JPH0339304A - Adamantyl monocrotonate-based polymer - Google Patents

Abstract

PURPOSE:To obtain the subject novel polymer useful for material of optics having excellent heat resistance, surface hardness, impact resistance and optical characteristics containing specific repeating unit. CONSTITUTION:The aimed polymer contains repeating unit expressed by formula I (R<1> to R<3> are H, lower alkyl, halogen or OH). Adamantyl monocrotonate derivative expressed by formula II is used as monomer component and subjected to anionic polymerization using solvent such as benzene, toluene, THF or ether and organic metallic compound such as Grignard reagent, e.g. n-butyllithium in an inert gas atmosphere such as nitrogen, argon or helium to afford the aimed polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polymer containing a novel adamantyl monocrotonate derivative as a polymerization component and having excellent heat resistance and optical properties.

[Prior Art] Certain unsaturated adamantane ester derivatives are already known; for example, diallyl adamantane dicarboxylate is disclosed in JP-A-60-100537. Further, JP-A-63-33350 discloses adamantyl mono(meth)acrylate derivatives developed by the present applicants. Polymers containing these derivatives as the main monomer components not only have excellent heat resistance, but also have high hardness and impact resistance, and also have many characteristics such as a high optical refractive index. Because of this, it is expected to be used as a variety of optical materials, including heat-resistant plastic materials and lenses for eyeglasses.

In other words, if we focus on applications for plastic lenses, for example, plastic lenses made of conventionally widely used acrylic resins, polycarbonate resins, allyl diglycol carbonate resins, polystyrene resins, etc. have poor heat resistance compared to glass lenses. Although they have the disadvantage of having a low optical refractive index, plastic lenses containing derivatives such as those mentioned above as main monomer components have extremely superior heat resistance compared to conventional plastic lenses. However, since it has a high level of light transmittance and a large optical refractive index, there are great expectations for improving the performance of plastic lenses.

On the other hand, most of the polymer materials currently used are 1,1-disubstituted ethylene type polymers represented by the following formula, and most of the adamantane unsaturated ester polymers are
, 1-disubstituted ethylene type. On the other hand, the 1,2-disubstituted ethylene polymer represented by the following formula exhibits unique physical properties such as being more rigid and having a higher softening point than the 1,1-disubstituted ethylene polymer described above. , some research is underway.

Generally, in anionic polymerization of β-substituted acrylic esters, the proportion of carbonyl addition increases compared to conjugate addition, so it is said to be difficult to obtain a high molecular weight polymer. For example, polymerization using Grignard reagents, alkyl lithiums or L i A I H4 does not yield high molecular weight polymers of methyl crotonate [T.
a et al.

Macromol, Chem, 103,128 (1
967), 1bid, 114.182 (1968)]
.

On the other hand, with bulky substituents, such as esters such as tertiary butyl, isopropyl, and secondary butyl, carbonyl addition is suppressed and molecular chain growth is likely to occur.
It has been reported that high molecular weight polymers can be synthesized [
M. L. Miller et al.

J, Polym, Sci., A2, 4551 (196
4L].

However, in any case, research on crotonic acid ester derivatives is lagging far behind because they have poor reactivity compared to the corresponding methacrylic acid ester derivatives.

[Problems to be Solved by the Invention] Under these circumstances, the present inventors have been actively conducting research on the practical application of crotonic acid ester derivatives and polymers thereof. The purpose of this study is to provide a novel rotonate ester-based polymer that is industrially useful.

[Disclosure of the Invention] The present invention, which has solved the above problems, provides a polymer having as a polymerization component an adamantyl monocrotonate derivative represented by the following general formula [I,] [wherein R1, R2,
R3 are the same or different and represent hydrogen, a lower alkyl group, halogen, or a hydroxyl group. Among the substituents represented by R1, R2, and R3 in the above formula [1], the lower alkyl group includes methyl, ethyl,
Examples include propyl, butyl, etc., but methyl is the most common. In addition, halogens include Br, CI, I
, F, but the most common are Br and CI.

The adamantyl monocrotonate polymer represented by the above formula [I] contains an adamantyl monocrotonate derivative 1 represented by the following formula [Ia] (in the formula, R1, ..., R3 have the same meanings as above) as a monomer component. , for example, benzene, aromatic hydrocarbons such as toluene, and tetrahydrofuran.

Using an ether solvent such as ether and an inert gas atmosphere such as nitrogen, argon, helium, etc., an anion is generated using an organometallic compound such as alkyl lithium such as n-butyllithium or a Grignard reagent such as phenylmagnesium bromide. C can be easily obtained by polymerization, and this polymerization reaction can also be accelerated by heat or light.

In addition, this adamantyl monocrotonate derivative [1a
In addition to being homopolymerized, l can be polymerized according to the use and purpose by copolymerizing 2 fi or more of the derivative [Ia] or copolymerizing with copolymerizable monomers other than the derivative [Ia]. A polymer with good physical properties can be obtained. The type of copolymerizable monomer used here is not particularly limited, but when the polymer of the present invention is to be used as an optical material, preferred copolymerizable monomers include acrylic acid,
Methacrylic acid and their polymerizable derivatives, diallyl dicarboxylate derivatives, aromatic or aliphatic vinyl compounds such as styrene, vinyl acetate, vinylcyclohexene, vinylnaphthalene, crotonic acid ester, fumaric acid ester, itaconic acid ester, cinnamon Non-limiting examples include monofunctional or polyfunctional monomers such as vinyl ester derivatives such as acid esters.

The method of polymerization or copolymerization is also not particularly limited, and for example, bulk polymerization, emulsion polymerization, solution polymerization, ultraviolet polymerization, radiation polymerization, etc. can be appropriately selected and employed.

In addition, among the adamantyl monocrotonate derivatives [Ia], those in which R1 to R'' are hydrogen or lower alkyl groups proceed efficiently in both homopolymerization and copolymerization with other polymerizable child nomers. Since those into which halogen or hydroxyl groups have been introduced have poor homopolymerizability, when using these derivatives, a copolymerization method with other copolymerizable monomers should be adopted.

The thus obtained adamantyl monocrotonate homopolymer or copolymer of the formula [1] of the present invention has excellent heat resistance and impact resistance, exhibits high light transmittance, and is hard and has a small polymerization shrinkage rate. It exhibits unique physical properties such as In particular, this polymer has a much higher melting point than conventional optical plastic materials, and has a number of properties such as being colorless and transparent, having high surface hardness, and also having a high optical refractive index. So, especially for glasses and contact lenses.

It is extremely useful as a material for optical members that utilize transmission and reflection, such as various lenses for camera lenses, prisms, photosensitive materials for recording, optical fibers such as optical fibers, videos, disks, compact disks, etc. It also has excellent gas permeability, so it can be expected to be used as oxygen enrichment membranes, gas separation membranes, etc.

The heat resistance of this polymer varies depending on the degree of polymerization, etc., but it has a higher melting point and surface hardness than general vinyl polymers and acrylic polymers, and has excellent heat resistance, so it is a heat-resistant plastic. It is also possible to develop applications as materials or materials for forming heat-resistant films.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples.

East 10 ships, 2nd grade butyl lithium 0.24g (371 Resol),
Tetrahydrofuran 100ml1. 9.7 g (44 mmol) of adamantyl monocrotonate (hedCr) was polymerized in a glass sealed tube at -78° C. for 3 hours under a nitrogen atmosphere.

After the reaction was completed, the polymer was precipitated by immersing it in methanol containing hydrochloric acid. The precipitate was collected by filtration and dried under reduced pressure overnight to obtain 8.8 g (yield: 91%) of adamantyl monocrotonate polymer (A) in the form of a white powder. This polymer was insoluble in methanol and water, soluble in benzene, tetrahydrofuran, chloroform, etc., and had a number average molecular weight of 6.6 x 10'.

Further, the 'H-NMR spectrum of the polymer (A) is shown in FIG. 1, and the 13C-NMR spectrum!・L is as shown in Figure 2, and as is clear from these spectra, no absorption based on carbon-carbon double bonds is observed, and polymerization proceeds by normal vinyl polymerization to form a polysubstituted methylene compound. It is confirmed that it is generated.

Wataru Shakeki uses secondary butyl lithium (66 mmol) as a polymerization initiator, and adamantyl methacrylate (9 mmol), a structural isomer of adamantyl monocrotonate, as a monomer component.
The polymerization reaction was carried out in the same manner as in Example 1 except that the polymer was used at 8°C for 24 hours to obtain an adamantyl methacrylate polymer. Yield: approx.
0%, number average molecular weight: 3J2xlO').

Tertiary amyl crotonate (t-BuC) is the main monomer.
r) and tertiary amyl crotonate (t-^mcr)
Polymerization was carried out according to the method of Comparative Example 1 using polyt-BuCr (number average molecular weight: 1.5X104) and polyt-^mcr (number average molecular weight = 0.4XIO').
) was obtained.

All weight analysis (TGA) of each polymer obtained in Example 1 and Control Examples 1 to 3 obtained above was carried out, and the decomposition initiation temperature (T
Table 1 shows the results of examining the decomposition rate peak temperature (T, . . .), and FIG. 3 shows an excerpt of the thermogravimetric analysis chart.

As is clear from Table 1 and FIG. 3, the adamantyl monocrotonate polymer of the present invention (Example 1) started to decompose more thermally than the other polymers listed as Control Examples 1 to 3. It can be seen that the temperature is very high and that it has excellent heat resistance. Moreover, in the polymers of Control Examples 1 to 3, 2 to 4 decomposition rate peak temperatures were confirmed, whereas the polymer of Example 1 showed only one decomposition rate peak temperature,
It can be seen that the polymer is homogeneous and has excellent thermal properties.

10 parts by weight of the adamantyl monocrotonate polymer obtained in Example 1 above was dissolved in 90 parts by weight of adamantyl methacrylate, and 2,2-jetoxyacetophenone 2 was dissolved therein.
% by weight, injected into a mold assembled with two glass plates and a gasket, and cured by irradiating ultraviolet rays for 5 to 10 minutes using a high-pressure mercury lamp to obtain a colorless and transparent polymer (B).
I got it.

Comparative Example 4 Polymer (C) was obtained in the same manner as in Example 2 above, except that adamantyl methacrylate was used as the monomer.

Polymer (B) obtained in Example 2 and Control Example 4 above.

The physical properties of (C) are summarized in Table 2 together with the physical properties of polymer (A) obtained in Example 1. However, regarding the polymer (^) of Example 1, the polymer (^) was dissolved in benzene,
It was cast onto a glass plate and dried to form a colorless and transparent film, which was then subjected to physical property tests.

(Test method) Refractive index: Measured using an Atsube refractometer using methylene iodide as a contact liquid.

Light transmittance: ^STM-D-1003-61 Surface hardness:
JIS-5400 Pencil hardness and softening point: Measure differential heat using a thermal analyzer.

Water absorption rate: ^STM-0570 (100℃-2h) No. table * 100℃.

H As is clear from Table 2, the polymer of the present invention exhibits optical properties and surface hardness that are equal to or higher than those of adamantyl methacrylate polymer [polymer (C)], and the softening point is lower than that of adamantyl methacrylate polymer [polymer (C)]. It shows a much higher value than the combined one, indicating that it has excellent heat resistance.

1 ml of adamantyl monocrotonate, 5 ml of vinyl acetate, and 4.9+ag of azobisisobutyronitrile (catalyst) were sealed in a deaerated glass tube, and polymerized at 60°C for 2 hours to produce zero reaction. The polymer was precipitated using n-hexane as a precipitant to obtain 0.25 g of a copolymer. The glass transition point of the copolymer was about 60°C, which was significantly higher than the glass transition point of vinyl acetate homopolymer (about 28°C).

[Effects of the Invention] The present invention is configured as described above, and its effects are summarized as follows.

(1) Polymers and copolymers obtained using the adamantyl monocrotonate derivative of the present invention as a monomer component are:
Compared to conventional general plastic materials, it has superior heat resistance and surface hardness, and also has good impact resistance, so it can be used as a heat-resistant hard plastic material for various molded objects and cast objects 9 surface protection material (coating material). It can be used for a wide range of purposes.

Moreover, the polymer of the present invention can be given any physical properties by changing the type of copolymerizable monomers used in combination or the copolymerization composition ratio, so that its range of application is further expanded.

(2) The repeating unit-containing polymers and copolymers of the present invention have very excellent optical properties such as light transmission and refractive index, and therefore have great practical value as optical materials.

[Brief explanation of drawings]

Figure 1.2 shows a polymer of adamantyl crotonate.
H-NMR spectrum, "C-NMR spectrum,"
FIG. 3 shows the thermal decomposition curve of a polymer of tertiary crotonic acid ester.

Claims (1)

[Claims] (1) An adamantyl monocrotonate polymer characterized by having a repeating unit represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1, R^2, and R^3 are the same or different and represent hydrogen, lower alkyl group, halogen, or hydroxyl group. ]