JP3021152B2 - Radical polymerizable bifunctional (meth) acrylate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel radically polymerizable bifunctional (meth) acrylate.

[0002]

2. Description of the Related Art Hitherto, polyfunctional (meth) acrylates have generally been used as raw materials for polymers, and various compounds have already been known. For example, aliphatic (meth) acrylate monomers such as hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl (meth) acrylate, bisphenol A polyethoxy (meth) ) Aromatic (meth) acrylates such as acrylates.

The above-mentioned polymers and copolymers of aliphatic and aromatic (meth) acrylates are generally used for electronic component materials, optical materials, dental materials, crosslinked materials of various polymers, and the like. However, aliphatic (meth) acrylates
In general, although excellent in polymerizability, strength and durability are low, and aromatic (meth) acrylates have been able to improve the disadvantages to some extent, but they have not been satisfactory yet.

[0004]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a monomer material having excellent physical strength and durability of a polymer or a copolymer.

[0005]

[Means for Solving the Problems] That is, the present invention provides a compound represented by the following general formula:

[0006]

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(Wherein R ₁ is —H or —CH ₃ , l is 0
Or 1, m is 2-4 and n is 2-12. ) Is a radical polymerizable bifunctional (meth) acrylate.

The above (meth) acrylate provided in the present invention may be any of those represented by the above general formula. Particularly preferred examples are as follows.

[0009]

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[0010]

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The (meth) acrylate of the present invention represented by the above general formula is a white solid at normal temperature and pressure and is soluble in common organic solvents such as alcohol, tetrahydrofuran and acetone, but is insoluble in water. .

The (meth) acrylate of the present invention can be confirmed by analysis by the following methods (a) to (d).

(A) Infrared absorption spectrum (IR) The (meth) acrylate represented by the above general formula of the present invention is prepared by the following method. R. Analysis shows that the absorption of the carbonyl group of (meth) acrylate is 1,718 cm ⁻¹ , the absorption of the double bond is 1,640 cm ⁻¹ , the absorption of the carbonyl group directly bonded to the biphenyl group is 1,730 cm ⁻¹ , and the carbonyl group of the urethane bond is At 1640 cm ^-1 . Also, an absorption based on a benzene ring appears at 1608 cm ^-1 .

Therefore, I.I. R. By analysis, the presence or absence of a methacryl group, a biphenyl group, a carbonyl group directly bonded to the biphenyl group, and a urethane bond can be confirmed.

(B) ¹ H Nuclear Magnetic Resonance Spectrum The product can be identified by examining the chemical shift of ¹ H. Specific identification of the compound of the present invention will be described later in Examples, but the identity of the compound of the present invention can be confirmed by ¹ H nuclear magnetic resonance spectrum.

(C) Mass spectrum The molecular ion peak M ⁺ can be confirmed by measuring the (meth) acrylate represented by the above general formula using a field ion-mass spectrometry.

(D) Elemental Analysis The identity of the (meth) acrylate of the present invention is determined by the ¹ H nuclear magnetic resonance spectrum.
By comparing the theoretically calculated values of the C and N elements with the results of elemental analysis of the compound actually obtained, more clear identification becomes possible.

The (meth) acrylate of the present invention can be identified by the analytical means as described in (a) to (d) above.

The (meth) acrylate of the present invention is a novel substance as described above, and can be widely used as a general raw material for polymers.

The above compound has a rigid biphenyl structure in the central skeleton and a flexible structure of alkylene at both ends, so that it exhibits orientation between monomers, and as a result, the resulting polymer has higher strength than before. .

The method for producing the (meth) acrylate of the present invention is not particularly limited, and it may be produced by any method. The following is a typical production method that can be generally preferably employed.

A typical method for producing the (meth) acrylate of the present invention will be described below. First, an alkyl diol represented by the general formula (1) HO— (CH ₂ ) _n —OH (1) (n is 2 to 12) and (meth) acrylic acid chloride or a general formula (2)

[0023]

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(Wherein R ₂ is —H or —CH ₃ , m =
The compound of the following formula (3) is obtained by reacting the isocyanatoalkyl (meth) acrylate represented by 2-4).

[0025]

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(Wherein R is —H, —CH ₃ , l is C or 1, m = 2-4, n = 2-12) This compound and a compound of the following formula (4) are converted to a suitable basic compound The reaction is carried out in the presence of a catalyst to obtain a novel compound represented by the general formula (meth) acrylate.

[0027]

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The production method will be described more specifically. First, (meth) acrylic acid chloride or isocyanate alkyl (meth) acrylate represented by the above general formula (2) is converted to pyridine when (meth) acrylic acid chloride is used. In the case of isocyanatoalkyl (meth) acrylate, a dibutyltin laurate is used as a catalyst in the presence of a basic catalyst such as triethylamine or the like, without using a diol represented by the above general formula (1) and a solvent, or tetrahydrofuran (THF), chloroform, benzene The reaction is carried out for 1 hour while stirring in an appropriate solvent under ice-cooling, and then the temperature is gradually raised to room temperature, and the reaction is further carried out for 1 to 2 hours. After completion of the reaction, excess diol is removed by washing with water to obtain the compound of the general formula (3). Further, the compound represented by the general formula (4) is reacted with the compound represented by the general formula (4) under a basic catalyst such as pyridine or triethylamine, and then recrystallized by using an appropriate solvent such as alcohol or ether. The (meth) acrylate of the invention is obtained.

The (meth) acrylate of the present invention can be a material having excellent strength when polymerized by itself, but exhibits excellent properties even when copolymerized with another monomer as a reactive diluent. Therefore, the (meth) acrylate of the present invention is an excellent raw material as a monomer for obtaining a polymer. For example, the (meth) acrylate of the present invention can be used alone or diluted with another monomer, added with an inorganic filler and a catalyst, and used as a dental filler. In that case, the strength can be improved by 20% or more as compared with the conventional monomer.

[0030]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 To a 100 ml eggplant-shaped flask were added 2.79 g (0.01 mol) of 4,4'biphenyldicarbonyl chloride, 70 ml of tetrahydrofuran, and 0.001 g of di-tert-butylmethylphenol, and the mixture was stirred with hydroxyethyl methacrylate. 2.86 g (0.022 mol),
A solution of 1.58 g (0.02 mol) of pyridine in 5 ml of tetrahydrofuran was stirred for 0.5 hour, and then heated to reflux for 3 hours. The reaction solution was filtered to remove tetrahydrofuran, and the obtained solid was recrystallized from ethanol to obtain 2.3 g of the objective white crystal of the following structural formula. The yield was 49.6%.

According to the infrared absorption spectrum of the obtained reaction product, the absorption due to the OH group at around 3400 cm ^-1 disappeared, and the absorption due to the carbonyl group of the carboxylate directly bonded to the phenyl group at 1730 cm ^-1 Was observed.
In addition, absorption of carbonyl and C お よ び C of methacrylate was observed at 1718 cm ⁻¹ and 1636 cm ⁻¹ , and absorption of biphenyl group was observed at 1608 cm ⁻¹ .

Next, the product was identified by using its ¹ H nuclear magnetic resonance spectrum. The results are as follows.

[0034]

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(A) = 5.51, 6.07 ppm (doublet, 4H) (b) = 1.93 ppm (singlet, 6
H) (c) + (d) = 4.57 ppm (singlet
let), 8H) (e) + (f) = 7.63 to 8.22 ppm (tetraplet, 8H) Furthermore, according to the mass spectrometry spectrum of the product, m / e = 4.
66 molecular ion peaks were observed.

The results of elemental analysis of the product are shown below.

[0037]

[Table 1]

From these results, the reaction product was:

[0039]

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Was confirmed.

The three-necked flask of Example 2 300 ml, 1,6-hexanediol 29.7g (0.251mol), triethyl amine <br/> emissions 10.56 g (0.104mol), tetrahydrofuran 200ml In addition, methacrylic acid chloride 1 under ice cooling
0.9 g (0.104 mol) was added dropwise. After completion of the dropwise addition, the mixture was heated to 40 ° C. and reacted for 15 hours. After the resulting precipitate was filtered off, the filtrate was concentrated, and water and benzene were added thereto for extraction and washing. The organic layer was concentrated, washed with n-hexane and further concentrated to obtain 6-methacryloxyhexanol 1. The yield was 52%.

In another 100 ml eggplant-shaped flask,
2.79 g of 4 'biphenyldicarbonyl chloride (0.
01 mol), 70 ml of tetrahydrofuran, di-te
3. Addition of 0.001 g of r-butylmethylphenol and 6-methacryloxyhexanol obtained above with stirring.
92 g (0.022 mol), pyridine 1.58 g
(0.02 mol) in tetrahydrofuran (5 ml) was added, and the mixture was stirred for 0.5 hour, and then heated and refluxed for 3 hours. After filtering the reaction solution to remove tetrahydrofuran, the obtained solid was recrystallized from ethanol to obtain 2.51 g of white crystals having the following structure. The yield was 33.3%.

The infrared absorption spectrum of this product showed the same absorption as in Example 1. Next, the product was identified using the ¹ H nuclear magnetic resonance spectrum.

The results were as follows.

[0045]

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(A) = 5.52, 6.08 ppm (doublet, 4H) (b) = 1.93 ppm (singlet, 6
H) (c) + (e) = 4.07-4.35 ppm (multiplet, 8H) (d) = 1.53-1.79 ppm (multiplet)
(multiplet), 16H) (f) + (g) = 7.61-8.20 ppm (tetraplet, 8H) The results of elemental analysis of the product were as follows.

[0047]

[Table 2]

Further, a molecular ion peak of m / e = 578 was observed in the mass spectrometry spectrum of the product.

From the above results, it was confirmed that the reaction product was methacrylate represented by the above structural formula.

The three-necked flask of Example 3 300 ml, 1,10-decanediol 6.35g (0 .2 51mol), triethyl amine <br/> down 10.56g (0 .1 04mol), tetrahydrofuran 200ml And methacrylic acid chloride 1 under ice cooling
09 g (0.0104 mol) was added dropwise. After dripping 4
The mixture was heated to 0 ° C. and reacted for 15 hours. After the resulting precipitate was filtered off, the filtrate was concentrated, and water and benzene were added thereto for extraction and washing. The organic layer was concentrated to give a further concentrated to 10 methacryloxy octadecanol washed with n- hexane.
The yield was 52%.

In a separate 100 ml eggplant-shaped flask,
2.79 g of 4 'biphenyldicarbonyl chloride (0.
01 mol), 70 ml of tetrahydrofuran, diter
Butyl methyl phenol 0.001g was added, with stirring obtained by the above 10-methacryloxy octadecanol
5.30 g (0.022 mol), pyridine 1.58 g
(0.02 mol) in 5 ml of tetrahydrofuran was added, and the mixture was stirred for 0.5 hour and heated under reflux for 3 hours. After filtering the reaction solution to remove tetrahydrofuran, the obtained solid was recrystallized from ethanol to obtain 3.44 g of white crystals having the following structural formula. The yield was 39.7%.

The infrared absorption spectrum of this product showed the same absorption as in Example 1. Next, the product was identified using the ¹ H nuclear magnetic resonance spectrum.

The results were as follows.

[0054]

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(A) = 5.53, 6.09 ppm (doublet, 4H) (b) = 1.94 ppm (singlet, 6
H) (c) + (e) = 4.10 to 4.39 ppm (multiplet, 8H) (d) = 1.51 to 1.79 ppm (multiplet)
(multiplet), 32H) (f) + (g) = 7.61-8.21 ppm (tetraplet, 8H) The results of elemental analysis of the product were as follows.

[0056]

[Table 3]

Further, a molecular ion peak at m / e = 690 was observed from the mass spectrum of the product.

From the above results, it was confirmed that the reaction product was methacrylate represented by the above structural formula.

[0059] A three necked flask of Example 4 300ml, 1, 8 - octa Njioru 29.7g (. 0 203 mol), triethyl amine <br/> down 10.56g (0 .1 04mol), tetrahydrofuran 200ml And add acrylic acid chloride 1 under ice cooling
0.9g (0 .1 04mol) was added dropwise. After dripping 4
The mixture was heated to 0 ° C. and reacted for 15 hours. After the resulting precipitate was filtered off, the filtrate was concentrated, and water and benzene were added thereto for extraction and washing. The organic layer was concentrated, washed with n-hexane, and further concentrated to obtain 6-acryloxyhexanol 1.
The yield was 52%.

In another 100 ml eggplant-shaped flask,
2.79 g of 4 'biphenyldicarbonyl chloride (0.
01 mol), 70 ml of tetrahydrofuran, diter
Added butyl methyl phenol 0.001 g, stirring obtained above 8 - acryloxy octa Nord 4.
40 g (0.022 mol), pyridine 1.58 g
(0.02 mol) in 5 ml of tetrahydrofuran was added, and the mixture was stirred for 0.5 hour and heated under reflux for 3 hours. After filtering the reaction solution to remove tetrahydrofuran, the obtained solid was recrystallized from ethanol to obtain 2.10 g of white crystals having the following structural formula. The yield was 28.9%.

The infrared absorption spectrum of this product showed the same absorption as in Example 1. Next, the product was identified using the ¹ H nuclear magnetic resonance spectrum.

The results were as follows.

[0063]

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(A) + (b) = 5.84 to 6.37 pp
m (multiplet, 6H) (c) + (e) = 3.95-4.28 ppm (multiplet, 8H) (d) = 1.44-1.83 ppm (multiplet)
(multiplet), 24H) (f) + (g) = 7.05-8.21 ppm (tetraplet, 8H) The results of elemental analysis of the product were as follows.

[0065]

[Table 4]

Further, a molecular ion peak of m / e = 606 was observed in the mass spectrometry spectrum of the product.

From the above results, it was confirmed that the reaction product was an acrylate represented by the above structural formula.

[0068] A three necked flask of Example 5 300 ml, 1,6-hexanediol 29.7g (0 .2 51mol), dibutyltin laurate 0. 1 mol and 200 ml of tetrahydrofuran were added, and 2- isocyanatoethyl methacrylate
5.6g (0 .1 04mol) was added dropwise. After dripping 4
The mixture was heated to 0 ° C. and reacted for 3 hours. After the resulting precipitate was filtered off, the filtrate was concentrated, and water and benzene were added thereto for extraction and washing. The organic layer was concentrated, washed with n-hexane and further concentrated to obtain the following compound (a).

[0069]

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The yield was 52%.

In another 100 ml eggplant-shaped flask,
2.79 g of 4 'biphenyldicarbonyl chloride (0.
01 mol), 70 ml of tetrahydrofuran, di-te
After adding 0.001 g of r-butylmethylphenol and stirring, 6.0 g of the above compound (a) (0.022 mol) was added.
l), a solution of 1.58 g (0.02 mol) of pyridine in 5 ml of tetrahydrofuran was added, and the mixture was stirred for 0.5 hour and heated under reflux for 3 hours. After filtering the reaction solution to remove tetrahydrofuran, the obtained solid was recrystallized from ethanol to give 5.10 g of white crystals of the following structural formula.
I got The yield was 55.0%.

The infrared absorption spectrum of this product showed almost the same absorption as in Example 1, and the absorption of a carbonyl group derived from a urethane bond appeared at 1640 cm ^-1 . Next, the product was identified using the ¹ H nuclear magnetic resonance spectrum.

The results were as follows.

[0074]

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(A) = 5.54, 6.08 ppm (doublet, 4H) (b) = 1.94 ppm (singlet, 6
H) (c) + (e) + (g) = 3.96-4.38 ppm
(Multiplet, 12H) (d) = 3.02 to 3.46 ppm (multiplet)
(multiplet), 4H) (f) = 1.51 to 1.78 ppm (multiplet)
(multiplet), 16H) (h) + (i) = 7.62 to 8.22 ppm (tetraplet, 8H) (j) = 4.78 ppm (broad, 2H) The results of the elemental analysis were as shown below.

[0076]

[Table 5]

Further, a molecular ion peak at m / e = 752 was observed in the mass spectrum of the product.

From the above results, it was confirmed that the reaction product was methacrylate represented by the above structural formula.

──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07C 69/76 C07C 271/16 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A compound represented by the general formula: (Wherein R ₁ is —H or —CH ₃ , 1 is 0 or 1, m
Is 2 to 4 and n is 2 to 12).