CN107384293A - A kind of preparation method of thermoplastic polyurethane hot melt adhesive - Google Patents
A kind of preparation method of thermoplastic polyurethane hot melt adhesive Download PDFInfo
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- CN107384293A CN107384293A CN201710507344.5A CN201710507344A CN107384293A CN 107384293 A CN107384293 A CN 107384293A CN 201710507344 A CN201710507344 A CN 201710507344A CN 107384293 A CN107384293 A CN 107384293A
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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
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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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
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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
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
- C08G18/70—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
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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
- 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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- 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
- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to a kind of preparation method of thermoplastic polyurethane hot melt adhesive, step are as follows：Polyethylene glycol, polytetrahydrofuran diol, PEPA, antioxidant, hydrolysis-resisting agent are placed in reaction in reactor and obtain polyol component；Polyol component and the isocyanates of metering are reacted when NCO content is less than theoretical value, the hydroxyethyl methacrylate reaction of metering is added dropwise, when NCO content is less than theoretical value, add the light trigger measured, BDO and TMP mixed chain extender, vacuumize removing bubble to terminate to react, obtain performed polymer；By certain mass than performed polymer, BDO and TMP mixed chain extender, catalyst, light trigger and polymerization inhibitor it is well mixed after, polyurethane hot melt is prepared.The thermoplastic polyurethane hot melt adhesive prepared using the inventive method has melt viscosity low, and melting range is wide, the good combination property such as intensity height.
Description
Technical field
The present invention relates to macromolecule material preparation area, and in particular to a kind of preparation side of thermoplastic polyurethane hot melt adhesive
Method.
Background technology
Thermoplastic polyurethane hot melt adhesive is a kind of environment-friendly adhesive, and development and application is more fast in the world at present
A kind of novel adhesive of speed.There is adhesive strength height, high temperature resistant simultaneously, resist cold, can reuse, combination property is excellent
Different, operating procedure is easy, without solvent；Because product itself is solid-state, it is easy to pack, transports, stores, pollution-free, solidification
The features such as speed is fast and enjoy favor.
PUR polyurethane elastomer is by line style or with a small amount of side chain polyether Glycols, low relative molecular mass
Chain extender and isocyanates react, raw catenulate high-molecular compound, then along with other tackifying resins are modified.Use
When be heated to certain temperature melt after be coated on substrate surface, solidify after cooling, solidification process mainly using hydrogen bond action send out
Raw physical solidification, it has, and adhesion strength is high, the performance such as low temperature resistant, wear-resisting, heat-resisting and solvent resistant.
From the point of view of existing research report, polyurethane hot melt is broadly divided into 2 classes：1st class is thermoplastic polyurethane hot melt
Glue, first prepares linear polyester, heats fusion coating in substrate surface during use, hydrogen bond action is utilized through cooling and solidifying
It is physical crosslinking and produces cementation, cooling and solidifying can be heated repeatedly, but adhesive strength is not high；2nd class is Reactive hot melt adhesive,
The polyurethane adhesive of the end group containing NCO is first prepared, in use, NCO end groups and ultraviolet light (UV) or sky in glue-line
Moisture in gas reacts, and produces chemical crosslinking cure so as to reach cementation.This method can be positioned with rapid curing,
But be difficult that solidification is thorough, storage is not sufficiently stable.
At present, the softening point of polyurethane hot melt is usually more than 200 DEG C, and this is due to the strength enhancing of polyurethane hot melt
Often it is difficult to meet simultaneously with softening point is reduced.Generally, only possesses certain Mr and intermolecular force matrix resin ability
Assign PUR enough intensity and toughness, i.e. Mr is bigger, when intermolecular force is stronger, the melting temperature of polyurethane hot melt
It is higher；However, for the products such as paper product, partly plastic and electronic device, the tolerable temperature of its adherend base material is less than
100 DEG C, the relation how balanced between two attributes is particularly important.
The content of the invention
It is an object of the invention to provide a kind of preparation method of thermoplastic polyurethane hot melt adhesive, to solve prior art
In polyurethane hot melt strength enhancing and reduce softening point the problem of being difficult to meet simultaneously.
The invention provides a kind of preparation method of thermoplastic polyurethane hot melt adhesive, step are as follows：
1) preparation of polyalcohol
Polyethylene glycol (PEG), polytetrahydrofuran diol (PTMG), PEPA, antioxidant, hydrolysis-resisting agent are placed in dress
In the reactor for having thermometer, agitator, reflux condenser, stirring is started, is warming up to 100~120 DEG C, 0.1~
1~15h of vacuum dehydration under 0.167kPa, is cooled to 60-70 DEG C, obtains polyol component；
The PEG, PTMG, the mass ratio of PEPA are 1：1-3：1-3；
The antioxidant accounts for the 0.1-1% of polyethylene glycol, polytetrahydrofuran diol and PEPA gross mass, described anti-
Hydrolytic reagent accounts for the 0.3-3% of polyethylene glycol, polytetrahydrofuran diol and PEPA gross mass；
2) synthesis of performed polymer
In the four-hole boiling flask with agitator, dropping funel, condenser pipe and thermometer, polyalcohol obtained by step 1) is added
Component and the isocyanates of metering, 110-120 DEG C of reaction is to slowly warm up to, treat-NCO content (uses two positive fourths less than theoretical value
Amine method detects) when, it is added dropwise the hydroxyethyl methacrylate (HEMA) of metering, 90 DEG C of reactions, when-NCO content is less than theoretical value,
Light trigger, Isosorbide-5-Nitrae butanediol (BDO) and metopycide (TMP) mixed chain extender of metering are added, vacuumizes removing gas
45-60min is steeped, terminates reaction, obtains performed polymer；
The mass ratio of polyol component and isocyanates is 18-20 in the step 1):1；The hydroxyethyl methacrylate second
Ester is the 10-20% of polyol component；
3) preparation of polyurethane hot melt
By certain mass than performed polymer, BDO and TMP mixed chain extender, catalyst, light trigger and polymerization inhibitor mix
After uniformly, polyurethane hot melt is prepared；
The mass ratio of the BDO and TMP are 1-5：1；
The mass percent of each auxiliary agent is in step 3)：
Further, the relative molecular weight of the polyethylene glycol is 500-8000.
Further, the number-average molecular weight of the polytetrahydrofuran diol is 500-6000, the number of the PEPA
Average molecular weight is 500-6000.
Further, one or more of the antioxidant in following substances：2,6- di-t-butyl -4- methylbenzenes
Phenol, four [β-(3,5-di-t-butyl 4- hydroxy phenyls) propionic acid] pentaerythritol esters, 3,5- di-t-butyl-4- hydroxy phenylpropionic acids 18
Ester.
Further, one or more of the hydrolysis-resisting agent in following substances：Two (2,6- diisopropyl phenyls)
Carbodiimides, two (1- (1- methyl isophthalic acids-phenylethyl) -2,6- diisopropyl phenyls) carbodiimides, two (4- phenoxy groups -
2,6- diisopropyl phenyls) carbodiimides, two (4- tert-butyl groups -2,6- diisopropyl phenyl) carbodiimides, it is carbonized two more
Imines, polycarbodiimide.
Further, the one or more that the catalyst is selected in following substances：Metatitanic acid methyl esters, tetraethyl titanate, metatitanic acid
Propyl ester, butyl titanate, stannous octoate, dibutyl tin laurate.
Further, the isocyanates is 4,4- methyl diphenylene diisocyanates, toluene di-isocyanate(TDI), different Fo Er
Ketone diisocyanate, hexylidene diisocyanate, p-isopropyl phenyl isocyanate and by introducing urea diketone, carbamic acid
4,4- methyl diphenylene diisocyanates that ester, carbodiimide, isocyanurate group are modified, toluene di-isocyanate(TDI),
One or more of combinations in IPDI, hexylidene diisocyanate, p-isopropyl phenyl isocyanate.
Further, the one or more that the light trigger is selected in following substances：2- hydroxy-methyls phenyl-propane-
1- ketone, 1- hydroxycyclohexyl phenyl ketones, 2- methyl isophthalic acids-(4- methyl mercaptos phenyl) -2- morpholinyl -1- acetone.
Further, the polymerization inhibitor is hydroquinones.
Beneficial effect using the invention described above technical scheme is：The thermoplastic polyurethane heat prepared using the inventive method
Melten gel has melt viscosity low, and melting range is wide, the good combination property such as intensity height, is specially：
(1) it is using PEG, PTMG and PEPA as polyalcohol in the inventive method, the polyester of different crystalline rates is more
First alcohol, PPG mix by a certain percentage, can destroy the molecular structure regularity of system, adjust the crystalline rate of system,
And it can effectively overcome system disadvantage such as internal stress caused by crystallization is too fast.
(2) BDO and TMP mixed chain extenders are selected in the present invention, wherein BDO has Liang Ge functional groups, and TMP has three officials
It can roll into a ball, the proportioning by adjusting TMP and BDO in chain extender can control the crosslinking degree of polymer；
(3) HEMA being introduced in the present invention, corresponding HMA has higher initial bond strength and final bond strength, and
Contain double bond in molecule, after double bond containing isocyanates and polyol reaction, have double bond and different simultaneously in the meeting of macromolecular chain segment
Cyanate radical, can the double solidifications of light/wet, light/wet double solidification HMA transparencies are higher than moisturecuring HMA isocyanates；
(4) hot-melt adhesive composition possesses lower melt viscosity in the present invention, and molecular weight has an increase after illumination
Process so that intensity raises, it is not necessary to just the prepolymer of reaction generation HMW provides initial strength in the preparation,
Relatively low melt viscosity is more prone to be glued, and is advantageous to the levelling of sizing equipment and glued membrane；
(5) the PUR melting range that prepared by the inventive method is wide, and different formula systems has different molding times,
Add its application.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described, it is clear that described embodiment is part of the embodiment of the present invention, rather than
Whole embodiments.
Embodiment 1
1) by 200g PEG (relative molecular weight 800), 200g PTMG (relative molecular weight 1000), 200g it is poly-
Ester polyol (relative molecular weight 1000), 0.6g 2,6- di-tert-butyl-4-methy phenols, 1.8g two (2,6- diisopropyls
Base phenyl) carbodiimides be placed in equipped with thermometer, agitator, reflux condenser reactor in, start stirring and be warming up to 100
~120 DEG C, the vacuum dehydration 7h under 0.1~0.167kPa, 70 DEG C are cooled to, obtains polyol component.
2) in the four-hole boiling flask with agitator, dropping funel, condenser pipe and thermometer, polyalcohol in step 1) is added
Component, 35g 4,4- methyl diphenylene diisocyanates are added, be to slowly warm up to 110 DEG C, reacted some time, treat that-NCO contains
When amount is less than theoretical value (being detected using di-n-butylamine method), 60g HEMA is added dropwise, 90 DEG C of reaction some times, treats-NCO content
During less than theoretical value, removing bubble 45min is vacuumized, terminates reaction and obtains performed polymer.
3) by 700g performed polymer, 62g BDO and TMP mixed chain extenders (BDO:TMP=1:1), 0.7g metatitanic acids methyl esters,
Thermoplastic poly ammonia is prepared after 0.7g 2- hydroxy-methyls phenyl-propane -1- ketone and 0.7g hydroquinones etc. are well mixed
Ester PUR.
Embodiment 2
1) by 200g PEG (relative molecular weight 800), 400g PTMG (relative molecular weight 2000), 200g it is poly-
Ester polyol (relative molecular weight 1000), 0.8g 2,6- di-tert-butyl-4-methy phenols, 2.4g two (2,6- diisopropyls
Base phenyl) carbodiimides be placed in equipped with thermometer, agitator, reflux condenser reactor in, start stirring and be warming up to 110
DEG C, the vacuum dehydration 8h under 0.1~0.167kPa, 70 DEG C are cooled to, obtains polyol component.
2) in the four-hole boiling flask with agitator, dropping funel, condenser pipe and thermometer, polyalcohol in step 1) is added
Component, 40g 4,4- methyl diphenylene diisocyanates are added, be to slowly warm up to 110 DEG C, reacted some time, treat that-NCO contains
When amount is less than theoretical value (being detected using di-n-butylamine method), 80g HEMA is added dropwise, 90 DEG C of reaction some times, treats-NCO content
During less than theoretical value, removing bubble 50min is vacuumized, terminates reaction and obtains performed polymer.
3) by 900g performed polymer, 89g BDO and TMP mixed chain extenders (BDO:TMP=1:2), 0.9g metatitanic acid first
Thermoplastic poly is prepared after hydroquinones of ester, 0.9g 2- hydroxy-methyls phenyl-propane -1- ketone and 0.9g etc. is well mixed
Urethane PUR.
Embodiment 3
1) by 200g PEG (relative molecular weight 800), 200g PTMG (relative molecular weight 2000), 200g it is poly-
Ester polyol (relative molecular weight 2000), 0.6g 2,6- di-tert-butyl-4-methy phenols, 1.8g two (2,6- diisopropyls
Base phenyl) carbodiimides be placed in equipped with thermometer, agitator, reflux condenser reactor in, start stirring and be warming up to 100
~120 DEG C, the vacuum dehydration 7h under 0.1~0.167kPa, it is cooled to 70 DEG C.
2) in the four-hole boiling flask with agitator, dropping funel, condenser pipe and thermometer, polyalcohol in step 1) is added
Component, 35g 4,4- methyl diphenylene diisocyanates are added, be to slowly warm up to 110 DEG C, reacted some time, treat that-NCO contains
When amount is less than theoretical value (being detected using di-n-butylamine method), 60g HEMA is added dropwise, 90 DEG C of reaction some times, treats-NCO content
During less than theoretical value, removing bubble 45min is vacuumized, terminates reaction and obtains performed polymer.
3) by 700g performed polymer, 62g BDO and TMP mixed chain extenders (BDO:TMP=1:1), 0.7g metatitanic acid first
Thermoplastic poly is prepared after hydroquinones of ester, 0.7g 2- hydroxy-methyls phenyl-propane -1- ketone and 0.7g etc. is well mixed
Urethane PUR.
Comparative example 1
1) by 200g PEG (relative molecular weight 800), 200g PTMG (relative molecular weight 2000), 200g it is poly-
Ester polyol (relative molecular weight 2000), 0.6g 2,6- di-tert-butyl-4-methy phenols, 1.8g two (2,6- diisopropyls
Base phenyl) carbodiimides be placed in equipped with thermometer, agitator, reflux condenser reactor in, start stirring and be warming up to 100
~120 DEG C, the vacuum dehydration 7h under 0.1~0.167kPa, it is cooled to 70 DEG C.
2) in the four-hole boiling flask with agitator, dropping funel, condenser pipe and thermometer, polyalcohol in step 1) is added
Component, 95g 4,4- methyl diphenylene diisocyanates are added, be to slowly warm up to 110 DEG C, reacted some time, treat that-NCO contains
When amount is less than theoretical value (being detected using di-n-butylamine method), 90 DEG C of reaction some times, when-NCO content is less than theoretical value, take out
Vacuum removal bubble 60min, terminate reaction and obtain performed polymer.
3) by 700g performed polymer, 62g BDO, 0.7g metatitanic acid methyl esters, 0.7g 2- hydroxy-methyl phenyl-propanes -1-
Thermoplastic polyurethane hot melt adhesive is prepared after ketone and 0.7g hydroquinones etc. is well mixed.
Above-described embodiment 1-3 and the physical performance data of comparative example 1 are compared as follows table：
Softening point：It is measured according to the standards of GB/T15332-1994；Tensile strength and elongation at break：According to GB/T
528-2009 standards are measured.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, either which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (9)
1. a kind of preparation method of thermoplastic polyurethane hot melt adhesive, it is characterised in that step is as follows：
1) preparation of polyalcohol
Polyethylene glycol, polytetrahydrofuran diol, PEPA, antioxidant, hydrolysis-resisting agent are placed in equipped with thermometer, stirring
Device, reflux condenser reactor in, start stirring, be warming up to 100~120 DEG C, the vacuum dehydration 1 under 0.1~0.167kPa
~15h, is cooled to 60-70 DEG C, obtains polyol component；
The polyethylene glycol, polytetrahydrofuran diol, the mass ratio of PEPA are 1：1-3：1-3, the antioxidant account for poly-
The 0.1-1% of ethylene glycol, polytetrahydrofuran diol and PEPA gross mass, the hydrolysis-resisting agent account for polyethylene glycol, poly- four
The 0.3-3% of hydrogen furans glycol and PEPA gross mass；
2) synthesis of performed polymer
In the four-hole boiling flask with agitator, dropping funel, condenser pipe and thermometer, polyol component obtained by step 1) is added
With the isocyanates of metering, 110-120 DEG C of reaction is to slowly warm up to, when-NCO content is less than theoretical value, the first of metering is added dropwise
Base hydroxy-ethyl acrylate, 90 DEG C of reactions, when-NCO content is less than theoretical value, add the light trigger of metering, Isosorbide-5-Nitrae butanediol and
Metopycide mixed chain extender, removing bubble 45-60min is vacuumized, terminates reaction, obtains performed polymer；
The mass ratio of polyol component and isocyanates is 18-20 in the step 1):1；The hydroxyethyl methacrylate is
The 10-20% of polyol component；
3) preparation of polyurethane hot melt
By certain mass than the performed polymer, mixed chain extenders of 1,4 butanediols and metopycide, catalyst, light-initiated
After agent and polymerization inhibitor are well mixed, polyurethane hot melt is prepared；
The mass ratio of 1,4 butanediol and metopycide is 1-5：1；
Wherein, the mass percent of each auxiliary agent is in step 3)：
A kind of 2. preparation method of thermoplastic polyurethane hot melt adhesive according to claim 1, it is characterised in that the poly- second
The relative molecular weight of glycol is 500-8000.
3. the preparation method of a kind of thermoplastic polyurethane hot melt adhesive according to claim 1, it is characterised in that described poly- four
The number-average molecular weight of hydrogen furans glycol is 500-6000, and the number-average molecular weight of the PEPA is 500-6000.
A kind of 4. preparation method of thermoplastic polyurethane hot melt adhesive according to claim 1, it is characterised in that the antioxygen
One or more of the agent in following substances：2,6- di-tert-butyl-4-methy phenols, four [β-(3,5-di-t-butyl 4- hydroxyls
Phenyl) propionic acid] pentaerythritol ester, 3,5- di-t-butyl -4- hydroxy phenylpropionic acid octadecyl esters.
A kind of 5. preparation method of thermoplastic polyurethane hot melt adhesive according to claim 1, it is characterised in that the water resistant
Solve one or more of the agent in following substances：Two (2,6- diisopropyl phenyl) carbodiimides, two (1- (1- methyl isophthalic acids-
Phenylethyl) -2,6- diisopropyl phenyls) carbodiimides, two (4- phenoxy groups -2,6- diisopropyl phenyls) carbonization two be sub-
Amine, two (4- tert-butyl groups -2,6- diisopropyl phenyl) carbodiimides, more carbodiimides, polycarbodiimide.
A kind of 6. preparation method of thermoplastic polyurethane hot melt adhesive according to claim 1, it is characterised in that the catalysis
The one or more that agent is selected in following substances：Metatitanic acid methyl esters, tetraethyl titanate, titanium propanolate, butyl titanate, stannous octoate, two
Dibutyl tin laurate.
A kind of 7. preparation method of thermoplastic polyurethane hot melt adhesive according to claim 1, it is characterised in that the isocyanide
Acid esters is 4,4- methyl diphenylene diisocyanates, toluene di-isocyanate(TDI), IPDI, the isocyanide of hexylidene two
Acid esters, p-isopropyl phenyl isocyanate and by introducing urea diketone, carbamate, carbodiimide, isocyanurate group
4,4- methyl diphenylene diisocyanates, toluene di-isocyanate(TDI), IPDI, the hexylidene that group is modified
One or more of combinations in diisocyanate, p-isopropyl phenyl isocyanate.
8. the preparation method of a kind of thermoplastic polyurethane hot melt adhesive according to claim 1, it is characterised in that the light draws
Send out the one or more that agent is selected in following substances：2- hydroxy-methyl phenyl-propane -1- ketone, 1- hydroxycyclohexyl phenyl ketones,
2- methyl isophthalic acids-(4- methyl mercaptos phenyl) -2- morpholinyl -1- acetone.
A kind of 9. preparation method of thermoplastic polyurethane hot melt adhesive according to claim 1, it is characterised in that the inhibition
Agent is hydroquinones.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108753236A (en) * | 2018-06-22 | 2018-11-06 | 安徽索亚装饰材料有限公司 | A method of improving polyurethane hot melt adhesion strength |
| CN109097998A (en) * | 2018-08-17 | 2018-12-28 | 佛山市森昂生物科技有限公司 | A kind of waterproof roll and preparation method thereof |
| CN109401719A (en) * | 2018-09-26 | 2019-03-01 | 上海智冠高分子材料有限公司 | A kind of pair of solidification polyurethane hot melt and preparation method thereof and application method |
| CN109439056A (en) * | 2018-09-27 | 2019-03-08 | 广州亮豹涂料科技有限公司 | A kind of non-ionic associative type aqueous polyurethane thickener and preparation method thereof |
| 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 |
| CN113308207A (en) * | 2021-05-31 | 2021-08-27 | 东莞市雄林新材料科技股份有限公司 | Water-splashing-preventing TPU hot melt adhesive film and preparation method thereof |
| CN117089313A (en) * | 2023-10-19 | 2023-11-21 | 山东凯恩新材料科技有限公司 | PUR hot melt adhesive for composite board and production process thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1548042A2 (en) * | 2003-12-24 | 2005-06-29 | Henkel Kommanditgesellschaft auf Aktien | Highly elastic polyurethane hot melt adhesives |
| CN103080167A (en) * | 2010-09-06 | 2013-05-01 | Dic株式会社 | Active-energy-ray-curable hot-melt urethane resin composition, member for electronic device which comprises the composition, and packing |
| CN103102861A (en) * | 2013-02-22 | 2013-05-15 | 中国工程物理研究院化工材料研究所 | Low-softening point thermoplastic polyurethane hot melt adhesive and preparation method thereof |
| CN103396753A (en) * | 2013-08-15 | 2013-11-20 | 西安大天新材料有限公司 | Preparation method of hot-melt polyurethane resin for bonding material |
| CN103865026A (en) * | 2014-03-18 | 2014-06-18 | 山东大学 | Preparation method of organic fluorosiloxane modified polyurethane emulsion containing short fluoroalkyl chain |
| CN103890032A (en) * | 2011-10-24 | 2014-06-25 | Dic株式会社 | Moisture-curable polyurethane hot-melt resin composition, adhesive agent, and article |
| JP2016113552A (en) * | 2014-12-16 | 2016-06-23 | Dic株式会社 | Moisture-curable hot-melt urethane composition and adhesive |
-
2017
- 2017-06-28 CN CN201710507344.5A patent/CN107384293A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1548042A2 (en) * | 2003-12-24 | 2005-06-29 | Henkel Kommanditgesellschaft auf Aktien | Highly elastic polyurethane hot melt adhesives |
| CN103080167A (en) * | 2010-09-06 | 2013-05-01 | Dic株式会社 | Active-energy-ray-curable hot-melt urethane resin composition, member for electronic device which comprises the composition, and packing |
| CN103890032A (en) * | 2011-10-24 | 2014-06-25 | Dic株式会社 | Moisture-curable polyurethane hot-melt resin composition, adhesive agent, and article |
| CN103102861A (en) * | 2013-02-22 | 2013-05-15 | 中国工程物理研究院化工材料研究所 | Low-softening point thermoplastic polyurethane hot melt adhesive and preparation method thereof |
| CN103396753A (en) * | 2013-08-15 | 2013-11-20 | 西安大天新材料有限公司 | Preparation method of hot-melt polyurethane resin for bonding material |
| CN103865026A (en) * | 2014-03-18 | 2014-06-18 | 山东大学 | Preparation method of organic fluorosiloxane modified polyurethane emulsion containing short fluoroalkyl chain |
| JP2016113552A (en) * | 2014-12-16 | 2016-06-23 | Dic株式会社 | Moisture-curable hot-melt urethane composition and adhesive |
Non-Patent Citations (1)
| Title |
|---|
| （德）厄特尔（OERTEL，GUNTER）编著；阎家宾等译校: "《聚氨酯手册》", 30 September 1992, 中国石化出版社 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108753236A (en) * | 2018-06-22 | 2018-11-06 | 安徽索亚装饰材料有限公司 | A method of improving polyurethane hot melt adhesion strength |
| CN109097998A (en) * | 2018-08-17 | 2018-12-28 | 佛山市森昂生物科技有限公司 | A kind of waterproof roll and preparation method thereof |
| CN109401719A (en) * | 2018-09-26 | 2019-03-01 | 上海智冠高分子材料有限公司 | A kind of pair of solidification polyurethane hot melt and preparation method thereof and application method |
| CN109401719B (en) * | 2018-09-26 | 2021-09-10 | 上海智冠高分子材料有限公司 | Dual-curing polyurethane hot melt adhesive as well as preparation method and application method thereof |
| CN109439056A (en) * | 2018-09-27 | 2019-03-08 | 广州亮豹涂料科技有限公司 | A kind of non-ionic associative type aqueous polyurethane thickener and preparation method thereof |
| CN109439056B (en) * | 2018-09-27 | 2022-03-25 | 丁贤勇 | Nonionic associative type water-based polyurethane thickener and preparation method thereof |
| 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 |
| CN113308207A (en) * | 2021-05-31 | 2021-08-27 | 东莞市雄林新材料科技股份有限公司 | Water-splashing-preventing TPU hot melt adhesive film and preparation method thereof |
| CN117089313A (en) * | 2023-10-19 | 2023-11-21 | 山东凯恩新材料科技有限公司 | PUR hot melt adhesive for composite board and production process thereof |
| CN117089313B (en) * | 2023-10-19 | 2023-12-26 | 山东凯恩新材料科技有限公司 | PUR hot melt adhesive for composite board and production process thereof |
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