CN114181354B - UV (ultraviolet) photocuring composition with low moisture vapor transmission rate and preparation method thereof - Google Patents
UV (ultraviolet) photocuring composition with low moisture vapor transmission rate and preparation method thereof Download PDFInfo
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- CN114181354B CN114181354B CN202111562394.6A CN202111562394A CN114181354B CN 114181354 B CN114181354 B CN 114181354B CN 202111562394 A CN202111562394 A CN 202111562394A CN 114181354 B CN114181354 B CN 114181354B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention provides a UV (ultraviolet) photocuring composition with low moisture vapor transmission rate, which is prepared from the following raw materials: 25-30 parts by weight of an acrylate monomer; 70-75 parts by weight of a polybutadiene modified urethane acrylate oligomer; 3-5 parts of a photoinitiator; 3-5 parts by weight of a chain transfer agent; 6-10 parts by weight of hydrophobic fumed silica. Compared with the prior art, the UV photocuring composition with low moisture vapor transmission rate provided by the invention adopts components with specific content, so that better interaction is realized, and the cured product obtained from the product has low moisture vapor transmission rate on the basis that the tensile strength, the elongation and the hardness meet the application requirements, and is suitable for sealing rings with higher moisture resistance requirements. Experimental results show that the tensile strength of the cured product of the UV photocuring composition with low moisture vapor transmission rate is 2.8-4.8 MPa, the elongation is 150-250%, the hardness (Shore A) is 52-58, and the moisture transmission rate is 3.5g/m2～5.2g/m2。
Description
Technical Field
The invention relates to the technical field of sealing rings, in particular to a UV (ultraviolet) photocuring composition with low moisture and air permeability and a preparation method thereof.
Background
The application of sealing rings is very widespread in many industrial segments. The sealing ring is usually in the form of a preformed seal, and is embedded or a planar gasket at the joint of the parts to be sealed, so as to play a sealing role. The production of such sealing rings usually requires the formation of the sealing rings by means of a mold by means of rubber vulcanization or glue curing. The rapid development of photocuring molding technology has made the realization of "in-situ molded gaskets" (Gasket-in-Place). Compared with a sealing ring formed by a traditional mode, the in-situ forming mode has the advantages of no die, customization, high production efficiency and the like. But is limited by the limitations of the photo-curing mechanism, the range of selectable materials and the application scene, and compared with the traditional rubber-based sealing rings such as ethylene propylene diene monomer, fluororubber, natural rubber and the like, the sealing ring formed by photo-curing has obvious disadvantage on the moisture transmittance.
The commercial photo-curing adhesive for the sealing ring formed in situ at present mainly technically comprises two categories of urethane acrylate oligomer and organic silicon modified acrylic acid oligomer, wherein the properties of the body strength, the elongation and the like of the cured product meet the application requirements, but the moisture permeability is higher; the cured body strength of the latter is not high, and the moisture vapor transmission rate is higher than that of the former. Thus both solutions have drawbacks for applications with higher moisture resistance requirements.
Disclosure of Invention
In view of the above, the present invention provides a low moisture vapor transmission rate UV light-curable composition and a preparation method thereof, and the low moisture vapor transmission rate UV light-curable composition provided by the present invention has a low moisture vapor transmission rate compared with the conventional UV-curable sealing ring, and satisfies the application in high temperature and high humidity occasions.
The invention provides a UV (ultraviolet) photocuring composition with low moisture vapor transmission rate, which is prepared from the following raw materials:
25-30 parts by weight of an acrylate monomer;
70-75 parts by weight of a polybutadiene modified urethane acrylate oligomer;
3-5 parts of a photoinitiator;
3-5 parts by weight of a chain transfer agent;
6-10 parts by weight of hydrophobic fumed silica;
the main chain of the polybutadiene modified polyurethane acrylate oligomer has a repeating structural unit of a formula (a) and/or a formula (b), and contains a structural unit of a formula (c), and the terminal group contains at least 2 structures of a formula (d);
wherein R is1、R3Is independently selected from-CH2-, aliphatic carbon chain, alicyclic carbon chain, aromatic ring-containing carbon chain or derivative thereof, R2Is selected from-H-or-CH3。
Preferably, the acrylate monomer is selected from one or more of isobornyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, N-dimethylacrylamide, cyclotrimethylolpropane formal acrylate, diphenoxyethyl acrylate, β -hydroxyethyl acrylate, and tetrahydrofurfuryl (meth) acrylate.
Preferably, the polybutadiene modified polyurethane acrylate oligomer is prepared from the following components in a mass ratio of (2.5-4.5): 1 and a second polybutadiene-modified urethane acrylate oligomer;
the glass transition temperature Tg of the first polybutadiene modified polyurethane acrylate oligomer is-25 ℃ to-15 ℃, and the viscosity at 50 ℃ is 50 Pa.s to 70 Pa.s;
the glass transition temperature Tg of the second polybutadiene modified polyurethane acrylate oligomer is-35 ℃ to-25 ℃, and the viscosity at 60 ℃ is 20 Pa.s to 30 Pa.s.
Preferably, the photoinitiator is selected from one or more of a radical cleavage type initiator, a hydrogen abstraction type initiator, and a cleavage type organic sulfur-containing photoinitiator.
Preferably, the chain transfer agent is selected from tertiary amine chain transfer agents and/or thiols containing ester structures.
Preferably, the hydrophobic fumed silica is prepared from the following components in percentage by mass (0.6-2): 1 and a second hydrophobic fumed silica;
the first hydrophobic fumed silica is hydrophobic fumed silica with the surface treated by silane or siloxane containing acrylate groups, and the BET specific surface area is 125m2/g～175m2/g；
The second hydrophobic fumed silica is a hydrophobic fumed silica, BETThe area is 135m2/g～185m2/g。
The invention also provides a preparation method of the UV photocuring composition with low moisture and air permeability, which comprises the following steps:
a) mixing an acrylate monomer, a polybutadiene modified polyurethane acrylate oligomer, a photoinitiator and a chain transfer agent for the first time to obtain a mixture;
b) adding hydrophobic fumed silica into the mixture obtained in the step a), mixing for the second time, and defoaming to obtain the UV photocuring composition with low moisture vapor transmission rate.
Preferably, the first mixing process in step a) specifically comprises:
dissolving a photoinitiator into an acrylate monomer 1.5-2.5 times the mass of the photoinitiator, adding a polybutadiene modified polyurethane acrylate oligomer, a chain transfer agent and the rest acrylate monomer, and stirring for 15-20 min at 15-25 r/min to obtain a mixture.
Preferably, the second mixing process in step b) specifically comprises:
after hydrophobic fumed silica is added into the obtained mixture, the mixture is firstly stirred for 5min to 15min at the speed of 15r/min to 25r/min and then is dispersed for 20min to 30min at the speed of 30r/min to 40r/min, so that the raw materials are uniformly mixed.
Preferably, the defoaming mode in the step b) is vacuum defoaming; the vacuum degree of the vacuum defoaming is-0.08 MPa to-0.07 MPa.
The invention provides a UV (ultraviolet) photocuring composition with low moisture and gas transmission rate, which is prepared from the following raw materials: 25-30 parts by weight of an acrylate monomer; 70-75 parts by weight of a polybutadiene modified urethane acrylate oligomer; 3-5 parts of a photoinitiator; 3-5 parts by weight of a chain transfer agent; 6-10 parts by weight of hydrophobic fumed silica; the main chain of the polybutadiene modified polyurethane acrylate oligomer has a repeating structural unit of a formula (a) and/or a formula (b), and contains a structural unit of a formula (c), and the terminal group contains at least 2 structures of a formula (d);
wherein R is1、R3Is independently selected from-CH2-, aliphatic carbon chain, alicyclic carbon chain, aromatic ring-containing carbon chain or derivative thereof, R2Is selected from-H-or-CH3. Compared with the prior art, the UV photocuring composition with low moisture vapor transmission rate provided by the invention adopts components with specific content, so that better interaction is realized, and the cured product obtained from the product has low moisture vapor transmission rate on the basis that the tensile strength, the elongation and the hardness meet the application requirements, and is suitable for sealing rings with higher moisture resistance requirements. Experimental results show that the tensile strength of the cured product of the UV photocuring composition with low moisture vapor transmission rate is 2.8-4.8 MPa, the elongation is 150-250%, the hardness (Shore A) is 52-58, and the moisture transmission rate is 3.5g/m2～5.2g/m2。
In addition, the preparation method provided by the invention is simple, mild in condition, easy to control, low in production cost, easy to carry out industrial large-scale production and wide in application prospect.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a UV (ultraviolet) photocuring composition with low moisture vapor transmission rate, which is prepared from the following raw materials:
25-30 parts by weight of an acrylate monomer;
70-75 parts by weight of a polybutadiene modified urethane acrylate oligomer;
3-5 parts of a photoinitiator;
3-5 parts by weight of a chain transfer agent;
6-10 parts by weight of hydrophobic fumed silica;
the main chain of the polybutadiene modified polyurethane acrylate oligomer has a repeating structural unit of a formula (a) and/or a formula (b), and contains a structural unit of a formula (c), and the terminal group contains at least 2 structures of a formula (d);
wherein R is1、R3Is independently selected from-CH2-, aliphatic carbon chain, alicyclic carbon chain, aromatic ring-containing carbon chain or derivative thereof, R2Is selected from-H-or-CH3。
In the present invention, the low moisture vapor transmission UV photocurable composition is prepared from raw materials including an acrylate monomer, a polybutadiene-modified urethane acrylate oligomer, a photoinitiator, a chain transfer agent, and hydrophobic fumed silica, and is preferably prepared from an acrylate monomer, a polybutadiene-modified urethane acrylate oligomer, a photoinitiator, a chain transfer agent, and hydrophobic fumed silica.
In the present invention, the acrylate monomer is preferably one or more selected from the group consisting of isobornyl acrylate (IBOA), tetrahydrofurfuryl acrylate (THFA), Methyl Methacrylate (MMA), N-Dimethylacrylamide (DMAA), Cyclic Trimethylolpropane Formal Acrylate (CTFA), diphenoxyethyl acrylate (PHEA), β -hydroxyethyl acrylate and tetrahydrofurfuryl (meth) acrylate, more preferably isobornyl acrylate (IBOA). The source of the acrylate monomer is not particularly limited in the present invention, and commercially available products of the above monofunctional acrylate monomers known to those skilled in the art may be used.
In the invention, the main chain of the polybutadiene modified polyurethane acrylate oligomer has a repeating structural unit of a formula (a) and/or a formula (b), and contains a structural unit of a formula (c), and the terminal group contains at least 2 structures of a formula (d);
wherein R is1、R3Is independently selected from-CH2-, aliphatic carbon chain, alicyclic carbon chain, aromatic ring-containing carbon chain or derivative thereof, R2Is selected from-H-or-CH3. The source of the polybutadiene-modified urethane acrylate oligomer is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the invention, the polybutadiene modified polyurethane acrylate oligomer is preferably prepared by mixing the following components in a mass ratio of (2.5-4.5): 1 and a second polybutadiene-modified urethane acrylate oligomer; wherein the glass transition temperature Tg of the first polybutadiene modified polyurethane acrylate oligomer is-25 ℃ to-15 ℃, and the viscosity at 50 ℃ is 50 Pa.s to 70 Pa.s; in a preferred embodiment of the present invention, the first polybutadiene-modified urethane acrylate oligomer is hydrophobic polybutadiene urethane acrylate BR-641D; the glass transition temperature Tg of the second polybutadiene modified polyurethane acrylate oligomer is-35 ℃ to-25 ℃, and the viscosity at 60 ℃ is 20 pas to 30 pas; in a preferred embodiment of the present invention, the second polybutadiene-modified urethane acrylate oligomer is hydrophobic polybutadiene urethane acrylate BR-641E.
In the invention, the UV light-cured composition with low moisture vapor transmission rate comprises 25-30 parts by weight of acrylate monomer and 70-75 parts by weight of polybutadiene modified polyurethane acrylate oligomer; in a preferred embodiment of the present invention, the total amount of the acrylate monomer and the polybutadiene-modified urethane acrylate oligomer is 100 parts by weight.
In the present invention, the photoinitiator is preferably selected from one or more of a radical cleavage type initiator, a hydrogen abstraction type initiator, and a cleavage type organic sulfur-containing photoinitiator; wherein the free radical cracking initiator mainly comprises aromatic alkyl ketones, including benzoin and derivatives thereof, benzil derivatives, dialkyl oxyacetophenone, alpha-hydroxyalkyl phenone, alpha-amine alkyl phenone, acyl phosphine oxide and benzoyl formate; the cracking type organic sulfur-containing photoinitiator comprises: alpha-aryl mercaptoacetophenone and derivatives, benzophenone thioether derivatives, alpha-sulfone acetophenone derivatives; IRGACURE 184, IRGACURE 651, IRGACURE819, IRGACURE 907, IRGACURE 369, LUCIRIN TPO, Darocur 1173 are particularly preferred. The present invention is not particularly limited as to the source of the photoinitiator, and commercially available products well known to those skilled in the art may be used.
In the invention, the low-moisture-permeability UV light curing composition comprises 3-5 parts by weight of a photoinitiator.
In the present invention, the chain transfer agent is preferably selected from tertiary amine chain transfer agents and/or mercaptans containing an ester structure; wherein the tertiary amine chain transfer agent, such as: isooctyl p-dimethylaminobenzoate (EHA), ethyl p-dimethylaminobenzoate (EDB); the ester structure-containing thiol is a thiol containing ester structure obtained by esterification of a mercaptocarboxylic acid with a polyhydric alcohol, such as KarenzMT PE1, BD1, TMPMP (trimethylolpropane tri (3-mercaptopropionate)), and PETMP (pentaerythritol tetrakis (3-mercaptopropionate)) of Showa Denko (Showa Denko). The source of the chain transfer agent is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the invention, the UV light-curing composition with low moisture vapor transmission rate comprises 3-5 parts by weight of chain transfer agent.
In the invention, the hydrophobic fumed silica is preferably prepared from the following components in a mass ratio of (0.6-2): 1 of a first hydrophobic fumed silica and a second hydrophobic fumed silica; wherein the first hydrophobic fumed silica is preferably hydrophobic fumed silica with the surface treated by silane or siloxane containing acrylate groups, and the BET specific surface area is 125m2/g～175m2(iv)/g, recommended Aerosil R711, Aerosil R974; the second hydrophobic fumed silica is preferably a hydrophobic fumed silica having a BET specific surface area of 135m2/g～185m2Perg, recommended aerosil R8200 and aerosil R9200. On the basis, the invention adopts a second hydrophobic layerThe water-based fumed silica is matched with the first hydrophobic fumed silica, so that thixotropy can be better adjusted. The source of the hydrophobic gas phase oxidation is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the invention, the UV light curing composition with low moisture vapor transmission rate comprises 6-10 parts by weight of hydrophobic gas phase oxidation.
The UV photocuring composition with low moisture vapor transmission rate provided by the invention adopts components with specific content, so that better interaction is realized, and the cured product obtained from the product has low moisture vapor transmission rate on the basis that the tensile strength, the elongation and the hardness meet the application requirements, and is suitable for sealing rings with higher moisture resistance requirements.
The invention also provides a preparation method of the UV photocuring composition with low moisture and air permeability, which comprises the following steps:
a) mixing an acrylate monomer, a polybutadiene modified polyurethane acrylate oligomer, a photoinitiator and a chain transfer agent for the first time to obtain a mixture;
b) adding hydrophobic fumed silica into the mixture obtained in the step a), mixing for the second time, and defoaming to obtain the UV photocuring composition with low moisture vapor transmission rate.
Firstly, mixing an acrylate monomer, a polybutadiene modified polyurethane acrylate oligomer, a photoinitiator and a chain transfer agent for the first time to obtain a mixture. In the present invention, the acrylate monomer, the polybutadiene modified urethane acrylate oligomer, the photoinitiator and the chain transfer agent are the same as those in the above technical solution, and are not described herein again.
In the present invention, the first mixing process preferably includes:
dissolving a photoinitiator into an acrylate monomer 1.5-2.5 times of the mass of the photoinitiator, adding a polybutadiene modified polyurethane acrylate oligomer, a chain transfer agent and the rest acrylate monomer, and stirring for 15-20 min at 15-25 r/min to obtain a mixture;
more preferably:
dissolving a photoinitiator into an acrylate monomer 2 times the mass of the photoinitiator, adding a polybutadiene modified polyurethane acrylate oligomer, a chain transfer agent and the rest acrylate monomer, and stirring at a high speed of 20r/min for 20min to obtain a mixture.
After the mixture is obtained, the hydrophobic fumed silica is added into the obtained mixture, the mixture is mixed for the second time, and the UV photocuring composition with low moisture vapor transmission rate is obtained after defoaming. In the present invention, the hydrophobic fumed silica is the same as in the above technical solution, and is not described herein again.
In the present invention, the second mixing process preferably includes:
after hydrophobic fumed silica is added into the obtained mixture, the mixture is firstly stirred for 5min to 15min at the speed of 15r/min to 25r/min and then is dispersed for 20min to 30min at the speed of 30r/min to 40r/min, so that the raw materials are uniformly mixed;
more preferably:
after hydrophobic fumed silica is added into the obtained mixture, the mixture is firstly stirred at a low speed for 10min at 20r/min to fully soak the powder, and then the mixture is dispersed at a high speed for 25min at 35r/min to uniformly mix the raw materials.
In the present invention, the defoaming is preferably performed in vacuum; the vacuum degree of the vacuum defoaming is preferably-0.08 MPa to-0.07 MPa, and more preferably-0.075 MPa.
The preparation method provided by the invention is simple, mild in condition, easy to control, low in production cost, easy to carry out industrial large-scale production and wide in application prospect.
The invention provides a UV (ultraviolet) photocuring composition with low moisture and gas transmission rate, which is prepared from the following raw materials: 25-30 parts by weight of an acrylate monomer; 70-75 parts by weight of a polybutadiene modified urethane acrylate oligomer; 3-5 parts of a photoinitiator; 3-5 parts by weight of a chain transfer agent; 6-10 parts by weight of hydrophobic fumed silica; the main chain of the polybutadiene modified polyurethane acrylate oligomer has a repeating structural unit of a formula (a) and/or a formula (b), and contains a structural unit of a formula (c), and the terminal group contains at least 2 structures of a formula (d);
wherein R is1、R3Is independently selected from-CH2-, aliphatic carbon chain, alicyclic carbon chain, aromatic ring-containing carbon chain or derivative thereof, R2Is selected from-H-or-CH3. Compared with the prior art, the UV photocuring composition with low moisture vapor transmission rate provided by the invention adopts components with specific content, so that better interaction is realized, and the cured product obtained from the product has low moisture vapor transmission rate on the basis that the tensile strength, the elongation and the hardness meet the application requirements, and is suitable for sealing rings with higher moisture resistance requirements. Experimental results show that the cured product of the UV photocuring composition with low moisture permeability has the tensile strength of 2.8-4.8 MPa, the elongation of 150-250%, the hardness (Shore A) of 52-58 and the moisture permeability of 3.5g/m2～5.2g/m2。
In addition, the preparation method provided by the invention is simple, mild in condition, easy to control, low in production cost, easy to carry out industrial large-scale production and wide in application prospect.
In order to further illustrate the present invention, the following examples are provided for illustrative purposes. The raw materials used in the following examples of the present invention are all commercially available products, and specifically include:
a: oligomer 1: hydrophobic polybutadiene urethane acrylate BR-641D (DYMAX corporation), Tg (DMA) at-20 ℃ and a viscosity at 50 ℃ of 60 Pa.s;
b: oligomer 2: hydrophobic polybutadiene urethane acrylate BR-641E (DYMAX corporation), Tg (DMA) at-28 ℃ and a viscosity at 60 ℃ of 25 pas;
c: acrylate monomer (IBOA): isobornyl acrylate, Sartomer company;
d: chain transfer agent (KarenzMT PE1), showa electrician;
e: photoinitiator (Irgacure 184), poplar sail chemical;
f: hydrophobic silicon 1: methacrylate-functionalized silica aerosil R711 (Wiegendega), BET of 125-175 m2/g(Tamped Density＝140g/L)；
g: hydrophobic silicon 2: hydrophobic fumed silica AerosilR8200 (winning Chuangdeisk), wherein BET is 135-185 m2/g(Tamped Density＝140g/L)；
h: BR-582E 8: polyether urethane acrylate, (DYMAX Corporation);
i: BR-744 SD: polyester urethane acrylate (dymax corporation).
Examples 1 to 6 and comparative examples 1 to 4
As shown in tables 1 to 2, Table 1 is a table of the composition of the raw materials of examples 1 to 6, and Table 2 is a table of the composition of the raw materials of comparative examples 1 to 4.
Table 1 composition of raw materials of examples 1 to 6
TABLE 2 raw material composition tables for comparative examples 1 to 4
| a | h | i | b | c | d | e | f | g | |
| Comparative example 1 | - | 56 | - | 14 | 30 | 3 | 3 | 5 | 5 |
| Comparative example 2 | - | - | 56 | 14 | 30 | 3 | 3 | 5 | 5 |
| Comparative example 3 | - | 28 | 28 | 14 | 30 | 3 | 3 | 5 | 5 |
| Comparative example 4 | 70 | - | - | - | 30 | 3 | 3 | 5 | 5 |
The preparation method comprises the following steps:
referring to a raw material composition table of tables 1-2, firstly, mixing all photoinitiators e and partial acrylate monomers c according to a mass ratio of 1: 2 into the acrylate monomer c, adding the oligomer 1, the oligomer 2, the chain transfer agent d and the residual acrylate monomer c into the reactor, and dispersing at the rotating speed of 20rpm for 20min to be uniform; and adding hydrophobic gas silicon 1 and hydrophobic gas silicon 2, dispersing for 10min at the rotating speed of 20rpm to fully soak the powder, then dispersing for 25min at the rotating speed of 35rpm, vacuumizing to-0.075 MPa, defoaming for 10min fully, and discharging to obtain the UV photocuring composition.
Adopting a UV area light source: model UPP1010AF-001, 365nm wavelength, 100mm × 100mm evata (shanghai) precision optoelectronics ltd, UV illuminometer: UE530 model, 200mW/cm light emphasis2And irradiating for 30s to finish curing.
And (3) performance testing:
the moisture vapor transmission rate test method comprises the following steps: GBT 1037(1988) test method for water vapor permeability of plastic films and sheets.
Bulk tensile and elongation at break (using GB/T528 type 2 specimens); the stretching speed is 500 mm/min; the gauge length is 20 mm.
The hardness test method comprises the following steps: GBT 531.1-2008 vulcanized rubber or thermoplastic rubber press-in hardness test method part 1: shore durometer (shore hardness).
The test results are shown in table 3.
TABLE 3 data of test results of examples 1 to 6 and comparative examples 1 to 4
As shown in Table 1, in comparative examples 1 to 3, polyether urethane acrylate oligomer, polyester urethane acrylate oligomer and blend of the polyether urethane acrylate oligomer and the polyester urethane acrylate oligomer are respectively adopted to replace polybutadiene modified urethane acrylic acid, although the tensile strength of a cured product is very high (more than 6MPa), the moisture permeability is very high (more than 10 g/m) compared with that of examples 1 to 62) (ii) a Comparative example 4 is not preferable to the examples because the hardness of the polybutadiene-modified polyurethane acrylic acid (BR641D) cured product is 65 although the tensile strength and elongation moisture permeability are good; compared with example 6, in the case that the sum of the contents of BR641D and 641E is constant, example 1 with a relatively high content of BR641D can obtain a cured product with higher hardness and tensile strength but relatively lower elongation; similarly, in example 3, compared with example 1, when the relative amounts of BR641D and 641E are constant, the total amount is slightly lower, and the cured product obtained has better combination properties of elongation, hardness and moisture permeability besides slightly lowering the strength. Therefore, the cured product obtained from the UV light curing composition provided by the invention has low moisture vapor transmission rate on the basis that the body strength, the elongation and the hardness meet the application requirements, and is suitable for sealing rings with higher moisture resistance requirements.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A UV light-cured composition with low moisture vapor transmission rate is prepared from the following raw materials:
25-30 parts by weight of an acrylate monomer;
70-75 parts by weight of a polybutadiene modified urethane acrylate oligomer;
3-5 parts of a photoinitiator;
3-5 parts by weight of a chain transfer agent;
6-10 parts by weight of hydrophobic fumed silica;
the polybutadiene modified polyurethane acrylate oligomer is prepared from the following components in percentage by mass (2.5-4.5): 1 and a second polybutadiene-modified urethane acrylate oligomer; the first polybutadiene modified polyurethane acrylate oligomer is hydrophobic polybutadiene polyurethane acrylate BR-641D, and the second polybutadiene modified polyurethane acrylate oligomer is hydrophobic polybutadiene polyurethane acrylate BR-641E.
2. The low moisture vapor transmission UV photocurable composition according to claim 1, wherein said acrylate monomer is selected from one or more of isobornyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, cyclic trimethylolpropane formal acrylate, diphenoxyethyl acrylate, β -hydroxyethyl acrylate and tetrahydrofurfuryl (meth) acrylate.
3. The low moisture vapor transmission UV photocurable composition of claim 1 wherein said photoinitiator is selected from one or more of the group consisting of free radical cleavage type initiators and hydrogen abstraction type initiators.
4. The low moisture vapor transmission UV photocurable composition according to claim 1 wherein the chain transfer agent is selected from the group consisting of tertiary amine chain transfer agents and/or ester structure-containing thiols.
5. The UV light-curable composition with low moisture vapor transmission rate according to claim 1, wherein the hydrophobic fumed silica is prepared from the following components in a mass ratio of (0.6-2): 1 and a second hydrophobic fumed silica;
the first hydrophobic fumed silica is hydrophobic fumed silica with the surface treated by silane or siloxane containing acrylate groups, and the BET specific surface area is 125m2/g~175m2/g；
The second hydrophobic fumed silica is hydrophobic fumed silica with a BET specific surface area of 135m2/g~185m2/g。
6. A method for preparing the low moisture vapor transmission UV curable composition of any one of claims 1 to 5, comprising the steps of:
a) mixing an acrylate monomer, a polybutadiene modified polyurethane acrylate oligomer, a photoinitiator and a chain transfer agent for the first time to obtain a mixture;
b) adding hydrophobic fumed silica into the mixture obtained in the step a), mixing for the second time, and defoaming to obtain the UV photocuring composition with low moisture vapor transmission rate.
7. The preparation method according to claim 6, wherein the first mixing in step a) comprises:
dissolving a photoinitiator into an acrylate monomer 1.5-2.5 times the mass of the photoinitiator, adding a polybutadiene modified polyurethane acrylate oligomer, a chain transfer agent and the rest acrylate monomer, and stirring at 15-25 r/min for 15-20 min to obtain a mixture.
8. The preparation method according to claim 6, wherein the second mixing in step b) is specifically performed by:
after the hydrophobic fumed silica is added into the obtained mixture, the mixture is stirred for 5-15 min at the speed of 15-25 r/min, and then is dispersed for 20-30 min at the speed of 30-40 r/min, so that all the raw materials are uniformly mixed.
9. The method according to claim 6, wherein the defoaming in step b) is vacuum defoaming; the vacuum degree of the vacuum defoaming is-0.08 MPa to-0.07 MPa.
Priority Applications (1)
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| JP2009269217A (en) * | 2008-04-30 | 2009-11-19 | Mitsui Chemicals Inc | Gas-barrier film and method for producing gas-barrier film |
| JP2011116965A (en) * | 2009-11-09 | 2011-06-16 | Nippon Soda Co Ltd | Terminal modified (hydrogenation) polybutadiene |
| CN106029817A (en) * | 2014-02-28 | 2016-10-12 | 古河电气工业株式会社 | Resin composition for sealing electronic device, and electronic device |
| JP2018070783A (en) * | 2016-10-31 | 2018-05-10 | 日本ゼオン株式会社 | Gas barrier material |
| JP2018100379A (en) * | 2016-12-21 | 2018-06-28 | アイカ工業株式会社 | Photocurable resin composition for gasket |
| EP3498400A1 (en) * | 2017-12-12 | 2019-06-19 | ArianeGroup SAS | Method for manufacturing a pyrotechnic product |
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| JP2009269217A (en) * | 2008-04-30 | 2009-11-19 | Mitsui Chemicals Inc | Gas-barrier film and method for producing gas-barrier film |
| JP2011116965A (en) * | 2009-11-09 | 2011-06-16 | Nippon Soda Co Ltd | Terminal modified (hydrogenation) polybutadiene |
| CN106029817A (en) * | 2014-02-28 | 2016-10-12 | 古河电气工业株式会社 | Resin composition for sealing electronic device, and electronic device |
| JP2018070783A (en) * | 2016-10-31 | 2018-05-10 | 日本ゼオン株式会社 | Gas barrier material |
| JP2018100379A (en) * | 2016-12-21 | 2018-06-28 | アイカ工業株式会社 | Photocurable resin composition for gasket |
| EP3498400A1 (en) * | 2017-12-12 | 2019-06-19 | ArianeGroup SAS | Method for manufacturing a pyrotechnic product |
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