CN109468114A - High performance polyurethane adhesive - Google Patents
High performance polyurethane adhesive Download PDFInfo
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- CN109468114A CN109468114A CN201811522313.8A CN201811522313A CN109468114A CN 109468114 A CN109468114 A CN 109468114A CN 201811522313 A CN201811522313 A CN 201811522313A CN 109468114 A CN109468114 A CN 109468114A
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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
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- Chemical Kinetics & Catalysis (AREA)
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- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention proposes high performance polyurethane adhesive, which includes component A and B component, and component A and B component press the mass ratio of 5:1 after evenly mixing to get high performance polyurethane adhesive.Compared to traditional high performance polyurethane adhesive, the present invention is applied widely, can be coated with high concentration (50%), it is suitble to aluminizer, aluminium foil, boiling etc. to use, it is good using rear appearance, lacquer disk(-sc) long service life, meets the needs of energy conservation and environmental protection upgrading.
Description
Technical field
The present invention relates to laminated film technical field of soft package, and in particular to high performance polyurethane adhesive.
Background technique
Adhesive is suitable for different materials, different thicknesses, the bonding of different size, different component.And polyurethane adhesive
With excellent resistance to low temperature, water resistance, oil resistivity and flexibility, while adhesive strength with higher, it is answered extensively
For industries such as synthetic leather, laminated films.However existing polyurethane adhesive cannot meet the bonding of various material simultaneously, only
Energy specific aim uses, and especially in flexible packing material, there is presently no can meet the poly- of a variety of flexible packing materials simultaneously
Urethane adhesive, it is necessary to add different components for different flexible packing materials and bonding effect is realized with this, so increase
The multiple switch sequence of glue in compound work, and then a large amount of manpowers are wasted, labor productivity is reduced, simultaneously as using not
Same adhesive, cost increase, and storage area increases, and reduce the convenience of laminating production.Polyurethane adhesive makes simultaneously
Also easily occurs the problems such as peel strength is poor in, and existing polyurethane adhesive causes VOCs to arrange there is also upper gum concentration is low
Let off high the problem of bringing pressure to environmental protection.
Summary of the invention
For the deficiency in the presence of the prior art, the present invention provides high performance polyurethane adhesive, and which solve existing
Some polyurethane adhesives cannot meet that the bonding of various material, peel strength is poor, upper gum concentration is low in use leads to ring simultaneously
The big problem of packing pressure.
To achieve the above object, present invention employs the following technical solutions: high performance polyurethane adhesive, the high-performance
Polyurethane adhesive includes component A and B component, and component A and B component are poly- to get high-performance after evenly mixing by the mass ratio of 5:1
Urethane adhesive；
According to parts by weight, component A, B component include raw material below:
Component A:
12 parts -19 parts of ethylene glycol, 18 parts -25 parts of 1-4 butanediol, 32 parts -40 parts of diethylene glycol (DEG), 31 parts -41 parts of neopentyl glycol,
42 parts -48 parts of M-phthalic acid, 0.005 part -0.01 part of catalyst A, 60 parts -80 parts of binary acid, 44 parts -59 parts of adipic acid, resist
0.01 part -0.02 part of oxygen agent, 5 parts -10 parts of castor oil polyhydric alcohol, 60 parts -70 parts of ethyl acetate, 10 parts -15 parts of chain extender, carbonization
1.8 parts -2.7 parts of diimine, 1.8 parts -2.7 parts of organo-silicon coupling agent；
B component:
48 parts -52 parts of trimethylolpropane, 14 parts -18 parts of trimethylpentanediol, 230 parts of chain extender, 95 parts of ethyl acetate -
105 parts, 0.003 part -0.005 part of catalyst B, 10 parts -15 parts of hexamethylene diisocyanate derivative.
Further, the binary acid is one or more of decanedioic acid, azelaic acid.
Further, the hexamethylene diisocyanate derivative be one of HDI trimer, HDI biuret or
It is several.Using the polyurethane adhesive that HDI trimer, HDI biuret are produced as raw material, have the characteristics that not yellowing, weatherability are strong.
Further, the chain extender is one of MDI-50, MDI-100, MDI-103C, MDI-100LL, TDI-80
Or it is several.
Further, the catalyst A is one or more of tetra-n-butyl titanate, zinc acetate, and the catalyst B is
One or more of organotin, organo-bismuth.
Further, the antioxidant is triphenyl phosphite.
Further, the castor oil polyhydric alcohol is the HF-1300 of her rattan production of Japan.
The present invention additionally uses the following technical solution:
The production method of high performance polyurethane adhesive, comprising the following steps:
The preparation of S1:A component: by formula ratio by ethylene glycol, 1-4 butanediol, diethylene glycol (DEG), neopentyl glycol, M-phthalic acid,
Catalyst A, binary acid, adipic acid, antioxidant, castor oil polyhydric alcohol, ethyl acetate, chain extender, carbodiimides, organosilicon are even
Join agent addition reaction kettle to be uniformly mixed, component A is made；
The preparation of S2:B component: by formula ratio by trimethylolpropane, trimethylpentanediol, chain extender, ethyl acetate, urge
Agent B, hexamethylene diisocyanate derivative are added reaction kettle and are uniformly mixed, and B component is made；
S3: component A and B component are obtained into high performance polyurethane adhesive by the mass ratio of 5:1 after evenly mixing.
Further, in S1 component A preparation the following steps are included:
S11: by ethylene glycol, 1-4 butanediol, diethylene glycol (DEG), neopentyl glycol and M-phthalic acid mix, stir evenly to be formed it is mixed
It is placed in reaction kettle after closing object A；
S12: being heated to 190 DEG C of stopping heatings for the mixture A in S11, catalyst A be then added and waits for its reaction,
Form mixture B；
S13: when the mixture B reaction water outlet famous dictum stoichiometric in S12, be added binary acid and continuous warming to 150 DEG C into
Row mixing esterification, forms mixture C；
S14: when the mixture C reaction water outlet famous dictum stoichiometric in S13, adipic acid and continuous warming is added to 210 DEG C, so
After be added antioxidant, form mixture D；
S15: by the mixture D persistently overheating in S14 to the polycondensation reaction of 235 DEG C of progress 4 hours, until sampling analysis hydroxyl
Value is 50-55mgKOH/g, and when acid value≤2.0mgKOH/g, cooling discharge obtains polyester polyol；
S16: castor oil polyhydric alcohol, ethyl acetate will be added in the polyester polyol in S15, is warming up to 60 after mixing evenly
DEG C formed mixture E；
S17: being warming up to 80 DEG C of successive reactions 2 hours after chain extender is added dropwise in the mixture E in S16, forms mixture F；
S18: the mixture F in sampling and testing S17, when its viscosity is at 2500 ± 500mPaS (25 DEG C), cooling simultaneously adds
Enter ethyl acetate, carbodiimides, organo-silicon coupling agent be sufficiently stirred within 30 minutes, forms mixture G；
S19: continuing to stir the mixture G in S18, and be sampled test to it, when its viscosity is 200-500mPaS
(25 DEG C), solid content filter when being 50% ± 1, obtain component A.
Further, in S2 B component preparation the following steps are included:
S21: trimethylolpropane, trimethylpentanediol are mixed 1.5 hours in 120 DEG C of environment and is dehydrated, form mixing
Object H；
S22: chain extender and ethyl acetate are mixed and heated to 60 DEG C, the mixture H in S21 is added dropwise, forms mixture
I；
S23: the mixture I in S22 is warming up to 80 ± 2 DEG C, reflux heat preservation 4 hours forms mixture J；
S24: to the mixture J sampling and testing in S24, when NCO is 13 ± 0.8, catalyst B is added in mixture J
Reaction 1 hour forms mixture K；
S25: adding hexamethylene diisocyanate derivative, ethyl acetate after mixture K is cooled to 60 DEG C, is formed mixed
Object L is closed, and when adding hexamethylene diisocyanate derivative, ethyl acetate to mixture L sampling and testing, when its NCO exists
6.0-6.5%, viscosity obtain B component at 100-300mPaS (25 DEG C).
Compared with the prior art, the invention has the following beneficial effects:
1., be applicable in bonding multiple material: high performance polyurethane adhesive of the present invention can be suitable for various material
Bonding, and the bonding of most of flexible packing material on the market can be met simultaneously, without taking traditional adhesive
Human resources have been saved in the multiple switching of glue in compound work, are improved production efficiency, are reduced cost, and excessive storage face is not necessarily to
Product, substantially increases the convenience of laminating production；
2., have excellent performance: high performance polyurethane adhesive of the present invention has extremely strong heat seal strength and removing strong
Degree, can be effectively reduced broken rate, and the tensile strength of the high performance polyurethane adhesive and elongation at break are traditional glue
2 times or more, residual solvent less than 3 milligrams, while can enhance product it is compound after barrier property, resistance oxygen, moisture barrier property be complete
It is up to state standards entirely；
3., energy-saving and emission-reduction excellent performance: high performance polyurethane adhesive of the present invention is founded state the compound beginning of interior dry type,
Realize the high cable gluing of high concentration, VOCs discharges more traditional glue and reduces 60%, and curing temperature is low, the time is short, is effectively reduced
Power consumption and raising working efficiency；
4., reduce composite cost 10%~20%: high performance polyurethane adhesive of the present invention has excellent viscous
Relay simultaneously realizes that high solids content glues, and butt spread is 15~20 ℅ fewer than traditional glue, and glue per ton can use 1 ton of retarder thinner less
~1.2 tons, every square metre of composite cost 2 of comprehensive reduction divides money or so；
5., reduce enterprise's expenses of taxation: because high performance polyurethane adhesive of the present invention realize high concentration gluing, solvent
Usage amount sharp fall, every dry compound machine year reduce VOSs discharge expense about 80,000 yuan of (tax) (every equivalent is based on 1.2 yuan)；
6., the production method of high performance polyurethane adhesive of the present invention, with high-performance according to the present invention
The component of polyurethane adhesive is one with weight ratio and completely combines, interrelated between them, mutually restrict, and appoints
The change of one component or weight ratio and the change of production method can all influence the effect of final finished.
To sum up, compared to traditional high performance polyurethane adhesive, the present invention is applied widely, can be applied with high concentration (50%)
Cloth is suitble to aluminizer, aluminium foil, boiling etc. to use, and good using rear appearance, lacquer disk(-sc) long service life meets energy conservation and environmental protection
The needs of upgrading.
Specific embodiment
The present invention is described further below.
Embodiment one
High performance polyurethane adhesive, including component A and B component, component A are uniformly mixed with B component by the mass ratio of 5:1
Afterwards to get high performance polyurethane adhesive；
According to parts by weight, component A, B component include raw material below:
Component A:
12 parts of ethylene glycol, 18 parts of 1-4 butanediol, 32 parts of diethylene glycol (DEG), 31 parts of neopentyl glycol, 42 parts of M-phthalic acid, catalysis
0.005 part of agent A, 60 parts of binary acid, 44 parts of adipic acid, 0.01 part of triphenyl phosphite, her castor oil of rattan production of Japan is polynary
5 parts of alcohol HF-1300,60 parts of ethyl acetate, 10 parts of chain extender, 1.8 parts of carbodiimides, 1.8 parts of organo-silicon coupling agent；
B component:
48 parts of trimethylolpropane, 14 parts of trimethylpentanediol, 230 parts of chain extender, 95 parts of ethyl acetate, catalyst
B0.003 parts, 10 parts of hexamethylene diisocyanate derivative.
The binary acid is decanedioic acid, and the hexamethylene diisocyanate derivative is HDI trimer, the chain extender
It is tetra-n-butyl titanate for MDI-50, the catalyst A, the catalyst B is organo-bismuth, and the organo-silicon coupling agent is ethylene
Base silane coupling agent.
By formula ratio by ethylene glycol, 1-4 butanediol, diethylene glycol (DEG), neopentyl glycol, M-phthalic acid, tetra-n-butyl titanate, the last of the ten Heavenly stems
Diacid, adipic acid, triphenyl phosphite, HF-1300, ethyl acetate, MDI-50, carbodiimides, organo-silicon coupling agent are added
Reaction kettle be uniformly mixed, be made component A, specifically, prepare component A the step of it is as follows:
S11: by 12 parts of ethylene glycol, 18 parts of 1-4 butanediol, 32 parts of diethylene glycol (DEG), 31 parts of neopentyl glycol and M-phthalic acid 42
Part mixing, stir evenly to form mixture A after be placed in reaction kettle in；
S12: the mixture A in S11 is heated to 190 DEG C of stopping heatings, tetra-n-butyl titanate 0.005 is then added
Part forms mixture B to its reaction；
S13: by weight, when the mixture B reaction in S12 is discharged 10.3 parts of famous dictum stoichiometric, 60 parts of decanedioic acid are added
And continuous warming carries out mixing esterification to 150 DEG C, forms mixture C；
S14: by weight, when the mixture C reaction in S13 is discharged 10.6 parts of famous dictum stoichiometric, 44 parts of adipic acid are added
And then continuous warming is added 0.01 part of triphenyl phosphite to 210 DEG C, form mixture D；
S15: by the mixture D persistently overheating in S14 to the polycondensation reaction of 235 DEG C of progress 4 hours, until sampling analysis hydroxyl
Value is 50mgKOH/g, and when acid value is 1.0mgKOH/g, cooling discharge obtains polyester polyol；
S16: 5 parts of HF-1300,20 parts of ethyl acetate will be added in the polyester polyol in S15, heats up after mixing evenly
To 60 DEG C of formation mixture Es；
S17: being warming up to 80 DEG C of successive reactions 2 hours after the mixture E in S16 is added dropwise 10 parts of MDI-50, forms mixing
Object F；
S18: the mixture F in sampling and testing S17, when its viscosity is at 2000mPaS (25 DEG C), cools down and vinegar is added
40 parts of acetoacetic ester, 1.8 parts of carbodiimides, 1.8 parts of vinyl silicane coupling agent be sufficiently stirred within 30 minutes, form mixing
Object G；
S19: continuing to stir the mixture G in S18, and be sampled test to it, when its viscosity is 200mPaS (25
DEG C), solid content be 49% when filter, obtain component A.
By formula ratio by trimethylolpropane, trimethylpentanediol, MDI-50, ethyl acetate, organo-bismuth, HDI trimer
Be added reaction kettle be uniformly mixed, be made B component, specifically, prepare B component the step of it is as follows:
S21: 48 parts of trimethylolpropane, 14 parts of trimethylpentanediol being mixed 1.5 hours in 120 DEG C of environment and are dehydrated,
Form mixture H, moisture content 0.002%；
S22: 230 parts of MDI-50 are mixed and heated to 60 DEG C with 32 parts of ethyl acetate, the mixture H in S21, shape is added dropwise
Resulting mixture I；
S23: the mixture I in S22 is warming up to 78 DEG C, reflux heat preservation 4 hours forms mixture J；
S24: to the mixture J sampling and testing in S24, when NCO is 12.2, organo-bismuth 0.003 is added in mixture J
Part reaction 1 hour, forms mixture K；
S25: adding 10 parts of HDI trimer, 63 parts of ethyl acetate after mixture K is cooled to 60 DEG C, forms mixture L,
And when adding HDI trimer, ethyl acetate to mixture L sampling and testing, when its NCO is 6.0%, viscosity is in 100mPaS
When (25 DEG C), B component is obtained.
Component A and B component press the mass ratio of 5:1 after evenly mixing to get high performance polyurethane adhesive.
Embodiment two
High performance polyurethane adhesive, including component A and B component, component A are uniformly mixed with B component by the mass ratio of 5:1
Afterwards to get high performance polyurethane adhesive；
According to parts by weight, component A, B component include raw material below:
Component A:
19 parts of ethylene glycol, 25 parts of 1-4 butanediol, 40 parts of diethylene glycol (DEG), 41 parts of neopentyl glycol, 48 parts of M-phthalic acid, catalysis
0.01 part of agent A, 80 parts of binary acid, 59 parts of adipic acid, 0.02 part of triphenyl phosphite, her castor oil of rattan production of Japan is polynary
10 parts of alcohol HF-1300,70 parts of ethyl acetate, 15 parts of chain extender, 2.7 parts of carbodiimides, 2.7 parts of organo-silicon coupling agent；
B component:
52 parts of trimethylolpropane, 18 parts of trimethylpentanediol, 230 parts of chain extender, 105 parts of ethyl acetate, catalyst B
0.005 part, 15 parts of hexamethylene diisocyanate derivative.
The binary acid is azelaic acid, and the hexamethylene diisocyanate derivative is HDI biuret, the chain extender
It is zinc acetate for MDI-100, the catalyst A, the catalyst B is organotin, and the organo-silicon coupling agent is vinyl silicon
Alkane coupling agent.
By formula ratio by ethylene glycol, 1-4 butanediol, diethylene glycol (DEG), neopentyl glycol, M-phthalic acid, tetra-n-butyl titanate, nonyl
Diacid, adipic acid, triphenyl phosphite, HF-1300, ethyl acetate, MDI-100, carbodiimides, organo-silicon coupling agent are added
Reaction kettle be uniformly mixed, be made component A, specifically, prepare component A the step of it is as follows:
S11: by 19 parts of ethylene glycol, 25 parts of 1-4 butanediol, 40 parts of diethylene glycol (DEG), 41 parts of neopentyl glycol and M-phthalic acid 48
Part mixing, stir evenly to form mixture A after be placed in reaction kettle in；
S12: the mixture A in S11 is heated to 190 DEG C of stopping heatings, is then added 0.01 part of zinc acetate to it
Reaction forms mixture B；
S13: by weight, when the mixture B reaction in S12 is discharged 11.8 parts of famous dictum stoichiometric, 80 parts of azelaic acid are added
And continuous warming carries out mixing esterification to 150 DEG C, forms mixture C；
S14: by weight, when the mixture C reaction in S13 is discharged 14.2 parts of famous dictum stoichiometric, 59 parts of adipic acid are added
And then continuous warming is added 0.02 part of triphenyl phosphite to 210 DEG C, form mixture D；
S15: by the mixture D persistently overheating in S14 to the polycondensation reaction of 235 DEG C of progress 4 hours, until sampling analysis hydroxyl
Value is 55mgKOH/g, and when acid value is 2.0mgKOH/g, cooling discharge obtains polyester polyol；
S16: 10 parts of HF-1300,20 parts of ethyl acetate will be added in the polyester polyol in S15, heats up after mixing evenly
To 60 DEG C of formation mixture Es；
S17: being warming up to 80 DEG C of successive reactions 2 hours after the mixture E in S16 is added dropwise 15 parts of MDI-100, is formed mixed
Close object F；
S18: the mixture F in sampling and testing S17, when its viscosity is at 3000mPaS (25 DEG C), cools down and vinegar is added
50 parts of acetoacetic ester, 2.7 parts of carbodiimides, 2.7 parts of vinyl silicane coupling agent be sufficiently stirred within 30 minutes, form mixing
Object G；
S19: continuing to stir the mixture G in S18, and be sampled test to it, when its viscosity is 500mPaS (25
DEG C), solid content be 51% when filter, obtain component A.
By formula ratio by trimethylolpropane, trimethylpentanediol, MDI-100, ethyl acetate, organotin, HDI biuret
Be added reaction kettle be uniformly mixed, be made B component, specifically, prepare B component the step of it is as follows:
S21: 52 parts of trimethylolpropane, 18 parts of trimethylpentanediol being mixed 1.5 hours in 120 DEG C of environment and are dehydrated,
Form mixture H, moisture content 0.05%；
S22: being mixed and heated to 60 DEG C with 35 parts of ethyl acetate for 230 parts of MDI-100, the mixture H in S21 be added dropwise,
Form mixture I；
S23: the mixture I in S22 is warming up to 82 DEG C, reflux heat preservation 4 hours forms mixture J；
S24: to the mixture J sampling and testing in S24, when NCO is 13.8, organotin 0.005 is added in mixture J
Part reaction 1 hour, forms mixture K；
S25: adding 15 parts of HDI biuret, 70 parts of ethyl acetate after mixture K is cooled to 60 DEG C, forms mixture L,
And when adding HDI biuret, ethyl acetate to mixture L sampling and testing, when its NCO is 6.5%, viscosity is in 300mPaS
When (25 DEG C), B component is obtained.
Component A and B component press the mass ratio of 5:1 after evenly mixing to get high performance polyurethane adhesive.
Embodiment three
High performance polyurethane adhesive, including component A and B component, component A are uniformly mixed with B component by the mass ratio of 5:1
Afterwards to get high performance polyurethane adhesive；
According to parts by weight, component A, B component include raw material below:
Component A:
15 parts of ethylene glycol, 22 parts of 1-4 butanediol, 37 parts of diethylene glycol (DEG), 36 parts of neopentyl glycol, 44 parts of M-phthalic acid, catalysis
0.007 part of agent A, 70 parts of binary acid, 51 parts of adipic acid, 0.015 part of triphenyl phosphite, her castor oil of rattan production of Japan is more
7 parts of first alcohol HF-1300,65 parts of ethyl acetate, 13 parts of chain extender, 2.3 parts of carbodiimides, 2.3 parts of organo-silicon coupling agent；
B component:
50 parts of trimethylolpropane, 16 parts of trimethylpentanediol, 230 parts of chain extender, 100 parts of ethyl acetate, catalyst B
0.004 part, 13 parts of hexamethylene diisocyanate derivative.
The binary acid includes decanedioic acid, azelaic acid, specifically, including 30 parts of decanedioic acid, 40 parts of azelaic acid；Described six is sub-
Methyl diisocyanate derivative includes HDI trimer, HDI biuret, specifically, including 6 parts of HDI trimer, HDI biuret
7 parts；The chain extender is MDI-103C, and the catalyst A includes tetra-n-butyl titanate, zinc acetate, specifically, including metatitanic acid four
0.003 part of N-butyl, 0.004 part of zinc acetate；The catalyst B includes organotin, organo-bismuth, specifically, including organotin
0.002 part, 0.002 part of organo-bismuth；The organo-silicon coupling agent is vinyl silicane coupling agent.
By formula ratio by ethylene glycol, 1-4 butanediol, diethylene glycol (DEG), neopentyl glycol, M-phthalic acid, catalyst A, binary acid,
Reaction kettle is added in adipic acid, antioxidant, castor oil polyhydric alcohol, ethyl acetate, chain extender, carbodiimides, organo-silicon coupling agent
Be uniformly mixed, be made component A, specifically, prepare component A the step of it is as follows:
S11: by 15 parts of ethylene glycol, 22 parts of 1-4 butanediol, 37 parts of diethylene glycol (DEG), 36 parts of neopentyl glycol and M-phthalic acid 44
Part mixing, stir evenly to form mixture A after be placed in reaction kettle in；
S12: the mixture A in S11 is heated to 190 DEG C of stopping heatings, tetra-n-butyl titanate 0.003 is then added
Part, 0.004 part of zinc acetate to its reaction, form mixture B；
S13: by weight, when the mixture B reaction in S12 is discharged 11.0 parts of famous dictum stoichiometric, 30 parts of decanedioic acid of addition,
40 parts of azelaic acid and continuous warming carry out mixing esterification to 150 DEG C, form mixture C；
S14: by weight, to 12.4 parts of famous dictum stoichiometric of water outlet of mixture C reaction in S13, addition adipic acid is simultaneously continuous
210 DEG C are warming up to, is then added 0.015 part of triphenyl phosphite, forms mixture D；
S15: by the mixture D persistently overheating in S14 to the polycondensation reaction of 235 DEG C of progress 4 hours, until sampling analysis hydroxyl
Value is 53mgKOH/g, and when acid value 1.5mgKOH/g, cooling discharge obtains polyester polyol；
S16: 7 parts of HF-1300,20 parts of ethyl acetate will be added in the polyester polyol in S15, heats up after mixing evenly
To 60 DEG C of formation mixture Es；
S17: being warming up to 80 DEG C of successive reactions 2 hours after the mixture E in S16 is added dropwise 13 parts of MDI-103C, is formed mixed
Close object F；
S18: the mixture F in sampling and testing S17, when its viscosity is at 2500mPaS (25 DEG C), cools down and vinegar is added
45 parts of acetoacetic ester, 2.3 parts of carbodiimides, 2.3 parts of vinyl silicane coupling agent be sufficiently stirred within 30 minutes, form mixing
Object G；
S19: continuing to stir the mixture G in S18, and be sampled test to it, when its viscosity is 350mPaS (25
DEG C), solid content be 50% when filter, obtain component A.
By formula ratio by trimethylolpropane, trimethylpentanediol, MDI-103C, ethyl acetate, organotin, organo-bismuth,
HDI trimer, HDI biuret be added reaction kettle be uniformly mixed, be made B component, specifically, prepare B component the step of it is as follows:
S21: 50 parts of trimethylolpropane, 16 parts of trimethylpentanediol being mixed 1.5 hours in 120 DEG C of environment and are dehydrated,
Form mixture H, moisture content 0.02%；
S22: 60 DEG C are mixed and heated to 33 parts of ethyl acetate by 230 parts of MDI-103C, the mixture in S21 is added dropwise
H forms mixture I；
S23: the mixture I in S22 is warming up to 80 DEG C, reflux heat preservation 4 hours forms mixture J；
S24: to the mixture J sampling and testing in S24, when NCO is 13, organotin 0.002 is added in mixture J
Part, 0.002 part of organo-bismuth react 1 hour, formed mixture K；
S25: adding 6 parts of HDI trimer, 7 parts of HDI biuret, 67 parts of ethyl acetate after mixture K is cooled to 60 DEG C,
Mixture L is formed, and when adding hexamethylene diisocyanate derivative, ethyl acetate to mixture L sampling and testing, when it
For NCO 6.3%, viscosity obtains B component at 200mPaS (25 DEG C).
Example IV
The present embodiment is identical as the scheme of embodiment one, and chain extender is only replaced with MDI-100LL.
Embodiment five
The present embodiment is identical as the scheme of embodiment two, and chain extender is only replaced with TDI-80.
Embodiment six
The present embodiment is identical as the scheme of embodiment three, only chain extender replace with including MDI-50, MDI-100LL,
TDI-80, wherein by weight, in the preparation of component A, need 5 parts of MDI-50,5 parts of MDI-100LL, 3 parts of TDI-80, B component
Preparation in, need 100 parts of MDI-50,100 parts of MDI-100LL, 30 parts of TDI-80.
Embodiment seven
High performance polyurethane adhesive, including component A and B component, component A are uniformly mixed with B component by the mass ratio of 5:1
Afterwards to get high performance polyurethane adhesive；
According to parts by weight, component A, B component include raw material below:
Component A:
14 parts of ethylene glycol, 23 parts of 1-4 butanediol, 38 parts of diethylene glycol (DEG), 33 parts of neopentyl glycol, 45 parts of M-phthalic acid, catalysis
0.008 part of agent A, 77 parts of binary acid, 48 parts of adipic acid, 0.013 part of triphenyl phosphite, her castor oil of rattan production of Japan is more
8 parts of first alcohol HF-1300,66 parts of ethyl acetate, 12 parts of chain extender, 2.1 parts of carbodiimides, 2.6 parts of organo-silicon coupling agent, two
6 parts of silica, 3 parts of dimethyl carbonate；
B component:
52 parts of trimethylolpropane, 15 parts of trimethylpentanediol, 230 parts of chain extender, 102 parts of ethyl acetate, catalyst
B0.003 parts, 12 parts of hexamethylene diisocyanate derivative.
The binary acid is decanedioic acid；The hexamethylene diisocyanate derivative is HDI trimer；The chain extender
It is tetra-n-butyl titanate for TDI-80, the catalyst A；The catalyst B is organotin；The organo-silicon coupling agent is ethylene
Base silane coupling agent.
The step of preparing component A is as follows:
S11: by 14 parts of ethylene glycol, 23 parts of 1-4 butanediol, 38 parts of diethylene glycol (DEG), 33 parts of neopentyl glycol and M-phthalic acid 45
Part, 3 parts of dimethyl carbonate mixing, stir evenly to form mixture A after be placed in reaction kettle in；
S12: the mixture A in S11 is heated to 190 DEG C of stopping heatings, tetra-n-butyl titanate 0.008 is then added
Part forms mixture B to its reaction；
S13: by weight, when the mixture B reaction in S12 is discharged 11.0 parts of famous dictum stoichiometric, 77 parts of decanedioic acid are added
And continuous warming carries out mixing esterification to 150 DEG C, forms mixture C；
S14: 6 parts of silica are added in mixture C, are dispersed 5min with dispersion machine with 500r/min, are added 0.04 part
TDI reacts 1h, obtains mixture X, and mixture X is warming up to 50 DEG C of addition dibutyl tin dilaurate reaction 1h, is mixed
Object Y, and 48 parts of adipic acid and continuous warming is added to 210 DEG C, it is then added 0.013 part of triphenyl phosphite, forms mixture
D；
S15: by the mixture D persistently overheating in S14 to the polycondensation reaction of 235 DEG C of progress 4 hours, until sampling analysis hydroxyl
Value is 53mgKOH/g, and when acid value 1.5mgKOH/g, cooling discharge obtains polyester polyol；
S16: 8 parts of HF-1300,20 parts of ethyl acetate will be added in the polyester polyol in S15, heats up after mixing evenly
To 60 DEG C of formation mixture Es；
S17: being warming up to 80 DEG C of successive reactions 2 hours after the mixture E in S16 is added dropwise 12 parts of TDI-80, forms mixing
Object F；
S18: the mixture F in sampling and testing S17, when its viscosity is at 2500mPaS (25 DEG C), cools down and vinegar is added
46 parts of acetoacetic ester, 2.1 parts of carbodiimides, 2.6 parts of vinyl silicane coupling agent be sufficiently stirred within 30 minutes, form mixing
Object G；
S19: continuing to stir the mixture G in S18, and be sampled test to it, when its viscosity is 350mPaS (25
DEG C), solid content be 50% when filter, obtain component A.
The step of preparing B component is as follows:
S21: 52 parts of trimethylolpropane, 15 parts of trimethylpentanediol being mixed 1.5 hours in 120 DEG C of environment and are dehydrated,
Form mixture H, moisture content 0.02%；
S22: being mixed and heated to 60 DEG C with 32 parts of ethyl acetate for 230 parts of TDI-80, the mixture H in S21 be added dropwise,
Form mixture I；
S23: the mixture I in S22 is warming up to 80 DEG C, reflux heat preservation 4 hours forms mixture J；
S24: to the mixture J sampling and testing in S24, when NCO is 13,0.003 part of organotin is added in mixture J
Reaction 1 hour forms mixture K；
S25: adding 12 parts of HDI trimer, 70 parts of ethyl acetate after mixture K is cooled to 60 DEG C, forms mixture L,
And when adding hexamethylene diisocyanate derivative, ethyl acetate to mixture L sampling and testing, when its NCO is 6.3%,
Viscosity obtains B component at 200mPaS (25 DEG C).
It is used for the high performance polyurethane adhesive that embodiment one to embodiment seven obtains to bond PET12/VMPET12/
CPE40, and the finished product data after bonding are tested for the property, the result is as follows:
It can be seen that the finished product data after embodiment one is bonded to embodiment seven have extremely strong heat seal strength and removing strong
Degree can be effectively reduced broken rate, and tensile strength and elongation at break are the 2 times or more of traditional glue, and embodiment is real always
Finished product after applying the high performance polyurethane adhesive bonding that example seven obtains, be all satisfied requirement of the QB/T 2358 to heat seal strength with
And requirement of the GB13022 to tensile strength, elongation at break, heat seal strength have reached required by QB/T 2,358 3 times or more,
Tensile strength and elongation at break are also 2-3 times or more required by having reached GB13022.Especially made from embodiment seven
Polyurethane adhesive, it is more environmentally-friendly without free isocyanates in glue, and polyurethane adhesive glue film can be improved again
Hardness and tensile strength can also be substantially reduced glue film water absorption rate.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (10)
1. high performance polyurethane adhesive, it is characterised in that: the high performance polyurethane adhesive includes component A and B component, A group
Divide with B component by the mass ratio of 5:1 after evenly mixing to get high performance polyurethane adhesive；
According to parts by weight, component A, B component include raw material below:
Component A:
12 parts -19 parts of ethylene glycol, 18 parts -25 parts of 1-4 butanediol, 32 parts -40 parts of diethylene glycol (DEG), 31 parts -41 parts of neopentyl glycol, isophthalic
42 parts -48 parts of dioctyl phthalate, 0.005 part -0.01 part of catalyst A, 60 parts -80 parts of binary acid, 44 parts -59 parts of adipic acid, antioxidant
0.01 part -0.02 part, 5 parts -10 parts of castor oil polyhydric alcohol, 60 parts -70 parts of ethyl acetate, 10 parts -15 parts of chain extender, carbonization two is sub-
1.8 parts -2.7 parts of amine, 1.8 parts -2.7 parts of organo-silicon coupling agent；
B component:
48 parts -52 parts of trimethylolpropane, 14 parts -18 parts of trimethylpentanediol, 230 parts of chain extender, 95 part -105 of ethyl acetate
Part, 0.003 part -0.005 part of catalyst B, 10 parts -15 parts of hexamethylene diisocyanate derivative.
2. high performance polyurethane adhesive as described in claim 1, it is characterised in that: the binary acid is decanedioic acid, nonyl two
One or more of acid.
3. high performance polyurethane adhesive as described in claim 1, it is characterised in that: the hexamethylene diisocyanate spreads out
Biology is one or more of HDI trimer, HDI biuret.
4. high performance polyurethane adhesive as described in claim 1, it is characterised in that: the chain extender is MDI-50, MDI-
100, one or more of MDI-103C, MDI-100LL, TDI-80.
5. high performance polyurethane adhesive as described in claim 1, it is characterised in that: the catalyst A is the positive fourth of metatitanic acid four
One or more of ester, zinc acetate, the catalyst B are one or more of organotin, organo-bismuth.
6. high performance polyurethane adhesive as described in claim 1, it is characterised in that: the antioxidant is phosphorous triphenyl phosphate
Ester.
7. high performance polyurethane adhesive as described in claim 1, it is characterised in that: the castor oil polyhydric alcohol be Japan she
The HF-1300 of rattan production.
8. the production method of any high performance polyurethane adhesive as described in claim 1-7, it is characterised in that: including with
Lower step:
The preparation of S1:A component: formula ratio is pressed by ethylene glycol, 1-4 butanediol, diethylene glycol (DEG), neopentyl glycol, M-phthalic acid, catalysis
Agent A, binary acid, adipic acid, antioxidant, castor oil polyhydric alcohol, ethyl acetate, chain extender, carbodiimides, organo-silicon coupling agent
Reaction kettle is added to be uniformly mixed, component A is made；
The preparation of S2:B component: formula ratio is pressed by trimethylolpropane, trimethylpentanediol, chain extender, ethyl acetate, catalyst
B, hexamethylene diisocyanate derivative is added reaction kettle and is uniformly mixed, and B component is made；
S3: component A and B component are obtained into high performance polyurethane adhesive by the mass ratio of 5:1 after evenly mixing.
9. the production method of high performance polyurethane adhesive as claimed in claim 8, it is characterised in that:
In S1 component A preparation the following steps are included:
S11: ethylene glycol, 1-4 butanediol, diethylene glycol (DEG), neopentyl glycol and M-phthalic acid are mixed, stir evenly to form mixture
It is placed in reaction kettle after A；
S12: the mixture A in S11 is heated to 190 DEG C of stopping heatings, catalyst A is then added and waits for its reaction, is formed
Mixture B；
S13: when the mixture B reaction water outlet famous dictum stoichiometric in S12, binary acid and continuous warming is added and is mixed to 150 DEG C
Esterification is closed, mixture C is formed；
S14: when the mixture C reaction water outlet famous dictum stoichiometric in S13, being added adipic acid and continuous warming to 210 DEG C, then plus
Enter antioxidant, forms mixture D；
S15: by the mixture D persistently overheating in S14 to the polycondensation reaction of 235 DEG C of progress 4 hours, until sampling analysis hydroxyl value is
When 50-55mgKOH/g, acid value≤2.0mgKOH/g, cooling discharge obtains polyester polyol；
S16: castor oil polyhydric alcohol, ethyl acetate will be added in the polyester polyol in S15, is warming up to 60 DEG C of shapes after mixing evenly
Resulting mixture E；
S17: being warming up to 80 DEG C of successive reactions 2 hours after chain extender is added dropwise in the mixture E in S16, forms mixture F；
S18: the mixture F in sampling and testing S17, when its viscosity is at 2500 ± 500mPaS (25 DEG C), cools down and vinegar is added
Acetoacetic ester, carbodiimides, organo-silicon coupling agent be sufficiently stirred within 30 minutes, form mixture G；
S19: continuing to stir the mixture G in S18, and be sampled test to it, when its viscosity is 200-500mPaS (25
DEG C), solid content be 50% ± 1 when filter, obtain component A.
10. the production method of high performance polyurethane adhesive as claimed in claim 8, it is characterised in that:
In S2 B component preparation the following steps are included:
S21: trimethylolpropane, trimethylpentanediol are mixed 1.5 hours in 120 DEG C of environment and is dehydrated, form mixture H；
S22: chain extender and ethyl acetate are mixed and heated to 60 DEG C, the mixture H in S21 is added dropwise, forms mixture I；
S23: the mixture I in S22 is warming up to 80 ± 2 DEG C, reflux heat preservation 4 hours forms mixture J；
S24: to the mixture J sampling and testing in S24, when NCO is 13 ± 0.8, catalyst B reaction 1 is added in mixture J
Hour, form mixture K；
S25: adding hexamethylene diisocyanate derivative, ethyl acetate after mixture K is cooled to 60 DEG C, forms mixture
L, and when adding hexamethylene diisocyanate derivative, ethyl acetate to mixture L sampling and testing, when its NCO is in 6.0-
6.5%, viscosity obtains B component at 100-300mPaS (25 DEG C).
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| CN111171775A (en) * | 2020-02-20 | 2020-05-19 | 南京玄思新材料有限公司 | Preparation method of low-VOC polyurethane adhesive for flexible package |
| CN111621258A (en) * | 2020-06-05 | 2020-09-04 | 美邦（黄山）胶业有限公司 | Low-friction-coefficient bi-component solvent-free polyurethane adhesive |
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| CN109468114B (en) | 2021-03-19 |
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