CN109651994A - Ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive and preparation method thereof - Google Patents
Ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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- CN109651994A CN109651994A CN201811475689.8A CN201811475689A CN109651994A CN 109651994 A CN109651994 A CN 109651994A CN 201811475689 A CN201811475689 A CN 201811475689A CN 109651994 A CN109651994 A CN 109651994A
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- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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Abstract
本发明公开了一种耐老化性能优异阻燃湿气固化聚氨酯热熔胶及其制备方法，特点是包括1～20份的聚醚二元醇、1～50份的阻燃聚醚多元醇、1～40份的液态聚酯二元醇、1～40份的结晶型聚酯二元醇、1～45份的含磷阻燃型聚有机硅丙烯酸酯共聚物、20～60份的异氰酸酯、0.01～1份的催化剂、0.01～1份的抗氧剂和0.1～2份的硅烷偶联剂。本发明合成了聚（甲基丙烯酰氧丙基单封端二甲基聚硅氧烷‑无规‑2‑甲基‑2‑丙烯酸‑2‑羟乙基酯磷酸酯‑无规‑丙烯酸丁酯‑无规‑甲基丙烯酸羟乙酯），加入了到聚氨酯预聚体，引入有机硅丙烯酸酯共聚物链段和反应型阻燃剂，含羟基丙烯酸功能单体能将含磷阻燃型聚有机硅丙烯酸酯共聚物部分参与到聚氨酯预聚体合成反应，配方成份高效协同作用，改善聚氨酯热熔胶的耐老化性能和阻燃性能。The invention discloses a flame-retardant moisture-curable polyurethane hot-melt adhesive with excellent aging resistance and a preparation method thereof, which are characterized by comprising 1-20 parts of polyether diol, 1-50 parts of flame-retardant polyether polyol, 1-40 parts of liquid polyester diol, 1-40 parts of crystalline polyester diol, 1-45 parts of phosphorus-containing flame retardant polyorganosilicon acrylate copolymer, 20-60 parts of isocyanate, 0.01-1 part of catalyst, 0.01-1 part of antioxidant and 0.1-2 part of silane coupling agent. The present invention synthesizes poly(methacryloyloxypropyl mono-terminated dimethylpolysiloxane-random-2-methyl-2-acrylic acid-2-hydroxyethyl phosphate ester-random-acrylic acid butyl) ester-random-hydroxyethyl methacrylate), added to the polyurethane prepolymer, the introduction of silicone acrylate copolymer segments and reactive flame retardants, hydroxyl-containing acrylic functional monomers can convert phosphorus-containing flame retardant The polyorganosilicon acrylate copolymer partially participates in the synthesis reaction of the polyurethane prepolymer, and the ingredients of the formula have an efficient synergy to improve the aging resistance and flame retardant properties of the polyurethane hot melt adhesive.
Description
Technical field
The invention belongs to structure glue technical fields, and in particular to a kind of ageing-resistant performance excellent flame damp solidifying polyurethane
Hot melt adhesive and preparation method thereof, which are mainly applied to electronics and appliance industry, automobile industry, weaving and shoe industry, food packing industry,
Wood material processing and furniture industry isostructuralism are bonded field.
Background technique
Polyurethane hot melt be a new generation can provide superior adhesion can structure glue, it is to be with polyurethane prepolymer
Material of main part is equipped with a hot melt adhesive prepared by various auxiliary agents.Polyurethane hot melt is easy to use 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 is different by cured form, can be divided into thermoplastic polyurethane elastomer hot melt
Glue and reactive polyurethane hot melt；Reactive polyurethane hot melt is different by its principle of solidification, can be divided into response type and closing
Type；Reaction type polyurethane hot-melt adhesive (PUR) is a kind of one pack system hot melt adhesive, is melted after heating, and flows scatter coated in substrate
Surface cools down after adherend bonding and forms excellent first adhesive property, then due to substrate surface contain micro-moisture or its
His compound containing active hydrogen reacts with isocyano (- NCO) and chemical crosslink reaction occurs, thus generate have it is highly cross-linked
A kind of structural bonding hot melt adhesive of network and cohesive force greatly.
Reaction type polyurethane hot-melt adhesive has technically obtained unprecedented development at present, mainly around high-adhesive-strength, eutectic
Body viscosity, open hour reprocess and the progress performances such as cured form are optimized and revised." reactive hot-melt is viscous disclosed in Chinese patent
Mixture ", application number are 201480080313.0, prepare it is a kind of with the removable polyurethane-hot melt adhesive reprocessed, more
It is suitable for high-end electronic product scope application." solvent-free damp solidifying polyurethane hotmelt combination disclosed in Chinese patent
Object ", application number are 201180047316.0, prepare it is a kind of low toxicity quickly establish adhesive property polyacrylate and polyester preparation
Polyurethane-hot melt viscose binder.It is " organic disclosed in Chinese patent in order to improve the cured form of reaction type polyurethane hot-melt adhesive
Silicon modified polyurethane sealant ", application number are 2017102717258, prepare a kind of organic silicon modified polyurethane sealant, are used
Silane coupling agent replaces isocyano (- NCO), is more suitable for applying under high humidity environment.Currently, reaction type polyurethane hot-melt adhesive is ground
Hair technology meets different type high-end electronic product scope application in fast development.Although reaction type polyurethane hot-melt adhesive can be
Highly cross-linked network is formed after solidification, but there is also the performances deficiency problems such as ageing-resistant, fire-retardant.This main cause is most
Number reaction type polyurethane hot-melt adhesive joined a large amount of non-reacted thermoplasticity thickening resin or more to improve its initial cohesiveness
First acrylic copolymer.These non-reaction system thickening resins can not participate in solidification and generate cross-linked network, to easily reduce poly- ammonia
The ageing-resistant performance of rouge hot melt adhesive coating.
Summary of the invention
A kind of ageing-resistant performance excellent flame moisture-curable is provided the purpose of the present invention is overcome the deficiencies in the prior art
Polyurethane hot melt and preparation method thereof, due to being introduced in ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive
Silane segment and reactive flame retardant can further improve ageing-resistant performance, flame retardant property of polyurethane coating etc..
In order to achieve the above object, the technology of ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive of the invention
Scheme is achieved in that it is characterized by comprising 1~20 part of polyether Glycols, 1~50 part of flame retardant polyether polyol, 1
~40 parts of liquid polyesters dihydric alcohol, 1~40 part of crystalline polyester dihydric alcohol, 1~45 part of phosphor-containing flame-proof type poly-organosilicon
Acrylate copolymer, 20~60 parts of isocyanates, 0.01~1 part of catalyst, 0.01~1 part of antioxidant and 0.1~2
The silane coupling agent of part；It is above mass fraction；The chemistry knot of the phosphor-containing flame-proof type poly-organosilicon acrylate copolymer
Structure is: poly- (methacryloxypropyl list blocks the random -2- methyl -2- 2-hydroxyethyl acrylate of dimethyl polysiloxane -
Phosphate-is random-and butyl acrylate-is random-hydroxyethyl methacrylate) i.e. P(MAPDMS-r-HMP-r-BA-r-HEMA), contain
The number-average molecular weight of phosphorus flame retardant type 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 or polytetrahydrofuran ether glycol PTMG；
The flame retardant polyether polyol is WANOL FR-130, the WANOL of Wanhua Chemical Group Co., Ltd.'s production
One or two kinds of any combination of FR-212 or WANOL FR-312；
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 preparation of ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive of the invention
The technical solution of method is achieved in that it is characterized in that preparation step is as follows:
Step 1 synthesizes phosphor-containing flame-proof type poly-organosilicon acrylate copolymer
1~20 part of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 1~40 part of 2- methyl -2-
2-hydroxyethyl acrylate phosphate HMP, 1~40 part of butyl acrylate BA and 1~5 part of hydroxyethyl methacrylate
HEMA is dissolved in 50~100 parts of toluene, is controlled in 40~110 DEG C, under nitrogen protection, 0.1~2 part of heat is added and causes
Agent peroxidating 2 ethyl hexanoic acid tert-pentyl ester polymerization reaction 2~50 hours, after rotary evaporation removes toluene, obtains phosphor-containing flame-proof type
Poly-organosilicon acrylate copolymer, the number-average molecular weight of phosphor-containing flame-proof type poly-organosilicon acrylate copolymer is 1000~
50000；The number-average molecular weight of the methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS is 1000；
Step 2 synthesizes ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive
By 1~20 part of polyether Glycols, 1~50 part of flame retardant polyether polyol, 1~40 part of liquid polyesters dihydric alcohol, 1~
40 parts of crystalline polyester dihydric alcohol, 1~45 part of phosphor-containing flame-proof type poly-organosilicon acrylate copolymer, 0.01~1 part
After catalyst and the mixing of 0.01~1 part of antioxidant, 120~150 DEG C are calorified, water removal about 1~3 hour is vacuumized, until mixed
The water content for closing object is lower than 280ppm, cools down in 70~100 DEG C, under nitrogen protection, 20~60 parts of isocyanates is added,
It carries out polymerization reaction 1~10 hour, sampling analysis polymerizate NCO% content reaches 1%~3%, and viscosity reaches 3000 at 100 DEG C
0.1~2 part of silane coupling agent is added in~15000 mPa.s, obtains ageing-resistant performance excellent flame damp solidifying polyurethane heat
Melten gel is mass fraction above.
In the technical scheme, with Brookfield DV-C digital viscometer viscosity.
Compared with prior art, the present invention have following advantages and effects
1, in the technical solution of the present invention, phosphor-containing flame-proof type poly-organosilicon acrylate copolymer is a kind of organic silicon monomer, third
Olefin(e) acid ester phosphorous-containing monomers, acrylate monomer and hydroxy acryl acid function monomer are copolymerized.Organic silicon monomer can promote heat
The chemicals-resistant corrosive nature and ageing-resistant performance of melten gel.The flame retardant property of hot melt adhesive and attached can be improved in acrylate phosphorous-containing monomers
Put forth effort.Acrylate monomer can promote hot melt adhesive tack.Hydroxy acryl acid function monomer can gather phosphor-containing flame-proof type organic
Si acrylate copolymer subparticipation is formulated efficiently synergistic effect to base polyurethane prepolymer for use as synthetic reaction, shows preferable
Compatibility, the other raw material compositions of a successive step of going forward side by side and content, improve ageing-resistant performance, flame retardant property and adhesive force；
2, thickening resin acrylic copolymer random polycondensation is introduced base polyurethane prepolymer for use as by the present invention, is improved thickening resin and is gathered
The compatibility of urethane further solves the problems, such as reaction type polyurethane hot-melt adhesive chemicals-resistant corrosive nature deficiency；
3, the present invention solves the problems, such as that traditional reaction type polyurethane hot-melt adhesive is poor to substrate wet performance, improves hot melt adhesive and applies
The flow leveling of glue, packaging and Process of Applying Glue are not likely to produce bubble.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Number involved in following embodiment is mass fraction.
Embodiment one
It is a kind of ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1 synthesizes phosphor-containing flame-proof type poly-organosilicon acrylate copolymer
11 parts of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 13 parts of 2- methyl -2- acrylic acid -
2- hydroxyethyl ester phosphate HMP, 18 parts of butyl acrylate BA and 3 parts of hydroxyethyl methacrylate HEMA are dissolved in 60 parts
In toluene, 85 DEG C are controlled in, under nitrogen protection, 1.6 parts of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester, polymerization is added
Reaction 45 hours after rotary evaporation removes toluene, obtains phosphor-containing flame-proof type poly-organosilicon acrylate copolymer, phosphor-containing flame-proof type
The number-average molecular weight of poly-organosilicon acrylate copolymer is 15000, and chemical structure is: poly- (methacryloxypropyl list
Block the random -2- methyl -2- 2-hydroxyethyl acrylate phosphate-of dimethyl polysiloxane-it is random-butyl acrylate-nothing
Rule-hydroxyethyl methacrylate) i.e. P(MAPDMS-r-HMP-r-BA-r-HEMA)；The methacryloxypropyl list sealing end
The number-average molecular weight of dimethyl polysiloxane MAPDMS is 1000, No. CAS: 146632-07-7；
Step 2 synthesizes ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive
5 parts of polyoxypropyleneglycol PPG, 15 parts of polyethylene glycol adipate glycol PEA, 10 parts of flame retarding polyether is polynary
The phosphor-containing flame-proof type that the step of alcohol WANOL FR-130,7320,20 parts of crystalline polyester dihydric alcohol of 25 parts one synthesizes gathers organic
After Si acrylate copolymer, 0.06 part of phosphoric acid and the mixing of 0.08 part of irgasfos 168,150 DEG C are calorified, water removal is vacuumized
1 hour, until the water content of mixture is lower than 280ppm, cools down in 70 DEG C, under nitrogen protection, 30 parts of modification two is added
4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer of phenylmethane -), it carries out polymerization reaction 2 hours, sampling analysis is poly-
It closes product NCO% content and reaches 2.6%, viscosity reaches 4500 mPa.s, 0.8 part of silane coupling agent ND-42 is added, obtains resistance to
Ageing properties excellent flame damp solidifying polyurethane hot melt adhesive, is mass fraction above；The polyoxypropyleneglycol PPG's
Number-average molecular weight is 1000, and the number-average molecular weight of the polyethylene glycol adipate glycol PEA is 500, uses Brookfield
DV-C digital viscometer viscosity, 100 DEG C of test setting temperature.
Embodiment two
It is a kind of ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1 synthesizes phosphor-containing flame-proof type poly-organosilicon acrylate copolymer
16 parts of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 26 parts of 2- methyl -2- acrylic acid -
2- hydroxyethyl ester phosphate HMP, 25 parts of butyl acrylate BA and 4 parts of hydroxyethyl methacrylate HEMA are dissolved in 80 parts
In toluene, 90 DEG C are controlled in, under nitrogen protection, 1.2 parts of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester, polymerization is added
Reaction 30 hours after rotary evaporation removes toluene, obtains phosphor-containing flame-proof type poly-organosilicon acrylate copolymer, phosphor-containing flame-proof type
The number-average molecular weight of poly-organosilicon acrylate copolymer is 22000, and chemical structure is: poly- (methacryloxypropyl list
Block the random -2- methyl -2- 2-hydroxyethyl acrylate phosphate-of dimethyl polysiloxane-it is random-butyl acrylate-nothing
Rule-hydroxyethyl methacrylate) i.e. P(MAPDMS-r-HMP-r-BA-r-HEMA)；The methacryloxypropyl list sealing end
The number-average molecular weight of dimethyl polysiloxane MAPDMS is 1000, No. CAS: 146632-07-7；
Step 2 synthesizes ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive
By 10 parts of polytetrahydrofuran ether glycol PTMG, 20 parts of polyadipate -1,6- hexylene glycol esterdiol PHA, 15 parts of resistance
The phosphorous resistance that the step of combustible polyether glycol WANOL FR-212,7360,15 parts of crystalline polyester dihydric alcohol of 25 parts one synthesizes
After combustion type poly-organosilicon acrylate copolymer, 0.2 part of triethanolamine and the mixing of 0.3 part of irgasfos 168,140 are calorified
DEG C, water removal 2.5 hours is vacuumized, until the water content of mixture is lower than 280ppm, is cooled down in 80 DEG C, under nitrogen protection,
40 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer of modified diphenylmethane-is added), carry out polymerization reaction 5
Hour, sampling analysis polymerizate NCO% content reaches 2.2%, and viscosity reaches 5400 mPa.s, and 0.6 part silane coupled is added
Agent ND-42 obtains ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive, is above mass fraction；Described poly- four
The number-average molecular weight of hydrogen furans ether glycol PTMG is 2000, the equal molecule of number of polyadipate -1,6- hexylene glycol esterdiol PHA
Amount is 1000, with Brookfield DV-C digital viscometer viscosity, 100 DEG C of test setting temperature.
Embodiment three
It is a kind of ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1 synthesizes phosphor-containing flame-proof type poly-organosilicon acrylate copolymer
17 parts of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 30 parts of 2- methyl -2- acrylic acid -
2- hydroxyethyl ester phosphate HMP, 15 parts of butyl acrylate BA and 2 parts of hydroxyethyl methacrylate HEMA are dissolved in 90 parts
In toluene, 95 DEG C are controlled in, under nitrogen protection, 0.5 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester, polymerization is added
Reaction 10 hours after rotary evaporation removes toluene, obtains phosphor-containing flame-proof type poly-organosilicon acrylate copolymer, phosphor-containing flame-proof type
The number-average molecular weight of poly-organosilicon acrylate copolymer is 31000, and chemical structure is: poly- (methacryloxypropyl list
Block the random -2- methyl -2- 2-hydroxyethyl acrylate phosphate-of dimethyl polysiloxane-it is random-butyl acrylate-nothing
Rule-hydroxyethyl methacrylate) i.e. P(MAPDMS-r-HMP-r-BA-r-HEMA)；The methacryloxypropyl list sealing end
The number-average molecular weight of dimethyl polysiloxane MAPDMS is 1000, No. CAS: 146632-07-7；
Step 2 synthesizes ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive
10 parts of polyoxypropyleneglycol PPG, 17 parts of polyethylene glycol adipate glycol PEA, 15 parts of flame retarding polyether is more
The phosphor-containing flame-proof type that the step of first alcohol WANOL FR-312,7360,25 parts of crystalline polyester dihydric alcohol of 30 parts one synthesizes is poly- to be had
After machine Si acrylate copolymer, 0.1 part of 2,2- dimorpholine base Anaesthetie Ether and the mixing of 0.1 part of antioxidant 1010, heating
In 150 DEG C, water removal 3 hours is vacuumized, until the water content of mixture is lower than 280ppm, is cooled down in 80 DEG C, in nitrogen protection
Under, 45 parts of 4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer of modified diphenylmethane-is added), polymerize anti-
It answers 3 hours, sampling analysis polymerizate NCO% content reaches 2.8%, and viscosity reaches 7100 mPa.s, and it is even that 0.8 part of silane is added
Join agent ND-42, obtains ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive, be above mass fraction；It is described poly-
The number-average molecular weight of propylene oxide glycol PPG is 3000, and the number-average molecular weight of the polyethylene glycol adipate glycol PEA is
1500, with Brookfield DV-C digital viscometer viscosity, 100 DEG C of test setting temperature.
Example IV
It is a kind of ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive, is prepared by the following steps to obtain:
Step 1 synthesizes phosphor-containing flame-proof type poly-organosilicon acrylate copolymer
20 parts of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 13 parts of 2- methyl -2- acrylic acid -
2- hydroxyethyl ester phosphate HMP, 37 parts of butyl acrylate BA and 5 parts of hydroxyethyl methacrylate HEMA are dissolved in 100 parts
Toluene in, be controlled in 100 DEG C, under nitrogen protection, 0.3 part of thermal initiator peroxidating 2 ethyl hexanoic acid tert-pentyl ester be added,
Polymerization reaction 7 hours, after rotary evaporation removes toluene, obtain phosphor-containing flame-proof type poly-organosilicon acrylate copolymer, phosphorous resistance
The number-average molecular weight of combustion type poly-organosilicon acrylate copolymer is 42000, and chemical structure is: poly- (methacryloxypropyl third
Base list block the random -2- methyl -2- 2-hydroxyethyl acrylate phosphate-of dimethyl polysiloxane-it is random-butyl acrylate -
Randomly-hydroxyethyl methacrylate) i.e. P(MAPDMS-r-HMP-r-BA-r-HEMA)；The methacryloxypropyl list envelope
The number-average molecular weight for holding dimethyl polysiloxane MAPDMS is 1000, No. CAS: 146632-07-7；
Step 2 synthesizes ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive
By 20 parts of polyoxypropyleneglycol PPG, 20 parts of polyadipate -1,4-butanediol esterdiol PBA, 25 parts fire-retardant poly-
The phosphor-containing flame-proof type that the step of ethoxylated polyhydric alcohol WANOL FR-312,7380,40 parts of crystalline polyester dihydric alcohol of 20 parts one synthesizes
After poly-organosilicon acrylate copolymer, 0.3 part of triethanolamine and the mixing of 0.8 part of irgasfos 168,150 DEG C are calorified, is taken out
Vaccum dewatering 2 hours, until the water content of mixture is lower than 280ppm, cools down in 90 DEG C, under nitrogen protection, be added 50 parts
4,4 '-diisocyanate Desmodur CD-C(MDI performed polymer of modified diphenylmethane -), carry out polymerization reaction 4 hours, take
Sample analysis polymerizate NCO% content reaches 2.7%, and viscosity reaches 8500 mPa.s, and 0.6 part of silane coupling agent ND-42 is added,
Ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive is obtained, is above mass fraction；The polypropylene oxide two
The number-average molecular weight of alcohol PPG is 4000, and the polyadipate -1,4-butanediol esterdiol PBA number-average molecular weight is 2000, is used
Brookfield DV-C digital viscometer viscosity, 100 DEG C of test setting temperature.
Performance test
The ageing-resistant performance excellent flame that the present invention obtains the four kinds of above embodiments referring to the universal method of current hot melt adhesive
Damp solidifying polyurethane hot melt adhesive carries out melt viscosity, open hour, shore hardness, elongation at break, shear strength, oxygen index (OI)
With 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, if
Set 100 DEG C.Open hour are tested referring to ASTM D4497-1994 (2004) method.Shore hardness is referring to GB-T2411-
2008 standards are tested.Elongation at break is tested referring to GB/T30776-2014 standard.Shear strength is referring to GB/
T7124-2004 standard is tested.Oxygen index (OI) uses GB/T5454-1997 " textile combustion performance test-oxygen index method "
Measurement.The specific test method of chemical resistance index is to prepare sample with reference to test shear strength method, and it is small that sample places 72
When solidification after, sample is soaked in oleic acid (purity 98%) solution 24 hours, takes out sample, is placed in 85 DEG C and 85% relatively wet
It spends under environment, after carrying out aging 1000 hours, then carries out shear strength test.Water contact angle is marked with reference to GB/T 30693-2014
Standard 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 ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive tool that the present invention synthesizes from the data of table 1
There are excellent chemicals-resistant corrosive nature and flame retardant property.
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 ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive, it is characterised in that including 1~20 part of polyethers
Dihydric alcohol, 1~50 part of flame retardant polyether polyol, 1~40 part of liquid polyesters dihydric alcohol, 1~40 part of crystalline polyester two
First alcohol, 1~45 part of phosphor-containing flame-proof type poly-organosilicon acrylate copolymer, 20~60 parts of isocyanates, 0.01~1 part
Catalyst, 0.01~1 part of antioxidant and 0.1~2 part of silane coupling agent；It is above mass fraction；The phosphor-containing flame-proof
The chemical structure of type poly-organosilicon acrylate copolymer is: poly- (methacryloxypropyl list blocks dimethyl polysiloxane-
Randomly -2- methyl -2- 2-hydroxyethyl acrylate phosphate-it is random-butyl acrylate-is random-hydroxyethyl methacrylate)
That is P(MAPDMS-r-HMP-r-BA-r-HEMA), the number-average molecular weight of phosphor-containing flame-proof type poly-organosilicon acrylate copolymer is
1000~50000.
2. ageing-resistant performance excellent flame damp solidifying 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 flame retardant polyether polyol is WANOL FR-130, the WANOL of Wanhua Chemical Group Co., Ltd.'s production
One or two kinds of any combination of FR-212 and WANOL FR-312；
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 preparation method of ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive, it is characterised in that preparation step
It is as follows:
Step 1 synthesizes phosphor-containing flame-proof type poly-organosilicon acrylate copolymer
1~20 part of methacryloxypropyl list is blocked into dimethyl polysiloxane MAPDMS, 1~40 part of 2- methyl -2-
2-hydroxyethyl acrylate phosphate HMP, 1~40 part of butyl acrylate BA and 1~5 part of hydroxyethyl methacrylate
HEMA is dissolved in 50~100 parts of toluene, is controlled in 40~110 DEG C, under nitrogen protection, 0.1~2 part of heat is added and causes
Agent peroxidating 2 ethyl hexanoic acid tert-pentyl ester polymerization reaction 2~50 hours, after rotary evaporation removes toluene, obtains phosphor-containing flame-proof type
Poly-organosilicon acrylate copolymer, the number-average molecular weight of phosphor-containing flame-proof type poly-organosilicon acrylate copolymer is 1000~
50000；The number-average molecular weight of the methacryloxypropyl list sealing end dimethyl polysiloxane MAPDMS is 1000；
Step 2 synthesizes ageing-resistant performance excellent flame damp solidifying polyurethane hot melt adhesive
By 1~20 part of polyether Glycols, 1~50 part of flame retardant polyether polyol, 1~40 part of liquid polyesters dihydric alcohol, 1~
40 parts of crystalline polyester dihydric alcohol, 1~45 part of phosphor-containing flame-proof type poly-organosilicon acrylate copolymer, 0.01~1 part
After catalyst and the mixing of 0.01~1 part of antioxidant, 120~150 DEG C are calorified, water removal about 1~3 hour is vacuumized, until mixed
The water content for closing object is lower than 280ppm, cools down in 70~100 DEG C, under nitrogen protection, 20~60 parts of isocyanates is added,
It carries out polymerization reaction 1~10 hour, sampling analysis polymerizate NCO% content reaches 1%~3%, and viscosity reaches 3000 at 100 DEG C
0.1~2 part of silane coupling agent is added in~15000 mPa.s, obtains ageing-resistant performance excellent flame damp solidifying polyurethane heat
Melten gel is mass fraction above.
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| CN110804414A (en) * | 2019-11-25 | 2020-02-18 | 杭州之江新材料有限公司 | Reactive polyurethane hot melt adhesive |
| CN114774061A (en) * | 2022-06-07 | 2022-07-22 | 广州市盛邦康体场地材料有限公司 | Adhesive for prefabricated rubber track |
| CN115109309A (en) * | 2021-03-22 | 2022-09-27 | 万华化学集团股份有限公司 | Method for improving storage stability of polyurethane prepolymer |
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| CN102504752A (en) * | 2011-11-30 | 2012-06-20 | 山东北方现代化学工业有限公司 | Room-temperature moisture-curable single-component flame-retardant polyurethane sealant |
| CN104245769A (en) * | 2012-04-12 | 2014-12-24 | Dic株式会社 | Moisture-curable polyurethane hot melt resin composition, adhesive and article |
| CN104262553A (en) * | 2014-09-19 | 2015-01-07 | 厦门大学 | Flame-retardant block copolymer containing nitrogen and phosphorus and preparation method thereof |
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| 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 |
| CN102504752A (en) * | 2011-11-30 | 2012-06-20 | 山东北方现代化学工业有限公司 | Room-temperature moisture-curable single-component flame-retardant polyurethane sealant |
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| CN110804414A (en) * | 2019-11-25 | 2020-02-18 | 杭州之江新材料有限公司 | Reactive polyurethane hot melt adhesive |
| CN115109309A (en) * | 2021-03-22 | 2022-09-27 | 万华化学集团股份有限公司 | Method for improving storage stability of polyurethane prepolymer |
| CN115109309B (en) * | 2021-03-22 | 2023-12-19 | 万华化学集团股份有限公司 | Method for improving storage stability of polyurethane prepolymer |
| CN114774061A (en) * | 2022-06-07 | 2022-07-22 | 广州市盛邦康体场地材料有限公司 | Adhesive for prefabricated rubber track |
| CN114774061B (en) * | 2022-06-07 | 2023-09-22 | 广州市盛邦康体场地材料有限公司 | A kind of adhesive for prefabricated rubber track bonding |
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