CN109679563A - Graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive and preparation method thereof - Google Patents
Graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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- CN109679563A CN109679563A CN201811475685.XA CN201811475685A CN109679563A CN 109679563 A CN109679563 A CN 109679563A CN 201811475685 A CN201811475685 A CN 201811475685A CN 109679563 A CN109679563 A CN 109679563A
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
Abstract
The invention discloses a kind of graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive and preparation method thereof, feature is the polyether Glycols for including 1~20 part, 1~40 part of flame retardant polyether polyol, 1~40 part of liquid polyesters dihydric alcohol, 1~40 part of crystalline polyester dihydric alcohol, 1~40 part of phosphor-containing flame-proof type poly-organosilicon acrylate copolymer, 10~50 parts of isocyanates, 0.01~1 part of catalyst, 0.01~1 part of antioxidant, 0.1~2 part of silane coupling agent and the graphene oxide with 1~100 part.The present invention synthesized first it is poly- (methacryloxypropyl list block the random -2- methyl -2- 2-hydroxyethyl acrylate phosphate-of dimethyl polysiloxane-it is random-Isooctyl acrylate monomer-is random-hydroxy-ethyl acrylate), it is added in base polyurethane prepolymer for use as, carry out high efficiency dispersion graphene oxide, it is further introduced into organic silicon acrylic ester copolymer segment and reactive flame retardant, formula efficiently acts synergistically, and improves ageing-resistant performance, flame retardant property, heating conduction and the comprehensive mechanical property of polyurethane hot melt.
Description
Technical field
The invention belongs to structure glue technical fields, and in particular to a kind of graphene oxide modified flame-retardant damp solidifying polyurethane
Hot melt adhesive and preparation method thereof, which are mainly applied to electronics and appliance industry, automobile industry, weaving and shoe industry, food packing industry,
Wood 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 and 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 is different by cured form, can be divided into thermoplastic polyurethane elastomer hot melt
Glue and reactive polyurethane hot melt；Reactive polyurethane hot melt is different by its principle of solidification, can be divided into response type and closing
Type；Reaction type 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.
Reaction type polyurethane hot-melt adhesive has technically obtained unprecedented development at present, mainly around high-adhesive-strength, eutectic
Body viscosity, open hour reprocess and the progress performances such as cured form are optimized and revised." reactive hot-melt is viscous disclosed in Chinese patent
Mixture ", application number are 201480080313.0, prepare it is a kind of with the removable polyurethane-hot melt adhesive reprocessed, more
It is suitable for high-end electronic product scope application." solvent-free damp solidifying polyurethane hotmelt combination disclosed in Chinese patent
Object ", application number are 201180047316.0, prepare it is a kind of low toxicity quickly establish adhesive property polyacrylate and polyester preparation
Polyurethane-hot melt viscose binder.In order to improve the cured form of Research of Moisture-curable Polyurethane Hot-melt Adhesive, " have disclosed in Chinese patent
Machine silicon modified polyurethane sealant ", application number is 2017102717258, prepares a kind of organic silicon modified polyurethane sealant,
Replace isocyano (- NCO) with silane coupling agent, is more suitable for applying under high humidity environment.Currently, reaction type polyurethane hot-melt adhesive
Research and development technology meets different type high-end electronic product scope application in fast development.Although reaction type polyurethane hot-melt adhesive energy
Form highly cross-linked network after hardening, but there is also the performances such as chemicals-resistant corrosivity, heat-resisting, ageing-resistant, fire-retardant not
Sufficient problem.This main cause is most of reaction type polyurethane hot-melt adhesives to improve its initial cohesiveness, be joined a large amount of non-
Reactive thermoplasticity thickening resin or polynary acrylic copolymer.These non-reaction system thickening resins can not participate in solidification and generate
Cross-linked network, to easily reduce the chemicals-resistant corrosive nature, heat resistance, ageing-resistant performance etc. of polyurethane hot melt adhesive coating.
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 graphene oxide modified flame-retardant moisture-curable is provided the purpose of the present invention is overcome the deficiencies in the prior art
Polyurethane hot melt and preparation method thereof, since graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive introduces silane chain
Section, reactive flame retardant and graphene oxide can further improve the chemicals-resistant corrosivity performance, fire-retardant of polyurethane coating
Performance, heating conduction etc..
In order to achieve the above object, the technology of graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive of the invention
Scheme is achieved in that it is characterized by comprising 1~20 part of polyether Glycols, 1~40 part of flame retardant polyether polyol, 1
~40 parts of liquid polyesters dihydric alcohol, 1~40 part of crystalline polyester dihydric alcohol, 1~40 part of phosphor-containing flame-proof type poly-organosilicon
Acrylate copolymer, 10~50 parts of isocyanates, 0.01~1 part of catalyst, 0.01~1 part of antioxidant, 0.1~2
The silane coupling agent and 1~100 part of graphene oxide of part；It is above mass fraction；The phosphor-containing flame-proof type poly-organosilicon
The chemical structure of acrylate copolymer is: poly- (methacryloxypropyl list blocks the random -2- first of dimethyl polysiloxane -
Base -2- 2-hydroxyethyl acrylate phosphate-is random-and Isooctyl acrylate monomer-is random-hydroxy-ethyl acrylate) i.e. P(MAPDMS-
R-HMP-r-EHA-r-HEA), the number-average molecular weight of phosphor-containing flame-proof type poly-organosilicon acrylate copolymer is 1000~50000.
In the technical scheme, the polyether Glycols are polyoxypropyleneglycol of the number-average molecular weight 500~4000
(PPG) or one or two kinds of any combination of polytetrahydrofuran ether glycol (PTMG)；
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 liquid polyesters dihydric alcohol is polyethylene glycol adipate glycol PEA of the number-average molecular weight 200~2000, gathers oneself two
Acid -1,6- hexylene glycol esterdiol PHA or any group of polyadipate -1,4-butanediol esterdiol PEHA one or more
It closes；
The crystalline polyester dihydric alcohol is to win wound Degussa model 7320, and model 7360 and model 7380 are one or more kinds of
Any combination；
The isocyanates is modified diphenylmethane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer)；
The catalyst is triethanolamine, one or more kinds of any groups of 2,2- dimorpholine base Anaesthetie Ethers 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；
For the graphene oxide with a thickness of 0.55 ~ 1.2nm, 0.5 ~ 3 μm of diameter and the number of plies are 1 ~ 5 layer.
In order to achieve the above object, graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive preparation side of the invention
The technical solution of method is achieved in that it is characterized in that preparation step is as follows:
Step 1 synthesizes phosphor-containing flame-proof type poly-organosilicon acrylate copolymer
1~20 part of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 1~40 part of 2- methyl -2-
2-hydroxyethyl acrylate phosphate HMP, 1~40 part of Isooctyl acrylate monomer EHA and 1~5 part of hydroxy-ethyl acrylate HEA are molten
Solution is controlled in 40~110 DEG C in 50~100 parts of toluene, under nitrogen protection, 0.1~2 part of thermal initiator peroxide is added
Change 2 ethyl hexanoic acid tert-pentyl ester, polymerization reaction 2~50 hours, after rotary evaporation removes toluene, acquisition phosphor-containing flame-proof type gathered organic
Si acrylate copolymer, the number-average molecular weight of phosphor-containing flame-proof type poly-organosilicon acrylate copolymer are 1000~50000；First
The number-average molecular weight that base acryloxypropyl list blocks dimethyl polysiloxane MAPDMS is 1000；
Step 2 synthesizes graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive
By 1~20 part of polyether Glycols, 1~40 part of flame retardant polyether polyol, 1~40 part of liquid polyesters dihydric alcohol, 1~
40 parts of crystalline polyester dihydric alcohol, 1~40 part of phosphor-containing flame-proof type poly-organosilicon acrylate copolymer, 0.01~1 part
After catalyst, 1~100 part of graphene oxide and the mixing of 0.01~1 part of antioxidant, it is small to carry out mechanical stirring dispersion 1~5
When, 120~150 DEG C are calorified, water removal about 1~3 hour is vacuumized, until the water content of mixture is lower than 280ppm, cooling
In 70~100 DEG C, under nitrogen protection, 10~50 parts of isocyanates is added, carries out polymerization reaction 1~10 hour, sampling point
Analysis polymerizate NCO% content reaches 1%~3%, and tested viscosity reaches 6000~30000 mPa.s at 100 DEG C, is added 0.1~2
The silane coupling agent of part obtains graphene oxide modified flame-retardant damp solidifying 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, the present invention is solved by introducing silicone segments and reactive flame retardant in base polyurethane prepolymer for use as, is improved resistance to
Chemicals corrosive nature, flame retardant property and ageing-resistant performance；
2, 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 the problems, such as reaction type polyurethane hot-melt adhesive chemicals-resistant corrosive nature deficiency；
3, graphene oxide, which is added, in the present invention can further improve the mechanical property of traditional reaction type polyurethane hot-melt adhesive and thermally conductive
Performance reduces cure shrinkage.
4, organic silicon acrylic ester copolymer can play the effect of dispersing agent, promote graphene oxide and disperse energy in colloid
Power reduces the Viscosity of colloid.
5, the present invention solves the problems, such as that traditional reaction type polyurethane hot-melt adhesive is poor to substrate wet performance, improves hot melt
The flow leveling of glue 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 flame-retardant damp solidifying polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1 synthesizes phosphor-containing flame-proof type poly-organosilicon acrylate copolymer
7 parts of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 7 parts of 2- methyl -2- acrylic acid -2-
Hydroxyethyl ester phosphate HMP, 30 parts of Isooctyl acrylate monomer EHA and 2 parts of hydroxy-ethyl acrylate HEA are dissolved in 60 parts of toluene
In, 85 DEG C are controlled in, under nitrogen protection, 1.7 parts of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester, polymerization reaction is added
20 hours, after rotary evaporation removes toluene, phosphor-containing flame-proof type poly-organosilicon acrylate copolymer is obtained, phosphor-containing flame-proof type is poly- to be had
The number-average molecular weight of machine Si acrylate copolymer is 7500, and chemical structure is: poly- (methacryloxypropyl list sealing end two
Random -2- methyl -2- 2-hydroxyethyl acrylate the phosphate-of methyl polysiloxane-is random-Isooctyl acrylate monomer-random-the third
Olefin(e) acid hydroxyl ethyl ester) i.e. P(MAPDMS-r-HMP-r-EHA-r-HEA)；The methacryloxypropyl list blocks the poly- silicon of dimethyl
The number-average molecular weight of oxygen alkane MAPDMS is 1000, No. CAS: 146632-07-7；
Step 2 synthesizes graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive
10 parts of polyoxypropyleneglycol PPG, 10 parts of polyethylene glycol adipate glycol PEA, 10 parts of flame retarding polyether is more
The phosphor-containing flame-proof type that the step of first alcohol WANOL FR-130,7320,10 parts of crystalline polyester dihydric alcohol of 25 parts one synthesizes is poly- to be had
After machine Si acrylate copolymer, 0.05 part of phosphoric acid, 5 parts of graphene oxide and the mixing of 0.08 part of irgasfos 168, carry out
Mechanical stirring is dispersed 1 hour, calorifies 150 DEG C, vacuumizes water removal 1 hour, until the water content of mixture is lower than 280ppm,
Cool down in 70 DEG C, under nitrogen protection, 35 parts of 4,4 '-diisocyanate Desmodur CD-C of modified diphenylmethane-is added
(MDI performed polymer) carries out polymerization reaction 2 hours, and sampling analysis polymerizate NCO% content reaches 2.2%, and viscosity reaches 7500
MPa.s, 0.5 part of silane coupling agent ND-42 is added, obtains graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive,
It is above mass fraction；The number-average molecular weight of the polyoxypropyleneglycol PPG is 1000, the polyethylene glycol adipate
The number-average molecular weight of glycol PEA is 500, and with Brookfield DV-C digital viscometer viscosity, test temperature is set as
100℃。
Embodiment two
It is a kind of graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1 synthesizes phosphor-containing flame-proof type poly-organosilicon acrylate copolymer
10 parts of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 15 parts of 2- methyl -2- acrylic acid -
2- hydroxyethyl ester phosphate HMP, 35 parts of Isooctyl acrylate monomer EHA and 4 parts of hydroxy-ethyl acrylate HEA are dissolved in 80 parts of first
In benzene, 90 DEG C are controlled in, under nitrogen protection, 1.4 parts of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added, polymerization is anti-
It answers 15 hours, after rotary evaporation removes toluene, obtains phosphor-containing flame-proof type poly-organosilicon acrylate copolymer, phosphor-containing flame-proof type is poly-
The number-average molecular weight of organic silicon acrylic ester copolymer is 15000, and chemical structure is: poly- (methacryloxypropyl list envelope
Hold the random -2- methyl -2- 2-hydroxyethyl acrylate phosphate-of dimethyl polysiloxane-it is random-Isooctyl acrylate monomer-nothing
Rule-hydroxy-ethyl acrylate) i.e. P(MAPDMS-r-HMP-r-EHA-r-HEA)；It is poly- that methacryloxypropyl list blocks dimethyl
The number-average molecular weight of siloxanes MAPDMS is 1000, No. CAS: 146632-07-7；
Step 2 synthesizes graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive
By 10 parts of polytetrahydrofuran ether glycol PTMG, 20 parts of polyadipate -1,6- hexylene glycol esterdiol PHA, 15 parts of resistance
The phosphorous resistance that the step of combustible polyether glycol WANOL FR-212,7360,15 parts of crystalline polyester dihydric alcohol of 25 parts one synthesizes
Combustion type poly-organosilicon acrylate copolymer, 0.2 part of triethanolamine, 10 parts of graphene oxide and 0.3 part of irgasfos 168
It after mixing, carries out mechanical stirring and disperses 2 hours, calorify 140 DEG C, vacuumize water removal 2.5 hours, until the moisture content of mixture contains
Amount 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 2 hours, sampling analysis polymerizate NCO% content reaches 2.4%,
Viscosity reaches 8600 mPa.s, and 0.5 part of silane coupling agent ND-42 is added, and obtains graphene oxide modified flame-retardant moisture-curable
Polyurethane hot melt is mass fraction above；The number-average molecular weight of the polytetrahydrofuran ether glycol PTMG is 2000, described
The number-average molecular weight of polyadipate -1,6- hexylene glycol esterdiol PHA is 1000, is measured with Brookfield DV-C digital viscometer
Viscosity is measured, test temperature is set as 100 DEG C.
Embodiment three
It is a kind of graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1 synthesizes phosphor-containing flame-proof type poly-organosilicon acrylate copolymer
15 parts of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 20 parts of 2- methyl -2- acrylic acid -
2- hydroxyethyl ester phosphate HMP, 35 parts of Isooctyl acrylate monomer EHA and 2 parts of hydroxy-ethyl acrylate HEA are dissolved in 90 parts of first
In benzene, 95 DEG C are controlled in, under nitrogen protection, 0.7 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added, polymerization is anti-
It answers 10 hours, after rotary evaporation removes toluene, obtains phosphor-containing flame-proof type poly-organosilicon acrylate copolymer, phosphor-containing flame-proof type is poly-
The number-average molecular weight of organic silicon acrylic ester copolymer is 24000, and chemical structure is: poly- (methacryloxypropyl list envelope
Hold the random -2- methyl -2- 2-hydroxyethyl acrylate phosphate-of dimethyl polysiloxane-it is random-Isooctyl acrylate monomer-nothing
Rule-hydroxy-ethyl acrylate) i.e. P(MAPDMS-r-HMP-r-EHA-r-HEA)；It is poly- that methacryloxypropyl list blocks dimethyl
The number-average molecular weight of siloxanes MAPDMS is 1000, No. CAS: 146632-07-7；
Step 2 synthesizes graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive
10 parts of polyoxypropyleneglycol PPG, 15 parts of polyethylene glycol adipate glycol PEA, 20 parts of flame retarding polyether is more
The phosphor-containing flame-proof type that the step of first alcohol WANOL FR-312,7360,20 parts of crystalline polyester dihydric alcohol of 30 parts one synthesizes is poly- to be had
Machine Si acrylate copolymer, 0.1 part of 2,2- dimorpholine base Anaesthetie Ether, 15 parts of graphene oxide and 0.1 part of antioxygen
It after agent 1010 mixes, carries out mechanical stirring and disperses 2 hours, calorify 150 DEG C, vacuumize water removal 3 hours, until the water of mixture
Part content is lower than 280ppm, cools down in 80 DEG C, under nitrogen protection, 40 parts of 4,4 '-diisocyanate of modified diphenylmethane-is added
Ester Desmodur CD-C(MDI performed polymer), it carries out polymerization reaction 3 hours, sampling analysis polymerizate NCO% content reaches
2.4%, viscosity reaches 9400 mPa.s, and 0.5 part of silane coupling agent ND-42 is added, and obtains graphene oxide modified flame-retardant moisture
Solidify polyurethane hot melt, is above mass fraction；The number-average molecular weight of the polyoxypropyleneglycol PPG is 3000, institute
The number-average molecular weight for stating polyethylene glycol adipate glycol PEA is 1500, viscous with Brookfield DV-C digital viscometer
Degree, test temperature are set as 100 DEG C.
Example IV
It is a kind of graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1 synthesizes phosphor-containing flame-proof type poly-organosilicon acrylate copolymer
20 parts of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 15 parts of 2- methyl -2- acrylic acid -
2- hydroxyethyl ester phosphate HMP, 40 parts of Isooctyl acrylate monomer EHA and 5 parts of hydroxy-ethyl acrylate HEA are dissolved in 100 parts
In toluene, 100 DEG C are controlled in, under nitrogen protection, 0.4 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added, gathers
Reaction 7 hours is closed, after rotary evaporation removes toluene, obtains phosphor-containing flame-proof type poly-organosilicon acrylate copolymer, phosphor-containing flame-proof
The number-average molecular weight of type poly-organosilicon acrylate copolymer is 33000, and chemical structure is: poly- (methacryloxypropyl
Single random -2- methyl -2- 2-hydroxyethyl acrylate phosphate-of sealing end dimethyl polysiloxane-is random-Isooctyl acrylate monomer -
Randomly-hydroxy-ethyl acrylate) i.e. P(MAPDMS-r-HMP-r-EHA-r-HEA)；Methacryloxypropyl list blocks dimethyl
The number-average molecular weight of polysiloxanes MAPDMS is 1000, No. CAS: 146632-07-7；
Step 2 synthesizes graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive
By 20 parts of polyoxypropyleneglycol PPG, 20 parts of polyadipate -1,4-butanediol esterdiol PEHA, 25 parts fire-retardant
The phosphor-containing flame-proof that the step of polyether polyol WANOL FR-312,7380,30 parts of crystalline polyester dihydric alcohol of 20 parts one synthesizes
Type poly-organosilicon acrylate copolymer, 0.3 part of triethanolamine, 20 parts of graphene oxide and 0.8 part of irgasfos 168 are mixed
It after conjunction, carries out mechanical stirring and disperses 2 hours, calorify 150 DEG C, vacuumize water removal 2 hours, until the water content of mixture is low
In 280ppm, cool down in 90 DEG C, under nitrogen protection, 50 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 2.7%,
Viscosity reaches 12500 mPa.s, and 0.5 part of silane coupling agent ND-42 is added, and obtains graphene oxide modified flame-retardant moisture-curable
Polyurethane hot melt is mass fraction above；The number-average molecular weight of the polyoxypropyleneglycol PPG is 4000, described poly-
Adipic acid -1,4-butanediol esterdiol PEHA number-average molecular weight is 2000, with Brookfield DV-C digital viscometer
Viscosity, test temperature are set as 100 DEG C.
Performance test
The graphene oxide modified flame-retardant that the present invention obtains the four kinds of above embodiments referring to the universal method of current hot melt adhesive
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.Water contact angle is marked with reference to GB/T 30693-2014
Standard is tested.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 flame-retardant damp solidifying polyurethane hot melt adhesive tool that the present invention synthesizes from the data of table 1
There are excellent chemicals-resistant corrosive nature, ageing-resistant performance 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 flame-retardant damp solidifying polyurethane hot melt adhesive, it is characterised in that including 1~20 part of polyethers
Dihydric alcohol, 1~40 part of flame retardant polyether polyol, 1~40 part of liquid polyesters dihydric alcohol, 1~40 part of crystalline polyester two
First alcohol, 1~40 part of phosphor-containing flame-proof type poly-organosilicon acrylate copolymer, 10~50 parts of isocyanates, 0.01~1 part
Catalyst, 0.01~1 part of antioxidant, 0.1~2 part of silane coupling agent and 1~100 part of graphene oxide；It is above
Mass fraction；The chemical structure of the phosphor-containing flame-proof type poly-organosilicon acrylate copolymer is: poly- (methacryloxypropyl
Single random -2- methyl -2- 2-hydroxyethyl acrylate phosphate-of sealing end dimethyl polysiloxane-is random-Isooctyl acrylate monomer -
Randomly-hydroxy-ethyl acrylate) i.e. P(MAPDMS-r-HMP-r-EHA-r-HEA), phosphor-containing flame-proof type poly-organosilicon acrylate is total
The number-average molecular weight of polymers is 1000~50000.
2. graphene oxide modified flame-retardant damp solidifying 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 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 liquid polyesters dihydric alcohol is polyethylene glycol adipate glycol PEA of the number-average molecular weight 200~2000, gathers oneself two
Acid -1,6- hexylene glycol esterdiol PHA or any group of polyadipate -1,4-butanediol esterdiol PEHA one or more
It closes；
The crystalline polyester dihydric alcohol is to win wound Degussa model 7320, and model 7360 and model 7380 are one or more kinds of
Any combination；
The isocyanates is modified diphenylmethane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer)；
The catalyst is triethanolamine, one or more kinds of any groups of 2,2- dimorpholine base Anaesthetie Ethers 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；
For the graphene oxide with a thickness of 0.55 ~ 1.2nm, 0.5 ~ 3 μm of diameter and the number of plies are 1 ~ 5 layer.
3. a kind of graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive preparation method, it is characterised in that preparation step is such as
Under:
Step 1 synthesizes phosphor-containing flame-proof type poly-organosilicon acrylate copolymer
1~20 part of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 1~40 part of 2- methyl -2-
2-hydroxyethyl acrylate phosphate HMP, 1~40 part of Isooctyl acrylate monomer EHA and 1~5 part of hydroxy-ethyl acrylate HEA are molten
Solution is controlled in 40~110 DEG C in 50~100 parts of toluene, under nitrogen protection, 0.1~2 part of thermal initiator peroxide is added
Change 2 ethyl hexanoic acid tert-pentyl ester, polymerization reaction 2~50 hours, after rotary evaporation removes toluene, acquisition phosphor-containing flame-proof type gathered organic
Si acrylate copolymer, the number-average molecular weight of phosphor-containing flame-proof type poly-organosilicon acrylate copolymer are 1000~50000；First
The number-average molecular weight that base acryloxypropyl list blocks dimethyl polysiloxane MAPDMS is 1000；
Step 2 synthesizes graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive
By 1~20 part of polyether Glycols, 1~40 part of flame retardant polyether polyol, 1~40 part of liquid polyesters dihydric alcohol, 1~
40 parts of crystalline polyester dihydric alcohol, 1~40 part of phosphor-containing flame-proof type poly-organosilicon acrylate copolymer, 0.01~1 part
After catalyst, 1~100 part of graphene oxide and the mixing of 0.01~1 part of antioxidant, it is small to carry out mechanical stirring dispersion 1~5
When, 120~150 DEG C are calorified, water removal about 1~3 hour is vacuumized, until the water content of mixture is lower than 280ppm, cooling
In 70~100 DEG C, under nitrogen protection, 10~50 parts of isocyanates is added, carries out polymerization reaction 1~10 hour, sampling point
Analysis polymerizate NCO% content reaches 1%~3%, and tested viscosity reaches 6000~30000 mPa.s at 100 DEG C, is added 0.1~2
The silane coupling agent of part obtains graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive, is above mass fraction.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848900A (en) * | 2020-08-07 | 2020-10-30 | 宁波耀众模塑科技有限公司 | Flame-retardant formula of polyurethane foaming product |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1901942A (en) * | 2003-12-30 | 2007-01-24 | 庄臣及庄臣视力保护公司 | Antimicrobial contact lenses and methods for their production |
| 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 |
-
2018
- 2018-12-04 CN CN201811475685.XA patent/CN109679563A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1901942A (en) * | 2003-12-30 | 2007-01-24 | 庄臣及庄臣视力保护公司 | Antimicrobial contact lenses and methods for their production |
| 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848900A (en) * | 2020-08-07 | 2020-10-30 | 宁波耀众模塑科技有限公司 | Flame-retardant formula of polyurethane foaming product |
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