JPS62235318A - Method for simultaneous ipns (interpenetrating polymer networks) by photo-setting - Google Patents

Abstract

PURPOSE:To obtain the titled substance by one process rapidly with reduced energy, by subjecting an epoxy compound containing two or more epoxy groups and a vinyl compound containing two or more vinyl groups to photo-setting by using a specific triarylsulfonium salt as a photoinitiator. CONSTITUTION:(A) An epoxy compound (e.g. bisphenol A type epoxy resin, etc.) containing two or more epoxy groups is blended with (B) a vinyl compound (e.g. acrylic acid ester of bisphenol A type epoxy resin, etc.) containing two or more vinyl groups and (C) a triarylsulfonium salt shown by the formula Ar3S<+>X<-> (X<-> is BF4<->, PF6<->, AsF6<-> or SbF6<->) as a photoinitiator and then subjected to photo-setting to give the aimed simultaneous IPNs (Interpenetrating Polymer Networks). The amount of the photoinitiator C used is preferably 0.1-10wt% based on the blended amount of the compounds A and B.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for the synthesis of simultaneous IPNs by photocuring.

(Problems to be solved by conventional technology and inventions) In recent years, as an alternative to homopolymers and copolymers, a product called a friend polymer alloy, which is made by blending different types of polymers, has been introduced in response to diversifying market needs. It is attracting attention for its design and production methods of molecular materials.

Generally speaking, different types of polymers show only compatibility with each other when physically mixed, but we have engineered polymers with poor compatibility by making the polymer networks intertwine with each other by using a chemical reaction. , it is I P that tries to alloy it.
Na (InterpenetratingPolym
er Networks).

There are two methods for synthesizing IPNs: sequential IPNs and simultaneous IPNs.

In sequential IPNs, first a polymer with a three-dimensional structure,
To make it three-dimensional, add a bonding agent and add a monomer to make it sufficiently swell, and then make it three-dimensional to form IPNs. In reality, tetraethylene glycol as a crosslinking agent and benzoin as a sensitizer are added to ethyl acrylate, and the mixture is photocontaminated with ultraviolet rays, then dried under reduced pressure, sufficiently swollen with a mixture of styrene and divinylbenzene, and then benzoin is added. This is a very complicated method of curing with ultraviolet light in the presence of.

The other simultaneous IPNs are three-dimensional monomers, 1)
Alternatively, two or more prepolymers are mixed together and made three-dimensional at the same time. As an example of this, the product name Epicoat 828 (manufactured by Yuka Shell Co., Ltd.) is made into a pre-cured prepolymer with phthalic anhydride, diethylene glycol dimethacrylate is added to n-butyl acrylate, and a mixture is added and cured by heating. , bisphenol A type diglycidyl ether j? Mixture of methacrylates total 4.
There is a method of curing with 9-dioxadodecane-1,12-diamine and benzoyl peroxide, but in both cases heating is essential for making it three-dimensional. The present invention relates to simultaneous IPNs, and more specifically, it focuses on the drawback of heat curing of conventional simultaneous IPNs and improves this by radical polymerization.

Using a photoinitiator triarylsulfonium salt that has the ability to initiate both cationic polymerization, a mixture of an epoxy compound having an epoxide with a K of 24161 or more in the molecule and a vinyl compound having two or more vinyl groups in the molecule can be simultaneously produced. Photopolymerized simultaneous IPNs (Simultaneous
Interpenetrating Polymer
0 triarylsulfonium salt Ar5SX is exposed to ultraviolet light at 19
It photolyzes and undergoes both radical and cationic polymerization.

hν Ar5S
r5S"X-)*Arts++Ar・+X-Ar*S+
ZH--→Arts H+Z・Arc S" -H-
−→Art S +H”2Ars −−→Ar
Ar Ar*+ZH--→Ar-H+Z・ (In the above formula, ZH is the monomer, fC is the m medium, and X″n
B Fs-, P Fa-, AaFs-1fc Vl 5
Expressed as bFs-. ) Therefore, if this triarylsulfonium salt is added to a mixture of an epoxy compound that becomes three-dimensional through cationic polymerization and a vinyl compound that becomes three-dimensional through radical polymerization and irradiated with ultraviolet light, cationic polymerization and radical polymerization occur simultaneously. IPNet can be synthesized in one step.

A method of using triarylsulfonium salts as curing agents for epoxy compounds is described by Crivello.
) etc. ( Am, Chem.

Soc, Symp, Set, + 1141 (19
79J), but this is a method that uses only cationic citrus, and it is a completely new finding that radical polymerization and cationic polymerization can be carried out simultaneously by using both radical citrus and cationic citrus.

The epoxy compound used in the present invention is not particularly limited as long as it has two or more epoxy groups in the molecule.
Furthermore, it is also possible to use a mixture of bipolar or higher epoxy compounds. Also, there are no restrictions on vinyl compounds;
It is preferable that the vinyl compound has at least one vinyl group, and two or more types of vinyl compounds may be mixed and used. A compound having one or more epoxy groups and one or more vinyl groups in the molecule can also be used as one component.

The amount of triarylsulfonium salt added is preferably 0.01 to 20% by weight, preferably 0.1 to 10% by weight, based on the amount of the mixture of the epoxy compound and the vinyl compound.

It is also possible to use coloring agents, fillers, etc. as additives if necessary for epoxy compounds that have only one epoxy group in the molecule, and vinyl compounds that have only one vinyl group in the molecule. In addition, non-reactive diluents, epoxy groups,
Diluents having reactive groups other than vinyl groups can also be used. As a light source for photocuring, it is effective to use a high-pressure mercury lamp such as a mercury lamp. The curing speed becomes faster as the mixture layer is thinner and the intensity of the ultraviolet rays is stronger, but excessive ultraviolet irradiation may cause decomposition of the polymer skeleton, so it is best to adjust the curing speed appropriately. After completion of photocuring, heating may be performed as post-curing.

A cured product consisting of a mixture of an epoxy compound having only one epoxy group as a functional group in the molecule and a vinyl compound having only one vinyl group as a functional group in the molecule is I.
0 that cannot be synthesized into PNs' Next, the non-invention will be explained in detail.

It should be noted that the embodiments are merely illustrative, and it goes without saying that all modifications and improvements may be made without departing from the spirit of the present invention.

(Execution 1+111) Bisphenol Affi epoxy resin [Epicote 828 (Yuka Shell)] was used as the epoxy compound.

Acrylic acid ester of bisphenol A type epoxy resin [Lipoxy 5P-1509 (Showa Kobunshi)] is used as a vinyl compound and BDS is used as a photoinitiator for the composition shown in Table 1.
(PFa) (B18-[4(Diphenylsul
forio) phenyt) 5ulfide-
Bis-Hexafluor.

Using a 33% propylene carbonate solution of
A uniformly mixed and dispersed mixture was prepared, and the reaction thermosetting behavior during curing was measured using a DSC apparatus shown in FIG. In FIG. 1, 1 is a casing, 2 is a plex glass window, 3 is a shutter, 4 is a water lamp, and 5 is a sample.

Table 1 Epicote 828 100 - 80 50
20 The light source was a 400 W mercury lamp, and the distance to the sample was 100 m. The reaction atmosphere was 2a [in air and nitrogen gas]. The following sample was used, with 7 mg dispersed in an aluminum cell. As a result, exothermic peaks associated with the polymerization reaction shown in Table 2 were obtained as shown in FIG.

Table 2 Formulation number N in air, C in air - 151 seconds
42 seconds R-13630 I-130, 18030, 230 I-218, 75015, 680 I-32420 I-
1, Epicote 828 and Lipoxy 5P shown in I-2
-2 exothermic peaks of the mixture system of -1509 appeared,
After irradiation, the first peak is due to radical polymerization of the vinyl group of Lipoxy 5P-1509, and the second peak is due to cationic polymerization of the epoxy group of Epicoat 828. This shows that in a mixture system, different reactions, radical polymerization and cationic polymerization, proceed in the same system to synthesize IPNs.

The method of infrared analysis shown in Figure 3 is as follows.
In system 1, light irradiation was stopped at the parent type, m part of Nijimachi was extracted into tetrahydrofuran, the infrared spectra of the insoluble part and soluble part were measured before irradiation, and the absorption of carbonyl by acrylic acid ester was compared. As a result, the insoluble portion was a polymer of acrylic acid ester Lipoxy 5P-1509, and the soluble portion was epoxy resin Epicoat 828.

(Example 2) For the compositions I-1, I-2, and I-3 shown in Table 1, 33 thipropylene carbonate solution a with photoinitiator B Initiator is 2.0th
In addition to uniformly mixing and dispersing, add and mix tetrahydrofuran so that each composition is 3%, pour this solution into a flat tray, and remove tetrahydrofuran under reduced pressure. A cured film of 50 pm was obtained by irradiating with a mercury lamp for 10 minutes. Using a part of this cured film, the dynamic viscosity was measured and the glass transition points shown in Table 3 were obtained.

Table 3 Formulation number I-I I-2 I-3 Glass transition point 'C106,792,796,7 Sample size: 30
X 3-OX -050■ (Example 3) For each composition in Table 4, a 33% solution of the photoinitiator BDS (PFs)* in globylene carbonate was added at an initiator concentration of 2.
After adding the mixture to OmIf%, mixing, stirring and defoaming, pour it into a silicone rubber mold coated with a release coating.
A dumbbell test piece with a thickness of 1 mm was used as a test piece for a tensile test by irradiating a 400 W mercury lamp rough zero distance for 1930 minutes, and a soluble part of the cured product in acetone was used as a test piece for a tensile test.
20X70X as a test piece to investigate insoluble parts
Obtain 1■ test piece. The tensile test is carried out at a tensile speed of 1/min. To measure the soluble and non-soluble parts in acetone, the test piece was crushed and subjected to Soxhlet extraction for 24 hours.
As a result, the values shown in Table 4, C-1, C-2°R-1, I-1, and I-4, were obtained. After being irradiated with a mercury lamp for 30 minutes, further post-curing was performed, and C-1-Hl and C- of Table 4 were applied.
1-Hl.

The values shown in l-1-Hl and l-4-Hl were obtained. Post-cure conditions were 80°C x 5 hours for C-1-Hz, and 150°C x 2 hours for other conditions.

The above example described PF, - in Ar5SX, but s BFa + AsFa + 5bF
The same procedure can be applied to s.

(Effects of the Invention) According to the present invention, a triarylsulfonium salt is used as a photoinitiator to form an epoxy compound having two or more epoxy groups in the molecule and a vinyl compound having two or more vinyl groups in the molecule. IPNs can be rapidly synthesized by photo-curing a mixture with a vinyl compound having a group.

Unlike the conventional method of simultaneously synthesizing IPNs, IPNs can be synthesized using an energy-saving and resource-saving method called photocuring.

[Brief explanation of drawings]

Figure 1 shows the DSC device, Figure 2 shows the polymerization reaction characteristics, and Figure 3 shows the results of infrared analysis. l...Casing 2...Window 3...Shutter 4...Mercury lamp 5...Sample

Claims (1)

[Claims] A triarylsulfonium salt represented by the following formula is Ar_3S^+X^- (wherein X^- is BF_4^-, PF_6^-, AsF_
6^- and SbF_6^-) As a photoinitiator, a mixture of an epoxy compound having two or more epoxy groups in the molecule and a vinyl compound having two or more vinyl groups in the molecule is photocured to produce simultaneous IPNs. A method for simultaneously synthesizing IPNs by photocuring, characterized by synthesizing.