JPH03218335A - Polybutyleneglycol dimethacrylate and flexible and low water-absorptive composition containing the same compound - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel polybutylene glycol dimethacrylate and a flexible and low water absorption composition containing the same. The present invention also relates to polybutylene gellicol dimethacrylate useful for use in plastics in fields where good halrance is required, and a flexible, low water absorption composition containing the same.

[Conventional technology]

Today, plastics are widely used in various fields such as molding materials, optical lenses, optical disks, electrical and electronic parts, films, mechanical parts, and laminated glass.

Plastics commonly used in these fields are desired to have improved performance such as toughness, flexibility, and impact resistance. In order to improve these various properties, it is necessary to improve the flexibility of the polymer, and generally, as a means of improving flexibility, polyether, polyurethane, polyester, etc. are added to the polymer molecular chain.
More resilient structures such as polycarbonate have been introduced. The introduction of such structures has been applied to monomers or oligomers before polymerization.

On the other hand, if the performance required of the plastic is moisture resistance, it is desirable that the polymer has low water absorption. The improvement of the low water absorption of this polymer is due to the presence of hydrocarbon chains in its molecules.
Aromatic rings, halogen atoms, etc. have been introduced.

By the way, when cast polymerization is applied to the production of polymers, a low viscosity of 1,000 polymers is desired from the viewpoint of workability.
A polyether structure is optimal for a structure with high elasticity of polymer molecular chains. Monomers providing this polyether structure mainly include polyethylene glycol di(meth)acrylate and polypropylene glycol di(meth)acrylate. The flexibility of the polymer improves in proportion to the increase in the number of repeating units of ethylene oxide or propylene oxide in this monomer.

(Problems to be Solved by the Invention) However, if a hydrocarbon chain, an aromatic ring, a halogen atom, etc. are introduced into the polymer molecule, although the polymer can be made to have low water absorption, the flexibility of the polymer will be lost. Although polyethylene glycol di(meth)acrylate and the like having a useful polyether structure applied to cast polymerization can be improved to some extent in terms of flexibility, the polymer itself has a water absorption rate of 10 to 20%. However, it could not be said to be a polymer with low water absorption.

The purpose of the present invention is to eliminate the above-mentioned disadvantages, and to provide polybutylene glycol dimethacrylate I, which provides a polymer having a good balance of flexibility and low water absorption, and a flexible, low water absorption composition containing the same. It is to provide.

[Means to solve the problem]

The polybutylene glycol dimethacrylate of the present invention is General formula: (In the formula, n is an integer from 5 to 16) This is also shown in .

Moreover, the flexible and low water absorption composition of the present invention comprises (A) a polybutylene glycol dimethacrylate represented by the general formula: (wherein n is an integer of 5 to 16)
10 to 90 parts by weight (B) Compound having at least one polymerizable double bond in the molecule
It is characterized by comprising 10 to 90 parts by weight.

The polybutylene glycol dimethacrylate of the present invention is obtained by sealing both ends of polybutylene glycol with a degree of polymerization of 5 to 16 with two methacrylic acids. The degree of polymerization means the number of repeating units represented by the formula: (CllzCtlzCHzCllzO), and is from 5 to 16. If the degree of polymerization is less than 5, sufficient flexibility cannot be obtained, and if it exceeds 16, water absorption increases and crosslinking density decreases, leading to a decrease in polymer hardness and heat resistance. Furthermore, since the viscosity of the monomer increases, casting workability also decreases. Preferably it is 7-12. Of course, it goes without saying that the polybutylene glycol dimethacrylate of the present invention is a mixture of polymers having different degrees of polymerization in a normal distribution.

Specific examples of the polybutylene glycol dimethacrylate of the present invention include pentabutylene glycol dimethacrylate, hexabutylene glycol dimethacrylate, heptabutylene glycol dimethacrylate, octabutylene glycol dimethacrylate, nonabutylene glycol dimethacrylate, decabutylene glycol dimethacrylate, undecabutylene glycol dimethacrylate, dodecabutylene glycol dimethacrylate-1,
Examples include tridecabutylene glycol dimethacrylate, tetradecabutylene glycol dimethacrylate, pentadecaptylene glycol dimethacrylate, and hexadecabutylene glycol dimethacrylate.

Polybutylene glycol dimethacrylate of the present invention 1-
can be easily produced by, for example, a condensation reaction between polybutylene glycol obtained by ring-opening polymerization of tetrahydrofuran and methacrylic acid, or a transesterification reaction between polybutylene glycol and methyl methacrylate. These manufacturing methods should be selected arbitrarily depending on the final use of the polymer; for example,
If it is desired to obtain a transparent material from this monomer, a transesterification reaction that yields a colorless and transparent heptanomer is selected.

The component CB) used in the flexible and low water absorption composition of the present invention is a component for imparting heat resistance and surface hardness, and has at least one polymerizable double bond in its molecule. It can be anything. This (B
) Components include, for example, methyl (meth)acrylate,
Ethyl (meth)acrylate, Probyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, mo-butyl (meth)acrylate, pentyl (meth)acrylate, (meth)acrylate ) 2-ethylhexyl acrylate, n-hexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (
Butoxyethyl meth)acrylate, allyl (meth)acrylate, methallyl (meth)acrylate, glycidyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-(meth)acrylate Diethylaminoethyl, 2-cyanoethyl (meth)acrylate, (
Dibromopvir meth)acrylate, N-vinyl-2-pyrrolitone (meth)acrylate, polyethylene glycol monoalkyl ether (meth)acrylate, (meth)acrylate
Polypropylene glycol monoalkyl ether acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-(meth)acrylate
Hydroxybutyl, tetrahydrofurfuryl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, norbornyl (meth)acrylate , isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclobentanyl (meth)acrylate, phosphoethyl (meth)acrylate, phthalate (meth)acrylate Ethyl, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyprobyl (meth)acrylate, phenylglycidyl (meth)acrylate, phenyl cellosolve (meth)acrylate, ( Nonylphenoxyethyl (meth)acrylate, biphenyl (meth)acrylate, naphthyl (meth)acrylate, propophenyl (meth)acrylate, tribromophenyl (meth)acrylate, pentab-mophenyl (meth)acrylate, (meth)acrylate ) A9 Chlorobenzyl acrylate, promohenzyl (meth)acrylate, tribromohenzyl (meth)acrylate, (
Mono(meth)acrylate compounds such as meth)acrylic acid 2-phenylphenol; ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, Dimethacrylates of polyethylene glycol such as bentaethylene glycol di(meth)acrylate and nonaethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate 1,3-butylene glycol di(meth)acrylate, 1.4-butylene Glycol di(meth)acrylate, 1,10 6-hexamethylene di(meth)acrylate, ■,14
- di(meth)acrylate of carbrolactone additives of tetradeoxymethylglycol di(meth)acrylate, inopentyl glycol di(meth)acrylate 1, neopentyl hydroxypyhalate glycol di(meth)acrylate, and neopentyl glycol hydroxybihalate. ) acrylate, neobentyl glycol adipate di(meth)acrylate 1., dicyclopentenyl di(meth)acrylate, dicyclobentanyl di(meth)acrylate, 2-(2-
Hydroxy-1,1-dimethylethyl)-5-hydroxymethyl-5-ethyl-1,3-dioxane di(meth)
Acrylate, trimethylolpropane tri(meth)
acrylate, ditrimethylolpropante I-la(meth)acrylate 1, pentaerythritol tri(meth)acrylate, pentaerythritolte 1-la(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate ) Acryl 1~, di(meth)acryloxyconinanoreisocyanu■ ■ Re 1, tris(meth)acryloxyethyl isocyanurate, 2,2'-bis(4-(mec)acryloxyphenyl)-propane ,2,2'-bis(4-(meta)
acryloxyethoxyphenyl)propane, 2.2'
-bis(4-(meth)acryloxydiethoxyphenyl)-propane, 2,2'-bis(4-(meth)acryloxypentaethoxyphenyl)-propane, 2,2'-bis(4-(meth)acryl Roxyethoxy-3,5-cibromophenyl)-propane, 2,2'-bis(4-(meth)acryloxydiethoxy-3,5-dibromophenyl)-propane, 2,2'-bis(4 -(meth)acryloxypentaethoxy-3,5-dibromophenyl)-
Propane, 2,2'-bis(4-(meth)acryloxyethoxy-3,5-dimethylphenyl)-propane, 2
,2'-bis(4-(meth)acryloxyethoxy-3
-phenylphenyl)-propane, 2,2'-bis(4
-(meth)acryloxyethoxyphenyl)-sulfone, 2,2'-bis(4-(meth)acryloxyethoxyphenyl)-sulfone, 2,2'-bis(4-(meth)acryloxy pentaethoxyphenyl)-sulfone, 2.
2'-bis(4-(meth)acryloxyethoxy-3-
Phenylphenyl-sulfone, 2,2'-his(4-
Polyfunctional (meth) acryloxe] xy-3,5-dimethylphenyl) monosulfone, di((meth)acryloxyethoxy) phosphate, tri((meth)acryloxy ethoxy) phosphate, etc. ) Acrylic compounds; Vinyl compounds such as styrene, vinyltoluene, chlorostyrene, promostyrene, divinylbenzene, ■-vinylnaphthalene, 2-vinylnaphthalene, N-vinylpyrrolidone; diethylene glycol bisallyl carbonate, trimethylolpropane diallyl, diallyl Allyl compounds such as phthalate, dimethallyl phthalate, and allyl methacrylate; Examples include (meth)acrylic acid and metal salts of halium, lead, antimony, titanium, tin, zinc, and the like.

These may be used alone or in a mixed system of two or more.

13 (A) and (in the flexible/low water absorption composition of the present invention)
The blending ratio of both components of B) is usually 10 to 90.
Parts by weight. If component (A) is less than 10 parts by weight, sufficient flexibility cannot be imparted to the resulting polymer, and water absorption cannot be suppressed.

On the other hand, if it exceeds 90 parts, the heat resistance and surface hardness of the produced polymer will decrease, which is undesirable. Preferably 20~
It is 60 parts by weight.

The flexible and low water absorption composition of the present invention may contain various additives such as antioxidants, anti-yellowing agents, ultraviolet absorbers, bluing agents, pigments, etc., as necessary, to impair the effects of the present invention. It may be blended within a certain range.

The flexible, low water absorption composition of the present invention can be easily manufactured by mixing and stirring the above-described components (A) and (B) in a conventional manner, and further adding optional additives as necessary. I can do it.

The flexible, low water absorption composition of the present invention is suitably cured depending on the intended use, and then used for various uses. Examples of the polymerization initiator applied to this curing include henzoyl peroxide,
Organic peroxides such as t-butylperoxyisobutyrole, t-butylperoxy-2-ethylhexanoate; 2,2'-azobisisobutyronitrile, 2,2'-azobis(2 , 4-dimethylhalenitrile); 2-hydroxy-2-
Examples include photopolymerization initiators such as methyl-1-phenylpropan-1-one, methylph-14ylglio-1-cyley-1.,2,4.6-}limethylbenzoyldiphenylphosphine oxide.

These may be used alone or in a mixed system of two or more.

The blending ratio of this polymerization initiator is a total of 1 of (A) and (B).
0.00 parts by weight, it is usually 0.005 to 5 parts by weight. In addition, the curing method may include, for example, preparing a mold according to the intended use, injecting the composition of the present invention containing a polymerization initiator through a gasket, etc., and irradiating active energy rays from one or both sides of the mold. , or by heat treatment.

Alternatively, a combination of irradiation and heating may be used. Here, molds depending on the purpose include, for example, when molding optical lenses, laminated glass, optical discs, and films, molds of glass and glass, glass and plastic plates, glass and metal plates, or combinations thereof. There is a mold. Next, after polymerization and curing, depending on the application, it may be released from the mold or it may be used as is, such as laminated glass.

The present invention can be used in various applications such as molding materials, optical lenses, optical discs, electrical and electronic parts, films, mechanical parts, laminated glass, etc. Among them, optical materials, lenses, optical discs, laminated glass,
Application to film is extremely useful.

〔Example〕

The present invention will be explained in more detail with reference to Examples and Comparative Examples below. The abbreviations of the monomers are as follows.

9BGDM: Nonabutylene glycol dimethacrylate 12BGDM; Dodecabutylene glycol dimethacrylate 9BGDA: Nonabutylene glycol diacrylate 1 6 l ■ Rate MMA: Methyl methacrylate St: Styrene 2 GDM: Diethylene glycol dimethacrylate n-BMA: n-butyl methacrylate 9EGDM
: Nonaethylene glycol dimethacrylate 1, 9EGDA : Nonaethylene glycol diacrylate 9 PGDM : Nonapropylene glycol dimethacrylate 4 EGDM : Tetrade ethylene glycol dimethacrylate 1, 4 EGDA : Tetradecaethylene glycol diacrylate 1 Esuru 9BGDMO Man? ■ 5! In the fourth flask, add 17 liters of nonabutylene glycol (average molecular weight = 680, manufactured by Hodogaya Chemical Co., Ltd., product name:
PTG-6 50 SN) 2.0 kg, MM
2.0 kg of A and 0.5 g of hyperquinone monomethyl ether were charged, and using 50 g of titanium tetra-n-butoxide as a catalyst, the tanol produced in the reaction was azeotropically removed with MMA while stirring at 100 to 120'C. , and reacted for 3 hours. After the reaction, excess MMA was distilled off under reduced pressure, 1 kg of toluene was added to the residue, and after washing with alkaline water, toluene was distilled off under reduced pressure to obtain 9BGDM of the present invention.

The obtained 9BGDM was colorless and transparent, and purity analysis by bromine addition showed it to be 100%.

12BGDM people 5I by 2 people! ．． Dodecabutylene glycol (average molecular weight 2890, manufactured by Hodogaya Chemical Co., Ltd., product name:
PTG8 5 0 SN) 2.0 kg, }15 kg of toluene, 0.6 kg of methacrylic acid, 1 g of hydroquinone, and 50 g of sulfuric acid were added, and while stirring at 120°C, by-produced water was azeotropically removed with toluene. Reacted for 18 hours. After the reaction, 1kg of 1.toluene was added, washed with alkaline water, and toluene was distilled off under reduced pressure to obtain 12BC of the present invention.
, got a DM.

The obtained 12BGDM was pale yellow and transparent, and purity analysis by bromine addition showed it to be 98.0%.

Using component A and component B as shown in Tables 3 to 8, add 0.02 g of 2,2'-azobis(2,4-dimethylhaleronitrile) to both components, mix and stir at room temperature. A composition of the present invention was obtained.

Next, inside a mold made of reinforced glass with a length of 100 mm, a width of 100 mm, and a thickness of 5 mm, and a vinyl chloride tubular gasket with an outer diameter of 6 mm (for a plate thickness of 2 mm) and an outer diameter of 10 mm (for a plate thickness of 5M). was injected with the above composition and heated at 80°C for 3
It was then heat cured for 3 hours at 120'C. The cured product was removed from the mold and heat-treated in the shade at 100° C. for 1 hour to remove internal distortion of the cured product.

One molded plate of the obtained cured product (Examples 3 to 8) 9 The following physical property evaluations were conducted. The results are shown in the table.

Total light transmittance (%): Measured according to ASTM D100361.

Elongation (%) by bending test: ASTM D790-7
Measured according to 1.

Saturated water absorption rate (weight %): Using a disc-shaped flat plate with a thickness of 5 strokes and a diameter of 75 mm, it was left in a 100% saturated steam tank at 70"C for 3 days, and the increase in weight was measured.

Condition after water absorption test: The condition of the molded plate after the water absorption test was visually determined.

Falling ball test: A 2 mm thick flat plate was tested according to FDA standards. However, the maximum weight of the steel ball is shown when the steel ball is dropped from a height of 127 cm.

Comparative molded products were prepared in the same manner as in Examples 3 to 8, except that component A and component B were used as shown in this table, and evaluated in the same manner. The results are also shown in the table.

Using component A and component B as shown in Table 1 of the 209 film, 0.1 g of 2,2'-azobis(2,4-dimethylhaleronitrile) was added to both components, and the mixture was thoroughly mixed and stirred. A composition of the present invention was obtained.

Next, the obtained composition was 200 mm long and 200 mm wide.
The mixture was poured onto a 5 mm thick tempered glass and covered with a polyester film (thickness = 200 μm) to prevent bubbles from entering.

At the same time, a polyester film having a width of 10 mm and a thickness of 200 μm was sandwiched between all edges of the tempered glass as a gasket. A glass of the same shape was placed on top of this polyester film, and heated at 80°C for 1 hour and then heated at 120°C.
It was heated and cured at C for 3 hours. The molded film was peeled off from the polyester film and glass, and the physical properties were evaluated in the same manner as in Examples 3 to 8, and a tensile strength test was conducted. The results are shown in the table.

In addition, the tensile strength test was measured according to JIS K-7113. As the test piece, a No. 2 test piece for tensile test cut out from a molded film was used.

2l The elongation to break was about 50%.

A molded film for comparison was prepared in the same manner as in Example 9, except that the monomers shown in the W table were used, and evaluated in the same manner. The results are also shown in the table. The elongation until breakage is approximately 4
%Met.

10 Component A and component B were used as shown in the table, and 0.5 g and 1 g of t-butylperoxy 2-ethylhexanoate and T-mercabutpropyl trimethoxysilane were added to both components, respectively. The mixture was thoroughly mixed and stirred at room temperature to obtain a composition of the present invention.

Next, the above composition was injected into a mold made of two pieces of soda glass and butyl seal rubber, each having a length of 300rr, a width of 300mm, and a thickness of 3mm.
The laminated glass was formed by standing at °C for 5 hours.

Regarding this laminated glass, 22 The physical properties were evaluated. The results are also shown in the table.

As is clear from the table, it was confirmed that the obtained laminated glass was optically uniform and had excellent impact resistance.

This tJ(LJ) A comparative laminated glass was prepared in the same manner as in Example 10, except that the monomers were used as shown in the table, and evaluated in the same manner. The results are also shown in the table.

This laminated glass weighed 100 g according to a falling ball test, but peeling occurred between the glass and the resin layer after the moisture resistance test.

Margin below 23 [Effects of the Invention] As detailed above, the polybutylene glycol dimethacrylate of the present invention can impart flexibility and low water absorption to various plastics, and the advantages of the present invention The flexible and low water absorption composition provides a polymer having good flexibility and low water absorption without impairing heat resistance, impact resistance, surface hardness, etc., so it can be used, for example, in optical materials, lenses, etc. It is useful for applications such as optical disks, laminated glass, and films, and its industrial value is extremely large.

Claims (1)

[Claims] 1. Polybutylene glycol dimethacrylate represented by the general formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, n is an integer from 5 to 16). 2. (A) General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, n is an integer from 5 to 16) Polybutylene glycol dimethacrylate 1 represented by
A flexible, low water absorption composition characterized by comprising 0 to 90 parts by weight (B) 10 to 90 parts by weight of a compound having at least one polymerizable double bond in the molecule.