CN109651991A - Wet-cured type organic silicon modified polyurethane hot melt adhesive and preparation method thereof - Google Patents
Wet-cured type organic silicon modified polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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- CN109651991A CN109651991A CN201811474111.0A CN201811474111A CN109651991A CN 109651991 A CN109651991 A CN 109651991A CN 201811474111 A CN201811474111 A CN 201811474111A CN 109651991 A CN109651991 A CN 109651991A
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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- C08G18/40—High-molecular-weight compounds
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- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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Abstract
The invention discloses a kind of wet-cured type organic silicon modified polyurethane hot melt adhesive and preparation method thereof, feature is the polyether Glycols for including 5~40 parts, 1~25 part of liquid polyesters dihydric alcohol, 1~25 part of crystalline polyester dihydric alcohol, 5~40 parts of hydroxy-end capped poly-organosilicon acrylate copolymer, 1~30 part of isocyanates, 0.1~2 part of catalyst, 0.01~1 part of antioxidant and 0.1~1 part of silane coupling agent.By synthesis of hydroxy block it is poly- (methacryloxypropyl list block dimethyl polysiloxane-it is random-methyl methacrylate-is random-random-N- vinyl formamide of methyl acrylate -), organic silicon acrylic ester copolymer segment is introduced in base polyurethane prepolymer for use as, can further promote the solvent resistance and waterproof performance of polyurethane gel.The present invention solves traditional Research of Moisture-curable Polyurethane Hot-melt Adhesive solvent resistance and the insufficient defect of waterproof performance.
Description
Technical field
The invention belongs to structure glue technical fields, and in particular to a kind of wet-cured type organic silicon modified polyurethane hot melt adhesive and
Preparation method, which are mainly applied to electronics and appliance industry, automobile industry, weaving and shoe industry, food packing industry, wood materials to add
Work and furniture industry isostructuralism are bonded field.
Background technique
Polyurethane hot melt be a new generation can provide superior adhesion can structure glue, it is to be with polyurethane prepolymer
Material of main part is equipped with a hot melt adhesive prepared by various auxiliary agents.Polyurethane hot melt is easy to use and environmentally friendly, and performance again can be with
Solvent-based thermal melten gel compares favourably.Nearly ten years, polyurethane hot melt is obtained in the high-end fields such as electronics and appliance industry, automobile industry
It is fast-developing and be widely used.Polyurethane hot melt can be divided into thermoplastic polyurethane elastomer hot melt adhesive by cured form difference
And reactive polyurethane hot melt；Reactive polyurethane hot melt is different by its principle of solidification, and can be divided into wet-cured type and envelope
Closed form.Research of Moisture-curable Polyurethane Hot-melt Adhesive (PUR) is a kind of one pack system hot melt adhesive, is melted after heating, and flow scatter coated in
Substrate surface cools down after adherend bonding and forms excellent first adhesive property, then since substrate surface contains micro-moisture
Or other compounds containing active hydrogen, it is reacted with isocyano (- NCO) and chemical crosslink reaction occurs, so that generating has height
A kind of structural bonding hot melt adhesive of cross-linked network and cohesive force greatly.
Research of Moisture-curable Polyurethane Hot-melt Adhesive has technically obtained unprecedented development at present, low mainly around high-adhesive-strength
Melt viscosity, open hour reprocess and the progress performances such as cured form are optimized and revised." reactive hot-melt disclosed in Chinese patent
Adhesive ", application number are 201480080313.0, are prepared a kind of with the removable polyurethane-hot melt bonding reprocessed
Agent, more suitable for high-end electronic product scope application." solvent-free damp solidifying polyurethane hotmelt disclosed in Chinese patent
Composition ", application number are 201180047316.0, prepare a kind of low toxicity and quickly establish adhesive property polyacrylate and poly-
The polyurethane-hot melt viscose binder of ester preparation.In order to improve the cured form of Research of Moisture-curable Polyurethane Hot-melt Adhesive, Chinese patent is public
" the organic silicon modified polyurethane sealant " opened, application number is 2017102717258, prepares a kind of organic-silicon-modified poly- ammonia
Ester sealant replaces isocyano (- NCO) with silane coupling agent, is more suitable for applying under high humidity environment.Currently, wet-cured type is poly-
The research and development technology of urethane hot melt adhesive meets different type high-end electronic product scope application in fast development.The poly- ammonia of wet-cured type
Although ester hot melt adhesive can form highly cross-linked network after hardening, there is also solvent resistant, ageing-resistant performance and water resistances
It can insufficient problem.This main cause is most of Research of Moisture-curable Polyurethane Hot-melt Adhesive to improve its initial cohesiveness, be joined big
The non-reacted thermoplasticity thickening resin of amount or polynary acrylic copolymer.These non-reaction system thickening resins can not participate in solid
Metaplasia is at cross-linked network, to easily reduce solvent resistance and ageing-resistant performance of polyurethane hot melt adhesive coating etc..
Summary of the invention
A kind of wet-cured type organic silicon modified polyurethane heat is provided the purpose of the present invention is overcome the deficiencies in the prior art
Melten gel and preparation method thereof, this novel wet curing type silicone modified polyurethane hot melt adhesive are improved by organic-silicon-modified
Solvent resistance, ageing-resistant performance, waterproof performance of polyurethane coating etc..
In order to achieve the above object, the technical solution of wet-cured type organic silicon modified polyurethane hot melt adhesive of the invention is this
What sample was realized, it is characterised in that including 5~40 parts of polyether Glycols, 1~25 part of liquid polyesters dihydric alcohol, 1~25 part
Crystalline polyester dihydric alcohol, 5~40 parts of hydroxy-end capped poly-organosilicon acrylate copolymer, 1~30 part of isocyanates,
0.1~2 part of catalyst, 0.01~1 part of antioxidant and 0.1~1 part of silane coupling agent, are mass fraction above；Institute
The chemical structure for stating hydroxy-end capped poly-organosilicon acrylate copolymer is: hydroxy-end capped poly- (methacryloxypropyl list envelope
Hold dimethyl polysiloxane-it is random-methyl methacrylate-is random-random-N- vinyl formamide of methyl acrylate -) i.e. P
(MAPDMS-r-MMA-r-MA-r-NVF), average each macromolecular chain in hydroxy-end capped poly-organosilicon acrylate copolymer
1~2 hydroxy functional group is contained in end, and the number-average molecular weight of hydroxy-end capped poly-organosilicon acrylate copolymer is 1000~
50000。
In the technical scheme, the polyether Glycols are polyoxypropyleneglycol of the number-average molecular weight 500~4000
One or two kinds of any combination of PPG and polytetrahydrofuran ether glycol PTMG；
The liquid polyesters dihydric alcohol be number-average molecular weight 200~2000 polyethylene glycol adipate glycol PEA, gather oneself two
Acid -1,6- hexylene glycol esterdiol PHA and polyadipate -1,4-butanediol esterdiol PBA one or more any combination；
The crystalline polyester dihydric alcohol is to win 7380 one or more of wound Degussa model 7320, model 7360 and model
Any combination；
The isocyanates is modified diphenylmethane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer)；
The catalyst is one or more kinds of any groups of triethanolamine, 2,2- dimorpholine base Anaesthetie Ether and phosphoric acid
It closes；
The antioxidant is one or both of 168 and 1010 any combination；
The silane coupling agent is anilinomethyl triethoxysilane ND-42.
In order to achieve the above object, the technology of wet-cured type organic silicon modified polyurethane hot melt adhesive preparation method of the invention
Scheme is achieved in that it is characterized in that preparation step is as follows:
Step 1 synthesis of hydroxy blocks poly-organosilicon acrylate copolymer
1~20 part of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 1~30 part of methacrylic acid
Methyl esters MMA, 1~30 part of methyl acrylate MA and 1~15 part of N- vinyl formamide NVF are dissolved in 50~100 parts of toluene
In, 40~80 DEG C are controlled in, under nitrogen protection, 0.1~3 part of thermal initiator 4 is added, 4'- azo is bis- (4- cyano amylalcohol),
Polymerization reaction 0.5~30 hour, after rotary evaporation removes toluene, obtain hydroxy-end capped poly-organosilicon acrylate copolymer, hydroxyl
The number-average molecular weight that base blocks poly-organosilicon acrylate copolymer is 1000~50000；The methacryloxypropyl list
The number-average molecular weight for blocking dimethyl polysiloxane MAPDMS is 1000；
Step 2 synthesizes wet-cured type organic silicon modified polyurethane hot melt adhesive
5~40 parts of polyether Glycols, 1~25 part of liquid polyesters dihydric alcohol, 1~25 part of crystalline polyester dihydric alcohol, 5~
Hydroxy-end capped poly-organosilicon acrylate copolymer that 40 parts of the step of one synthesize, 0.1~2 part of catalyst and 0.01~1 part
Antioxidant mixing after, calorify 120~150 DEG C, vacuumize water removal about 1~3 hour, until the water content of mixture is lower than
280ppm cools down in 70~100 DEG C, under nitrogen protection, 1~30 part of isocyanates is added, it is small to carry out polymerization reaction 1~5
When, sampling analysis polymerizate NCO% content reaches 1%~3%, and viscosity reaches 3000~15000 mPa.s, is added 0.1~1 part
Silane coupling agent, obtain wet-cured type organic silicon modified polyurethane hot melt adhesive, be above mass fraction.
In the technical scheme, with Brookfield DV-C digital viscometer viscosity, test setting temperature is 100
℃。
Compared with prior art, the present invention have following advantages and effects
1, the present invention solves the defect of the deficiencies of traditional Research of Moisture-curable Polyurethane Hot-melt Adhesive solvent resistance, ageing-resistant performance；
In the technical solution of the present invention, hydroxy-end capped poly-organosilicon acrylate copolymer will be organic using hydroxyl radical initiator
Silicon monomer (MAPDMS), acrylic ester monomer (MMA and MA) and adhesive force function monomer (NVF) copolymerization are sealed into hydroxyl
Hold poly-organosilicon acrylate copolymer.Organic silicon monomer can promote the solvent resistance and ageing-resistant performance of hot melt adhesive.Propylene
Esters of gallic acid monomer can promote hot melt adhesive tack and cooling velocity.Hydroxyl blocks poly-organosilicon acrylate copolymer part ginseng
With to base polyurethane prepolymer for use as synthetic reaction, efficiently acts synergistically, show preferable compatibility, the other raw materials of a successive step of going forward side by side
Composition and content improve solvent resistance and adhesive force.
2, thickening resin acrylic copolymer random polycondensation is introduced base polyurethane prepolymer for use as by the present invention, improves thickening resin
With the compatibility of polyurethane, Research of Moisture-curable Polyurethane Hot-melt Adhesive solvent resistance is further solved；
3, the present invention solves the problems, such as that traditional Research of Moisture-curable Polyurethane Hot-melt Adhesive is poor to substrate wet performance, improves hot melt adhesive
The flow leveling of sizing, packaging and Process of Applying Glue are not likely to produce bubble.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Number involved in following embodiment is mass fraction.
Embodiment one
It is a kind of wet-cured type organic silicon modified polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1 synthesis of hydroxy blocks poly-organosilicon acrylate copolymer
10 parts of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 20 parts of methyl methacrylate
MMA, 10 parts of methyl acrylate MA and 5 parts of N- vinyl formamide NVF are dissolved in 70 parts of toluene, are controlled in 60 DEG C,
Under nitrogen protection, 2.8 parts of thermal initiator 4 is added, 4'- azo is bis- (4- cyano amylalcohol), and polymerization reaction 2 hours, rotation was steamed
After hair removes toluene, hydroxy-end capped poly-organosilicon acrylate copolymer, hydroxy-end capped poly-organosilicon acrylic ester copolymer are obtained
The number-average molecular weight of object is 12000, and chemical structure is: hydroxy-end capped poly- (it is poly- that methacryloxypropyl list blocks dimethyl
Siloxanes-is random-and methyl methacrylate-is random-random-N- vinyl formamide of methyl acrylate -) i.e. P(MAPDMS-r-
MMA-r-MA-r-NVF), in hydroxy-end capped poly-organosilicon acrylate copolymer average each macromolecular chain end contain 1~
2 hydroxy functional groups；The number-average molecular weight of the methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS is 1000,
No. CAS: 146632-07-7；
Step 2 synthesizes wet-cured type organic silicon modified polyurethane hot melt adhesive
By 20 parts of polyoxypropyleneglycol PPG, 25 parts of polyethylene glycol adipate glycol PEA, 15 parts of crystalline polyester
Hydroxy-end capped poly-organosilicon acrylate copolymer, 0.1 part of the phosphoric acid and 0.04 of the synthesis of 7360,10 parts of dihydric alcohol the step of one
After the irgasfos 168 mixing of part, 120 DEG C are calorified, water removal 2 hours is vacuumized, until the water content of mixture is lower than
280ppm cools down in 80 DEG C, under nitrogen protection, 14 parts of 4,4 '-diisocyanate of modified diphenylmethane-is added
Desmodur CD-C(MDI performed polymer), it carries out polymerization reaction 2 hours, sampling analysis polymerizate NCO% content reaches 2.0%,
Viscosity reaches 4500 mPa.s, 0.2 part of silane coupling agent ND-42 is added, obtains wet-cured type organic silicon modified polyurethane heat
Melten gel is mass fraction above；The number-average molecular weight of the polyoxypropyleneglycol PPG is 1000, the polyadipate second
The number-average molecular weight of glycol esterdiol PEA is 500, measures viscosity at 100 DEG C with Brookfield DV-C Digital Viscometer.
Embodiment two
It is a kind of wet-cured type organic silicon modified polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1 synthesis of hydroxy blocks poly-organosilicon acrylate copolymer
14 parts of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 25 parts of methyl methacrylate
MMA, 20 parts of methyl acrylate MA and 7 parts of N- vinyl formamide NVF are dissolved in 80 parts of toluene, are controlled in 65 DEG C,
Under nitrogen protection, 1 part of thermal initiator 4 is added, 4'- azo is bis- (4- cyano amylalcohol), and polymerization reaction 10 hours, rotary evaporation
After removing toluene, hydroxy-end capped poly-organosilicon acrylate copolymer, hydroxy-end capped poly-organosilicon acrylate copolymer are obtained
Number-average molecular weight be 31000, chemical structure is: it is hydroxy-end capped it is poly- (methacryloxypropyl list block the poly- silicon of dimethyl
Oxygen alkane-is random-and methyl methacrylate-is random-random-N- vinyl formamide of methyl acrylate -) i.e. P(MAPDMS-r-
MMA-r-MA-r-NVF), in hydroxy-end capped poly-organosilicon acrylate copolymer average each macromolecular chain end contain 1~
2 hydroxy functional groups；The number-average molecular weight of the methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS is 1000,
No. CAS: 146632-07-7；
Step 2 synthesizes wet-cured type organic silicon modified polyurethane hot melt adhesive
By 28 parts of polytetrahydrofuran ether glycol PTMG, 20 parts of polyadipate -1,6- hexylene glycol esterdiol PHA, 20 parts of knot
The hydroxy-end capped poly-organosilicon acrylate copolymer of the synthesis of 7380,14 parts of crystalline polyester dihydric alcohol the step of one, the three of 0.4 part
After ethanol amine and the mixing of 0.1 part of irgasfos 168,130 DEG C are calorified, water removal 2.5 hours is vacuumized, until the moisture content of mixture
Content is lower than 280ppm, cools down in 70 DEG C, under nitrogen protection, 20 parts of 4,4 '-diisocyanate of modified diphenylmethane-is added
Desmodur CD-C(MDI performed polymer), it carries out polymerization reaction 3 hours, sampling analysis polymerizate NCO% content reaches 2.5%,
Viscosity reaches 5700 mPa.s, and 0.4 part of silane coupling agent ND-42 is added, and obtains wet-cured type organic silicon modified polyurethane heat
Melten gel is mass fraction above；The number-average molecular weight of the polytetrahydrofuran ether glycol PTMG is 2000, described to gather oneself two
The number-average molecular weight of acid -1,6- hexylene glycol esterdiol PHA is 1000, with Brookfield DV-C Digital Viscometer at 100 DEG C
Measure viscosity.
Embodiment three
It is a kind of wet-cured type organic silicon modified polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1 synthesis of hydroxy blocks poly-organosilicon acrylate copolymer
17 parts of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 30 parts of methyl methacrylate
MMA, 15 parts of methyl acrylate MA and 10 parts of N- vinyl formamide NVF are dissolved in 90 parts of toluene, are controlled in 75 DEG C,
Under nitrogen protection, 0.8 part of thermal initiator 4 is added, 4'- azo is bis- (4- cyano amylalcohol), and polymerization reaction 15 hours, rotation was steamed
After hair removes toluene, hydroxy-end capped poly-organosilicon acrylate copolymer, hydroxy-end capped poly-organosilicon acrylic ester copolymer are obtained
The number-average molecular weight of object is 39000, and chemical structure is: hydroxy-end capped poly- (it is poly- that methacryloxypropyl list blocks dimethyl
Siloxanes-is random-and methyl methacrylate-is random-random-N- vinyl formamide of methyl acrylate -) i.e. P(MAPDMS-r-
MMA-r-MA-r-NVF), in hydroxy-end capped poly-organosilicon acrylate copolymer average each macromolecular chain end contain 1~
2 hydroxy functional groups；The number-average molecular weight of the methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS is 1000,
No. CAS: 146632-07-7；
Step 2 synthesizes wet-cured type organic silicon modified polyurethane hot melt adhesive
By 35 parts of polyoxypropyleneglycol PPG, 27 parts of polyethylene glycol adipate glycol PEA, 10 parts of crystalline polyester
Hydroxy-end capped poly-organosilicon acrylate copolymer, 0.7 part of the 2,2- dimorpholine of the synthesis of 7320,17 parts of dihydric alcohol the step of one
After base Anaesthetie Ether and the mixing of 0.5 part of antioxidant 1010,150 DEG C are calorified, water removal 3 hours is vacuumized, until mixture
Water content is lower than 280ppm, cools down in 80 DEG C, under nitrogen protection, 25 parts of 4,4 '-two isocyanide of modified diphenylmethane-is added
Acid esters Desmodur CD-C(MDI performed polymer), it carries out polymerization reaction 4 hours, sampling analysis polymerizate NCO% content reaches
2.7%, viscosity reaches 6800 mPa.s, and 0.7 part of silane coupling agent ND-42 is added, and obtains the organic-silicon-modified poly- ammonia of wet-cured type
Ester hot melt adhesive is mass fraction above；The number-average molecular weight of the polyoxypropyleneglycol PPG is 3000, described to gather oneself two
The number-average molecular weight of sour glycol ester glycol PEA is 1500, is measured at 100 DEG C with Brookfield DV-C Digital Viscometer
Viscosity.
Example IV
It is a kind of wet-cured type organic silicon modified polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1 synthesis of hydroxy blocks poly-organosilicon acrylate copolymer
20 parts of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 10 parts of methyl methacrylate
MMA, 30 parts of methyl acrylate MA and 15 parts of N- vinyl formamide NVF are dissolved in 100 parts of toluene, are controlled in 75
DEG C, under nitrogen protection, 0.4 part of thermal initiator 4 being added, 4'- azo is bis- (4- cyano amylalcohol), and polymerization reaction 25 hours, rotation
After turning evaporation removing toluene, hydroxy-end capped poly-organosilicon acrylate copolymer, hydroxy-end capped poly-organosilicon acrylate are obtained
The number-average molecular weight of copolymer is 46000, and chemical structure is: hydroxy-end capped poly- (methacryloxypropyl list sealing end diformazan
Based polysiloxane-is random-and methyl methacrylate-is random-random-N- vinyl formamide of methyl acrylate -) i.e. P
(MAPDMS-r-MMA-r-MA-r-NVF), average each macromolecular chain in hydroxy-end capped poly-organosilicon acrylate copolymer
Contain 1~2 hydroxy functional group in end；The number of the methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS is divided equally
Son amount is 1000, No. CAS: 146632-07-7；
Step 2 synthesizes wet-cured type organic silicon modified polyurethane hot melt adhesive
By 40 parts of polyoxypropyleneglycol PPG, 30 parts of polyadipate -1,4-butanediol esterdiol PBA, 20 parts of crystal type
Hydroxy-end capped poly-organosilicon acrylate copolymer, 1.0 parts of three ethyl alcohol of the synthesis of 7360,20 parts of polyester diol the step of one
After amine and the mixing of 0.8 part of irgasfos 168,150 DEG C are calorified, water removal 2 hours is vacuumized, until the water content of mixture is low
In 280ppm, cool down in 90 DEG C, under nitrogen protection, 29 parts of 4,4 '-diisocyanate of modified diphenylmethane-is added
Desmodur CD-C(MDI performed polymer), it carries out polymerization reaction 5 hours, sampling analysis polymerizate NCO% content reaches 2.6%,
Viscosity reaches 7600 mPa.s, and 0.9 part of silane coupling agent ND-42 is added, and obtains wet-cured type organic silicon modified polyurethane heat
Melten gel is mass fraction above；The number-average molecular weight of the polyoxypropyleneglycol PPG is 4000, the polyadipate -1,
The number-average molecular weight of 4- butyl glycol ester diol PBA is 2000, is measured at 100 DEG C with Brookfield DV-C Digital Viscometer
Viscosity.
Performance test
The present invention is organic-silicon-modified referring to the wet-cured type that the universal method of current hot melt adhesive obtains the four kinds of above embodiments
Polyurethane hot melt carry out melt viscosity, the open hour, shore hardness, elongation at break, shear strength and with the energy of resistance to acidity of oil
Index test.Melt viscosity is tested referring to HG/T3660-1999 standard, selects No. 27 rotors, is arranged 100 DEG C.When open
Between tested referring to ASTM D4497-1994 (2004) method.Shore hardness is surveyed referring to GB-T2411-2008 standard
Examination.Elongation at break is tested referring to GB/T30776-2014 standard.Shear strength is carried out referring to GB/T7124-2004 standard
Test.The specific test method of solvent resistance index is to prepare sample with reference to test shear strength method, and sample is placed 72 hours
After solidification, sample is soaked in oleic acid (purity 98%) solution 24 hours, sample is taken out, is placed in 85 DEG C and 85% relative humidity
Under environment, after carrying out aging 1000 hours, then shear strength test is carried out.Water contact angle refers to GB/T 30693-2014 standard
It is tested.All test data comparative situations are see the following table 1.
Each embodiment specific performance of table 1 tests control case
It can be seen that the wet-cured type organic silicon modified polyurethane hot melt adhesive of the invention synthesized with excellent from the data of table 1
Solvent resistant corrosive nature, ageing-resistant performance and hydrophobic performance.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (3)
1. a kind of wet-cured type organic silicon modified polyurethane hot melt adhesive, it is characterised in that including 5~40 parts of polyether Glycols, 1
~25 parts of liquid polyesters dihydric alcohol, 1~25 part of crystalline polyester dihydric alcohol, 5~40 parts of hydroxy-end capped poly-organosilicon third
Olefin(e) acid ester copolymer, 1~30 part of isocyanates, 0.1~2 part of catalyst, 0.01~1 part of antioxidant and 0.1~1 part
Silane coupling agent is mass fraction above；The chemical structure of the hydroxy-end capped poly-organosilicon acrylate copolymer is: hydroxyl
Base sealing end it is poly- (methacryloxypropyl list block dimethyl polysiloxane-it is random-methyl methacrylate-is random-acrylic acid
Random-N- the vinyl formamide of methyl esters -) i.e. P(MAPDMS-r-MMA-r-MA-r-NVF), in hydroxy-end capped poly-organosilicon propylene
1~2 hydroxy functional group is contained in average each macromolecular chain end in acid ester copolymer, and hydroxy-end capped poly-organosilicon acrylate is total
The number-average molecular weight of polymers is 1000~50000.
2. wet-cured type organic silicon modified polyurethane hot melt adhesive according to claim 1, it is characterised in that:
The polyether Glycols are polyoxypropyleneglycol PPG and polytetrahydrofuran ether two of the number-average molecular weight 500~4000
One or two kinds of any combination of alcohol PTMG；
The liquid polyesters dihydric alcohol be number-average molecular weight 200~2000 polyethylene glycol adipate glycol PEA, gather oneself two
Acid -1,6- hexylene glycol esterdiol PHA and polyadipate -1,4-butanediol esterdiol PBA one or more any combination；
The crystalline polyester dihydric alcohol is to win 7380 one or more of wound Degussa model 7320, model 7360 and model
Any combination；
The isocyanates is modified diphenylmethane -4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer)；
The catalyst is one or more kinds of any groups of triethanolamine, 2,2- dimorpholine base Anaesthetie Ether and phosphoric acid
It closes；
The antioxidant is one or both of 168 and 1010 any combination；
The silane coupling agent is anilinomethyl triethoxysilane ND-42.
3. a kind of wet-cured type organic silicon modified polyurethane hot melt adhesive preparation method, it is characterised in that preparation step is as follows:
Step 1 synthesis of hydroxy blocks poly-organosilicon acrylate copolymer
1~20 part of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 1~30 part of methacrylic acid
Methyl esters MMA, 1~30 part of methyl acrylate MA and 1~15 part of N- vinyl formamide NVF are dissolved in 50~100 parts of toluene
In, 40~80 DEG C are controlled in, under nitrogen protection, 0.1~3 part of thermal initiator 4 is added, 4'- azo is bis- (4- cyano amylalcohol),
Polymerization reaction 0.5~30 hour, after rotary evaporation removes toluene, obtain hydroxy-end capped poly-organosilicon acrylate copolymer, hydroxyl
The number-average molecular weight that base blocks poly-organosilicon acrylate copolymer is 1000~50000；The methacryloxypropyl list
The number-average molecular weight for blocking dimethyl polysiloxane MAPDMS is 1000；
Step 2 synthesizes wet-cured type organic silicon modified polyurethane hot melt adhesive
5~40 parts of polyether Glycols, 1~25 part of liquid polyesters dihydric alcohol, 1~25 part of crystalline polyester dihydric alcohol, 5~
Hydroxy-end capped poly-organosilicon acrylate copolymer that 40 parts of the step of one synthesize, 0.1~2 part of catalyst and 0.01~1 part
Antioxidant mixing after, calorify 120~150 DEG C, vacuumize water removal about 1~3 hour, until the water content of mixture is lower than
280ppm cools down in 70~100 DEG C, under nitrogen protection, 1~30 part of isocyanates is added, it is small to carry out polymerization reaction 1~5
When, sampling analysis polymerizate NCO% content reaches 1%~3%, and viscosity reaches 3000~15000 mPa.s at 100 DEG C, is added
0.1~1 part of silane coupling agent obtains wet-cured type organic silicon modified polyurethane hot melt adhesive, is above mass fraction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019088A (en) * | 2019-12-26 | 2020-04-17 | 烟台德邦科技有限公司 | Preparation method of organic silicon modified polyurethane hot melt adhesive |
| CN114163972A (en) * | 2021-12-30 | 2022-03-11 | 烟台信友新材料有限公司 | High-wettability environment-friendly three-proofing adhesive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1901942A (en) * | 2003-12-30 | 2007-01-24 | 庄臣及庄臣视力保护公司 | Antimicrobial contact lenses and methods for their production |
| CN104245769A (en) * | 2012-04-12 | 2014-12-24 | Dic株式会社 | Moisture-curable polyurethane hot melt resin composition, adhesive and article |
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2018
- 2018-12-04 CN CN201811474111.0A patent/CN109651991A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1901942A (en) * | 2003-12-30 | 2007-01-24 | 庄臣及庄臣视力保护公司 | Antimicrobial contact lenses and methods for their production |
| CN104245769A (en) * | 2012-04-12 | 2014-12-24 | Dic株式会社 | Moisture-curable polyurethane hot melt resin composition, adhesive and article |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019088A (en) * | 2019-12-26 | 2020-04-17 | 烟台德邦科技有限公司 | Preparation method of organic silicon modified polyurethane hot melt adhesive |
| CN114163972A (en) * | 2021-12-30 | 2022-03-11 | 烟台信友新材料有限公司 | High-wettability environment-friendly three-proofing adhesive and preparation method thereof |
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