CN107629753A - Water process curtain type film assembly polyurethane pouring sealant and preparation method thereof - Google Patents
Water process curtain type film assembly polyurethane pouring sealant and preparation method thereof Download PDFInfo
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- CN107629753A CN107629753A CN201710728852.6A CN201710728852A CN107629753A CN 107629753 A CN107629753 A CN 107629753A CN 201710728852 A CN201710728852 A CN 201710728852A CN 107629753 A CN107629753 A CN 107629753A
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Abstract
The invention provides one kind to be applied to fixed water process curtain type film assembly high rigidity dual-component polyurethane casting glue, by hydroxy compounds modified isocyanate component A and polymeric MDI modified hydroxyl compound group into B component according to weight ratio 50 90:100 mix.The polyurethane pouring sealant of the present invention has the advantages that suitable solidification hardness height, mixing viscosity, convenient construction, curing rate is moderate, exothermic peak is low, non-foaming, adhesive effect is good, environment friendly and pollution-free, meanwhile, acid and alkali-resistance and weather resistance are excellent.Its technique is simple, and condition is easily-controllable, it is easy to accomplish automated production.The polyurethane pouring sealant of the present invention fully meets requirements of water process curtain type film assembly and uses technique and the technical requirements of properties of product to casting glue.
Description
Technical field
The present invention relates to field of adhesive technology, it is suitable for water process curtain type film assembly with new more particularly, to one kind
High hardness polyurethane casting glue and preparation method thereof.
Background technology
It using pressure differential is the membrane filtering method of motive force for ultrafiltration membrance filter to use milipore filter.Milipore filter is suitable to processing solution
The separation of middle solute and enrichment, the separation of colloidal suspensions that other isolation technics are difficult to complete is also commonly used for, is widely used in doctor
Medicine industry, food industry, environmental project etc..Kynoar（PVDF）It is current most popular ultrafiltration membrane material, corrosion resistant
Corrosion is good, and stain resistance is strong, belongs to a kind of difficult viscous material, and milipore filter prepared therefrom has good filtering accuracy and machinery strong
Degree.Milipore filter is typically formed as the form of hollow fiber film wire, and only clean water can pass through film wire wall under hydraulic pressure effect
On aperture enter hollow tube in, then, be collected by clean water.Typically ultrafiltration membrane filaments are got one's things ready and fit over milipore filter group
In part, the both ends of film wire beam are fixed in ABS putamina components using casting glue end-blocking, and its outer end is cut after embedding adhesive curing,
So that the hollow endoporus of film wire exposes, and then with output clean water and can be collected.
Embedding glue material is mainly used in bonding and the fixation of the film wire of Pvdf Microporous Hollow Fiber Membrane.For fixed ultrafiltration
The casting glue of film wire one end, it is desirable to which it is before liquid that it, which reacts, is gradually solidified into solid-state after reaction, and it is whole to form termination
Body.This end-blocking casting glue typically has two kinds of polyurethane and epoxy resin, most of at present to use epoxy resin.Epoxy resin encapsulated
Glue has excellent caking property, mechanical strength and corrosion resistance, but gelatin viscosity is larger, mobility is poor, is not suitable for tiny
The embedding in gap, while have that solidification needs heating, hardening time is long, property is crisp, fatigue durability and the shortcomings that poor impact resistance.When
After ultrafiltration membrane filaments end-blocking, climbed inside film wire by brittle epoxy resin, film wire can be caused brittle, easy fracture.Because epoxy fills
More than sealing a variety of shortcomings and the long and narrow special construction of curtain type film assembly ABS shells so that curtain type film assembly can only be selected poly-
Urethane casting glue.
And polyurethane pouring sealant can solidify rapidly at normal temperatures, hardness can adjust, epoxy resin embedding adhesive can be overcome
Disadvantage mentioned above.Encapsulating polyurethane adhesiveness is less than epoxy resin, good fluidity, is advantageous to improve life in curtain type film assembly embedding
Produce efficiency and product quality.After ultrafiltration membrane filaments are climbed by the polyurethane resin of toughness, film wire remains in that toughness, not easy to break.
In addition, polyurethane material finished product is nontoxic, pollution-free, its product can reach drinking-water level even medical grade health level, can be used for
In various water treatment facilities.
At present, it is relatively low and suitable for some small household appliances to be concentrated mainly on hardness for the domestic research to polyurethane pouring sealant
System, i.e., prepare polybutadiene polyurethane electron pouring sealant using end hydroxy butadiene as primary raw material, Shore A hardness is fitted in 30-40
For the mounted circuit board and dish-washing machine wiring board etc. of doing washing.Curtain type film assembly shell is ABS plastic, and its shore D hardness is left in 80D
The right side, when curtain type membrane end-blocking is cut, when two kinds of material hardness differences are larger, easily casting glue is caused to be opened with membrane module shell
Split.And the polyurethane pouring sealant shore D hardness that in the market uses at present, in 40D or so, there is an urgent need to provide water process curtain type membrane
The high hardness polyurethane casting glue that component uses, ensure its production safety and stability and efficiently.
The content of the invention
Based on the problems of above-mentioned prior art, the present invention provides one kind and is applied to water process curtain type film assembly application
High hardness polyurethane casting glue, solve curtain type film assembly ABS elongated enclosures casting glue flowing slowly and solidification cutting it is easy to crack
The problem of.Meanwhile its adhesive force is high, resistance to acids and bases is good, weathering excellent performance, environment friendly and pollution-free, possesses excellent operability.
Another technical problem to be solved by this invention is to provide water process curtain type film assembly end-blocking polyurethane pouring sealant
Preparation method, its technique is simple, and condition is easily-controllable, it is easy to accomplish automated production.
To solve the above-mentioned technical problem of existing casting glue, reach above-mentioned two aspects purpose, the present invention uses following technology
Scheme：
A kind of water process curtain type film assembly high hardness polyurethane casting glue, it reacts to obtain by following components：
A) isocyanic acid（NCO）The modified isocyanate of end-blocking；
B) polymeric MDI modified hydroxyl compound；
Component a) and component b) weight compares 50-90:100；Preferably 55-80:100；
The modified isocyanate of the NCO end-blockings is hydroxy compounds and isocyanates reacted product under certain condition；
Alternatively, hydroxyl be compound be TMN-400, TMN-700, TMN-1000, TMD1000, TMD3000, TMD-5000,
GEP-330N, DL-400, DL-1000, refined caster oil, rilanit special, Baycoll AV1210, Desmophen 1150,
Bayer Rucote 103、BASF Sovermol 750、BASF Sovermol 760、BASF Sovermol 805、BASF
Sovermol 815, Kuraray Polyol P-510, Kuraray Polyol P-520 and Kuraray Polyol P-1010
Any of or it is a variety of；Isocyanates is the one or more in diisocyanate and polyisocyanates；
Preferably, isocyanates is toluene di-isocyanate(TDI), diphenyl methane -4,4'- diisocyanate, liquefied mdi, more methylenes
Quito polyphenyl polyisocyanate（PAPI, polymeric MDI）And hexamethylene diisocyanate（HDI）Any of or it is a variety of；
Alternatively, polymeric MDI modified hydroxyl compound be TMN-400, TMN-700, TMN-1000, TMD1000, TMD3000,
TMD-5000, GEP-330N, DL-400, DL-1000, refined caster oil, rilanit special, Baycoll AV1210,
Desmophen 1150、Bayer Rucote 103、BASF Sovermol 750、BASF Sovermol 760、BASF
Sovermol 805, BASF Sovermol 815, Kuraray Polyol P-510, Kuraray Polyol P-520 and
Any of Kuraray Polyol P-1010 or a variety of and polymeric MDI reacted product under certain condition.
Alternatively, component a) outward appearances are colourless, yellow or yellowish-brown；At 25 DEG C, viscosity is 10-2000 cps, and NCO contains
Measure as 10%-30%；
Preferably, viscosity is 100-1500 cps；NCO content is 20%-30%.
Alternatively, component b) outward appearances are yellow or yellowish-brown, and at 25 DEG C, viscosity is 400-10000 cps；Hydroxyl value is 50
mg KOH/ g-500 mg KOH/ g；
Preferably, viscosity 500-4000cps；Hydroxyl value is 100 mg KOH/ g-300 mg KOH/ g.
Alternatively, also containing one kind in antioxidant and catalyst or mixing in component a)；Also containing expansion in component b)
Chain agent, inorganic filler, defoamer, the one or more in silane coupler and catalyst.
Preferably, weight/mass percentage composition of the antioxidant in component a) is 0.1-0.3%, catalyst 0.01-1%；Group
In dividing b), in terms of weight/mass percentage composition, chain extender 0.1%-15%, more preferably 0.1%-5%；Inorganic filler is 0.1-15%, is disappeared
Infusion is 0.1-1%, silane coupler 0.1-1%, catalyst 0.01-1%.
Preferably, antioxidant is BHT, the double [β-(the 3- tert-butyl group -4- hydroxyls of triethylene-glycol
Base -5- aminomethyl phenyls) propionic ester], 1,3,5- tri- (the 4- tert-butyl group -3- hydroxyl -2,6- dimethyl benzyls) 1,3,5- triazine -2,4,
Double [1,1- dimethyl-the 2- [(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] of 6- (1H, 3H, 5H)-triketone, 3,9-
Ethyl] -2,4,8,10- four oxaspiro [5,5] hendecane, four [β-(3,5- di-tert-butyl-hydroxy phenyls)] pentaerythritol esters
（Antioxidant 1010）With the different monooctyl ester of 3,5- di-t-butyl -4- hydroxy phenylpropionic acids（IRGANOX 1135）Any of or it is more
Kind.
Preferably, chain extender be trimethylolpropane, glycerine, dipropylene glycol, diglycol, 1,2 propane diols,
1,3 propane diols, 1,4 butanediols and the chloro- 4,4'- diaminodiphenyl-methanes of 3,3'- bis-（MOCA）Any of or it is a variety of.
Preferably, inorganic filler is calcium carbonate, calcined kaolin, talcum powder, anhydrous calcium oxide, 3A molecular sieve activations powder and
It is any one or more in aerosil.
Preferably, defoamer is defoamer for solvent-free system, one in EFKA 2720 and BYK series defoamers
Kind is a variety of.
Preferably, organo-silicon coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane, the ethoxy of γ-aminopropyl three
Base silane and N-（β-aminoethyl）Any of-γ-aminopropyltrimethoxysilane is a variety of.
Preferably, catalyst is any of monooctyl ester stannous, dibutyl tin laurate and triethylenediamine or more
Kind.
A kind of preparation method of the new high hardness polyurethane casting glue of above-mentioned water process curtain type film assembly, including following step
Suddenly：
(1) hydroxy compounds high-temperature vacuum is dehydrated, and isocyanates and catalyst are added after cooling, is reacted under atmosphere protection, is determined
NCO content obtains component a) to cooling after terminal；
(2) hydroxy compounds high-temperature vacuum is dehydrated, and polymeric MDI reaction is added after cooling, is dropped after measure hydroxyl value content to terminal
Temperature, vacuumizing and defoaming, logical nitrogen are packed, and obtain component b)；
(3) said components a) and component b) are compared into 50-90 according to weight:100 is well mixed, obtains water process curtain type film assembly use
High hardness polyurethane casting glue.
Alternatively, step（1）Middle vacuum dehydration temperature is 110 DEG C -120 DEG C；Reaction temperature is 70 DEG C -80 DEG C；During reaction
Between be 2-4h；Protective gas is inert gas or nitrogen.
Preferably, step（1）Middle catalyst adds reaction system with isocyanates；Reaction adds antioxygen after reaching terminal
Agent；It is highly preferred that it is less than 50 DEG C that antioxidant, which adds temperature,.
Alternatively, step（2）Middle vacuum dehydration temperature is 110 DEG C -120 DEG C；Reaction temperature is 70 DEG C -80 DEG C.
Preferably, step（2）Inorganic filler, chain extender, organo silane coupling agent, defoaming are added after terminal is reached after middle reaction
One or more in agent and catalyst are well mixed；
It is highly preferred that step（2）The middle temperature for adding inorganic filler, chain extender, organo silane coupling agent, defoamer and catalyst
For less than 50 DEG C.
The step（1）And step（2）Without sequencing.
Beneficial effects of the present invention：
The present invention is used as host using the modified isocyanate of NCO end-blockings as curing agent using polymeric MDI modified hydroxyl compound.Adopt
Reacted with different components and isocyanates, structure design is carried out to the modified isocyanate of NCO end-blockings, passes through difference point
The hydroxy compounds combination of the three-functionality-degree of son amount, and with the polymeric MDI of polyfunctionality components are carried out with cross-linking modified, choosing
Select suitable chain extender, inorganic filler, organo-silicon coupling agent, defoamer etc. so that the polyurethane pouring sealant has solidification hardness
It is high, mixing viscosity is suitable, convenient construction, curing rate is moderate, exothermic peak is low, non-foaming, adhesive effect is good, environment friendly and pollution-free
The advantages that, meanwhile, acid and alkali-resistance and weather resistance are excellent.Its technique is simple, and condition is easily-controllable, it is easy to accomplish automated production.Prepare
Obtain polyurethane pouring sealant and fully meet requirements of the technical requirements that water process curtain type film assembly uses casting glue technique and properties of product.
Embodiment
With reference to embodiment, the present invention will be further described, but the present invention is not limited by following embodiments.Implement
Raw material can be commercially available by commercial sources described in example.
Embodiment 1
The present embodiment provides the new high hardness polyurethane casting glue a kind of curtain type film assembly suitable for water process, its preparation side
Method specifically includes：
1. prepare component a)：
（1）Equipped with thermometer, agitating device, condenser dried and clean three-necked flask in add 50.0g refined castor-oil plant
Oil, two hours of vacuum dehydration at 115 DEG C；
（2）Less than 80 DEG C of cooling, 950.0g PAPI is then added, 80 DEG C are reacted 2 hours, and course of reaction carries out logical nitrogen and protected
Component a) is made close to theoretical value in shield, measure NCO content；
2. prepare component b)：
（1）Equipped with thermometer, agitating device, condenser dried and clean three-necked flask in add 50.0g GEP-330N,
570.0g refined caster oil, 300.0g Desmophen 1150 vacuum dehydration 2 hours at 115 DEG C；Less than 80 DEG C of cooling
Add 30g polymeric MDIs and be modified reaction, measure hydroxyl value content stops reaction close to after theory；
（2）Less than 50 DEG C of cooling adds the two of 40.0g 1,4- butanediols, 5g EFKA 2720,4.7g KH 560 and 0.3g
Month silicic acid dibutyl tin, it is well mixed, and vacuumizing and defoaming, logical nitrogen are packed, and component b) is made；
3. prepare polyurethane pouring sealant：R values are fixed as 1.3, calculate to obtain A:B=60:100, by the component a) and group of above-mentioned preparation
Part is b) according to 60:100 weight ratios are weighed, and are sufficiently mixed uniform vacuumizing and defoaming, and the polyurethane pouring sealant is made.
Performance test：
1. outward appearance：Range estimation
2. viscosity：According to GB/T 2794-2013《The measure of adhesive viscosity》Standard is measured.
3. setting time：According to GB/T 7193-2008《Unsaturated polyester resin test method》Standard is measured.
4. solid content：According to GB/T 2793-1995《The measure of adhesive non-volatile content》Standard is measured.
5. cure shrinkage：According to GB/T 24148.9-2014《Plastics unsaturated polyester resin（UP-R）9th part：
Cumulative volume shrinkage determination》Standard is measured.
6. mechanics performance determining：Tensile strength and the measure of elongation at break are carried out according to GB/T 528-2009, according to
GB/T 529-2009 carry out the measure of tearing strength, and the measure of hardness is carried out according to GB/T 531-2008；Sample block condition of cure,
23 DEG C ± 2 DEG C, place 7 days under 50% ± 5% RH environment.
7. chemical resistance is tested：First, will be placed 7 days under condition of cure of the blob of viscose in 6, then by blob of viscose
It is fully immersed in the alkali lye that temperature is 23 DEG C ± 2 DEG C（20% NaOH）Or acid solution（20% HNO3）In.When being soaked as defined in reaching
Between after, blob of viscose is thoroughly cleaned with clear water, and surface is wiped with suitable l Water Paper or cloth and removes residual liquid.Then, glue is observed
Block whether there is discoloration, bubble, spot, phenomena such as coming off, and the resistance to chemical reagents energy of blob of viscose is judged with this.
Above items measurement result is shown in Table 1.
Embodiment 2
The present embodiment and the preparation technology of embodiment 1 are essentially identical, and its difference is：Component a) and component b) raw material composition and again
Amount is slightly different.The polyurethane pouring sealant and preparation method thereof specifically includes：
1. prepare component a)：
（1）Equipped with thermometer, agitating device, condenser dried and clean three-necked flask in add 97.0g refined castor-oil plant
Oil, vacuum dehydration 2 hours at 115 DEG C；
（2）Less than 80 DEG C of cooling, 900.0g PAPI is then added, 80 DEG C are reacted 2 hours, and course of reaction carries out logical nitrogen and protected
Shield, NCO content is determined close to theoretical value.Less than 50 DEG C of cooling, 3g IRGANOX 1135 is added, component a) is made.
2. prepare component b)：
（1）Equipped with thermometer, agitating device, condenser dried and clean three-necked flask in add 50.0g GEP-330N,
570.0g refined caster oil, 321.0g Desmophen 1150 vacuum dehydration 2 hours at 115 DEG C；Less than 80 DEG C of cooling
Add 10g polymeric MDIs and be modified reaction, measure hydroxyl value content stops reaction close to after theory；
（2）Less than 50 DEG C of cooling adds 38.0g diglycol, 5g EFKA 2720,5.7g KH 560 and 0.3g
Dibutyl tin dilaurate, it is well mixed, and vacuumizing and defoaming, logical nitrogen are packed, and component b) is made.
3. prepare polyurethane pouring sealant：R values are fixed as 1.3, calculate to obtain A:B=65:100, by the component a) of above-mentioned preparation
With component b) according to 65:100 weight ratios are weighed, and are sufficiently mixed uniform vacuumizing and defoaming, and the polyurethane pouring sealant is made.
Method of testing the results are shown in Table 1 with embodiment 1.
Embodiment 3
The present embodiment and the preparation technology of embodiment 1 are essentially identical, and its difference is：Component a) and component b) raw material composition and again
Amount is slightly different.The polyurethane pouring sealant and preparation method thereof specifically includes：
1. prepare component a)：
（1）Equipped with thermometer, agitating device, condenser dried and clean three-necked flask in add 95.0g TMD-3000,
Two hours of vacuum dehydration at 115 DEG C；
（2）Less than 80 DEG C of cooling, 900.0g liquefied mdi is then added, 80 DEG C are reacted 2 hours, and course of reaction carries out logical nitrogen
Protection, NCO content is determined close to theoretical value.Less than 50 DEG C of cooling, 5g IRGANOX 1135 is added, component a) is made.
2. prepare component b)：
（1）Equipped with thermometer, agitating device, condenser dried and clean three-necked flask in add 50.0g 520.0g
Refined caster oil, 414.0g Desmophen 1150 vacuum dehydration 2 hours at 115 DEG C；Less than 80 DEG C of cooling adds 20g and gathered
Close MDI and be modified reaction, measure hydroxyl value content stops reaction close to after theory；
（2）Less than 50 DEG C of cooling adds 36.0g diglycol, 5g EFKA 2720,4.7g KH 560 and 0.3g
Dibutyl tin dilaurate, it is well mixed, and vacuumizing and defoaming, logical nitrogen are packed, and component b) is made.
3. prepare polyurethane pouring sealant：
R values are fixed as 1.3, calculate to obtain A:B=66:100, by the component a) of above-mentioned preparation and component b) according to 66:100 weight ratios
Weighed, be sufficiently mixed uniform vacuumizing and defoaming, the polyurethane pouring sealant is made.
Method of testing the results are shown in Table 1 with embodiment 1.
Embodiment 4
The present embodiment and the preparation technology of embodiment 1 are essentially identical, and its difference is：Component a) and component b) raw material composition and again
Amount is slightly different.The polyurethane pouring sealant and preparation method thereof specifically includes：
1. prepare component a)：
（1）Equipped with thermometer, agitating device, condenser dried and clean three-necked flask in add 47.0g TMD-3000,
Two hours of vacuum dehydration at 115 DEG C；
（2）Less than 80 DEG C of cooling, 950.0g liquefied mdi is then added, 80 DEG C are reacted 2 hours, the close theory of measure NCO content
Value, course of reaction carry out logical nitrogen protection.Less than 50 DEG C of cooling, 3g IRGANOX 1135 is added, component a) is made.
2. prepare component b)：
（1）Equipped with thermometer, agitating device, condenser dried and clean three-necked flask in add 50.0g 619.0g
Refined caster oil, 300.0g Desmophen 1150 vacuum dehydration 2 hours at 115 DEG C；Less than 80 DEG C of cooling adds 40g and gathered
Close MDI and be modified reaction, measure hydroxyl value content stops reaction close to after theory；
（2）Less than 50 DEG C of cooling adds the two of 31.0g 1,4 butanediols, 5g EFKA 2720,4.7g KH 560 and 0.3g
Month silicic acid dibutyl tin, it is well mixed, and vacuumizing and defoaming, logical nitrogen are packed, and component b) is made.
3. prepare polyurethane pouring sealant：
R values are fixed as 1.3, calculate to obtain A:B=67:100, by the component a) of above-mentioned preparation and component b) according to 67:100 weight ratios
Weighed, be sufficiently mixed uniform vacuumizing and defoaming, the polyurethane pouring sealant is made.
Method of testing the results are shown in Table 1 with embodiment 1.
Comparative example 1
Using certain import water process curtain type membrane end-blocking polyurethane pouring sealant product, polyurethane pouring sealant component A is faint yellow
Bright thick liquid, B component are yellow viscous liquid, and mixed weight ratio is 60：100.Method of testing the results are shown in Table with embodiment 1
1。
Comparative example 2
Using certain domestic water process curtain type membrane end-blocking polyurethane pouring sealant product, polyurethane pouring sealant component A is that brown color is saturating
Bright thick liquid, B component are brown color thick liquid, and mixed weight ratio is 55:100.As a result method of testing is shown in embodiment 1
Table 1.
The physicochemical property of 1 each polyurethane adhesive of table
From the point of view of test result, polyurethane adhesive made from the embodiment of the present invention fully meets water process curtain type film assembly to height
The technical requirements of durometric polyurethane casting glue.On the premise of a series of premium properties of embedding adhesive curing caudacoria component are met, solution
Certainly cemented in place hardness and flexible problem, cutting are not ftractureed, and excellent in mechanical performance, acid-proof alkaline is excellent, solves mixed
Close viscosity and climb the contradiction of silk height.The manufacturing process of a variety of base material hyperfiltration membrane assemblies is can be widely used for, at water
Manage the end-blocking shaping of curtain type film assembly.
Show and elaborate above technical characteristic, realization means and the outstanding advantages of the present invention.The technical staff of the industry
It should be appreciated that the present invention is not limited to the above embodiments, the content illustrated in above-described embodiment and specification simply illustrates this
The formation basic theory of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, this
A little changes and improvements are both fallen within claimed right.The claimed scope of the invention is by appended claim
Book and its equivalent thereof.
Claims (13)
1. a kind of water process curtain type film assembly high hardness polyurethane casting glue, it is characterised in that reacted by following components
Arrive：
A) modified isocyanate of NCO end-blockings；
B) polymeric MDI modified hydroxyl compound；
Component a) and component b) weight compares 50-90:100；
The modified isocyanate of the NCO end-blockings is hydroxy compounds and isocyanates reacted product under certain condition.
2. water process curtain type film assembly high hardness polyurethane casting glue according to claim 1, it is characterised in that component
A) the weight ratio with component b) is 55-80:100.
3. water process curtain type film assembly high hardness polyurethane casting glue according to claim 1, it is characterised in that hydroxyl
Be TMN-400, TMN-700 for compound, TMN-1000, TMD1000, TMD3000, TMD-5000, GEP-330N, DL-400,
DL-1000, refined caster oil, rilanit special, Baycoll AV1210, Desmophen 1150, Bayer Rucote 103,
BASF Sovermol 750、BASF Sovermol 760、BASF Sovermol 805、BASF Sovermol 815、
Any of Kuraray Polyol P-510, Kuraray Polyol P-520 and Kuraray Polyol P-1010 or
It is a variety of；
Isocyanates is the one or more in diisocyanate and polyisocyanates.
4. according to any described water process curtain type film assembly high hardness polyurethane casting glue of claim 1 or 3, its feature exists
In isocyanates is toluene di-isocyanate(TDI), diphenyl methane -4,4'- diisocyanate, liquefied mdi, polymethylene polyphenyl
Any of polyisocyanates and hexamethylene diisocyanate are a variety of.
5. water process curtain type film assembly high hardness polyurethane casting glue according to claim 1, it is characterised in that component
A) outward appearance is colourless, yellow or yellowish-brown；At 25 DEG C, viscosity is 10-2000 cps, NCO content 10%-30%；
Component b) outward appearances are yellow or yellowish-brown；At 25 DEG C, viscosity is 400-10000 cps；Hydroxyl value is 50 mg KOH/ g-
500 mg KOH/ g。
6. water process curtain type film assembly high hardness polyurethane casting glue according to claim 1, it is characterised in that component
A) viscosity is 100-1500 cps；NCO content is 20%-30%；
Component b) viscosity is 500-4000cps；Hydroxyl value is 100 mg KOH/ g-300 mg KOH/ g.
7. water process curtain type film assembly high hardness polyurethane casting glue according to claim 1, it is characterised in that component
A) also containing one kind in antioxidant and catalyst or mixing in；
Also contain chain extender in component b), inorganic filler, defoamer, the one or more in silane coupler and catalyst.
8. water process curtain type film assembly high hardness polyurethane casting glue according to claim 7, it is characterised in that antioxygen
Weight/mass percentage composition of the agent in component a) is 0.1-0.3%, catalyst 0.01-1%；In component b), contained with quality percentage
Gauge, chain extender 0.1%-15%；Inorganic filler is 0.1-15%, defoamer 0.1-1%, silane coupler 0.1-1%, is urged
Agent is 0.01-1%.
9. according to any described water process curtain type film assembly high hardness polyurethane casting glue of claim 7 or 8, its feature exists
In antioxidant is BHT, double [β-(the 3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) of triethylene-glycol
Propionic ester], 1,3,5- tri- (the 4- tert-butyl group -3- hydroxyl -2,6- dimethyl benzyls) 1,3,5- triazines -2,4,6- (1H, 3H, 5H) -
Double [1,1- dimethyl -2- [(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] ethyls] -2,4,8 of triketone, 3,9-,
The oxaspiros of 10- tetra- [5,5] hendecane, four [β-(3,5- di-tert-butyl-hydroxy phenyls)] bis- tertiary fourths of pentaerythritol ester and 3,5-
Any of different monooctyl ester of base -4- hydroxy phenylpropionic acids is a variety of；
Chain extender be trimethylolpropane, glycerine, dipropylene glycol, diglycol, 1,2 propane diols, 1,3 propane diols,
Any of 1,4 butanediols and the chloro- 4,4'- diaminodiphenyl-methanes of 3,3'- bis- are a variety of；
Inorganic filler is calcium carbonate, calcined kaolin, talcum powder, anhydrous calcium oxide, 3A molecular sieve activations powder and gas phase titanium dioxide
It is any one or more in silicon；
Defoamer is defoamer for solvent-free system, the one or more in EFKA 2720 and BYK series defoamers；
Organo-silicon coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane and N-
（β-aminoethyl）Any of-γ-aminopropyltrimethoxysilane is a variety of；
Catalyst is any of monooctyl ester stannous, dibutyl tin laurate and triethylenediamine or a variety of.
A kind of 10. water process curtain type film assembly as described in claim 1 or 7 preparation of new high hardness polyurethane casting glue
Method, it is characterised in that comprise the following steps：
(1) hydroxy compounds high-temperature vacuum is dehydrated, and isocyanates and catalyst are added after cooling, is reacted under atmosphere protection, is determined
NCO content obtains component a) to cooling after terminal；
(2) hydroxy compounds high-temperature vacuum is dehydrated, and polymeric MDI reaction is added after cooling, is cooled after measure hydroxyl value content to terminal,
Vacuumizing and defoaming, logical nitrogen are packed, and obtain component b)；
(3) said components a) and component b) are compared into 50-90 according to weight:100 is well mixed, obtains water process curtain type film assembly use
High hardness polyurethane casting glue.
11. preparation method according to claim 10, its feature is, step（1）With（2）In, hydroxy compounds dehydration
Temperature is 110 DEG C -120 DEG C；Reaction temperature is 70 DEG C -80 DEG C；
Step（1）Reaction time be 2-4h；Protective gas is inert gas or nitrogen.
12. preparation method according to claim 10, its feature is, step（1）Middle catalyst is with isocyanates
Add reaction system；Reaction adds antioxidant after reaching terminal；
Step（2）In, add inorganic filler, chain extender, organo silane coupling agent, defoamer and catalyst after terminal is reached after reaction
In one or more be well mixed.
13. preparation method according to claim 12, its feature is, add antioxidant, inorganic filler, chain extender,
The temperature of organo silane coupling agent, defoamer and catalyst is less than 50 DEG C.
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