CN103980456B - UV glue, urethane acrylate oligomer and preparation method thereof - Google Patents
UV glue, urethane acrylate oligomer and preparation method thereof Download PDFInfo
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- CN103980456B CN103980456B CN201410226531.2A CN201410226531A CN103980456B CN 103980456 B CN103980456 B CN 103980456B CN 201410226531 A CN201410226531 A CN 201410226531A CN 103980456 B CN103980456 B CN 103980456B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Abstract
The invention discloses a kind of UV glue, urethane acrylate oligomer and preparation method thereof, wherein preparation method comprises the steps: that S1. phenyl glycidyl ether, acrylic acid prepare intermediate product A；S2. intermediate product B is prepared in intermediate product A and isophorone diisocyanate reaction；S3. intermediate product C is prepared in bisphenol A polyethenoxy ether and acrylic acid reaction；S4. intermediate product B, C reaction；S5. reactive diluent, decompression distillation, filtration, discharging are added.Can be prepared by above-mentioned preparation method and there is relatively high refractive index, relatively low viscosity, the not sulfur-bearing of self-repair type, the urethane acrylate oligomer of halogen, its refraction index is more than 1.53, at 25 DEG C, viscosity is 8000～20000cps, and the UV glue mixed as main substance by it is spread evenly across in PET base material, preparing prismatic lens on forming machine after curing molding, scratch thereon can disappear in 1～3s.
Description
Technical field
The present invention relates to the field of chemical synthesis, particularly relate to a kind of urethane acrylate oligomer and
Preparation method and the UV glue containing this urethane acrylate oligomer.
Background technology
The light source being presently used for back light unit is generally cathode fluorescent tube (CCFL) or luminescence
Line source that diode (LED) produces or point source, for being converted into area source, then need to use expansion
Fall apart, diffusion sheet etc., so will cause more light loss.Accordingly, it would be desirable to use optical thin film to mend
Repaying the light of loss, optical thin film can use prismatic lens.
Being typically coated with coating on the prismatic lens used, this coating generally uses UV and solidifies resin, in order to
The image making liquid crystal display cells obtain becomes brighter, quality and is preferably promoted, and needs selective refraction rate
Higher resin.In order to improve the refractive index of UV solidification resin, it is possible to use sulfur generation, halogenated materials,
But so can cause a series of environmental problem.
Bulk composition in above-mentioned UV solidification resin is urethane acrylate, at present, and polyurethane propylene
The synthetic route of acid esters has two.Wherein, Article 1 synthetic route is that diisocyanate first reacts with glycol,
React with crylic acid hydroxy ester again；Article 2 synthetic route is that diisocyanate is the most anti-with crylic acid hydroxy ester
Acrylate should be generated, then react with glycol.Above two method has respective pluses and minuses, such as the former
Desirably prevent acrylate heated time long and be easily caused polymerization, gel, the latter is then conducive to anti-
Only the growth of strand and the system viscosity that causes increases.
But, the urethane acrylate no matter according to which kind of method above-mentioned synthesized, due to intermolecular amino
Hydrogen bond action strong between formic acid esters so that the viscosity of urethane acrylate is the biggest.
Therefore, for the problems referred to above, it is necessary to provide the preparation side of the urethane acrylate of a kind of improvement
Method.
Summary of the invention
In view of this, the invention provides a kind of urethane acrylate oligomer and preparation method thereof, with
And the UV glue containing this urethane acrylate oligomer.
To achieve these goals, the preparation method of a kind of urethane acrylate oligomer of the present invention,
It comprises the steps:
S1. phenyl glycidyl ether, acrylic acid are joined the first reactor according to mol ratio 1:1～1:1.05
In, then in the first reactor, add polymerization inhibitor and catalyst, obtain intermediate product A after reaction；
S2. in the first reactor, add the isophorone diisocyanate with intermediate product A equimolar amounts,
React, it is thus achieved that intermediate product B；
S3. by the bisphenol A polyethenoxy ether of 10EO, 20EO bisphenol A polyethenoxy ether according to mole
Than 1:1～4:1 formed mixed liquor join in the second reactor, then in the second reactor add catalyst,
Polymerization inhibitor and ortho phosphorous acid, and with 10EO and 20EO bisphenol A polyethenoxy ether equimolar amounts
Acrylic acid, obtains intermediate product C after reaction；
S4. intermediate product B and intermediate product C equimolar ratio are joined in the 3rd reactor, stir
React；
S5. in the 3rd reactor, reactive diluent is added, through decompression distillation, filtration, discharging, it is thus achieved that poly-
Urethane acrylate oligomer.
As a further improvement on the present invention, in described S1, raise the temperature in the first reactor extremely
95～120 DEG C, under this temperature conditions, react 3～7h, when in the first reactor, the acid number of system is less than
During 4mgKOH/g, stopped reaction, obtain intermediate product A.
As a further improvement on the present invention, in described S1, the mass fraction of the polymerization inhibitor of addition is
0.01wt%～0.1wt%, described polymerization inhibitor one in the following material: 4-methoxyl group phenol, 2,6-bis-uncle
Butyl paracresol, hydroquinone, the mass fraction of the catalyst of addition is 0.5wt%～2wt%, described in urge
Agent one in following material: 4 bromide, tetraethylammonium bromide, tetran-butylphosphonium bromide
Ammonium.
As a further improvement on the present invention, described S2 specifically includes: treat that in the first reactor, temperature declines
During to 40～70 DEG C, add different with the isophorone two of intermediate product A equimolar amounts in the first reactor
Cyanate, reacts 1～2h, when in the first reactor system-NCO group content reduces to the one of initial value
When half, stopped reaction, obtain intermediate product B.
As a further improvement on the present invention, in described S3, the temperature in the second reactor is warming up to
110～125 DEG C, under this temperature conditions, react 4～8h, when in the second reactor, water yield goes out more than theory
The water yield 95% time, stopped reaction, obtain intermediate product C.
As a further improvement on the present invention, in described S3, the mass fraction of the polymerization inhibitor of addition is
0.01wt%～0.1wt%, described polymerization inhibitor one in the following material: 4-methoxyl group phenol, 2,6-bis-uncle
Butyl paracresol, hydroquinone；The mass fraction of the catalyst added is 1wt%～3wt%, described catalysis
Agent is p-methyl benzenesulfonic acid or pyrovinic acid；The mass fraction of described ortho phosphorous acid is 0.1wt%～0.5wt%.
As a further improvement on the present invention, in described S4, the temperature in the 3rd reactor is warming up to
70～85 DEG C, drip 2～3 catalyst, react 3～6h, treat in the 3rd reactor-NCO group content is little
In 0.5% time, reaction terminates.
As a further improvement on the present invention, described reactive diluent is adjacent phenylphenoxy ethylacrylic acid
Ester.
To achieve these goals, the poly-ammonia that prepared by a kind of basis preparation method as above of the present invention
Ester acrylate oligomer, the molecule formula (I) of described urethane acrylate oligomer is as follows:
As a further improvement on the present invention, the span of described m is 5～10.
To achieve these goals, a kind of UV glue of the present invention, including according to preparation as above
Urethane acrylate oligomer prepared by method.
Compared with prior art, the invention has the beneficial effects as follows: by the urethane acrylate of the present invention
The preparation method of oligomer can be prepared has relatively high refractive index, relatively low viscosity, not the containing of self-repair type
Sulfur, the aliphatic urethane acrylate oligomer of halogen, its refraction index more than 1.53,25 DEG C
Lower viscosity is 8000～20000cps, and the UV glue mixed as main substance by it, and it is uniform
Coat on forming machine, in PET base material, after curing molding, prepare prismatic lens, after being scraped off, scratch energy
Enough disappearances in 1～3s.
So, it is possible not only to make prismatic lens brightening effect in backlight film group be improved, but also can
To avoid prismatic lens consequence such as the damage that causes during producing, cutting.Additionally, this polyurethane propylene
Acid esters oligomer also has relatively low viscosity so that it is physically easier to perform in actual production.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to reality
Execute the required accompanying drawing used in example or description of the prior art to be briefly described, it should be apparent that below,
Accompanying drawing in description is only some embodiments described in the present invention, for those of ordinary skill in the art
From the point of view of, on the premise of not paying creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the side of preparation method one detailed description of the invention of the urethane acrylate oligomer of the present invention
Method schematic flow sheet.
Detailed description of the invention
As it is shown in figure 1, the present invention discloses the preparation method of a kind of urethane acrylate oligomer, its bag
Include following steps:
Step S1. by phenyl glycidyl ether, that acrylic acid joins first according to mol ratio 1:1～1:1.05 is anti-
Answer in device, then in the first reactor, add polymerization inhibitor and catalyst, after reaction, obtain intermediate product A.
Preferably, phenyl glycidyl ether and acrylic acid are 1:1.01～1:1.03 according to mol ratio, phenyl glycidyl
Ether and acrylic acid are 1:1.01 according to mol ratio optimal value.
Wherein, in described S1, raise the temperature in the first reactor to 95～120 DEG C, be preferably
100～108 DEG C, optimal value is 105 DEG C.Under this temperature conditions, reaction 3～7h, preferably 4～5h, when
When in first reactor, the acid number of system is less than 4mgKOH/g, stopped reaction, obtain intermediate product A.
The mass fraction of the polymerization inhibitor added in S1 is 0.01wt%～0.1wt%, preferably 0.05wt%.Institute
Stating polymerization inhibitor can be selected from the one in following material: 4-methoxyl group phenol, DBPC 2,6 ditertiary butyl p cresol, right
Benzodiazepines.The mass fraction of the catalyst added in S1 is 0.5wt%～2wt%, is preferably
0.8wt%～1.5wt%, optimal value is 1.0wt%.Described catalyst one in following material: four
Methyl bromide ammonium, tetraethylammonium bromide, tetra-n-butyl ammonium bromide.
Step S2. is treated to be down to 40～70 DEG C at temperature in the first reactor, when preferably 55～65 DEG C, to
One reactor adds the isophorone diisocyanate with intermediate product A equimolar amounts, reacts 1～2h.
When in the first reactor system-NCO group content reduce to the half of initial value time, stopped reaction, obtain
Intermediate product B.
The solution that intermediate product A is formed with isophorone diisocyanate can use toluene as solvent.
Step S3. by the bisphenol A polyethenoxy ether of 10EO, 20EO bisphenol A polyethenoxy ether according to
The solution that mol ratio 1:1～4:1 are formed joins in the second reactor with water segregator, then to second
Reactor adds catalyst, polymerization inhibitor and ortho phosphorous acid, and with 10EO and 20EO bisphenol-A
The acrylic acid of polyoxyethylene ether equimolar amounts, acrylic acid and the hydroxyl of half in total bisphenol A polyethenoxy ether
It is esterified.Intermediate product C is obtained after reaction.Wherein, the bisphenol A polyethenoxy ether of 10EO and 20EO
The mol ratio of bisphenol A polyethenoxy ether be preferably 1:1～2.33:1, optimal value is 1.5:1.
Above-mentioned EO represents ethyoxyl, and the bisphenol A polyethenoxy ether of 10EO then represents has 10 ethoxies
The bisphenol A polyethenoxy ether of base, in like manner, the bisphenol A polyethenoxy ether of 20EO then represents has 20
The bisphenol A polyethenoxy ether of ethyoxyl.The bisphenol A polyethenoxy ether of 10EO and the bisphenol-A of 20EO
The solution that polyoxyethylene ether is formed can use toluene as solvent.
Further, in described S3, the temperature in the second reactor is warming up to 110～125 DEG C, preferably
It it is 115～120 DEG C.Under this temperature conditions, react 4～8h, when in the second reactor, water yield is more than reason
When discussing the 95% of water yield, stopped reaction, obtain intermediate product C.
The mass fraction of the polymerization inhibitor added in S3 is 0.01wt%～0.1wt%, preferably 0.05wt%.Institute
State polymerization inhibitor one in the following material: 4-methoxyl group phenol, DBPC 2,6 ditertiary butyl p cresol, to benzene two
Phenol.The mass fraction of the catalyst added is 1wt%～3wt%, preferably 1wt%～1.5wt%.Described urge
Agent is p-methyl benzenesulfonic acid or pyrovinic acid.The mass fraction of described ortho phosphorous acid is 0.1wt%～0.5wt%,
Being preferably 0.1wt%～0.3wt%, optimal value is 0.2wt%.
Intermediate product B and intermediate product C equimolar ratio are joined in the 3rd reactor by step S4., stirring
Uniformly react, so that second half hydroxyl reacts in bisphenol A polyethenoxy ether.
In described S4, the temperature in the 3rd reactor is warming up to 70～85 DEG C, preferably 70～75 DEG C.
Drip 2～3 catalyst, react 3～6h, in the 3rd reactor-NCO group content less than 0.5% time,
Reaction terminates.
Step S5. adds reactive diluent in the 3rd reactor, through decompression distillation, filtration, discharging, obtains
Obtain urethane acrylate oligomer.Wherein, when using toluene as solvent, in vacuum distillation process,
When toluene level is less than 500ppm, terminate decompression distillation.Described diluent can be adjacent phenylphenoxy second
Base acrylate.
Invention additionally discloses urethane acrylate prepared by a kind of basis preparation method as above oligomeric
Thing, the molecule formula (I) of described urethane acrylate oligomer is as follows:
Wherein, the span of the m in molecular formula is 5～10, thus the urethane acrylate of the present invention
The degree of polymerization of oligomer is relatively low.
Invention additionally discloses a kind of UV glue, this UV glue includes urethane acrylate as above
Oligomer, and urethane acrylate oligomer is as the bulk composition of this UV glue.
Below in conjunction with specific embodiment, the preparation method of the urethane acrylate oligomer of the present invention is entered
Row describes in detail.
Embodiment 1
30g phenyl glycidyl ether, 14.54g acrylic acid, 0.3g tetramethyl bromination is added in reactor
Ammonium, 0.0223g polymerization inhibitor 4-methoxyl group phenol, be warming up to 100 DEG C, react about 5h under stirring.In reactor
When the acid number of system is 2mgKOH/g, stopped reaction, obtain intermediate product substance A.
After system temperature is down to 60 DEG C in question response device, add 44.4g isophorone diisocyanate, 60g
Toluene, after stirring, then is added thereto to 3 dibutyl tin laurates, reacts 1.5h.Reaction
When in device, system-NCO group content reduces to the half of initial value, stopped reaction, obtain intermediate product B.
By 100.2g bisphenol A polyethenoxy ether (10EO), 55.4g bisphenol A polyethenoxy ether (20EO),
1.8g p-methyl benzenesulfonic acid, 0.08g polymerization inhibitor 4-methoxyl group phenol, 0.5g ortho phosphorous acid and 130g toluene are in separately
One reactor mixes.Then add 14.4g acrylic acid, be warming up to 115 DEG C, react 5h.Water yield
During for 3.5g, stopped reaction, obtain intermediate product C.
Intermediate product B, intermediate product C are added in a reactor together, mixes and be warming up to 70 DEG C.
Drip 2 dibutyl tin laurates, react about 3h.Intermediate product B and the reaction of intermediate product C place
In the system of device-< when 0.3%, reaction terminates NCO group content.Then in system, add 86g activity
Diluent neighbour's phenylphenoxy ethyl propylene acid esters (OPPEA), decompression distillation removes solvent, filters, discharging,
Obtain urethane acrylate oligomer.
Embodiment 2
30g phenyl glycidyl ether, 14.54g acrylic acid, 0.25g tetraethyl bromination is added in reactor
Ammonium, 0.0223g polymerization inhibitor 2,6 ditertiary butyl p cresol, be warming up to 108 DEG C, react about 4.5h under stirring.
When in reactor, system acid number is 1.6mgKOH/g, stopped reaction, obtain intermediate product A.
After system temperature is down to 55 DEG C, adds 44.4g isophorone diisocyanate, 60g toluene, stir
After mixing uniformly, then it is added thereto to 3 dibutyl tin laurates, reacts 1.5h.System in reactor
When-NCO group content reduces to the half of initial value, stopped reaction, obtain intermediate product B.
By 80.16g bisphenol A polyethenoxy ether (10EO), 88.64g bisphenol A polyethenoxy ether (20EO),
2.0g p-methyl benzenesulfonic acid, 0.09g polymerization inhibitor DBPC 2,6 ditertiary butyl p cresol, 0.5g ortho phosphorous acid and 130g
Toluene mixes in another reactor.Then add 14.4g acrylic acid, be warming up to 110 DEG C, react 4.5h.
When water yield is 3.5g, stopped reaction, obtain intermediate product C.
Intermediate product B, intermediate product C are added in a reactor together, mix and be warming up to 75 DEG C,
Drip 2 dibutyl tin laurates, react about 3h.Intermediate product B and the reaction of intermediate product C place
In the system of device-< when 0.3%, reaction terminates NCO group content.Then in system, add 90g activity
Diluent neighbour's phenylphenoxy ethyl propylene acid esters (OPPEA), decompression distillation removes solvent, filters, discharging,
Obtain urethane acrylate oligomer.
Embodiment 3
30g phenyl glycidyl ether, 14.54g acrylic acid, 0.3g tetra-n-butyl bromine is added in reactor
Change ammonium, 0.0212g polymerization inhibitor 2,6 ditertiary butyl p cresol, be warming up to 108 DEG C under stirring, react about 5h.
When in reactor, system acid number is 2.2mgKOH/g, stopped reaction, obtain intermediate product A.
After system temperature is down to 50 DEG C, adds 44.4g isophorone diisocyanate, 60g toluene, stir
After mixing uniformly, then it is added thereto to 4 dibutyl tin laurates, reacts 2h.System-NCO in reactor
When group content reduces to the half of initial value, stopped reaction, obtain intermediate product B.
By 80.16g bisphenol A polyethenoxy ether (10EO), 88.64g bisphenol A polyethenoxy ether (20EO),
2.2g p-methyl benzenesulfonic acid, 0.1g polymerization inhibitor DBPC 2,6 ditertiary butyl p cresol, 0.65g ortho phosphorous acid and 130g
Toluene mixes in another reactor, then adds 14.4g acrylic acid, is warming up to 112 DEG C, reacts 6h.
When water yield is 3.54g, stopped reaction, obtain intermediate product C.
Intermediate product B, intermediate product C are added in a reactor together, mix and be warming up to 75 DEG C,
Drip 2 dibutyl tin laurates, react about 3.5h.Intermediate product B and intermediate product C place are anti-
Answer in the system of device-< when 0.3%, reaction terminates NCO group content.Then in system, add 80g live
Property diluent neighbour's phenylphenoxy ethyl propylene acid esters (OPPEA), decompression distillation except solvent, is filtered, and goes out
Material, it is thus achieved that urethane acrylate oligomer.
Embodiment 4
Reactor adds in reactor 60g phenyl glycidyl ether, 29.1g acrylic acid, 0.89g tetra-
Ethyl phosphonium bromide ammonium, 0.0445g polymerization inhibitor 4-methoxyl group phenol, be warming up to 110 DEG C, react about 4h under stirring.
When in reactor, system acid number is down to 3.2mgKOH/g, stopped reaction, obtain intermediate product A.
After system temperature is down to 55 DEG C, add 88.8g isophorone diisocyanate, 120g toluene,
After stirring, then it is added thereto to 4～5 dibutyl tin laurates, reacts 2h.Body in reactor
When system-NCO group content reduces to the half of initial value, stopped reaction, obtain intermediate product B.
By 160.32g bisphenol A polyethenoxy ether (10EO), 177.28g bisphenol A polyethenoxy ether
(20EO), 4.4g p-methyl benzenesulfonic acid, 0.18g polymerization inhibitor 4-methoxyl group phenol, 1.2g ortho phosphorous acid and 260g
Toluene mixes in another reactor, then adds 28.8g acrylic acid, is warming up to 120 DEG C, reacts 6h.
When water yield is 7.04g, stopped reaction, obtain intermediate product C.
Intermediate product B, intermediate product C are added in a reactor together, mix and be warming up to 75 DEG C,
Drip 3 dibutyl tin laurates, react about 5h.Until system-NCO group content < when 0.3%, instead
Should terminate.Then in system, add 180g reactive diluent neighbour's phenylphenoxy ethyl propylene acid esters
(OPPEA), decompression distillation, except solvent, is filtered, discharging, it is thus achieved that urethane acrylate oligomer.
Test is carried out respectively real below for the urethane acrylate oligomer obtained in the various embodiments described above
Testing, the test event of test experiments includes: to the urethane acrylate oligomer obtained in each embodiment
Outward appearance carry out observing, its refractive index, viscosity and scratch resilience time being measured.Examination experimental result
As shown in table 1 below:
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Outward appearance | Micro-Huang is transparent | Micro-Huang is transparent | Micro-Huang is transparent | Micro-Huang is transparent |
| Refractive index | 1.5362 | 1.5348 | 1.5350 | 1.5346 |
| Viscosity (25 DEG C)/cps | 16000 | 15000 | 14600 | 13820 |
| Scratch resilience time/s | 5 | 2 | 3 | 3 |
Table 1
Wherein, refractive index and viscosity utilize corresponding instrument to measure, and survey the scratch resilience time
Amount is carried out according to following operation: first by low for urethane acrylate synthesized in each embodiment
Polymers and activated monomer diluent, light trigger, under the conditions of 50 DEG C, stir 30min on magnetic stirrer
After, it is spread evenly across in PET base material and carries out curing molding by forming machine, prepare brightness enhancement film prismatic lens.
Then, observe measurement and prepare the anti scuffing selfreparing resilience time of brightness enhancement film prismatic lens.
Knowable to test experiments result, the urethane acrylate oligomer of the present invention has certain refraction
Rate, and there is relatively low viscosity, and its resilience is good.
In sum, owing to the refractive index of molecule is inversely proportional to molecular volume, it is directly proportional to molar refraction,
The phenyl ring therefore with bigger polarizability and less molecular volume becomes the head improving molecular refractivity
Choosing.Bisphenol-A in target oligomer and the phenyl ring in 2-hydroxyl-3-phenoxy group propyl acrylate in the present invention
Structure imparts the refractive index that target oligomer is certain.
It addition, relative to the urethane acrylate of conventional symmetrical structure, the polyurethane third that this patent provides
Olefin(e) acid ester oligomer be one end directly and the polyurethane acroleic acid of dissymmetrical structure that obtains of acroleic acid esterification
Ester oligomer, thus greatly reduces the hard section carbamate structures in polyurethane molecular chain so that
Hydrogen bond action between strand reduces, and therefore the viscosity of oligomer the most just decreases.Meanwhile, adopt
Typically elastic preferably as the urethane oligomer of dihydroxylic alcohols Material synthesis with bisphenol A polyethenoxy ether, and
And increasing elasticity and also can improve further along with ethyoxyl (EO), but too many ethyoxyl also can make film
Sheet is the softest.The present invention uses the bisphenol A polyethenoxy ether containing 10EO and 20EO to compound, and prepares
Not only have after urethane oligomer film forming well elastic nor can be the softest.
Can be prepared by the preparation method of the urethane acrylate oligomer of the present invention and there is higher refractive power
Index, compared with low viscosity, the not sulfur-bearing of self-repair type, halogen aliphatic urethane acrylate low
Polymers, its refraction index is more than 1.53, and at 25 DEG C, viscosity is 8000～20000cps, and by it as master
What body material mixed be spread evenly across in PET base material carries out, by forming machine, the prism that curing molding prepares
Sheet, after being scraped off, scratch can disappear in 1～3s.
So, it is possible not only to make prismatic lens brightening effect in backlight film group be improved, but also can
To avoid prismatic lens consequence such as the damage that causes during producing, cutting.Additionally, this polyurethane propylene
Acid esters oligomer also has relatively low viscosity so that it is physically easier to perform in actual production.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment,
And without departing from the spirit or essential characteristics of the present invention, it is possible to real in other specific forms
The existing present invention.Therefore, no matter from the point of view of which point, embodiment all should be regarded as exemplary, and
Being nonrestrictive, the scope of the present invention is limited by claims rather than described above, therefore purport
All changes in falling in the implication of equivalency and scope of claim are included in the present invention.
Should not be considered as limiting involved claim by any reference in claim.
Moreover, it will be appreciated that although this specification is been described by according to embodiment, but the most each reality
Mode of executing only comprises an independent technical scheme, and this narrating mode of description is only for understand
Seeing, those skilled in the art should be using description as an entirety, and the technical scheme in each embodiment is also
Other embodiments that it will be appreciated by those skilled in the art that can be formed through appropriately combined.
Claims (11)
1. the preparation method of a urethane acrylate oligomer, it is characterised in that described preparation method
Comprise the steps:
S1. phenyl glycidyl ether, acrylic acid are joined the first reactor according to mol ratio 1:1～1:1.05
In, then in the first reactor, add polymerization inhibitor and catalyst, when the acid number of system in the first reactor
During less than 4mgKOH/g, stopped reaction, it is thus achieved that intermediate product A；
S2. in the first reactor, add the isophorone diisocyanate with intermediate product A equimolar amounts,
React, when in the first reactor system-NCO group content reduce to the half of initial value time, stop
Reaction, it is thus achieved that intermediate product B；
S3. by the bisphenol A polyethenoxy ether of 10EO, 20EO bisphenol A polyethenoxy ether according to mole
Than 1:1～4:1 formed mixed liquor join in the second reactor, then in the second reactor add catalyst,
Polymerization inhibitor and ortho phosphorous acid, and with 10EO and 20EO bisphenol A polyethenoxy ether equimolar amounts
Acrylic acid, when in the second reactor, water yield is more than the 95% of theoretical water yield, stopped reaction, it is thus achieved that
Intermediate product C；
S4. intermediate product B and intermediate product C equimolar ratio are joined in the 3rd reactor, stir
React, in the 3rd reactor-NCO group content less than 0.5% time, reaction terminates；
S5. in the 3rd reactor, reactive diluent is added, through decompression distillation, filtration, discharging, it is thus achieved that poly-
Urethane acrylate oligomer.
The preparation method of urethane acrylate oligomer the most according to claim 1, its feature exists
In, in described S1, raise the temperature in the first reactor to 95～120 DEG C, under this temperature conditions, instead
Answering 3～7h, when in the first reactor, the acid number of system is less than 4mgKOH/g, stopped reaction, in obtaining
Between product A.
The preparation method of urethane acrylate oligomer the most according to claim 1 and 2, it is special
Levying and be, in described S1, the mass fraction of the polymerization inhibitor of addition is 0.01wt%～0.1wt%, described resistance
Poly-agent one in following material: 4-methoxyl group phenol, 2,6 ditertiary butyl p cresol, hydroquinone,
The mass fraction of the catalyst added is 0.5wt%～2wt%, and described catalyst is selected from following material
Kind: 4 bromide, tetraethylammonium bromide, tetra-n-butyl ammonium bromide.
The preparation method of urethane acrylate oligomer the most according to claim 1, its feature exists
In, described S2 specifically includes: when being down to 40～70 DEG C at temperature in the first reactor, to the first reaction
Device adds the isophorone diisocyanate with intermediate product A equimolar amounts, reacts 1～2h, when first
In reactor system-NCO group content is when reducing to the half of initial value, stopped reaction, obtains middle product
Thing B.
The preparation method of urethane acrylate oligomer the most according to claim 1, its feature exists
In, in described S3, the temperature in the second reactor is warming up to 110～125 DEG C, under this temperature conditions,
Reaction 4～8h, when in the second reactor, water yield is more than the 95% of theoretical water yield, stopped reaction,
To intermediate product C.
The most according to claim 1 or 5, the preparation method of urethane acrylate oligomer, it is special
Levying and be, in described S3, the mass fraction of the polymerization inhibitor of addition is 0.01wt%～0.1wt%, described resistance
Poly-agent one in following material: 4-methoxyl group phenol, DBPC 2,6 ditertiary butyl p cresol, hydroquinone；
The mass fraction of the catalyst added is 1wt%～3wt%, and described catalyst is p-methyl benzenesulfonic acid or methyl sulphur
Acid；The mass fraction of described ortho phosphorous acid is 0.1wt%～0.5wt%.
The preparation method of urethane acrylate oligomer the most according to claim 1, its feature exists
In, in described S4, the temperature in the 3rd reactor is warming up to 70～85 DEG C, drips 2～3 catalyst,
Reaction 3～6h, in the 3rd reactor-NCO group content less than 0.5% time, reaction terminates.
The preparation method of urethane acrylate oligomer the most according to claim 1, its feature exists
In, described reactive diluent is adjacent phenylphenoxy ethyl propylene acid esters.
9. the urethane acrylate prepared according to the preparation method described in any one of claim 1～8
Oligomer, the molecule formula (I) of described urethane acrylate oligomer is as follows:
Urethane acrylate oligomer the most according to claim 9, it is characterised in that described m
Span be 5～10.
11. 1 kinds of UV glue, it is characterised in that described UV glue includes according to claim 1～8
Urethane acrylate oligomer prepared by the preparation method described in any one.
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