JPS6090204A - Production of polymer - Google Patents

Abstract

PURPOSE:To obtain a polymer, having improved transparency, heat resistance and moldability, capable of exhibiting low hygroscopicity and birefringence, and useful for optical element materials, etc., by polymerizing tricyclo[5.2.1.0<2>,<6>]dec- 8-yl (meth)acrylate. CONSTITUTION:Tricyclo[5.2.1.0<2>,<6>]dec-8-yl (meth)acrylate or its mixture with another polymerizable unsaturated monomer, e.g. methyl methacrylate, is suspension polymerized in the presence of a radical polymerization initiator, e.g. lauroyl peroxide, a suspensing agent, e.g. polyvinyl alcohol, and a suspension assistant, e.g. sodium dodecylbenzenesulfonate, in an aqueous medium to afford the aimed polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 41! of a novel polymer with excellent transparency, heat resistance, and moldability. ! Regarding the manufacturing method.

Conventionally, polymethyl methacrylate, polystyrene, methyl methacrylate-styrene copolymer, and the like are known as transparent thermoplastic resins. Although these resins are widely used as general-purpose transparent resins, all of them have relatively low heat deformation temperatures, so they cannot be used for applications that particularly require heat resistance. On the other hand, transparent resins with high heat resistance include polycarbonate resin and TPX resin, but they are expensive. Therefore, in order to improve the heat resistance of polymethyl methacrylate and polystyrene, a method has been proposed in which α-methylstyrene, maleic anhydride, etc. are copolymerized. Although the copolymer obtained by this method can certainly increase the heat deformation temperature sound, the flowability is greatly reduced and the moldability is significantly impaired. Furthermore, α-methylstyrene has poor reactivity and is extremely difficult to copolymerize with 1% styrene.

The first object of the present invention is to solve the problems of existing transparent resins and to provide a novel monomer with excellent clarity, heat resistance, and moldability.

In addition to transparency and heat resistance, the resin used for Gengaku elements also has low birefringence, low moisture absorption, and moldability, which are important for vorticity. However, at present, no transparent resin has been found that satisfies all of these requirements. Example C
For example, polymethyl methacrylate has excellent transparency and low birefringence, but has the problem of being extremely hygroscopic and prone to dimensional changes and creep deformation during use.

Boristile 7 resin has very low hygroscopicity but high birefringence, and its transparency tends to change over time.

It also has poor heat resistance, making it unsuitable as an optical element material. Furthermore, polycarboy resin has very excellent heat resistance and good hygroscopicity, but it has a large per-bag refraction and is somewhat inferior in transparency. Among these resins, various attempts have been made to improve the drawbacks of hygroscopicity and heat resistance of polymethyl methacrylate resin, which has a high potential for use in academic applications.

For example, JP-A No. 58-5318, JP-A No. 58-5
No. 354 j JP-A-58-11515, JP-A-58-13652, etc. propose a method in which methyl methacrylate is copolymerized with chlorine methacrylate or benzyl methacrylate. Although the hygroscopicity is considerably improved by this method, it is still not sufficient as a material for optical elements, and there is also the problem that the heat resistance is significantly reduced.

A second object of the present invention is to solve such problems and provide a material suitable for optical element materials.

The present invention provides tricyclo methacrylate [5,2,,1,0
'・6] Dec-8-yl or tricycloacrylate [
5,21,0''·6]deca-8-ylke.The method for producing the polymer according to the present invention includes tricyclomethacrylate[5,21,
It also includes copolymerizing the tricyclo[5,2,1,0''.6]thecar-8-yl acrylate with other polymerizable unsaturated monomers.

In the present invention, methacrylic acid tri7chloroC5,2,
1,0'.6]nacar-8-yl and tricycloC5,2,1,0'' acrylate and decar-8-yl r, each can be combined alone; In addition, these can be used alone or in combination, and other polymerizable unsaturated monomers that can be copolymerized with these can be blended for copolymerization.

Here, other polymerizable unsaturated monomers,
Examples include unsaturated fatty acid x stellates, aromatic vinyl compounds, vinyl cyanide compounds, and N-substituted maleimides. Examples of unsaturated fatty acid esters include methyl acrylate, ethyl acrylate,
Acrylic acid alkyl esters such as butyl acrylate and 2-ethylhexyl acrylate, acrylic acid cycloalkyl esters such as cyclohexyl acrylate, and phenyl acrylate.

Aromatic acrylic esters such as be/zyl acrylate, acrylic esters such as glycidyl acrylate, methyl methacrylate, and ethyl methacrylate.

Alkyl methacrylates such as propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cycloalkyl methacrylates such as cyclohexyl methacrylate, aromatic methacrylates such as phenyl methacrylate, benzyl methacrylate, etc. Examples include esters and methacrylic esters such as glycidyl methacrylate.

Examples of the aromatic vinyl compound include stereno-substituted styrenes, α-substituted styrenes such as α-methylstyrene and α-ethylstyrene, and nuclear-substituted styrenes such as chlorostyrene, vinyltoluene, and t-butylstyrene. Examples of vinyl cyanide compounds include acrylonitrile and metacyclonitrile. As the -substituted maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide.

Aliphatic N-substituted maleimides such as N-butylmaleimide and N-laurylmaleimide; alicyclic N-substituted maleimides such as N-cyclohexylmaleimide;

Examples include aromatic N-substituted maleimides such as N-phenylmaleimide, N-1f phenylmaleimide, N-chlorophenylmaleimide, and N-methoxyphenylmaleimide.

In order to obtain a polymer with excellent transparency and heat resistance as well as good moldability, the polymerizable monomers used are preferably blended as follows.

(1) Tricyclo methacrylate [5,2,1,0”・
6] Dec-8-yl or tricycloC5 acrylate,
2,1゜03.6]dec-8-yl (hereinafter referred to as “
component 1)) and other polymerizable unsaturated monomers 0 to 95'Jk-11%. If the amount of component I is too small, it will be difficult to sufficiently achieve the above effects.

Among other polymerizable unsaturated monomers, the heat resistance improves as the amount of N-substituted maleimide increases, but the moldability tends to decrease, so it is more preferable to mix it as follows.

(2) Component 1: 100 to 5% by weight, N-substituted maleimide, 0 to 50% by weight, and other polymerizable unsaturated monomers: 0 to 95% by weight, and the total amount is 100% by weight.

Furthermore, in order to make the material particularly suitable as a molding material, it is preferable that the glass transition point not be too low. For this purpose, the ingredients are mixed as follows.

(3) Ingredients! 100-5% by weight N-[converted maleimide 0-50% by weight Unsaturated monomer whose homopolymer glass transition point is 50°C or lower (hereinafter referred to as "component...") 0-50% by weight and other polymerizable components Unsaturated monomer: 0 to 95% by weight, and the total amount is 100% by weight.

Here, component (2) includes ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, and the like.

According to the method for producing a polymer according to the present invention, resins for various optical elements such as prisms, compensators, original fibers, optical connectors, and Optical Nice 21 light-emitting diodes can be obtained. , as well as transparency, heat resistance and moldability.

It is also considered to have excellent low birefringence, low hygroscopicity, etc. For this reason, it is particularly preferable to mix them as shown below.

(4) Component I 100-20% by weight N-substituted maleimide 0-30% by weight Component n 0-30% by weight and other polymerizable unsaturated monomers 0-80% by weight to give a total weight of 100 tons It is blended as follows.

Furthermore, in order to obtain a more complete sound that satisfies all of the characteristic sounds described above, the following composition is used.

(5) Ingredient 1100 to 50 weights 1 part N-substituted maleimide O to 30 parts 7 inches Ingredient ■ 0 to 3
0% by weight and other polymerizable unsaturated monomers: 0-50M 1 ml is blended so that the total amount is 100% by weight.

Furthermore, in 2 of the above (5), butyl acrylate, ethyl acrylate, or zoclohexfur acrylate is used as component (2), and other polymerizable unsaturated monomers include methyl methacrylate, styrene, substituted styrene, Preferred are nuclear-substituted styrene, acrylonitrile, and the like.

As a method for producing the polymer of the present invention, known methods such as radical polymerization and ionic polymerization can be applied. For example, it can be produced by methods such as bulk polymerization, solution polymerization, and suspension polymerization in the presence of a polymerization initiator. Polymerization methods are preferred.

Examples of initiators used in the polymerization include benzoyl peroxide, lauroyl peroxide, di-1-butylperoxyhexahydroterephthalate, t-butylperoxy-2-ethylhexanony), and 1,1-di-t-butyl. Organic peroxides such as peroxy-3,3,5-)limethylzoclohexane, azohisisoptilonitrile, azobis-4
-Azo compounds such as methoxy-2,4-dimethylvaleronitrile, azobis7chlorohexanone-1-carbonitrile, azodibenzoyl, water-soluble catalysts such as potassium persulfate, ammonium persulfate, and peroxides or persulfuric acids Any redox catalyst that can be used in conventional radical polymerization, such as a redox catalyst using a combination of a salt and a reducing agent, can be used. The polymerization catalyst is 0.01 to 1% of the total amount of nanatsumer.
Preferably, a range of 0% by weight is used. Mercaptan compounds, thioglyfur, carbon tetrabromide as polymerization regulators.

α-methylstyrene dimer or the like may be added as necessary to adjust the molecular cap.

It is preferable to select the temperature appropriately between 0 and 200°C, and preferably 9% and 50 to 120°C.

Solvents for solution polymerization include benzene, toluene,
Xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, dichloroethylene, etc.
Can be used for historical purposes.

Suspension polymerization is carried out in an aqueous medium, with the addition of suspending agents and, if necessary, suspension aids. Examples of M clouding agents include water bathable molecules such as polyvinyl alcohol, methylcellulose, and polyacrylamide, and sparingly soluble inorganic substances such as calcium phosphate and magnesium pyrophosphate. It is preferable to use 0.05 to 0.5% by weight of the slightly soluble inorganic substance based on the total amount of monomers.

Suspension aid 1. Anionic surfactants such as sodium dodecylbenzenesulfonate are used, and when a sparingly soluble inorganic substance is used as a suspending agent, it is preferable to use them together. Suspension aids are o, ooi to o, o2 based on the total amount of monomers.
It is preferable to use an amount of 3<3.

TricycloC5 methacrylate used in the present invention
, 2,1,02.6"dec-8-yl or tricyclo[5,2,1,0'-E-dec-8-yl acrylate can be prepared using generally known methods for the synthesis of methacrylic esters or acrylic esters. It can be obtained using

For example, by adding H2Ok to dicycbe/tadiene to give nzoclobentenyl alcohol, followed by a catalytic hydrogen addition reaction, tri7chloro[5,2,1,011.6]teca-8-ol is obtained. . It can be obtained by a condensation reaction between this alcohol and methacrylic acid, acrylic acid, methacrylic acid chloride, or acrylic acid chloride, or a transesterification reaction with methyl methacrylate or methyl acrylate.

The polymer obtained by the present invention can be molded as a transparent resin and is used as a material for optical elements.

The invention can be applied to rational thermoplastic resin particles, etc.

When using the obtained polymer according to the present invention, it is necessary to use antioxidants such as phenol-based, thioether-based, and phosphite-based antioxidants and m-agents, and antistatic agents to prevent deterioration of coalescence and improve moldability. Agents, ultraviolet absorbers, etc. may be added as needed.

Next, nine examples of the present invention will be shown.

Example 1 Component I lauroyl peroxide 0.4 n-dodecyl mercaptaf 0.2 Component U Deionized water 270 Soda sulfuric acid nose 0.3 Component I and component nt- were charged into a reaction vessel and mixed and stirred inside the reaction vessel. 60℃ after replacing the atmosphere with nitrogen gas?
Polymerization was carried out for 2 hours at 98°C for 4 hours.

The polymerization rate at this time was 99%. The polymerized particles are washed with acid, rinsed with water, and then dried.

Then, it was made into a pellet shape using an extruder and used as a sample for characteristic evaluation. The results are shown in Table 1.

In addition, the characteristic evaluation shown in the following examples was performed by the following method.

Light transmittance (%): ASTM 1) 1003 moisture absorption rate (
%): ASTM D570 Example 2 The monomer was acrylic acid tricycloC5,2,1,0"・6
] Dec-8-yl (hereinafter abbreviated as 'I'CI)-AA).

The same procedure as in Example 1 was carried out except for 7.

The results are shown in Table 1.

Example 3 Polymerization was carried out in accordance with Example 1 using the monomer compositions shown in Table 1, using the two monomer components 'l'cD-MA and 11-butyl acrylate, and the properties were evaluated. The results are shown in Table 1.

Example 4 Monomer component 2 'l' CD-M A and ethyl acrylate were used as two components, and the monomer composition shown in Table 1 was polymerized according to Example 1, and the characteristics were evaluated. The results are shown in Table 1.

Example 5 Characteristics were evaluated using M units according to Example 1 with the monomer composition shown in Table 1 using two monomer components: TCL)-MA and cyclohexyl acrylate. The results are summarized in Table 1.

Example 6 Monomer components (<'ll'c JJ-MA and methyl methacrylate were used as two components, and the monomer composition shown in Table 2 was polymerized according to Example 1, and 1% property evaluation was performed.Results are shown in Table 2.

Example 7 The monomer component was tricycloC5,2,1,0'' acrylate.
l') Deca-8-ino L (hereinafter abbreviated as TCD-AA) and methyl methacrylate were polymerized according to Example 1 using the monomer composition shown in Table 2, and the characteristics were evaluated. The results are shown in Table 2.

Example 8 Polymerization was carried out according to Example 1 with the monomer composition shown in Table 2, using two monomer components: 'l' CD-M A and cyclohexyl methacrylate, and 9% property evaluation was performed. .

The results are shown in Table 2.

Example 9 Two monomer components, iTcD-MA and styrene, were used, and the monomer composition shown in Figure 3 was weighed according to Example 1, and 9% property evaluation was performed. The results are shown in Table 4.

Example 10 Example 1 with the monomer composition shown in Table 4 using three monomer components: 'l'cD-MA, styrene, and acrylonitrile.
Polymerization was carried out according to the method and 1% property evaluation was performed.

The results are shown in Table 3.

Example 11 Polymerization was performed according to Example 1 using the monomer composition shown in Cloth 4, using two monomer components: 'rCD-AA and methylmaleimide, and properties were evaluated. The results are shown in Table 4.

Example 12 Monomer component t-'I' CD -A Two components of A and cyclohexylmaleimide were polymerized according to Example 1 with the monomer composition shown in Table 4, and characteristics were evaluated.

The results are shown in Table 4.

Example 13 Polymerization was carried out according to Example 1 with the monomer composition shown in Table 5 using three monomer components: TCD-MA, 'l' CD-A A, and methylmaleimide, and the characteristics were evaluated. . The results are shown in Table 4.

Example 14 Polymerization was carried out according to Example 1 with the monomer composition shown in Table 4 using Tel)-MA, n-butyl acrylate, and methylmaleimide as the monomer components, and the characteristics were evaluated. . The results are shown in Table 4.

Example 15 Polymerization was carried out according to Example 1 with the monomer composition shown in Table 4 using three components: TCD-MA, n-butyl acrylate, and cyclohexylmaleimite 0, and the characteristics were evaluated. Ta. The results were shown to the public.

Example 16 In a 500 cc Erlenmeyer flask equipped with a three-way stopcock, 2 U0 g of tricyclo[5,2,1,0''·6]dec-8-yl methacrylate, 0.8 g of lauroyl peroxide, and n-dode/lumel-based butane. 04g was added, mixed and dissolved, and after purging the inside of the flask with nitrogen gas, the mixture was heated to 60°C while stirring and shaking.
It was immersed in a constant temperature water bath and polymerized for 30 minutes under a nitrogen stream to obtain a partially polymerized product. Stylish.

This partial chassis was poured into a glass cell, polymerized at 60°C for 2 hours, and then bundled at 100°C for 2 hours to obtain a transparent sheet-like polymer. The total light transmittance of this polymer,
The water absorption rate was measured.

After dissolving 100 g of this polymer in 200 g of tetrahydrofuran, the solution was dissolved in 51 methanol.
The injected polymer was precipitated and separated under stirring, separated by d1, and dried to obtain a white powdery polymer. Table 5 shows the glass transition point and decomposition initiation point of this polymer.

Examples 17 to 21 1 was prepared in the same manner as in Example 1 using the formulations shown in Table 5.
The bonseki had a transparent/t-shaped superimposed body and a white number terminal-shaped main body. Test results similar to those in Example 16 are shown in Figure 1.

Tricyclo(5,2) methacrylate obtained according to the present invention
,,1,0"・6]dec-8-yl and/or tricyclo[s, 2.1.os・6]deca-8-yl acrylate
Single skeleton bodies of il and copolymers of these with monopolytic unsaturated monomers have excellent transparency, heat resistance, and moldability, and also exhibit low hygroscopicity and low birefringence. Can be done.

Continued from page 10 Inventor Mitsuharu Kato 14 Goi Minami Kaigan, Ichihara City
Inventor: Yutaka Hosoi 14 Goi Minamikaigan, Ichihara City Hitachi Chemical Co., Ltd. Goi Plant Hitachi Chemical Co., Ltd. Goi Plant

Claims (1)

[Claims] 1. Tricyclo methacrylate [5, 2, 1, 0, 6]
Dec-8-yl or tricyclo acrylate [5,21
,0'''') A method for producing a monomer, characterized by polymerizing dec-8-yl. 2 Tricyclo methacrylate [5,2,1,0”・6]
Dec-8-yl or tri/chloro acrylate: 5.
2. A method for producing a polymer according to claim 1, which comprises polymerizing decar-8-yl and other polymerizable unsaturated monomers. 3. Other polymerizable unsaturated monomers The polymer is unsaturated fatty acid ester, aromatic vinyl compound, vinyl cyanide compound and N
- The method for producing a polymer according to claim 2, which is at least one compound from the group consisting of substituted maleimides. 4. Tricyclo[5,11,0”-)dec-8-yl methacrylate or tricyclo[5,2,1 acrylate
゜0'''' 100-5% by weight of dec-8-yl and other polymerizable unsaturated monomers θ-9sJ! A method for producing a polymer according to claim 1, 2 or 3, in which t%'tl-polymerization is performed. 5. Tri7chloromethacrylate [5,2,1,U''#6
[#6] Decal or tri7chloro(5,2°i, O'-)dec-8-yl acrylate 100 to 5% by weight. 0 to 50% by weight of N-substituted maleimide and 7 other polymerizable unsaturated monomers of 0 to 95% by weight tqIb are blended and polymerized to a total of 100% by weight. A method for producing a polymer according to item 2, 3, or 4. 6. Tri7chloromethacrylate [5,2,1,01・6
]Dec-8-yl acrylic acid tricyclo[5,2
, 1°0I'.6]dec-8-yl 100-5% by weight. 0-50% by weight of N-substituted maleimide. 0 to 50% by weight of an unsaturated monomer with a homopolymer glass transition point of 50°C or less and 0 to 95% by weight of other monomer unsaturated monomers, with a total content of 1%.
Claims 1, 2, and 3 are blended and polymerized at a concentration of 0.00% by weight. Item 4. A method for producing the polymer according to item 5. 7. Trisic methacrylate 0[5,2,1,0'l'
) Dec-8-yl or acrylic acid tri/chloro[5,2
1,0"+']] f car 8-4 l00~202:
amount%. N-substituted maleimide 0-30 folds. 0 to 30% by weight of unsaturated monomers with a homopolymer glass transition point of 50'C or higher and 0 to 80% of unsaturated monomers having the same binding property as 100% by weight. Claims 1, 2, and 3 are blended and combined so that A method for producing the polymer according to item 4, 5, or 6. 8. Tricyclo methacrylate [5,2,1,O”I6
] Dec-8-yl or tricyclo[5,2 acrylate
1,0″I6]dec-8-yl 1oo to 50% by weight ts. N-substituted maleimide 0 to 30% by weight. 0 to 30% by weight of an unsaturated monomer whose homopolymer glass transition point is 50°C or less and others. 0 to 50% by weight of polymerizable unsaturated monomers, totaling 1% by weight
Claims 1, 2, and 3 are blended and polymerized at a concentration of 0.00% by weight. 4. A method for producing the polymer described in JA, Section 5, Section 6 or Section 7.