CN110256999A - A kind of high just intensity reaction type polyurethane hot-melt adhesive and preparation method thereof - Google Patents
A kind of high just intensity reaction type polyurethane hot-melt adhesive and preparation method thereof Download PDFInfo
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- CN110256999A CN110256999A CN201910530104.6A CN201910530104A CN110256999A CN 110256999 A CN110256999 A CN 110256999A CN 201910530104 A CN201910530104 A CN 201910530104A CN 110256999 A CN110256999 A CN 110256999A
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic 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
- C08G18/42—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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
Abstract
The invention discloses a kind of high just intensity reaction type polyurethane hot-melt adhesives, score meter by weight, including following component: 25-35 parts of crystalline polyester polyols, 30-45 parts of amorphism liquid polyesters polyalcohol, 5-10 parts of high molecular weight crystalline polyester, 6-9 parts of thermoplastic polyurethane, 0.1-0.3 parts of antioxidant, 14-19 parts of MDI, 0.3-0.5 parts of catalyst and 0.3-0.5 parts of silane coupling agent.A kind of high just intensity reaction type polyurethane hot-melt adhesive of the present invention is reacted using the crystal type and non-crystalline polyester polyalcohol of lower molecular weight with aromatic diisocyanate, reactivity with higher；Using high molecular weight crystallinity copolyesters, crosslink density with higher is, it can be achieved that higher initial adhesive strength and final adhesive strength；Using with the good thermoplastic polyurethane resin of polyester system compatibility, preferable flexibility can be kept again by improving initial bonding strength, compensate for the prior art using fast crystallization and high molecular weight polyesters improve just intensity bring hardness increase, flexibility decline problem.
Description
Technical field
The present invention relates to adhesive field more particularly to a kind of high just intensity reaction type polyurethane hot-melt adhesive and its preparation sides
Method.
Background technique
With the fast development of mobile electronic device, wearable device, car-mounted display equipment and artificial intelligence equipment, eventually
End display screen is increasingly intended to frivolous, flexible, folding trend；The display module of these equipment, component, shell knot
The assembling etc. of structure mostly uses reaction type polyurethane hot-melt adhesive to be bonded.
Reaction type polyurethane hot-melt adhesive is a kind of polyurethane prepolymer, after hot melt sizing, can be quickly cooled down, crystallize formation one
Determine initial bonding strength；Excessive reactive NCO group is reacted with moisture, substrate surface moisture and the active hydrogen group etc. in air, finally
It is cross-linked into the polyurethane macromolecular of reticular structure, higher adhesive strength and good sealing performance may be implemented.Electronic Assemblies
Preferable technique applicability is also needed with reaction type polyurethane hot-melt adhesive, is stablized, smooth, not wire drawing, is adapted to three coordinate glue spreaders
Track dispensing or injection sizing, it is desirable that good thermal stability, with guarantee for a long time, quick, high-precision glue-applying technique.
The manufacture of mobile electronic device has the characteristics that in high volume, fast and efficiently component, component material multiplicity are smart
It is close and structure is complicated, using the reaction type polyurethane hot-melt adhesive of the prior art, after sizing, only physics such as, crystallization cooling by glue-line
Change and form certain initial bonding strength, the polyurethane reaction of NCO group and moisture is still carrying out, general PC/PC drawing after being bonded 5min
Intensity is less than 5kgf/100mm2, be not able to satisfy rapid link positioning requirements, need using fixture, mold to bond precompressed and
Pressing, solidification 3-5h, to guarantee the reliability of bonding, which forms the long-time of a large amount of molds, fixture and equipment occupancy, sternly
Ghost image rings production efficiency.It is some to need rapid link, positioning and fixture inconvenient to use, mold in assembling production technology
The occasion of pressing for a long time needs the hot melt adhesive of high initial bonding strength, high just intensity, this just needs hot melt adhesive in sizing, precompressed 1min
To reach 10kgf/100mm afterwards2The above pull strength can just be such that bond fixes immediately, and have foot after being fully cured
Enough adhesive strengths, as pull strength reaches 50kgf/100mm2More than, tensile-sbear strength 6MPa or more.
Reaction type polyurethane hot-melt adhesive initial bond strenght is improved, current art generally uses the polyester of highly crystalline rate more
First alcohol, it is modified using macromolecule Thermoplastic polyacrylate, the open hour after sizing were shortened within 30 seconds, although can be fast
Crystallization improves some initial bonding strengths, but is far below 1min 10kg/100mm2Be initially adhesively fixed intensity；Macromolecule thermoplasticity
Acrylate and polyester system poor compatibility, need to improve compatibility using polyether polyol more, and the addition of polyethers can drop
Low initial bonding strength and initial bond strenght, and product melt viscosity is big, operable time is short, it is big to whole intensity effect；Using C5/C9
The tackifying resin of the preparations such as Petropols and rosin ester, coumarone indene resin has lower melt viscosity, it is possible to provide preferable first
Viscous force；But these methods for improving initial bonding strength reduce crosslink density, so that rear adhesive strength, which is fully cured, to be reduced, it is final to draw
It pulls out intensity and is generally less than 40kgf/100mm2；And glue-line is hard, and elasticity modulus is larger, and flexibility is poor, and general elongation at break is small
Component, finished product resistance to " roller falls " impact and hydrothermal aging after 500%, bonding is poor, so that the reliability decrease of bonding,
It is difficult to meet mobile electronic device manufacturing process and performance requirement.
Summary of the invention
The present invention is big for existing reaction type polyurethane hot-melt adhesive melt viscosity, initial bonding strength and initial bond strenght is low asks
Topic provides a kind of high just intensity reaction type polyurethane hot-melt adhesive and preparation method thereof.
The technical scheme to solve the above technical problems is that a kind of high just intensity reaction type polyurethane hot-melt adhesive,
It is characterized in that, score meter, including following component by weight: 25-35 parts of crystalline polyester polyols, amorphism liquid polyesters
30-45 parts of polyalcohol, 5-10 parts of high molecular weight crystalline polyester, 6-9 parts of thermoplastic polyurethane, 0.1-0.3 parts of antioxidant, MDI
14-19 parts, 0.3-0.5 parts of catalyst and 0.3-0.5 parts of silane coupling agent.
Further, the crystalline polyester polyols number-average molecular weight be 2000-5000, be adipic acid -1,6 hexylene glycol,
The combination of one or both of -1,4 butanediol of adipic acid, polycaprolactone diols or polycarbonate glycol.Such as: Xu Chuanization
XCP-3000, Qingdao Sunyu field POL-356 are learned, wound DYNACOLL7380,7360, poly- Renhua work polycaprolactone polyol are won
PCL2302, space portion chemistry polycarbonate glycol UH-CARB300.
Further, the amorphism liquid polyesters polyalcohol number-average molecular weight is 2000-3000, hydroxyl value 25-
75mgKOH/g is Phthalic acids polyester diol or polycaprolactone diols.Such as: winning wound DYNACOLL7230, Daicel liquid
State polycarbonate glycol G4672, Su Telin chemical industry ST8870, poly- Renhua work polycaprolactone polyol PCL2200C, health mould moral
Chemical industry CP-2059.
Further, the high molecular weight crystalline polyester number-average molecular weight be 15000-45000, hydroxyl value 3-8mgKOH/g,
Chemical industry high-molecular-weight poly ester polyol is very praised for Nanjing Su Telin chemical industry Linear Polymer crystalline polyester ST-260, Shanghai
S3049, the wound high-molecular-weight thermoplastic copolyesters DYNACOLLS1227 or poly- Renhua work high molecular weight polycaprolactone PCL- in Hunan is won
One of 6400.
Further, the thermoplastic polyurethane is Lu Borun thermoplastic polyurethane particle Pearlbond523, hydroxyl is created in Cohan
In the base polyester polyurethane particle Desmocoll 500 or Yantai auspicious green wood thermoplastic polyurethane elastomer particle TPU-H306 of U.S.
One kind.
Further, the antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters.Such as:
BASF anti-oxidant Irganox 1010 etc..
Further, the catalyst is triethylenediamine, in bis- (dimethylaminoethyl) ethers or double morpholine Anaesthetie Ethers
One kind.
Further, the silane coupling agent is one of KH590, KH560 or KH550.
The invention further relates to the preparation method of above-mentioned high just intensity reaction type polyurethane hot-melt adhesive, steps are as follows: by weight
Each component is weighed, by crystalline polyester polyol and noncrystalline liquid polyesters polyalcohol, high molecular weight crystalline polyester, thermo-plastic polyurethane
It is uniformly mixed with antioxidant, after 160 DEG C of meltings, is cooled to 110 DEG C and vacuumizes dehydration 2h, after testing water content≤200ppm,
60 DEG C are cooled to, MDI is added, 85-90 DEG C vacuumizes reaction 2-3h；Catalyst and silane coupling agent is added, vacuumizes mixing
30min, then vacuumizing and defoaming 30min discharge, and in encapsulating to hot melt pipe or aluminium foil bag, are filled with nitrogen, plastic packaging.
The beneficial effects of the present invention are: the high just intensity reaction type polyurethane hot-melt adhesive of the present invention uses the knot of lower molecular weight
Brilliant and noncrystalline liquid polyesters polyalcohol is reacted with aromatic diisocyanate, reactivity with higher；Using macromolecule
Crystallinity copolyesters is measured, crosslink density with higher is, it can be achieved that higher initial adhesive strength and final adhesive strength；Using with it is poly-
The good thermoplastic polyurethane resin of ester Miscibility, preferable flexibility can be kept again by improving initial bonding strength, be compensated for existing
Technology improves just intensity bring hardness increase using fast crystallization polyester and high molecular weight polyesters, flexibility declines problem.
High just intensity reaction type polyurethane hot-melt adhesive prepared by the present invention, open hour control was at 40-70 seconds, medium melting
Viscosity is in order to precise glue dispensing and injection sizing；Fixture precompressed 1minPC/PC pull strength is greater than 10kgf/100mm after bonding2,
5min can reach 20kgf/100mm2, it can be achieved that rapid link positions, it can be from fixture long-time pressure maintaining；After moisture reaction solidification
Pull strength reach 60kgf/100mm2More than, shear strength is greater than 8MPa；Elasticity modulus is moderate after solidification, and elongation at break is big
In 800%, there is good flexibility, it is ensured that multi-cycle " roller falls " test, impact vibration test, hydrothermal aging, cold and hot
The harsh inspection of impact test etc..
Specific embodiment
Below in conjunction with example, present invention is described, and the given examples are served only to explain the present invention, is not intended to limit this
The range of invention.
Embodiment 1
A kind of high just intensity reaction type polyurethane hot-melt adhesive, component and corresponding preparation method including following parts by weight:
By crystalline polyester polyol XCP-3000 (20 parts), POL-356 (10 parts), high molecular weight crystallized copolyester ST-260 (6 parts), liquid
State polyester polyol DYNACOLL7230 (25 parts), liquid polycarbonate glycol G4672 (15 parts), thermoplastic polyurethane solid
Resin Desmocoll 500 (8 parts) anti-oxidant Irganox 1010 (0.2 part) is added in four-hole bottle, is warming up to 160 DEG C of meltings
1h, cools to 110 DEG C of vacuum dehydration 2h, tests water content≤200PPm, is cooled to 60 DEG C, leads to nitrogen protection, while stirring plus
Enter (15 parts) of liquefied MDI-100 reactions, 85-90 DEG C of temperature control, reacts 2-3h, analysis NCO% content to be sampled reaches design value
Afterwards, the double morpholine Anaesthetie Ethers (0.5 part) of catalyst are added, KH590 silane coupling agent (0.3 part) is vacuumized and is stirred
30min is warming up to 120 DEG C, vacuumizing and defoaming 30min, discharges, and in encapsulating to hot melt pipe or aluminium foil bag, is filled with nitrogen, plastic packaging
To obtain the final product.
Embodiment 2
A kind of high just intensity reaction type polyurethane hot-melt adhesive, component and corresponding preparation method including following parts by weight:
By crystalline polyester polyol DYNACOLL7380 (18 parts), XCP-3000H (17 parts), high molecular weight crystallized copolyester S3049 (10
Part), liquid polyesters polyalcohol ST8870 (20 parts), liquid-state polycaprolactone polyalcohol PCL2200C (10 parts), thermoplastic polyurethane
Hard resin TPU-H306 (5 parts) anti-oxidant Irganox 1010 (0.3 part) is added in four-hole bottle, is warming up to 160 DEG C of meltings
1h, cools to 110 DEG C of vacuum dehydration 2h, tests water content≤200PPm, is cooled to 60 DEG C, lead to nitrogen protection, while stirring plus
Enter (19 parts) of liquefied MDI-100 reactions, 85-90 DEG C of temperature control, reacts 2-3h, analysis NCO% content to be sampled reaches design value
Afterwards, the double morpholine Anaesthetie Ethers (0.4 part) of catalyst are added, KH590 silane coupling agent (0.3 part) is vacuumized and is stirred
30min is warming up to 120 DEG C, vacuumizing and defoaming 30min, discharges, and in encapsulating to hot melt pipe or aluminium foil bag, is filled with nitrogen, plastic packaging
To obtain the final product.
Embodiment 3
A kind of high just intensity reaction type polyurethane hot-melt adhesive, component and corresponding preparation method including following parts by weight:
By crystalline polyester polyol DYNACOLL7380 (15 parts), polycaprolactone polyol PCL2302 (10 parts), high-molecular-weight poly is in oneself
Ester PCL-6400 (6 parts), liquid polyesters polyalcohol CP-2059 (30), liquid polycarbonate glycol G4672 (15 parts), thermoplasticity
Urethane solid resin Pearlbond523 (9 parts) anti-oxidant Irganox 1010 (0.3 part) is added in four-hole bottle, is warming up to
160 DEG C of melting 1h cool to 110 DEG C of vacuum dehydration 2h, test water content≤200PPm, are cooled to 60 DEG C, lead to nitrogen protection, side
It stirs side and liquefied (14 parts) of MDI-100 reactions is added, 85-90 DEG C of temperature control, react 2-3h, analysis NCO% content to be sampled reaches
To after design value, the double morpholine Anaesthetie Ethers (0.3 part) of catalyst are added, KH590 silane coupling agent (0.4 part) vacuumizes stirring
Mix 30min, be warming up to 120 DEG C, vacuumizing and defoaming 30min, discharging, in encapsulating to hot melt pipe or aluminium foil bag, be filled with nitrogen,
Plastic packaging to obtain the final product.
Embodiment 4
A kind of high just intensity reaction type polyurethane hot-melt adhesive, component and corresponding preparation method including following parts by weight:
By crystalline polyester polyol POL-356 (12 parts), polycarbonate glycol UH-CARB300 (20 parts), high molecular weight copolyester
DYNACOLL S1227 (5 parts), liquid-state polycaprolactone polyalcohol PCL2200C (23.9 parts), liquid polyesters polyalcohol
DYNACOLL7230 (15 parts), thermoplastic polyurethane hard resin Desmocoll 500 (7 parts) anti-oxidant Irganox 1010
(0.1 part) is added in four-hole bottle, is warming up to 160 DEG C of melting 1h, cools to 110 DEG C of vacuum dehydration 2h, and test water content≤
200PPm is cooled to 60 DEG C, leads to nitrogen protection, is added (17 parts) of liquefied MDI-100 reactions while stirring, and 85-90 DEG C of temperature control,
React 2-3h, after analysis NCO% content to be sampled reaches design value, add catalyst pair morpholine Anaesthetie Ether (0.4 part),
KH590 silane coupling agent (0.5 part), which vacuumizes, is stirred 30min, is warming up to 120 DEG C, vacuumizing and defoaming 30min, discharges, and fills
Glue is filled with nitrogen, plastic packaging into hot melt pipe or aluminium foil bag to obtain the final product.
Embodiment 5
A kind of high just intensity reaction type polyurethane hot-melt adhesive, component and corresponding preparation method including following parts by weight:
By crystalline polyester polyol DYNACOLL7380 (17 parts), XCP-3000H (14 parts), high molecular weight crystallized copolyester S3049 (7
Part), liquid polyesters polyalcohol ST8870 (15 parts), liquid polyesters polyalcohol CP-2059 (24 parts), thermoplastic polyurethane solid tree
Rouge Pearlbond523 (6 parts) anti-oxidant Irganox 1010 (0.2 part) is added in four-hole bottle, is warming up to 160 DEG C of melting 1h,
110 DEG C of vacuum dehydration 2h are cooled to, water content≤200PPm is tested, is cooled to 60 DEG C, leads to nitrogen protection, liquid is added while stirring
(16 parts) of MDI-100 reactions of change, react 2-3h by 85-90 DEG C of temperature control, after analysis NCO% content to be sampled reaches design value, then
The double morpholine Anaesthetie Ethers (0.5 part) of catalyst are added, KH590 silane coupling agent (0.3 part) vacuumizes and is stirred 30min, liter
Temperature is to 120 DEG C, vacuumizing and defoaming 30min, discharging, in encapsulating to hot melt pipe or aluminium foil bag, is filled with nitrogen, plastic packaging to obtain the final product.
Below to illustrate the invention, the reaction type polyurethane hot-melt adhesive composition and preparation method of the prior art are lifted
Example control.
The reaction type polyurethane hot-melt adhesive of the prior art, weight percent composition and the preparation method is as follows:
By 14-20 parts of addition four-hole bottles of polyether polyol, 12-20 parts of Thermoplastic polyacrylate particle are added, is warming up to
160 DEG C of stirring meltings；Crystallization and noncrystalline liquid polyester polyol 40-60 parts mixing, 110 DEG C of vacuum dehydration 2h are added；It is cooling
To 60 DEG C, 14-17 parts of aromatic diisocyanate of pre liquefied are added, are added organotin catalysts 0.1-0.2 parts, temperature control 85-
90 DEG C of reaction 1h, after analysis NCO% content to be sampled reaches design value, be added organic amine catalyst 0.3-0.5 parts, it is silane coupled
0.3-0.5 parts of agent vacuumize stirring 30min, vacuumizing and defoaming 30min under the conditions of being warming up to 120 DEG C, discharge, sealed package, i.e.,
?.
Wherein, the polyether polyol be PPG, PEG, PTMG series it is one or more, such as: PPG-2000, PTMEG-
2000 etc..
The polyester polyol be PEA, PBA, PHA series it is one or more.Such as: crystalline polyester polyol wins wound
DYNACOLL7380, DYNACOLL7360, Sunyu field POL-356, liquid polyester polyol DYNACOLL7230, health mould moral CP-
2056 etc..
The Thermoplastic polyacrylate particle is prepared by methyl methacrylate and butyl methacrylate, such as: being won
Create DYNACOLL AC1630, Mitsubishi DIANAL BR116 etc..
The aromatic diisocyanate is pure MDI, such as: Wan Hua MDI100.
Catalyst is the one or more of organotin catalysts or organic amine catalyst, pungent such as dibutyl tin dilaurate
Sour stannous, bis- (dimethylaminoethyl) ethers etc..
Silane coupling agent is KH590, KH550 etc..
Comparative example 1
Polyether polyol PPG-2000 (20 parts), (20 parts) of thermoplastic propene acid esters DYNACOLL AC1630 are added four
Mouth bottle heats 160 DEG C of stirrings meltings；Be added crystalline polyester polyol POL-356 (16 parts), DYNACOLL7360 (24 parts),
DYNACOLL7230 (15 parts), 110 DEG C of vacuum dehydration 2h；60 DEG C are cooled to, is added with stirring MDI100 (14 parts), February is added
Dilaurylate (0.1 part), 85-90 DEG C of reaction 1h of temperature control after analysis NCO% content to be sampled reaches design value, are added double
(dimethylaminoethyl) ether (0.5 part), Silane coupling agent KH550 (0.4 part) vacuumize stirring 30min, and 120 DEG C of heating vacuumizes
Deaeration, discharging, sealed package to get.
Comparative example 2
By polyether polyol PTMEG-2000 (14 parts), (12 parts) of thermoplastic propene's acid esters DIANALBR116 are added four mouthfuls
Bottle heats 160 DEG C of stirrings to melting；Crystalline polyester polyol DYNACOLL7360 (12 parts), DYNACOLL7380 (24 are added
Part), health modeling (20 parts) addition reaction kettles of moral CP-2056 in, be warming up to 110 DEG C of vacuum dehydrations, be cooled to 80 DEG C, while stirring instead
It should be added isocyanates MDI-100 (17 parts), be added stannous octoate (0.2 part), 85-90 DEG C of reaction 1h of temperature control, analysis to be sampled
After NCO% content reaches design value, bis- (dimethylaminoethyl) ethers (0.3 part), (0.5 part) of silane coupling agent KH590 pumping are added
Be stirred under vacuum 30min, heat up 120 DEG C of vacuumizing and defoamings, discharging, sealed package to get.
The sample of embodiment 1-5 and comparative example 1-2 are subjected to mechanical performance contrast test by the following method:
1, viscosity test (HG/T3660-1999): 30ml sample sebific duct is placed in SNB-AI fusion viscosimeter, sets 27#
10 turns of rotor, melt viscosity is tested in 110 DEG C of constant temperature.
2, sample preparation and test
1. tensile-sbear strength test specimen method for making sample (GB/T7124-2008):
Sample sebific duct sets three axis automatic dispensing machines, and 115 DEG C, air pressure 0.4MPa, 21# syringe needle program gluing track, often
Group 5 automatic glue applications of PC test piece；PC/PC bonding plane: 25mm × 12.5mm fixture clamps, and 25 DEG C of 50%RH solidifications are for 24 hours.With omnipotent
Testing machine tests tensile shear strength (PC/PC)
2. pull-out experiment method for making sample: (PT1198 pull-out test machine)
Sample sebific duct sets three axis automatic dispensing machines, and 115 DEG C, air pressure 0.4MPa, 21# syringe needle program gluing track, often
Group 5 automatic glue applications of PC test piece；The cross-lap joint face PC/PC: 10mm × 10mm, pressing machine 0.4MPa pressure press 1min, respectively
Test under 25 DEG C of 50%RH 1,5min and for 24 hours pull strength.
3. the open hour: under the conditions of 25 DEG C of 50%RH, testing the 1mm tree lace unsticking time.
4. hardness: 25 DEG C of 50%RH test blocks test shore D hardness by GB/T2411-2008.
5. elongation at break %:1mm tree lace solidifies for 24 hours under the conditions of 25 DEG C of 50%RH, and 10mm long tree lace tensile elongation=
(Xmm/10mm) × 100%
By the prior art reaction type polyurethane hot-melt adhesive performance comparison of sample made from embodiment 1-5 and comparative example 1-2
Test, the results are shown in Table 1.
1. embodiment 1-5 of table and comparative example 1-2 reaction type polyurethane hot-melt adhesive performance comparison
As it can be seen from table 1 the first intensity flexibility reaction type polyurethane hot-melt adhesive of height of the invention, than existing conventional skill
The reaction type polyurethane hot-melt adhesive of art preparation, by taking 1,5min pull strength as an example, 1min pull strength is greater than 10Kg/100mm2,
5min is greater than 17Kg/100mm2, initial bond strenght is significantly increased, and finally pull strength, tensile-sbear strength are bigger after solidifying；
Hardness and elasticity modulus are moderate, and elongation at break is high, and flexibility is more preferable；With good process applicability and preferable cementability
Can, higher initial bond strenght and flexibility are suitable for e-factory high-efficient automatic producing line, can exempt from pressure maintaining or shorten pressing
Time；Meet simultaneously roller fall, the harsh conditions environmental test requirement such as hydrothermal aging, cooling thermal impact.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of high just intensity reaction type polyurethane hot-melt adhesive, which is characterized in that score meter by weight, including following component: knot
25-35 parts of crystalline substance polyester polyol, 30-45 parts of amorphism liquid polyesters polyalcohol, 5-10 parts of high molecular weight crystalline polyester, heat
6-9 parts of plastic polyurethane, 0.1-0.3 parts of antioxidant, MDI14-19 parts, 0.3-0.5 parts of catalyst and silane coupling agent 0.3-0.5
Part.
2. high just intensity reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that the crystalline polyester
Polyalcohol number-average molecular weight is 2000-5000, is adipic acid -1,6 hexylene glycol, adipic acid-Isosorbide-5-Nitrae butanediol, polycaprolactone binary
The combination of one or both of alcohol or polycarbonate glycol.
3. high just intensity reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that the amorphism liquid
State polyester polyol number-average molecular weight be 2000-3000, hydroxyl value 25-75mgKOH/g, be Phthalic acids polyester diol or
Liquid polycaprolactone dihydric alcohol.
4. high just intensity reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that the high molecular weight knot
Brilliant polyester number-average molecular weight is 15000-45000, hydroxyl value 3-8mgKOH/g, is high molecular weight linear crystalline polyester, high score
One of sub- weight polyester polyalcohol, high-molecular-weight thermoplastic copolyesters or high molecular weight polycaprolactone.
5. high just intensity reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that the antioxidant is four
[β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
6. high just intensity reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that the catalyst is three
Ethyldiamine, one of bis- (dimethylaminoethyl) ethers or double morpholine Anaesthetie Ethers.
7. high just intensity reaction type polyurethane hot-melt adhesive according to claim 1, which is characterized in that the silane coupling agent
For one of KH590, KH560 or KH550.
8. a kind of preparation method of the described in any item high just intensity reaction type polyurethane hot-melt adhesives of such as claim 1-7, special
Sign is, step are as follows: each component is weighed by weight, by crystalline polyester polyol and noncrystalline liquid polyesters polyalcohol, high score
Son amount crystalline polyester, thermo-plastic polyurethane and antioxidant are uniformly mixed, and after 160 DEG C of meltings, are cooled to 110 DEG C and are vacuumized dehydration
2h is cooled to 60 DEG C after testing water content≤200ppm, is added MDI, 85-90 DEG C vacuumize reaction 2-3h after catalyst is added
And silane coupling agent, mixing 30min, then vacuumizing and defoaming 30min are vacuumized, is discharged, in encapsulating to hot melt pipe or aluminium foil bag,
It is filled with nitrogen, plastic packaging.
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