hydroxy-end capped phosphor-containing flame-proof that alcohol WANOL FR-312,30 parts of 7320,30 parts of step 1 of crystalline polyester dihydric alcohol synthesize contains
After fluo-copolymer, 0.5 part of 2,2- dimorpholine base Anaesthetie Ether, 30 parts of graphene oxide and the mixing of 1 part of antioxidant 1010,
150 DEG C are calorified, mechanical stirring is carried out and disperses 4 hours, vacuumize water removal 3 hours, until the water content of mixture is lower than
280ppm cools down in 80 DEG C, under nitrogen protection, 40 parts of 4,4 '-diisocyanate of modified diphenylmethane-is added
Desmodur CD-C(MDI performed polymer), it carries out polymerization reaction 5 hours, sampling analysis polymerizate NCO% content reaches 2.4%,
Viscosity reaches 17000 mPa.s, and 3 parts of silane coupling agent ND-42 is added, and obtains graphene oxide modified fluoride-containing flame retardant polyurethane
Hot melt adhesive is mass fraction above.The number-average molecular weight of polyoxypropyleneglycol PPG is 3000, polyethylene glycol adipate
The number-average molecular weight of glycol PEA is 1500, and test setting temperature is 100 DEG C.
Example IV
It is a kind of graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis of hydroxy blocks phosphor-containing flame-proof fluorinated copolymer
By 30 parts of acrylic acid trifluoro ethyl ester TFDMA, 20 parts of ethyl methacrylate EDMA, 40 parts of isodecyl
Ester DMA and 20 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP are dissolved in 100 parts of toluene, are controlled in 75
DEG C, under nitrogen protection, 0.8 part of thermal initiator 4 being added, 4'- azo is bis- (4- cyano amylalcohol), and polymerization reaction 10 hours, rotation
After turning evaporation removing toluene, hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer is obtained, hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer
Number-average molecular weight is 22300, and 1~2 hydroxyl is contained in average each macromolecular chain end in hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer
Base functional group, chemical structure are: it is hydroxy-end capped it is poly- (acrylic acid trifluoro ethyl ester-is random-ethyl methacrylate-is random-methyl
Random -2- methyl -2- 2-hydroxyethyl acrylate the phosphate of isodecyl acrylate -) i.e. P(TFDMA-r-EDMA-r-DMA-r-
HMP).
Step 2: synthesis graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive
15 parts of polyoxypropyleneglycol PPG, 15 parts of polyadipate -1,4-butanediol esterdiol PBA, 30 parts of flame retarding polyether
The hydroxy-end capped phosphorous resistance that polyalcohol WANOL FR-312,30 parts of 7360,40 parts of step 1 of crystalline polyester dihydric alcohol synthesize
After firing fluorinated copolymer, 1 part of triethanolamine, 40 parts of graphene oxide and the mixing of 1 part of irgasfos 168,150 are calorified
DEG C, it carries out mechanical stirring and disperses 5 hours, vacuumize water removal 2 hours, until the water content of mixture is lower than 280ppm, cooling
In 90 DEG C, under nitrogen protection, 50 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI of modified diphenylmethane-is added
Performed polymer), it carries out polymerization reaction 5 hours, sampling analysis polymerizate NCO% content reaches 2.0%, viscosity (100 DEG C of mPa.s@,
Brookfield DV-C Digital Viscometer) 24000 mPa.s, 5 parts of silane coupling agent ND-42 is added, obtains graphene oxide
Modified fluoride-containing flame retardant polyurethane hot melt adhesive, is mass fraction above.The number-average molecular weight of polyoxypropyleneglycol PPG is
4000, polyadipate -1,4-butanediol esterdiol PBA number-average molecular weight is 2000, and test setting temperature is 100 DEG C.
Performance test
Universal method of the present invention referring to current hot melt adhesive, the ageing-resistant performance excellent flame that the four kinds of above embodiments are obtained
Damp solidifying polyurethane hot melt adhesive carries out melt viscosity, open hour, shore hardness, elongation at break, shear strength, oxygen index (OI)
With with the energy of resistance to acidity of oil index test.Melt viscosity is tested referring to HG/T3660-1999 standard, selects No. 27 rotors, if
Set 100 DEG C.Open hour are tested referring to ASTM D4497-1994 (2004) method.Shore hardness is referring to GB-T2411-
2008 standards are tested.Elongation at break is tested referring to GB/T30776-2014 standard.Shear strength is referring to GB/
T7124-2004 standard is tested.Oxygen index (OI) uses GB/T5454-1997 " textile combustion performance test-oxygen index method "
Measurement.The specific test method of chemical resistance index is to prepare sample with reference to test shear strength method, and it is small that sample places 72
When solidification after, sample is soaked in oleic acid (purity 98%) solution 24 hours, takes out sample, is placed in 85 DEG C and 85% relatively wet
It spends under environment, after carrying out aging 1000 hours, then carries out shear strength test.All test data comparative situations are see the following table 1.
Each embodiment specific performance of table 1 tests control case
It can be seen that the graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive of the invention synthesized with excellent from the data of table 1
Good chemical resistance and flame retardant property.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (3)
1. a kind of graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive, it is characterised in that including 1~30 part of polyethers binary
Alcohol, 1~45 part of liquid polyesters dihydric alcohol, 1~50 part of flame retardant polyether polyol, 1~45 part of crystalline polyester dihydric alcohol,
1~50 part of hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer, 5~50 parts of isocyanates, 0.1~1 part of catalyst, 0.1~2
The antioxidant, 0.1~5 part of silane coupling agent and 20~80 parts of graphene oxide of part, are mass fraction above；The hydroxyl
The chemical structure of base sealing end phosphor-containing flame-proof fluorinated copolymer is: it is hydroxy-end capped it is poly- (acrylic acid trifluoro ethyl ester-is random-metering system
Acetoacetic ester-is random-random -2- methyl -2- 2-hydroxyethyl acrylate phosphate of isodecyl methacrylate -) i.e. P(TFDMA-
R-EDMA-r-DMA-r-HMP), average each macromolecular chain end contains 1~2 in hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer
Hydroxy functional group, the number-average molecular weight of hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer are 1000~50000.
2. graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive according to claim 1, it is characterised in that:
The polyether Glycols are polyoxypropyleneglycol PPG or polytetrahydrofuran ether two of the number-average molecular weight 500~4000
One or two kinds of any combination of alcohol PTMG；
The liquid polyesters dihydric alcohol be number-average molecular weight 200~2000 polyethylene glycol adipate glycol PEA, gather oneself two
Acid -1,6- hexylene glycol esterdiol PHA or polyadipate -1,4-butanediol esterdiol PBA one or more any combination；
The flame retardant polyether polyol is WANOL FR-130, the WANOL of Wanhua Chemical Group Co., Ltd.'s production
One or two kinds of any combination of FR-212 or WANOL FR-312；
The crystalline polyester dihydric alcohol is to win 7380 one or more of wound Degussa model 7320, model 7360 and model
Any combination；
The isocyanates is modified diphenylmethane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer)；
The catalyst is one or more kinds of any groups of triethanolamine, 2,2- dimorpholine base Anaesthetie Ether and phosphoric acid
It closes；
The antioxidant is one or both of 168 and 1010 any combination；
The silane coupling agent is anilinomethyl triethoxysilane ND-42；
The graphene oxide is with a thickness of 0.55 ~ 1.2nm, and diameter is 0.5 ~ 3 μm and the number of plies is 1 ~ 5 layer.
3. a kind of graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive preparation method, it is characterised in that preparation step is as follows:
Step 1: synthesis of hydroxy blocks phosphor-containing flame-proof fluorinated copolymer
By 1~30 part of acrylic acid trifluoro ethyl ester TFDMA, 1~40 part of ethyl methacrylate EDMA, 1~40 part of methyl
Isodecyl acrylate DMA and 1~30 part of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP are dissolved in 50~300 parts
Toluene in, be controlled in 40~100 DEG C, under nitrogen protection, 0.1~5 part of thermal initiator 4, bis- (the 4- cyanogen of 4'- azo be added
Base amylalcohol), polymerization reaction 1~40 hour, after rotary evaporation removes toluene, hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer is obtained,
The number-average molecular weight of hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer is 1000~50000；
Step 2: synthesis graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive
1~30 part of polyether Glycols, 1~45 part of liquid polyesters dihydric alcohol, 1~50 part of flame retardant polyether polyol, 1~45
The hydroxy-end capped phosphor-containing flame-proof fluorinated copolymer of one synthesis of the step of crystalline polyester dihydric alcohol of part, 1~50 part, 0.1~1 part
Catalyst, 20~80 parts of graphene oxide and 0.1~2 part antioxidant mixing after, calorify 120~150 DEG C, carry out machine
Tool is dispersed with stirring 1~5 hour, vacuumize water removal about 1~3 hour, until mixture water content be lower than 280ppm, cooling in
70~100 DEG C, under nitrogen protection, 5~50 parts of isocyanates is added, carries out polymerization reaction 1~5 hour, sampling analysis is poly-
It closes product NCO% content and reaches 1%~3%, tested viscosity reaches 5000~50000 mPa.s at 100 DEG C, is added 0.1~5 part
Silane coupling agent obtains graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive, is above mass fraction.
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Cited By (3)
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| CN112694862A (en) * | 2020-12-09 | 2021-04-23 | 南京理工大学北方研究院 | Graphene oxide modified polyurethane flame-retardant glass cement and preparation method thereof |
| CN114188522A (en) * | 2021-12-10 | 2022-03-15 | 湖南宸宇富基新能源科技有限公司 | Microcrystalline graphite/CNT @ C composite material, preparation method thereof and application thereof in lithium secondary battery |
| US11564315B2 (en) | 2021-02-10 | 2023-01-24 | Wuhan Tianma Micro-Electronics Co., Ltd. | Flexible circuit board, display panel, and insulating film |
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| CN104245769A (en) * | 2012-04-12 | 2014-12-24 | Dic株式会社 | Moisture-curable polyurethane hot melt resin composition, adhesive and article |
| CN104262553A (en) * | 2014-09-19 | 2015-01-07 | 厦门大学 | Flame-retardant block copolymer containing nitrogen and phosphorus and preparation method thereof |
| CN107474782A (en) * | 2017-08-16 | 2017-12-15 | 上海量子花光艺科技股份有限公司 | A kind of antistatic polyurethane casting glue and its application method |
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| CN102504752A (en) * | 2011-11-30 | 2012-06-20 | 山东北方现代化学工业有限公司 | Room-temperature moisture-curable single-component flame-retardant polyurethane sealant |
| CN104245769A (en) * | 2012-04-12 | 2014-12-24 | Dic株式会社 | Moisture-curable polyurethane hot melt resin composition, adhesive and article |
| CN104262553A (en) * | 2014-09-19 | 2015-01-07 | 厦门大学 | Flame-retardant block copolymer containing nitrogen and phosphorus and preparation method thereof |
| CN107474782A (en) * | 2017-08-16 | 2017-12-15 | 上海量子花光艺科技股份有限公司 | A kind of antistatic polyurethane casting glue and its application method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112694862A (en) * | 2020-12-09 | 2021-04-23 | 南京理工大学北方研究院 | Graphene oxide modified polyurethane flame-retardant glass cement and preparation method thereof |
| US11564315B2 (en) | 2021-02-10 | 2023-01-24 | Wuhan Tianma Micro-Electronics Co., Ltd. | Flexible circuit board, display panel, and insulating film |
| CN114188522A (en) * | 2021-12-10 | 2022-03-15 | 湖南宸宇富基新能源科技有限公司 | Microcrystalline graphite/CNT @ C composite material, preparation method thereof and application thereof in lithium secondary battery |
| CN114188522B (en) * | 2021-12-10 | 2024-05-14 | 湖南宸宇富基新能源科技有限公司 | Microcrystalline graphite/CNT@C composite material, preparation method thereof and application thereof in lithium secondary battery |
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Application publication date: 20190607 |