CN109679559A - The excellent damp solidifying polyurethane hot melt adhesive and preparation method thereof of oil resistance - Google Patents
The excellent damp solidifying polyurethane hot melt adhesive and preparation method thereof of oil resistance Download PDFInfo
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- CN109679559A CN109679559A CN201811474045.7A CN201811474045A CN109679559A CN 109679559 A CN109679559 A CN 109679559A CN 201811474045 A CN201811474045 A CN 201811474045A CN 109679559 A CN109679559 A CN 109679559A
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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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- C09J175/06—Polyurethanes from polyesters
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- 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
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- 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
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- 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
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- C08G18/40—High-molecular-weight compounds
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- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
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- C08G18/40—High-molecular-weight compounds
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- 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
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- 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
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- 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
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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Abstract
The invention discloses a kind of damp solidifying polyurethane hot melt adhesive and preparation method thereof that oil resistance is excellent, feature is the polyether Glycols for including 1~35 part, 1~40 part of liquid polyesters dihydric alcohol, 1~60 part of crystalline polyester dihydric alcohol, 1~45 part of polyacrylic acid fluorinated copolymer, 1~50 part of isocyanates, 0.1~2 part of catalyst, 0.1~3 part of antioxidant and 0.1~4 part of silane coupling agent.The present invention first synthesizes poly- (dodecafluoroheptyl methacrylate-is random-methyl methacrylate-is random-octadecyl methacrylate-is random-hydroxyethyl methacrylate), it is added in polyurethane prepolymer precursor reactant, hydroxy acryl acid function monomer can be by polyacrylic acid fluorinated copolymer subparticipation to base polyurethane prepolymer for use as synthetic reaction, introduce fluoro-acrylate copolymer segment, formula efficiently acts synergistically, show preferable compatibility, the other raw material compositions of a successive step of going forward side by side and content, improve polyurethane hot melt oil resistance.
Description
Technical field
The invention belongs to structure glue technical fields, and in particular to a kind of damp solidifying polyurethane that oil resistance is excellent hot melt
Glue and preparation method thereof, which are mainly applied to electronics and appliance industry, automobile industry, weaving and shoe industry, food packing industry, timber
Material processing and furniture industry isostructuralism are bonded field.
Background technique
Polyurethane hot melt be a new generation can provide superior adhesion can structure glue, it is to be with polyurethane prepolymer
Material of main part is equipped with a hot melt adhesive prepared by various auxiliary agents.Polyurethane hot melt is easy to use, environmentally friendly, and performance again can be with
Solvent-based thermal melten gel compares favourably.Nearly ten years, polyurethane hot melt is obtained in the high-end fields such as electronics and appliance industry, automobile industry
It is fast-developing and be widely used.Polyurethane hot melt can be divided into thermoplastic polyurethane elastomer hot melt adhesive by cured form difference
And reactive polyurethane hot melt, reactive polyurethane hot melt can be divided into 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 heat for establishing adhesive property polyacrylate and polyester preparation of low toxicity
Melten gel adhesive.In order to improve the cured form of reaction type polyurethane hot-melt adhesive, Chinese patent discloses a kind of entitled " a kind of
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.
Fluorine atom is claimed with the high molecular material prepared after hydrogen atom in the c h bond on the substituted polymer main side chain of C-F key
For fluoropolymer, such fluoropolymer has excellent weather resistance, water-fast compared to common fats hydrocarbon-based polymeric resin
Performance, chemical resistance etc..Fluoropolymer-containing to have excellent performance the fluorine carbon key mostly come from strand, fluorine atom electricity is negative
Property it is high, cause the fluorine atom on zigzag the high-polymer molecule main chain (C-C chain) to be spirally distributed, effectively shield and protect
The molecular backbone of high polymer is protected, therefore fluoropolymer shows excellent physical property.
Currently, the research and development technology of reaction type polyurethane hot-melt adhesive meets different type high-end electronic product in fast development
Field application.Although reaction type polyurethane hot-melt adhesive can form highly cross-linked network after hardening, there is also oil resistivitys
The performances deficiency problems such as energy, chemicals-resistant corrosivity.This main cause is most of reaction type polyurethane hot-melt adhesives to improve
Its initial cohesiveness joined a large amount of non-reacted thermoplasticity thickening resin or polynary acrylic copolymer.These non-reactants
System's thickening resin can not participate in solidification and generate cross-linked network, to easily reduce the oil resistance of polyurethane hot melt adhesive coating, resistance toization
Product corrosive nature, ageing-resistant performance etc..
Summary of the invention
A kind of poly- ammonia of the moisture-curable that oil resistance is excellent is provided the purpose of the present invention is overcome the deficiencies in the prior art
Ester hot melt adhesive and preparation method thereof can since the excellent damp solidifying polyurethane hot melt adhesive of oil resistance introduces fluorine-containing groups
Further improve oil resistance, the chemicals-resistant corrosivity performance heat resistance etc. of polyurethane coating.
In order to achieve the above object, the technical solution of the excellent damp solidifying polyurethane hot melt adhesive of oil resistance of the invention
It is achieved in that it is characterized by comprising 1~35 part of polyether Glycols, 1~40 part of liquid polyesters dihydric alcohol, 1~60
Part crystalline polyester dihydric alcohol, 1~45 part of polyacrylic acid fluorinated copolymer, 1~50 part of isocyanates, 0.1~2 part
Catalyst, 0.1~3 part of antioxidant and 0.1~4 part of silane coupling agent, are mass fraction above；The polyacrylic acid contains
The chemical structure of fluo-copolymer is: poly- (dodecafluoroheptyl methacrylate-is random-and methyl methacrylate-is random-methyl-prop
Olefin(e) acid octadecyl ester-is random-hydroxyethyl methacrylate) i.e. P(DFMA-r-MMA-r-SMA-r-HEMA) and, polyacrylic acid is fluorine-containing total
The number-average molecular weight of polymers 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 PSMA 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, oil resistance of the invention excellent damp solidifying polyurethane hot melt adhesive preparation method
Technical solution is achieved in that it is characterized in that preparation step is as follows:
Step 1: synthesis polyacrylic acid fluorinated copolymer
By 1~40 part of dodecafluoroheptyl methacrylate DFMA, 1~40 part of methyl methacrylate MMA, 1~40 part
Octadecyl methacrylate SMA and 1~10 part of hydroxyethyl methacrylate HEMA are dissolved in 50~100 parts of toluene, control
40~110 DEG C are formed on, under nitrogen protection, 0.1~2 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester, polymerization is added
Reaction 2~50 hours after rotary evaporation removes toluene, obtains polyacrylic acid fluorinated copolymer, polyacrylic acid fluorinated copolymer
Number-average molecular weight is 1000~50000；
Step 2: the excellent damp solidifying polyurethane hot melt adhesive of synthesis oil resistance
By 1~35 part of polyether Glycols, 1~40 part of liquid polyesters dihydric alcohol, 1~60 part of crystalline polyester dihydric alcohol, 1
After~45 parts of polyacrylic acid fluorinated copolymer, 0.1~2 part of catalyst and the mixing of 0.1~3 part of antioxidant, 120 are calorified
~150 DEG C, water removal about 1~3 hour is vacuumized, until the water content of mixture is lower than 280ppm, is cooled down in 70~100 DEG C,
Under nitrogen protection, 1~50 part of isocyanates is added, carries out polymerization reaction 1~10 hour, sampling analysis, polymerizate
NCO% content reaches 1%~3%, and tested viscosity reaches 3000~15000 mPa.s at 100 DEG C, and it is even that 0.1~4 part of silane is added
Join agent, obtains the excellent damp solidifying polyurethane hot melt adhesive of oil resistance, be 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 solves traditional insufficient defect of reaction type polyurethane hot-melt adhesive oil resistance, by base polyurethane prepolymer for use as
In introduce fluorine-containing groups, improve polyurethane hot melt oil resistance；
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 chemical resistance deficiency；
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 damp solidifying polyurethane hot melt adhesive that oil resistance is excellent, is prepared by the following steps to obtain:
Step 1: synthesis polyacrylic acid fluorinated copolymer
By 20 parts of dodecafluoroheptyl methacrylate DFMA, 20 parts of methyl methacrylate MMA, 20 parts of methacrylic acid
Octadecyl ester SMA and 4 parts of hydroxyethyl methacrylate HEMA are dissolved in 60 parts of toluene, 85 DEG C are controlled in, in nitrogen protection
Under, 1.9 parts of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added, polymerization reaction 30 hours, rotary evaporation removed toluene
Afterwards, polyacrylic acid fluorinated copolymer is obtained, the number-average molecular weight of polyacrylic acid fluorinated copolymer is 14000, and chemical structure is:
Poly- (dodecafluoroheptyl methacrylate-is random-and methyl methacrylate-is random-and octadecyl methacrylate-is random-methyl-prop
Olefin(e) acid hydroxyl ethyl ester) i.e. P(DFMA-r-MMA-r-SMA-r-HEMA).
Step 2: the excellent damp solidifying polyurethane hot melt adhesive of synthesis oil resistance
By 20 parts of polyoxypropyleneglycol PPG, 15 parts of polyethylene glycol adipate glycol PEA, 25 parts of crystalline polyester
Polyacrylic acid fluorinated copolymer, 0.1 part of phosphoric acid and 0.1 part of the irgasfos 168 of 7320,20 parts of step 1 of dihydric alcohol synthesis are mixed
After conjunction, calorify 150 DEG C, vacuumize water removal 1 hour, until mixture water content be lower than 280ppm, cool down in 70 DEG C,
Under nitrogen protection, 25 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer of modified diphenylmethane-is added), into
Row polymerization reaction 3 hours, sampling analysis polymerizate NCO% content reached 2.1%, and viscosity reaches 5300 mPa.s, it is added 0.8
The silane coupling agent ND-42 of part obtains the excellent damp solidifying polyurethane hot melt adhesive of oil resistance, is above mass fraction.
1000) number-average molecular weight of polyoxypropyleneglycol PPG is that the number-average molecular weight of polyethylene glycol adipate glycol PEA is
500, with Brookfield DV-C digital viscometer viscosity, test setting temperature is 100 DEG C.
Embodiment two
It is a kind of damp solidifying polyurethane hot melt adhesive that oil resistance is excellent, is prepared by the following steps to obtain:
Step 1: synthesis polyacrylic acid fluorinated copolymer
By 25 parts of dodecafluoroheptyl methacrylate DFMA, 30 parts of methyl methacrylate MMA, 10 parts of methacrylic acid
Octadecyl ester SMA and 6 parts of hydroxyethyl methacrylate HEMA are dissolved in 70 parts of toluene, 90 DEG C are controlled in, in nitrogen protection
Under, 1.7 parts of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added, polymerization reaction 20 hours, rotary evaporation removed toluene
Afterwards, polyacrylic acid fluorinated copolymer is obtained, the number-average molecular weight of polyacrylic acid fluorinated copolymer is 22000, and chemical structure is:
Poly- (dodecafluoroheptyl methacrylate-is random-and methyl methacrylate-is random-and octadecyl methacrylate-is random-methyl-prop
Olefin(e) acid hydroxyl ethyl ester) i.e. P(DFMA-r-MMA-r-SMA-r-HEMA).
Step 2: the excellent damp solidifying polyurethane hot melt adhesive of synthesis oil resistance
By 30 parts of polytetrahydrofuran ether glycol PTMG, 20 parts of polyadipate -1,6- hexylene glycol esterdiol PHA, 25 parts of knot
Polyacrylic acid fluorinated copolymer, 0.3 part of triethanolamine and 0.2 part of 7360,25 parts of step 1 of crystalline polyester dihydric alcohol synthesis
Irgasfos 168 mixing after, calorify 140 DEG C, vacuumize water removal 2.5 hours, until the water content of mixture is lower than
280ppm cools down in 80 DEG C, under nitrogen protection, 35 parts of 4,4 '-diisocyanate of modified diphenylmethane-is added
Desmodur CD-C(MDI performed polymer), it carries out polymerization reaction 6 hours, sampling analysis polymerizate NCO% content reaches 2.3%,
Viscosity reaches 6900 mPa.s, and 0.4 part of silane coupling agent ND-42 is added, and obtains the excellent poly- ammonia of moisture-curable of oil resistance
Ester hot melt adhesive is mass fraction above.The number-average molecular weight of polytetrahydrofuran ether glycol PTMG is 2000, polyadipate -1,
The number-average molecular weight of 6- hexylene glycol esterdiol PHA is 1000, with Brookfield DV-C digital viscometer viscosity, test
It is 100 DEG C that temperature, which is arranged,.
Embodiment three
It is a kind of damp solidifying polyurethane hot melt adhesive that oil resistance is excellent, is prepared by the following steps to obtain:
Step 1: synthesis polyacrylic acid fluorinated copolymer
By 35 parts of dodecafluoroheptyl methacrylate DFMA, 30 parts of methyl methacrylate MMA, 20 parts of methacrylic acid
Octadecyl ester SMA and 8 parts of hydroxyethyl methacrylate HEMA are dissolved in 90 parts of toluene, 95 DEG C are controlled in, in nitrogen protection
Under, 0.7 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added, polymerization reaction 10 hours, rotary evaporation removed toluene
Afterwards, polyacrylic acid fluorinated copolymer is obtained, the number-average molecular weight of polyacrylic acid fluorinated copolymer is 32000, and chemical structure is:
Poly- (dodecafluoroheptyl methacrylate-is random-and methyl methacrylate-is random-and octadecyl methacrylate-is random-methyl-prop
Olefin(e) acid hydroxyl ethyl ester) i.e. P(DFMA-r-MMA-r-SMA-r-HEMA).
Step 2: the excellent damp solidifying polyurethane hot melt adhesive of synthesis oil resistance
By 25 parts of polyoxypropyleneglycol PPG, 27 parts of polyethylene glycol adipate glycol PEA, 35 parts of crystalline polyester
7360,30 parts of step 1 of dihydric alcohol synthesis polyacrylic acid fluorinated copolymer, 0.3 part of 2,2- dimorpholine base Anaesthetie Ether and
After 0.3 part of antioxidant 1010 mixing, 150 DEG C are calorified, water removal 2 hours is vacuumized, until the water content of mixture is lower than
280ppm cools down in 80 DEG C, under nitrogen protection, 40 parts of 4,4 '-diisocyanate of modified diphenylmethane-is added
Desmodur CD-C(MDI performed polymer), it carries out polymerization reaction 7 hours, sampling analysis polymerizate NCO% content reaches 2.5%,
Viscosity reaches 7700 mPa.s, and 0.4 part of silane coupling agent ND-42 is added, and obtains the excellent poly- ammonia of moisture-curable of oil resistance
Ester hot melt adhesive is mass fraction above.The number-average molecular weight of polyoxypropyleneglycol PPG is 3000, polyadipate ethylene glycol
The number-average molecular weight of esterdiol PEA is 1500, with Brookfield DV-C digital viscometer viscosity, test setting temperature
It is 100 DEG C.
Example IV
It is a kind of damp solidifying polyurethane hot melt adhesive that oil resistance is excellent, is prepared by the following steps to obtain:
Step 1: synthesis polyacrylic acid fluorinated copolymer
By 40 parts of dodecafluoroheptyl methacrylate DFMA, 20 parts of methyl methacrylate MMA, 20 parts of methacrylic acid
Octadecyl ester SMA) 8 parts of hydroxyethyl methacrylate HEMA is dissolved in 100 parts of toluene, is controlled in 100 DEG C, protects in nitrogen
Under shield, 0.3 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester is added, polymerization reaction 8 hours, rotary evaporation removed toluene
Afterwards, polyacrylic acid fluorinated copolymer is obtained, the number-average molecular weight of polyacrylic acid fluorinated copolymer is 42000, and chemical structure is:
Poly- (dodecafluoroheptyl methacrylate-is random-and methyl methacrylate-is random-and octadecyl methacrylate-is random-methyl-prop
Olefin(e) acid hydroxyl ethyl ester) i.e. P(DFMA-r-MMA-r-SMA-r-HEMA).
Step 2: the excellent damp solidifying polyurethane hot melt adhesive of synthesis oil resistance
By 30 parts of polyoxypropyleneglycol PPG, 30 parts of polyadipate -1,4-butanediol esterdiol PSMA, 45 parts of crystallization
The polyacrylic acid fluorinated copolymer of 7380,40 parts of step 1 of type polyester diol synthesis, 0.5 part of triethanolamine and 0.6 part
After irgasfos 168 mixing, 150 DEG C are calorified, vacuumizes water removal 2 hours, until the water content of mixture is lower than 280ppm, drop
Temperature is in 90 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 3 hours, and sampling analysis polymerizate NCO% content reaches 2.7%, and viscosity reaches 8900
0.4 part of silane coupling agent ND-42 is added in mPa.s, obtains the excellent damp solidifying polyurethane hot melt adhesive of oil resistance, above
It is mass fraction.The number-average molecular weight of polyoxypropyleneglycol PPG is 4000, polyadipate -1,4-butanediol esterdiol
The number-average molecular weight of PSMA is 2000, and with Brookfield DV-C digital viscometer viscosity, test setting temperature is 100
℃。
Performance test
Universal method of the present invention referring to current hot melt adhesive, the excellent moisture of the oil resistance that the four kinds of above embodiments are obtained
Solidify polyurethane hot melt carry out melt viscosity, the open hour, shore hardness, elongation at break, shear strength and with resistance to oleic acid
Testing performance index.Melt viscosity is tested referring to HG/T3660-1999 standard, selects No. 27 rotors, is arranged 100 DEG C.It opens
Put the time is tested referring to ASTM D4497-1994 (2004) method.Shore hardness is carried out referring to GB-T2411-2008 standard
Test.Elongation at break is tested referring to GB/T30776-2014 standard.Shear strength referring to GB/T7124-2004 standard into
Row test.The specific test method of solvent 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.Oleic acid contact angle refers to GB/T 30693-2014
Standard is tested, and is tested with oleic acid.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 excellent damp solidifying polyurethane hot melt adhesive of the oil resistance of the invention synthesized with excellent from the data of table 1
Good oil resistance and chemicals-resistant corrosive nature.
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 damp solidifying polyurethane hot melt adhesive that oil resistance is excellent, it is characterised in that including 1~35 part of polyethers binary
Alcohol, 1~40 part of liquid polyesters dihydric alcohol, 1~60 part of crystalline polyester dihydric alcohol, 1~45 part of polyacrylic acid are fluorine-containing total
Polymers, 1~50 part of isocyanates, 0.1~2 part of catalyst, 0.1~3 part of antioxidant and 0.1~4 part it is silane coupled
Agent is mass fraction above；The chemical structure of the polyacrylic acid fluorinated copolymer is: poly- (ten difluoro heptan of methacrylic acid
Ester-is random-and methyl methacrylate-is random-and octadecyl methacrylate-is random-hydroxyethyl methacrylate) i.e. P(DFMA-
R-MMA-r-SMA-r-HEMA), the number-average molecular weight of polyacrylic acid fluorinated copolymer is 1000~50000.
2. the excellent damp solidifying polyurethane hot melt adhesive of oil resistance 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 PSMA 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 damp solidifying polyurethane hot melt adhesive preparation method that oil resistance is excellent, it is characterised in that preparation step is as follows:
Step 1: synthesis polyacrylic acid fluorinated copolymer
By 1~40 part of dodecafluoroheptyl methacrylate DFMA, 1~40 part of methyl methacrylate MMA, 1~40 part
Octadecyl methacrylate SMA and 1~10 part of hydroxyethyl methacrylate HEMA are dissolved in 50~100 parts of toluene, control
40~110 DEG C are formed on, under nitrogen protection, 0.1~2 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester, polymerization is added
Reaction 2~50 hours after rotary evaporation removes toluene, obtains polyacrylic acid fluorinated copolymer, polyacrylic acid fluorinated copolymer
Number-average molecular weight is 1000~50000；
Step 2: the excellent damp solidifying polyurethane hot melt adhesive of synthesis oil resistance
By 1~35 part of polyether Glycols, 1~40 part of liquid polyesters dihydric alcohol, 1~60 part of crystalline polyester dihydric alcohol, 1
After~45 parts of polyacrylic acid fluorinated copolymer, 0.1~2 part of catalyst and the mixing of 0.1~3 part of antioxidant, 120 are calorified
~150 DEG C, water removal about 1~3 hour is vacuumized, until the water content of mixture is lower than 280ppm, is cooled down in 70~100 DEG C,
Under nitrogen protection, 1~50 part of isocyanates is added, carries out polymerization reaction 1~10 hour, sampling analysis, polymerizate
NCO% content reaches 1%~3%, and tested viscosity reaches 3000~15000 mPa.s at 100 DEG C, and it is even that 0.1~4 part of silane is added
Join agent, obtains the excellent damp solidifying polyurethane hot melt adhesive of oil resistance, be above mass fraction.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110885663A (en) * | 2019-11-26 | 2020-03-17 | 塔威新材料科技(上海)有限公司 | UV (ultraviolet) moisture dual-curing reaction type polyurethane hot melt adhesive composition |
| CN112708387A (en) * | 2020-12-25 | 2021-04-27 | 烟台德邦科技股份有限公司 | PFPE modified polyurethane single-component hot melt adhesive and preparation method thereof |
| CN115124686A (en) * | 2022-08-31 | 2022-09-30 | 拓迪化学(上海)有限公司 | Adhesive and insulating adhesive of lithium ion battery and preparation method and application thereof |
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|---|---|---|---|---|
| CN104245769A (en) * | 2012-04-12 | 2014-12-24 | Dic株式会社 | Moisture-curable polyurethane hot melt resin composition, adhesive and article |
| 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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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104245769A (en) * | 2012-04-12 | 2014-12-24 | Dic株式会社 | Moisture-curable polyurethane hot melt resin composition, adhesive and article |
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110885663A (en) * | 2019-11-26 | 2020-03-17 | 塔威新材料科技(上海)有限公司 | UV (ultraviolet) moisture dual-curing reaction type polyurethane hot melt adhesive composition |
| CN112708387A (en) * | 2020-12-25 | 2021-04-27 | 烟台德邦科技股份有限公司 | PFPE modified polyurethane single-component hot melt adhesive and preparation method thereof |
| CN112708387B (en) * | 2020-12-25 | 2022-10-21 | 烟台德邦科技股份有限公司 | PFPE modified polyurethane single-component hot melt adhesive and preparation method thereof |
| CN115124686A (en) * | 2022-08-31 | 2022-09-30 | 拓迪化学(上海)有限公司 | Adhesive and insulating adhesive of lithium ion battery and preparation method and application thereof |
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