CN109679561A - Graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive and preparation method thereof - Google Patents
Graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN109679561A CN109679561A CN201811475157.4A CN201811475157A CN109679561A CN 109679561 A CN109679561 A CN 109679561A CN 201811475157 A CN201811475157 A CN 201811475157A CN 109679561 A CN109679561 A CN 109679561A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- silicon
- graphene oxide
- hydroxy
- hot melt
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/302—Water
- C08G18/307—Atmospheric humidity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6295—Polymers of silicium containing compounds having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- 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
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- 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
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive and preparation method thereof, feature is the polyether Glycols for including 1~30 part, 1~60 part of liquid polyesters dihydric alcohol, 1~45 part of flame retardant polyether polyol, 1~60 part of crystalline polyester dihydric alcohol, 1~45 part of hydroxy-end capped polyacrylate fluorine-silicon copolymer object, 5~60 parts of isocyanates, 0.1~4 part of catalyst, 0.01~2 part of antioxidant, 0.1~4 part of silane coupling agent and the graphene oxide with 1~150 part.Elder generation's synthesis of hydroxy of the present invention blocks polyacrylate fluorine-silicon copolymer object, its chemical structure is: hydroxy-end capped poly- (acrylic acid trifluoro ethyl ester-is random-methacryloxypropyl list sealing end dimethyl polysiloxane-is random-random -2- methyl -2- 2-hydroxyethyl acrylate phosphate of acrylic acid-2-ethyl caproite -), it is added into the high efficiency dispersion graphene oxide in base polyurethane prepolymer for use as, can further promote flame retardant property, hydrophobic performance, chemical resistance and the mechanical moduli of polyurethane gel.
Description
Technical field
The invention belongs to structure glue technical fields, and in particular to a kind of graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt
Glue and preparation method thereof, which are mainly applied to electronics and appliance industry, automobile industry, new energy lithium battery module group assembling isostructuralisms
Bonding 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 change type polyurethane hot melt adhesive can form highly cross-linked network after hardening, there is also solvent resistant, it is fire-retardant, heat-resisting,
Ageing-resistant performance deficiency problem.This main cause is most of Research of Moisture-curable Polyurethane Hot-melt Adhesive to improve its initial cohesiveness,
It joined a large amount of non-reacted thermoplasticity thickening resin or polynary acrylic copolymer.These non-reaction systems thickening resins without
Method participates in solidification and generates cross-linked network, to easily reduce the chemical resistance of polyurethane hot melt adhesive coating, heat resistance and resistance to
Ageing properties etc..
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
There is provided a kind of graphene oxide modified flame-retardant fluorine silicon poly- ammonia 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 flame-retardant fluorine-silicon polyurethane hot melt adhesive passes through fluorinated silicone modified, introducing
Reactive flame retardant and addition graphene oxide, improve chemical resistance, the flame retardant property, heat resistance of polyurethane coating
Deng.
In order to achieve the above object, the technical solution of graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive of the invention
It is achieved in that it is characterized by comprising 1~30 part of polyether Glycols, 1~60 part of liquid polyesters dihydric alcohol, 1~45
Flame retardant polyether polyol, 1~60 part of the crystalline polyester dihydric alcohol, 1~45 part of hydroxy-end capped polyacrylate fluorine silicon of part
Copolymer, 5~60 parts of isocyanates, 0.1~4 part of catalyst, 0.01~2 part of antioxidant, 0.1~4 part of silane are even
Join agent and the graphene oxide with 1~150 part, is above mass fraction；The hydroxy-end capped polyacrylate fluorine-silicon copolymer
The chemical structure of object is: it is hydroxy-end capped it is poly- (acrylic acid trifluoro ethyl ester-is random-methacryloxypropyl list sealing end dimethyl is poly-
Siloxanes-is random-random -2- methyl -2- 2-hydroxyethyl acrylate phosphate of acrylic acid-2-ethyl caproite -) i.e. P(TFMA-
R-EHAPDMS-r-EHA-r-HMP), average each macromolecular chain end is contained in hydroxy-end capped polyacrylate fluorine-silicon copolymer object
1~2 hydroxy functional group, the number-average molecular weight of hydroxy-end capped polyacrylate fluorine-silicon copolymer object are 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, the preparation method of graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive of the invention
Technical solution be achieved in that it is characterized in that preparation step is as follows:
Step 1: synthesis of hydroxy blocks polyacrylate fluorine-silicon copolymer object
1~30 part of acrylic acid trifluoro ethyl ester TFMA, 1~30 part of methacryloxypropyl list are blocked into the poly- silicon oxygen of dimethyl
Alkane MAPDMS, 1~60 part of acrylic acid-2-ethyl caproite EHA and 1~40 part of 2- methyl -2- 2-hydroxyethyl acrylate phosphorus
Acid esters HMP is dissolved in 50~300 parts of toluene, is controlled in 40~100 DEG C, under nitrogen protection, 0.1~4 part of heat is added
Initiator 4,4'- azo is bis- (4- cyano amylalcohol), polymerization reaction 0.5~30 hour, after rotary evaporation removes toluene, obtains hydroxyl
Blocking polyacrylate fluorine-silicon copolymer object, the number-average molecular weight of hydroxy-end capped polyacrylate fluorine-silicon copolymer object is 1000~
50000；
Step 2: synthesis graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive
By 1~30 part of polyether Glycols, 1~60 part of liquid polyesters dihydric alcohol, 1~45 part of flame retardant polyether polyol, 1~
The step of 60 parts of crystalline polyester dihydric alcohol, 1~45 part one synthesize hydroxy-end capped polyacrylate fluorine-silicon copolymer object, 1~
After 150 parts of graphene oxide, 0.1~4 part of catalyst and the mixing of 0.01~2 part of antioxidant, 120~150 DEG C are calorified,
Carry out mechanical dispersion, vacuumize water removal about 1~3 hour, until the water content of mixture is lower than 280ppm, cooling in 70~
100 DEG C, under nitrogen protection, 5~60 parts of isocyanates is added, carries out polymerization reaction 1~5 hour, sampling analysis polymerization produces
Object NCO% content reaches 1%~3%, and tested viscosity reaches 5000~30000 mPa.s at 100 DEG C, and 0.1~4 part of silane is added
Coupling agent obtains graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive, is above mass fraction.
In the technical scheme, in step 1 methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS number
Average molecular weight is 1000, No. CAS: 146632-07-7.
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 hydroxy-end capped polyacrylate fluorine-silicon copolymer object that the present invention synthesizes can be effectively improved and be promoted point of graphene oxide
The ability of dissipating, reduces the viscosity of glue；
2, the present invention introduces fluorine silicon segment and reactive flame retardant in base polyurethane prepolymer for use as, improves polyurethane gel
Chemicals-resistant, fire-retardant, heat resistance etc.；
3, graphene oxide can further decrease cure shrinkage and improve mechanical moduli；
4, 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；
5, 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 flame-retardant fluorine-silicon polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis of hydroxy blocks polyacrylate fluorine-silicon copolymer object
10 parts of acrylic acid trifluoro ethyl ester TFMA, 5 parts of methacryloxypropyl list are blocked into dimethyl polysiloxane
MAPDMS, 40 parts of acrylic acid-2-ethyl caproite EHA and 10 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP
It is dissolved in 100 parts of toluene, is controlled in 70 DEG C, under nitrogen protection, 3.6 parts of thermal initiator 4, the bis- (4- of 4'- azo are added
Cyano amylalcohol), polymerization reaction 7 hours, after rotary evaporation removes toluene, hydroxy-end capped polyacrylate fluorine-silicon copolymer object is obtained,
The chemical structure of hydroxy-end capped polyacrylate fluorine-silicon copolymer object is: it is hydroxy-end capped it is poly- (acrylic acid trifluoro ethyl ester-is random-methyl
Acryloxypropyl list block dimethyl polysiloxane-it is random-random -2- methyl -2- acrylic acid-of acrylic acid-2-ethyl caproite -
2- hydroxyethyl ester phosphate) i.e. P(TFMA-r-EHAPDMS-r-EHA-r-HMP), hydroxy-end capped polyacrylate fluorine-silicon copolymer object
In average each macromolecular chain end contain 1~2 hydroxy functional group, the number of hydroxy-end capped polyacrylate fluorine-silicon copolymer object is divided equally
Son amount is 4000；The number-average molecular weight that methacryloxypropyl list blocks dimethyl polysiloxane MAPDMS is 1000, CAS
Number: 146632-07-7.
Step 2: synthesis graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive
10 parts of polyoxypropyleneglycol PPG, 15 parts of polyethylene glycol adipate glycol PEA, 20 parts of flame retarding polyether are polynary
The hydroxy-end capped polyacrylate that alcohol WANOL FR-130,35 parts of 7360,20 parts of step 1 of crystalline polyester dihydric alcohol synthesize
After fluorine-silicon copolymer object, 40 parts of graphene oxide, 0.4 part of phosphoric acid and the mixing of 0.8 part of irgasfos 168,120 DEG C are calorified,
Mechanical dispersion is carried out, water removal 2 hours is vacuumized, until the water content of mixture is lower than 280ppm, is cooled down in 80 DEG C, in nitrogen
Under protection, 30 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer of modified diphenylmethane-is added), gathered
Reaction 3 hours is closed, sampling analysis polymerizate NCO% content reaches 1.8%, and viscosity reaches 8560 mPa.s, 2 parts of silicon is added
Alkane coupling agent ND-42 obtains graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive, is above mass fraction.Polyoxygenated
The number-average molecular weight of propylene glycol PPG is 1000, and the number-average molecular weight of polyethylene glycol adipate glycol PEA is 500, is used
Brookfield DV-C digital viscometer viscosity, test setting temperature are 100 DEG C.
Embodiment two
It is a kind of graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis of hydroxy blocks polyacrylate fluorine-silicon copolymer object
10 parts of acrylic acid trifluoro ethyl ester TFMA, 20 parts of methacryloxypropyl list are blocked into dimethyl polysiloxane
MAPDMS, 45 parts of acrylic acid-2-ethyl caproite EHA and 15 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP
It is dissolved in 120 parts of toluene, is controlled in 75 DEG C, under nitrogen protection, 2.6 parts of thermal initiator 4, the bis- (4- of 4'- azo are added
Cyano amylalcohol), polymerization reaction 6 hours, after rotary evaporation removes toluene, hydroxy-end capped polyacrylate fluorine-silicon copolymer object is obtained,
The chemical structure of hydroxy-end capped polyacrylate fluorine-silicon copolymer object is: it is hydroxy-end capped it is poly- (acrylic acid trifluoro ethyl ester-is random-methyl
Acryloxypropyl list block dimethyl polysiloxane-it is random-random -2- methyl -2- acrylic acid-of acrylic acid-2-ethyl caproite -
2- hydroxyethyl ester phosphate) i.e. P(TFMA-r-EHAPDMS-r-EHA-r-HMP), hydroxy-end capped polyacrylate fluorine-silicon copolymer object
In average each macromolecular chain end contain 1~2 hydroxy functional group, the number of hydroxy-end capped polyacrylate fluorine-silicon copolymer object is divided equally
Son amount is 9500；The number-average molecular weight that methacryloxypropyl list blocks dimethyl polysiloxane MAPDMS is 1000, CAS
Number: 146632-07-7.
Step 2: synthesis graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive
20 parts of polytetrahydrofuran ether glycol PTMG, 10 parts of polyadipate -1,6- hexylene glycol esterdiol PHA, 35 parts fire-retardant
Polyether polyol WANOL FR-130,35 parts 7380,35 parts of the hydroxy-end capped of step 1 synthesis of crystalline polyester dihydric alcohol gather
After acrylate fluorine-silicon copolymer object, 70 parts of graphene oxide, 0.8 part of triethanolamine and the mixing of 1.0 parts of irgasfos 168,
130 DEG C are calorified, mechanical dispersion is carried out, vacuumizes water removal 2.5 hours, until the water content of mixture is lower than 280ppm, drop
Temperature is in 70 DEG C, under nitrogen protection, 45 parts of 4,4 '-diisocyanate Desmodur CD-C of modified diphenylmethane-is added
(MDI performed polymer) carries out polymerization reaction 5 hours, and sampling analysis polymerizate NCO% content reaches 2.2%, and viscosity reaches 17210
2 parts of silane coupling agent ND-42 is added in mPa.s, obtains graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive, above equal
For mass fraction.The number-average molecular weight of polytetrahydrofuran ether glycol PTMG is 2000, polyadipate -1,6- hexylene glycol esterdiol
The number-average molecular weight of PHA is 1000, and with Brookfield DV-C digital viscometer viscosity, test setting temperature is 100
℃。
Embodiment three
It is a kind of graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis of hydroxy blocks polyacrylate fluorine-silicon copolymer object
20 parts of acrylic acid trifluoro ethyl ester TFMA, 15 parts of methacryloxypropyl list are blocked into dimethyl polysiloxane
MAPDMS, 50 parts of acrylic acid-2-ethyl caproite EHA and 15 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP
It is dissolved in 150 parts of toluene, is controlled in 75 DEG C, under nitrogen protection, 1.7 parts of thermal initiator 4, the bis- (4- of 4'- azo are added
Cyano amylalcohol), polymerization reaction 8 hours, after rotary evaporation removes toluene, hydroxy-end capped polyacrylate fluorine-silicon copolymer object is obtained,
The chemical structure of hydroxy-end capped polyacrylate fluorine-silicon copolymer object is: it is hydroxy-end capped it is poly- (acrylic acid trifluoro ethyl ester-is random-methyl
Acryloxypropyl list block dimethyl polysiloxane-it is random-random -2- methyl -2- acrylic acid-of acrylic acid-2-ethyl caproite -
2- hydroxyethyl ester phosphate) i.e. P(TFMA-r-EHAPDMS-r-EHA-r-HMP), hydroxy-end capped polyacrylate fluorine-silicon copolymer object
In average each macromolecular chain end contain 1~2 hydroxy functional group, the number of hydroxy-end capped polyacrylate fluorine-silicon copolymer object is divided equally
Son amount is 15200；The number-average molecular weight that methacryloxypropyl list blocks dimethyl polysiloxane MAPDMS is 1000, CAS
Number: 146632-07-7.
Step 2: synthesis graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive
10 parts of polyoxypropyleneglycol PPG, 10 parts of polyethylene glycol adipate glycol PEA, 40 parts of flame retarding polyether are polynary
The hydroxy-end capped polyacrylate that alcohol WANOL FR-312,40 parts of 7320,35 parts of step 1 of crystalline polyester dihydric alcohol synthesize
Fluorine-silicon copolymer object, 90 parts of graphene oxide, 0.5 part of 2,2- dimorpholine base Anaesthetie Ether and 0.9 part of antioxidant 1010 are mixed
After conjunction, 150 DEG C are calorified, carries out mechanical dispersion, vacuumizes water removal 3 hours, until the water content of mixture is lower than 280ppm,
Cool down in 80 DEG C, under nitrogen protection, 50 parts of 4,4 '-diisocyanate Desmodur CD-C of modified diphenylmethane-is added
(MDI performed polymer) carries out polymerization reaction 5 hours, and sampling analysis polymerizate NCO% content reaches 2.4%, and viscosity reaches 25420
3 parts of silane coupling agent ND-42 is added in mPa.s, obtains graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive, above equal
For mass fraction.The number-average molecular weight of polyoxypropyleneglycol PPG is 3000, and the number of polyethylene glycol adipate glycol PEA is equal
Molecular weight is 1500, and with Brookfield DV-C digital viscometer viscosity, test setting temperature is 100 DEG C.
Example IV
It is a kind of graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis of hydroxy blocks polyacrylate fluorine-silicon copolymer object
10 parts of acrylic acid trifluoro ethyl ester TFMA, 30 parts of methacryloxypropyl list are blocked into dimethyl polysiloxane
MAPDMS, 50 parts of acrylic acid-2-ethyl caproite EHA and 30 parts of 2- methyl -2- 2-hydroxyethyl acrylate phosphate HMP
It is dissolved in 150 parts of toluene, is controlled in 80 DEG C, under nitrogen protection, 0.8 part of thermal initiator 4, the bis- (4- of 4'- azo are added
Cyano amylalcohol), polymerization reaction 9 hours, after rotary evaporation removes toluene, hydroxy-end capped polyacrylate fluorine-silicon copolymer object is obtained,
The chemical structure of hydroxy-end capped polyacrylate fluorine-silicon copolymer object is: it is hydroxy-end capped it is poly- (acrylic acid trifluoro ethyl ester-is random-methyl
Acryloxypropyl list block dimethyl polysiloxane-it is random-random -2- methyl -2- acrylic acid-of acrylic acid-2-ethyl caproite -
2- hydroxyethyl ester phosphate) i.e. P(TFMA-r-EHAPDMS-r-EHA-r-HMP), hydroxy-end capped polyacrylate fluorine-silicon copolymer object
In average each macromolecular chain end contain 1~2 hydroxy functional group, the number of hydroxy-end capped polyacrylate fluorine-silicon copolymer object is divided equally
Son amount is 24200；The number-average molecular weight that methacryloxypropyl list blocks dimethyl polysiloxane MAPDMS is 1000, CAS
Number: 146632-07-7.
Step 2: synthesis graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive
20 parts of polyoxypropyleneglycol PPG, 10 parts of polyadipate -1,4-butanediol esterdiol PBA, 45 parts of flame retarding polyether
The hydroxy-end capped polypropylene that polyalcohol WANOL FR-312,60 parts of 7360,35 parts of step 1 of crystalline polyester dihydric alcohol synthesize
After acid esters fluorine-silicon copolymer object, 120 parts of graphene oxide, 0.8 part of triethanolamine and the mixing of 1.5 parts of irgasfos 168, heating
In 150 DEG C, mechanical dispersion is carried out, vacuumizes water removal 2 hours, until the water content of mixture is lower than 280ppm, is cooled down in 90
DEG C, under nitrogen protection, 60 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI pre-polymerization of modified diphenylmethane-is added
Body), it carries out polymerization reaction 5 hours, sampling analysis polymerizate NCO% content reaches 2.5%, and viscosity reaches 34300 mPa.s, adds
Enter 3 parts of silane coupling agent ND-42, obtains graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive, be above mass parts
Number.The number-average molecular weight of polyoxypropyleneglycol PPG is 4000, polyadipate -1,4-butanediol esterdiol PBA equal molecule of number
Amount is 2000, and with Brookfield DV-C digital viscometer viscosity, 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.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 fluorine-silicon polyurethane hot melt adhesive of the invention synthesized with excellent from the data of table 1
Good chemical resistance, flame retardant property, hydrophobic performance and mechanical moduli.
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 (4)
1. a kind of graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive, it is characterised in that including 1~30 part of polyethers binary
Alcohol, 1~60 part of liquid polyesters dihydric alcohol, 1~45 part of flame retardant polyether polyol, 1~60 part of crystalline polyester dihydric alcohol,
1~45 part of hydroxy-end capped polyacrylate fluorine-silicon copolymer object, 5~60 parts of isocyanates, 0.1~4 part of catalyst, 0.01
~2 parts of antioxidant, 0.1~4 part of silane coupling agent and the graphene oxide with 1~150 part, are mass fraction above；
The chemical structure of the hydroxy-end capped polyacrylate fluorine-silicon copolymer object is: it is hydroxy-end capped it is poly- (acrylic acid trifluoro ethyl ester-is random-
Methacryloxypropyl list block dimethyl polysiloxane-it is random-random -2- methyl -2- third of acrylic acid-2-ethyl caproite -
Olefin(e) acid -2- hydroxyethyl ester phosphate) i.e. P(TFMA-r-EHAPDMS-r-EHA-r-HMP), hydroxy-end capped polyacrylate fluorine silicon
1~2 hydroxy functional group is contained in average each macromolecular chain end in copolymer, hydroxy-end capped polyacrylate fluorine-silicon copolymer object
Number-average molecular weight is 1000~50000.
2. graphene oxide modified flame-retardant fluorine-silicon 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 preparation method of graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive, it is characterised in that preparation step is such as
Under:
Step 1: synthesis of hydroxy blocks polyacrylate fluorine-silicon copolymer object
1~30 part of acrylic acid trifluoro ethyl ester TFMA, 1~30 part of methacryloxypropyl list are blocked into the poly- silicon oxygen of dimethyl
Alkane MAPDMS, 1~60 part of acrylic acid-2-ethyl caproite EHA and 1~40 part of 2- methyl -2- 2-hydroxyethyl acrylate phosphorus
Acid esters HMP is dissolved in 50~300 parts of toluene, is controlled in 40~100 DEG C, under nitrogen protection, 0.1~4 part of heat is added
Initiator 4,4'- azo is bis- (4- cyano amylalcohol), polymerization reaction 0.5~30 hour, after rotary evaporation removes toluene, obtains hydroxyl
Blocking polyacrylate fluorine-silicon copolymer object, the number-average molecular weight of hydroxy-end capped polyacrylate fluorine-silicon copolymer object is 1000~
50000；
Step 2: synthesis graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive
By 1~30 part of polyether Glycols, 1~60 part of liquid polyesters dihydric alcohol, 1~45 part of flame retardant polyether polyol, 1~
The step of 60 parts of crystalline polyester dihydric alcohol, 1~45 part one synthesize hydroxy-end capped polyacrylate fluorine-silicon copolymer object, 1~
After 150 parts of graphene oxide, 0.1~4 part of catalyst and the mixing of 0.01~2 part of antioxidant, 120~150 DEG C are calorified,
Carry out mechanical dispersion, vacuumize water removal about 1~3 hour, until the water content of mixture is lower than 280ppm, cooling in 70~
100 DEG C, under nitrogen protection, 5~60 parts of isocyanates is added, carries out polymerization reaction 1~5 hour, sampling analysis polymerization produces
Object NCO% content reaches 1%~3%, and tested viscosity reaches 5000~30000 mPa.s at 100 DEG C, and 0.1~4 part of silane is added
Coupling agent obtains graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive, is above mass fraction.
4. the preparation method of graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive according to claim 3, feature
It is in step 1 that methacryloxypropyl list blocks dimethyl polysiloxane MAPDMS
Number-average molecular weight be 1000, No. CAS: 146632-07-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811475157.4A CN109679561A (en) | 2018-12-04 | 2018-12-04 | Graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811475157.4A CN109679561A (en) | 2018-12-04 | 2018-12-04 | Graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109679561A true CN109679561A (en) | 2019-04-26 |
Family
ID=66187040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811475157.4A Withdrawn CN109679561A (en) | 2018-12-04 | 2018-12-04 | Graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109679561A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111518255A (en) * | 2020-04-01 | 2020-08-11 | 华东师范大学 | Transparent hydrophobic silicon-fluorine-containing polyurethane coating and preparation method thereof |
| CN112382829A (en) * | 2020-10-14 | 2021-02-19 | 江西银汇新能源有限公司 | Functionalized flexible membrane and preparation method and application thereof |
| 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 |
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 CN201811475157.4A patent/CN109679561A/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 (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111518255A (en) * | 2020-04-01 | 2020-08-11 | 华东师范大学 | Transparent hydrophobic silicon-fluorine-containing polyurethane coating and preparation method thereof |
| CN111518255B (en) * | 2020-04-01 | 2022-04-05 | 华东师范大学 | Transparent hydrophobic silicon-fluorine-containing polyurethane coating and preparation method thereof |
| CN112382829A (en) * | 2020-10-14 | 2021-02-19 | 江西银汇新能源有限公司 | Functionalized flexible membrane and preparation method and application thereof |
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111019589B (en) | Two-component polyurethane adhesive, preparation method thereof and application thereof in soft package battery | |
| CN102827340B (en) | Organosilicon-modified waterborne polyurethane composite material and applications thereof | |
| CN109679561A (en) | Graphene oxide modified flame-retardant fluorine-silicon polyurethane hot melt adhesive and preparation method thereof | |
| CN109852320A (en) | Graphene oxide modified fluoride-containing flame retardant polyurethane hot melt adhesive and preparation method thereof | |
| CN101280061A (en) | Synthetic method of organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion | |
| CN103370389A (en) | Adhesive agent composition and laminated body | |
| CN109651994A (en) | Ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive and preparation method thereof | |
| CN109679559A (en) | The excellent damp solidifying polyurethane hot melt adhesive and preparation method thereof of oil resistance | |
| EP4077460A1 (en) | Polymeric material including a uretdione-containing material and inorganic filler, two-part compositions, products, and methods | |
| CN113817434A (en) | Halogen-containing flame-retardant polyurethane hot melt adhesive and preparation method thereof | |
| CN108570302B (en) | Low-temperature impact resistant epoxy adhesive composition and preparation method thereof | |
| CN109609078A (en) | Organic-silicon-modified flame retardant polyurethane hot melt adhesive of wet-cured type and preparation method thereof | |
| CN109651992A (en) | The excellent moisture-curable flame retardant polyurethane hot melt adhesive and preparation method thereof of weather resistance | |
| CN109679560A (en) | Thermally conductive organic-silicon-modified flame retardant polyurethane hot melt adhesive of moisture-curable and preparation method thereof | |
| CN109852322A (en) | Thermally conductive reaction-type flame-retarding polyurethane hot melt of one-component and preparation method thereof | |
| CN111630130B (en) | Single-component toughened epoxy adhesive | |
| CN109852323A (en) | Organic-silicon-modified one-component reaction type polyurethane hot-melt adhesive and preparation method thereof | |
| CN109651991A (en) | Wet-cured type organic silicon modified polyurethane hot melt adhesive and preparation method thereof | |
| CN109679564A (en) | Fluorinated silicone modified flame retardant polyurethane hot melt adhesive and preparation method thereof | |
| CN109651995A (en) | One-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive and preparation method thereof | |
| CN109679563A (en) | Graphene oxide modified flame-retardant damp solidifying polyurethane hot melt adhesive and preparation method thereof | |
| CN109666437A (en) | Oil resistance excellent flame damp solidifying polyurethane hot melt adhesive and preparation method thereof | |
| CN109679562A (en) | Novel moisture-curable flame retardant polyurethane hot melt adhesive and preparation method thereof | |
| CN109651996A (en) | High thermal conductivity flame retardant polyurethane hot melt adhesive and preparation method thereof | |
| CN109609076A (en) | Waterproof performance excellent flame polyurethane hot melt 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 | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190426 |