CN109666436A - Novel reaction type polyurethane hot melt adhesive and preparation method thereof - Google Patents
Novel reaction type polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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- CN109666436A CN109666436A CN201811475159.3A CN201811475159A CN109666436A CN 109666436 A CN109666436 A CN 109666436A CN 201811475159 A CN201811475159 A CN 201811475159A CN 109666436 A CN109666436 A CN 109666436A
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- 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
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- 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
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
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- 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
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- 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
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- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- 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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/635—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto unsaturated polymers
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- 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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/638—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers characterised by the use of compounds having carbon-to-carbon double bonds other than styrene and/or olefinic nitriles
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- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of novel reaction type polyurethane hot melt adhesive and preparation method thereof, feature be the polyether Glycols for including 1~40 part, 1~35 part of liquid polyesters dihydric alcohol, 1~35 part of crystalline polyester dihydric alcohol, 1~30 part containing the fluorine-containing siliceous copolymer of isocyanate-modified polyacrylic acid, 1~50 part of isocyanates, 0.01~1 part of catalyst, 0.01~1 part of antioxidant and 0.1~2 part of silane coupling agent.The present invention first uses free radical polymerization to synthesize the fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid, its chemical structure is: poly- (hexafluorobutyl acrylate-is random-and methacryloxypropyl list sealing end dimethyl polysiloxane-is random-and acrylic acid-2-ethyl caproite-is random-isocyanatoethyl), it adds it in base polyurethane prepolymer for use as and participates in chemical polycondensation reaction, introduce fluorine-containing Si acrylate copolymer segment, efficiently synergistic effect, show good compatibility, the other raw material compositions of a successive step of going forward side by side and content, it is ageing-resistant to improve synthesis, it is grease proofing, waterproof and solvent resistance.
Description
Technical field
The invention belongs to structure glue technical fields, and in particular to a kind of novel reaction type polyurethane hot melt adhesive and its preparation side
Method, 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 is 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 response type and enclosed type by its principle of solidification difference；
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,
It is cooled down after adherend bonding and forms excellent first adhesive property, then since substrate surface contains micro-moisture or other contain work
The compound for sprinkling hydrogen react with isocyano (- NCO) and chemical crosslink reaction occurs, thus generate with highly cross-linked network and
A kind of big structural bonding hot melt adhesive of cohesive force.
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.Chinese patent discloses one kind entitled " one
The application for a patent for invention of kind of reactive hot melt adhesive ", application number is 201480080313.0, is prepared a kind of with reprocessing
Removable polyurethane-hot melt adhesive, more suitable for high-end electronic product scope application.Chinese patent also discloses a kind of name
Referred to as the application for a patent for invention of " 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 reaction type polyurethane hot-melt adhesive, it is that " one kind has that Chinese patent, which discloses a kind of title,
The application for a patent for invention of machine silicon modified polyurethane sealant ", application number are 201710271725.8, prepare a kind of organosilicon and change
Property polyurethane sealant, with silane coupling agent replace isocyano (- NCO), be more suitable for applying under high humidity environment.Currently, reaction
The research and development technology of type polyurethane hot melt adhesive meets different type high-end electronic product scope application in fast development.Response type is poly-
Although urethane hot melt adhesive can form highly cross-linked network after hardening, there is also chemical corrosion resistance, heat resistance and
The deficiencies of ageing-resistant performance problem.This main cause is most of reaction type polyurethane hot-melt adhesives 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 resistance to chemical corrosion of polyurethane hot melt adhesive coating, heat resistance, resistance to
Ageing properties etc..
Summary of the invention
There is provided the purpose of the present invention is overcome the deficiencies in the prior art a kind of novel reaction type polyurethane hot melt adhesive and its
Preparation method can further improve polyurethane coating since novel reaction type polyurethane hot melt adhesive introduces silicon fluoride segment
Solvent resistance performance, heat resistance, ageing-resistant performance etc..
In order to achieve the above object, the technical solution of novel reaction type polyurethane hot melt adhesive of the invention is realized in
, it is characterised in that including 1~40 part of polyether Glycols, 1~35 part of liquid polyesters dihydric alcohol, 1~35 part of crystal type
Polyester diol, 1~30 part containing the fluorine-containing siliceous copolymer of isocyanate-modified polyacrylic acid, 1~50 part of isocyanates, 0.01
~1 part of catalyst, 0.01~1 part of antioxidant and 0.1~2 part of silane coupling agent, are mass fraction above；It is described to contain
The chemical structure of the isocyanate-modified fluorine-containing siliceous copolymer of polyacrylic acid is: poly- (hexafluorobutyl acrylate-is random-metering system
Monomethacryloxypropyl list block dimethyl polysiloxane-it is random-acrylic acid-2-ethyl caproite-is random-methacrylic acid isocyano group second
Ester) i.e. P(HFMA-r-MAPDMS-r-EHA-r-ICEMA), the number of the fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid is equal
Molecular weight 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 any group of polyadipate -1,4-butanediol esterdiol PEHA one or more
It closes；
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.
In order to achieve the above object, the technical solution of novel reaction type polyurethane hot melt adhesive preparation method of the invention is this
What sample was realized, preparation method is characterized in that:
Step 1: synthesis fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid
1~30 part of hexafluorobutyl acrylate HFMA, 1~30 part of methacryloxypropyl list are blocked into the poly- silicon oxygen of dimethyl
Alkane MAPDMS, 1~50 part of acrylic acid-2-ethyl caproite EHA and 1~10 part of isocyanatoethyl ICEMA are molten
Solution is in 50~100 parts of toluene, and temperature control is in 40~110 DEG C, 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, obtains containing isocyanate-modified poly-
The fluorine-containing siliceous copolymer of acrylic acid, the number-average molecular weight of the fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid is 1000~
50000；
Step 2: synthesizing new reaction type polyurethane hot-melt adhesive
By 1~40 part of polyether Glycols, 1~35 part of liquid polyesters dihydric alcohol, 1~35 part of crystalline polyester dihydric alcohol,
After 0.01~1 part of catalyst and the mixing of 0.01~1 part of antioxidant, 120~150 DEG C are calorified, water removal about 1~3 is vacuumized
Hour, until the water content of mixture is lower than 280ppm, cool down in 70~100 DEG C, under nitrogen protection, is added 1~50 part
Isocyanates and 1~30 part of the fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid, carry out polymerization reaction 1~10 it is small
When, sampling analysis polymerizate NCO% content reaches 1%~3%, and tested viscosity reaches 3000~15000 mPa.s at 100 DEG C, adds
Enter 0.1~2 part of silane coupling agent, obtains novel reaction type polyurethane hot melt adhesive, be above mass fraction.
In the technical scheme, the methacryloxypropyl list in step 1 blocks dimethyl polysiloxane MAPDMS's
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 present invention introduces fluorine silicon segment in base polyurethane prepolymer for use as, improves solvent resistance 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 the deficiencies of solving the problems, such as reaction type polyurethane hot-melt adhesive solvent resistance；
3, 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 adhesive and applies
The flow leveling of glue, 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 novel reaction type polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid
10 parts of hexafluorobutyl acrylate HFMA, 15 parts of methacryloxypropyl list are blocked into dimethyl polysiloxane
MAPDMS, 35 parts of acrylic acid-2-ethyl caproite EHA and 7 parts of isocyanatoethyl ICEMA are dissolved in 60 parts
In toluene, 90 DEG C are controlled in, under nitrogen protection, 1.9 parts of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester, polymerization is added
Reaction 7 hours after rotary evaporation removes toluene, obtains the fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid, contains isocyanic acid
The chemical structure of the ester modified fluorine-containing siliceous copolymer of polyacrylic acid is: poly- (hexafluorobutyl acrylate-is random-methacryloxypropyl third
Base list block dimethyl polysiloxane-it is random-acrylic acid-2-ethyl caproite-is random-isocyanatoethyl) i.e. P
(HFMA-r-MAPDMS-r-EHA-r-ICEMA), the number-average molecular weight of the fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid
It is 11200；Methacryloxypropyl list block dimethyl polysiloxane MAPDMS number-average molecular weight be 1000, No. CAS:
146632-07-7。
Step 2: synthesizing new reaction type polyurethane hot-melt adhesive
By 25 parts of polyoxypropyleneglycol PPG, 20 parts of polyethylene glycol adipate glycol PEA, 30 parts of crystalline polyester
After the phosphoric acid and 0.2 part of irgasfos 168 that 7320,0.1 parts of dihydric alcohol mix, 150 DEG C are calorified, vacuumizes water removal 1 hour, directly
Water content to mixture is lower than 280ppm, cools down in 70 DEG C, under nitrogen protection, 30 parts of modified diphenylmethane-is added
4,4 '-diisocyanate Desmodur CD-C(MDI performed polymers) and 10 parts of step 1 synthesis contain isocyanate-modified poly- third
The fluorine-containing siliceous copolymer of olefin(e) acid carries out polymerization reaction 2 hours, and sampling analysis polymerizate NCO% content reaches 2.5%, and viscosity reaches
5320 mPa.s, 0.6 part of silane coupling agent ND-42 is added, obtains novel reaction type polyurethane hot melt adhesive, is above matter
Measure number.The number-average molecular weight of polyoxypropyleneglycol PPG is 1000, the equal molecule of number of polyethylene glycol adipate glycol PEA
Amount is 500, and with Brookfield DV-C digital viscometer viscosity, test setting temperature is 100 DEG C.
Embodiment two
It is a kind of novel reaction type polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid
15 parts of hexafluorobutyl acrylate HFMA, 10 parts of methacryloxypropyl list are blocked into dimethyl polysiloxane
MAPDMS, 40 parts of acrylic acid-2-ethyl caproite EHA and 5 parts of isocyanatoethyl ICEMA are dissolved in 80 parts
In toluene, 100 DEG C are controlled in, under nitrogen protection, 1.5 parts of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added, gathers
Reaction 6 hours is closed, after rotary evaporation removes toluene, the fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid is obtained, contains isocyanide
The chemical structure of the fluorine-containing siliceous copolymer of acid esters modified polyacrylic acid is: poly- (hexafluorobutyl acrylate-is random-methacryloxypropyl
Propyl list block dimethyl polysiloxane-it is random-acrylic acid-2-ethyl caproite-is random-isocyanatoethyl) i.e. P
(HFMA-r-MAPDMS-r-EHA-r-ICEMA), the number-average molecular weight of the fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid
It is 17000；Methacryloxypropyl list block dimethyl polysiloxane MAPDMS number-average molecular weight be 1000, No. CAS:
146632-07-7。
Step 2: synthesizing new reaction type polyurethane hot-melt adhesive
By 20 parts of polytetrahydrofuran ether glycol PTMG, 15 parts of polyadipate -1,6- hexylene glycol esterdiol PHA, 30 parts of knot
After the triethanolamine and 0.5 part of irgasfos 168 that 7360,0.4 parts of crystalline polyester dihydric alcohol mix, 140 DEG C are calorified, is vacuumized
Water removal 2.5 hours cools down until the water content of mixture is lower than 280ppm in 80 DEG C, under nitrogen protection, is added 40 parts
Modified diphenylmethane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer) and 20 parts of step 1 synthesis contain isocyanide
The fluorine-containing siliceous copolymer of acid esters modified polyacrylic acid carries out polymerization reaction 4 hours, and sampling analysis polymerizate NCO% content reaches
2.5%, viscosity (100 DEG C of mPa.s@, Brookfield DV-C Digital Viscometer) reaches 7650 mPa.s, and 1.5 parts of silicon is added
Alkane coupling agent ND-42 obtains novel reaction type polyurethane hot melt adhesive, is above mass fraction.Polytetrahydrofuran ether glycol
The number-average molecular weight of PTMG is 2000, and the number-average molecular weight of polyadipate -1,6- hexylene glycol esterdiol PHA is 1000, is used
Brookfield DV-C digital viscometer viscosity, test setting temperature are 100 DEG C.
Embodiment three
It is a kind of novel reaction type polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid
20 parts of hexafluorobutyl acrylate HFMA, 20 parts of methacryloxypropyl list are blocked into dimethyl polysiloxane
MAPDMS, 45 parts of acrylic acid-2-ethyl caproite EHA and 8 parts of isocyanatoethyl ICEMA are dissolved in 85 parts
In toluene, 95 DEG C are controlled in, under nitrogen protection, 0.5 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester, polymerization is added
Reaction 10 hours after rotary evaporation removes toluene, obtains the fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid, contains isocyanic acid
The chemical structure of the ester modified fluorine-containing siliceous copolymer of polyacrylic acid is: poly- (hexafluorobutyl acrylate-is random-methacryloxypropyl third
Base list block dimethyl polysiloxane-it is random-acrylic acid-2-ethyl caproite-is random-isocyanatoethyl) i.e. P
(HFMA-r-MAPDMS-r-EHA-r-ICEMA), the number-average molecular weight of the fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid
It is 28000；Methacryloxypropyl list block dimethyl polysiloxane MAPDMS number-average molecular weight be 1000, No. CAS:
146632-07-7。
Step 2: synthesizing new reaction type polyurethane hot-melt adhesive
By 35 parts of polyoxypropyleneglycol PPG, 25 parts of polyethylene glycol adipate glycol PEA, 20 parts of crystalline polyester
After 7360,0.3 parts of dihydric alcohol of 2,2- dimorpholine base Anaesthetie Ether and the mixing of 0.3 part of antioxidant 1010,150 DEG C are calorified,
Water removal 3 hours is vacuumized, until the water content of mixture is lower than 280ppm, cools down in 80 DEG C, under nitrogen protection, is added 40
Part modified diphenylmethane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer) and 25 parts of step 1 containing of synthesizing
The isocyanate-modified fluorine-containing siliceous copolymer of polyacrylic acid carries out polymerization reaction 6 hours, and sampling analysis polymerizate NCO% content reaches
To 2.2%, viscosity (100 DEG C of mPa.s@, Brookfield DV-C Digital Viscometer) 9500 mPa.s, 1.4 parts of silane is added
Coupling agent ND-42 obtains novel reaction type polyurethane hot melt adhesive, is above mass fraction.The number of polyoxypropyleneglycol PPG
Average molecular weight is 3000, and the number-average molecular weight of polyethylene glycol adipate glycol PEA is 1500, with Brookfield DV-C number
Word viscosity meter viscosity, test setting temperature are 100 DEG C.
Example IV
It is a kind of novel reaction type polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1: synthesis fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid
25 parts of hexafluorobutyl acrylate HFMA, 25 parts of methacryloxypropyl list are blocked into dimethyl polysiloxane
MAPDMS, 50 parts of acrylic acid-2-ethyl caproite EHA and 9 parts of isocyanatoethyl ICEMA are dissolved in 100 parts
Toluene in, be controlled in 100 DEG C, under nitrogen protection, 0.2 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester be added,
Polymerization reaction 5 hours, after rotary evaporation removes toluene, the fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid is obtained, containing different
The chemical structure of the cyanate modified fluorine-containing siliceous copolymer of polyacrylic acid is: poly- (hexafluorobutyl acrylate-is random-methacryl
Oxygen propyl group list block dimethyl polysiloxane-it is random-acrylic acid-2-ethyl caproite-is random-isocyanatoethyl)
That is P(HFMA-r-MAPDMS-r-EHA-r-ICEMA), the equal molecule of the number of the fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid
Amount is 36000；Methacryloxypropyl list block dimethyl polysiloxane MAPDMS number-average molecular weight be 1000, No. CAS:
146632-07-7。
Step 2: synthesizing new reaction type polyurethane hot-melt adhesive
By 25 parts of polyoxypropyleneglycol PPG, 20 parts of polyadipate -1,4-butanediol esterdiol PEHA, 25 parts of crystallization
After the triethanolamine and 0.8 part of irgasfos 168 that 7380,0.2 parts of type polyester diol mix, 150 DEG C are calorified, vacuumizes and removes
Water 2 hours, until the water content of mixture is lower than 280ppm, cools down in 90 DEG C, under nitrogen protection, 45 parts of modification is added
Diphenyl-methane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer) and 30 parts of step 1 synthesis contain isocyanates
The fluorine-containing siliceous copolymer of modified polyacrylic acid carries out polymerization reaction 3 hours, and sampling analysis polymerizate NCO% content reaches 2.6%,
0.7 part of silane coupling agent is added in viscosity (100 DEG C of mPa.s@, Brookfield DV-C Digital Viscometer) 11200 mPa.s
ND-42 obtains novel reaction type polyurethane hot melt adhesive, is above mass fraction.The equal molecule of the number of polyoxypropyleneglycol PPG
Amount is 4000, and polyadipate -1,4-butanediol esterdiol PEHA number-average molecular weight is 2000, with Brookfield DV-C number
Word viscosity meter viscosity, test setting temperature are 100 DEG C.
Performance test
Universal method of the present invention referring to current hot melt adhesive, the novel reaction type polyurethane heat that the four kinds of above embodiments are obtained
Melten gel carry out melt viscosity, the open hour, shore hardness, elongation at break, shear strength and 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, is arranged 100 DEG C.Open hour are referring to ASTM
D4497-1994 (2004) method is tested.Shore hardness is tested referring to GB-T2411-2008 standard.Elongation at break
It is tested referring to GB/T30776-2014 standard.Shear strength is tested referring to GB/T7124-2004 standard.Solvent resistance
The energy specific test method of index is that sample is prepared with reference to test shear strength method, after sample places solidification in 72 hours, by sample
Product are soaked in oleic acid (purity 98%) solution 24 hours, take out sample, are placed under 85 DEG C and 85% relative humidity conditions, carry out old
After changing 1000 hours, then carry out shear strength test.Oleic acid and water contact angle are surveyed with reference to GB/T 30693-2014 standard
Examination.All test data comparative situations are see the following table 1.
Each embodiment specific performance of table 1 tests control case
Can be seen that the novel reaction type polyurethane hot melt adhesive that the present invention synthesizes from the data of table 1 has excellent solvent resistance
Energy, ageing-resistant performance, oil preventing performance and waterproof performance.
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 novel reaction type polyurethane hot melt adhesive, it is characterised in that including 1~40 part of polyether Glycols, 1~35 part
Liquid polyesters dihydric alcohol, 1~35 part of crystalline polyester dihydric alcohol, 1~30 part containing isocyanate-modified polyacrylic acid it is fluorine-containing
Siliceous copolymer, 1~50 part of isocyanates, 0.01~1 part of catalyst, 0.01~1 part of antioxidant and 0.1~2 part of silicon
Alkane coupling agent is mass fraction above；The chemical structure of the fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid is:
Poly- (hexafluorobutyl acrylate-is random-and methacryloxypropyl list sealing end dimethyl polysiloxane-is random-acrylic acid -2- second
The own ester-of base is random-isocyanatoethyl) i.e. P(HFMA-r-MAPDMS-r-EHA-r-ICEMA) and, contain isocyanates
The number-average molecular weight of the fluorine-containing siliceous copolymer of modified polyacrylic acid is 1000~50000.
2. novel reaction type 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 any group of polyadipate -1,4-butanediol esterdiol PEHA one or more
It closes；
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.
3. a kind of preparation method of novel reaction type polyurethane hot melt adhesive, preparation method are characterized in that:
Step 1: synthesis fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid
1~30 part of hexafluorobutyl acrylate HFMA, 1~30 part of methacryloxypropyl list are blocked into the poly- silicon oxygen of dimethyl
Alkane MAPDMS, 1~50 part of acrylic acid-2-ethyl caproite EHA and 1~10 part of isocyanatoethyl ICEMA are molten
Solution is in 50~100 parts of toluene, and temperature control is in 40~110 DEG C, 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, obtains containing isocyanate-modified poly-
The fluorine-containing siliceous copolymer of acrylic acid, the number-average molecular weight of the fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid is 1000~
50000；
Step 2: synthesizing new reaction type polyurethane hot-melt adhesive
By 1~40 part of polyether Glycols, 1~35 part of liquid polyesters dihydric alcohol, 1~35 part of crystalline polyester dihydric alcohol,
After 0.01~1 part of catalyst and the mixing of 0.01~1 part of antioxidant, 120~150 DEG C are calorified, water removal about 1~3 is vacuumized
Hour, until the water content of mixture is lower than 280ppm, cool down in 70~100 DEG C, under nitrogen protection, is added 1~50 part
Isocyanates and 1~30 part of the fluorine-containing siliceous copolymer containing isocyanate-modified polyacrylic acid, carry out polymerization reaction 1~10 it is small
When, sampling analysis polymerizate NCO% content reaches 1%~3%, and tested viscosity reaches 3000~15000 mPa.s at 100 DEG C, adds
Enter 0.1~2 part of silane coupling agent, obtains novel reaction type polyurethane hot melt adhesive, be above mass fraction.
4. the preparation method of novel reaction type polyurethane hot melt adhesive according to claim 3, it is characterised in that in step 1
Methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS number-average molecular weight be 1000, No. CAS: 146632-
07-7。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1845943A (en) * | 2003-06-09 | 2006-10-11 | 国家淀粉及化学投资控股公司 | Moisture curing reactive polyurethane hot melt adhesives modified with acrylic polymers |
| 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 |
| CN105601797A (en) * | 2015-12-31 | 2016-05-25 | 徐宪 | Environment-friendly fluorine-containing nanometer positive ion acrylic ester polymer emulsion and preparation method thereof |
-
2018
- 2018-12-04 CN CN201811475159.3A patent/CN109666436A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1845943A (en) * | 2003-06-09 | 2006-10-11 | 国家淀粉及化学投资控股公司 | Moisture curing reactive polyurethane hot melt adhesives modified with acrylic polymers |
| 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 |
| CN105601797A (en) * | 2015-12-31 | 2016-05-25 | 徐宪 | Environment-friendly fluorine-containing nanometer positive ion acrylic ester polymer emulsion and preparation method thereof |
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Application publication date: 20190423 |