JPH0320124B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a silicon atom-containing organic polymer compound. It has been known for a long time to form a film using a polymer compound with a linear structure, and then crosslink this material into a strong three-dimensional polymer. It is widely applied. For example, methods of introducing vinyl groups by polymer modification of polyvinyl alcohol such as vinyl cinnamate, methods of introducing vinyl groups into polysiloxane, methods of mixing reactive monomers or polymers, etc. are well known. However, by polymerizing monomers that have two unsaturated groups such as vinyl groups in one molecule using a normal polymerization method, only one unsaturated group is polymerized, and the other unsaturated group remains. Not much is known about how to obtain it. This is because when one unsaturated group is polymerized, the other unsaturated group is also polymerized at the same time, resulting in a three-dimensional polymer from the beginning. As a result of intensive research, the inventors of the present invention have selected and used a vinylsilane derivative that has an organic group having an ethylenic double bond and a vinyl group directly bonded to a silicon atom, which easily undergoes a polymerization reaction under normal polymerization reaction conditions. The present invention was completed based on the discovery that it is possible to easily obtain a linear polymer compound in which vinylsilyl groups capable of crosslinking remain. That is, the present invention is based on the general formula (In the formula, V is an organic group having a polymerizable ethylenic double bond, R ¹ and R ² are an alkyl group or phenyl group having 1 to 4 carbon atoms, n is a number from 0 to 3, where n = 0 (where V is not a vinyl group) is subjected to radical polymerization using a peroxide or an azo compound as a catalyst,
By anionic polymerization using a Grignard reagent as an initiator or anionic polymerization using an alkali metal compound of a hydrocarbon in a tetrahydrofuran solvent as an initiator, the vinyl silyl group remains and the ethylenic double bond in the organic group V is preferentially polymerized. The present invention relates to a method for producing a silicon atom-containing organic polymer compound, which is characterized by a reaction. To explain this, R ¹ and R ² in the vinylsilane derivative represented by the above general formula () are groups selected from a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group; ₂ )
V in the group represented by n- is an organic group having a polymerizable ethylenic double bond, and examples thereof are as follows. Vinyl phenyl group _CH2 =CH- _C6H4- ( _CH2 )n- (n= _0-3 ) Methacrylic acid group _CH2 =C( _CH3 )COO-( _CH2 )n- (n=1-3 ) Acrylic acid group _CH2 =CHCOO-( _CH2 )n- (n=1-3) Vinyl group _CH2 =CH-( _CH2 )n- (n=1-3) Propenyl group _CH3CH =CH- ( _CH2 )n- (n=1-3) Vinyloxy group _CH2 =CHO-( _CH2 )n- ( _n =1-3) Vinylpyridyl group _CH2 =CH- _C5H4N- ( _CH2 )n- (n=1 to 3) Vinylsilane derivatives having the respective molecular structures described above can be produced by known organic synthesis methods such as Gunyard reaction and hydrosilylation reaction using ordinary vinylchlorosilanes, alkylchlorosilanes, and hydrochlorosilanes as raw materials. It can be obtained by reaction. The vinylsilane derivative used in the present invention has the following characteristics. That is, the formula V-
The ethylenic double bond in (CH ₂ )n- is easily polymerized under normal polymerization reaction conditions (radical polymerization, anionic polymerization, cationic polymerization), but the vinyl group directly bonded to the silicon atom Due to steric hindrance caused by other organic groups (R ¹ , R ² ) bonded to the atoms, it has the property that almost no polymerization reaction occurs under normal polymerization conditions. For example, trimethylvinylsilane cannot be subjected to normal radical polymerization, and can only be easily polymerized by anionic polymerization using butyllithium and reacting at a temperature of 35°C for 400 hours (see West German Publication No. 2259951). ), the rate of this anionic polymerization is extremely slow. However, the vinylsilane derivative represented by the general formula () easily becomes a linear polymeric compound with residual vinylsilyl groups by radical polymerization, anionic polymerization or cationic polymerization under normal polymerization reaction conditions. In the polymerization of the vinyl silane derivative, other common vinyl monomers (comonomers) may be used in combination, if necessary. The linear polymer compound having residual vinylsilyl groups obtained in this way is soluble in organic solvents and easily crosslinks to become a tough three-dimensional polymer that is insoluble in solvents, so it can be used in photosensitive resins, rubbers, etc. It is said to be useful in a wide range of fields such as paints, adhesives, etc. Methods for crosslinking linear polymer compounds having residual vinyl silyl groups include a) irradiation with ultraviolet rays, electron beams, or A method using an organic compound having two molecules is mentioned. In addition, the above-mentioned peroxides include benzoyl peroxide, 2,4-
Examples of organic compounds having at least two functional groups include dichlorobenzoyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, etc.
Organosilane compounds or organopolysiloxane compounds having two or more functional groups in the molecule, or organopolysiloxanes having two or more functional groups represented by ≡Si-R-SH (R is a divalent hydrocarbon group) in one molecule. compound, and 2, which is a photocrosslinking agent.
Examples include 6-di(4azidobenzylidene)-cyclohexanone. Next, specific examples will be given. Example 1 12 g of magnesium and 200 ml of tetrahydrofuran were placed in a 500 ml flask, 0.5 ml of ethyl bromide was added to start the reaction, and 69 g of p-chlorostyrene was added dropwise over 3 hours at reflux temperature in a nitrogen stream. A Grignard reagent of p-chlorostyrene was synthesized by reaction. Next, 60 g of vinylmethylchlorosilane was added dropwise to the Grignard reagent at 20 to 30°C, followed by hydrolysis, and the organic layer was distilled under reduced pressure.

[Formula]) 75g was obtained. Next, it was dissolved in 150 ml of toluene containing 20 g of p-vinylphenyldimethylsilane and 0.5% azobisisobutyronitrile, and polymerized at 80° C. for 40 hours. This viscous liquid was poured into methanol 1 to separate the precipitate, and then washed and dried to obtain 14 g of a white polymer. This polymer was redissolved in toluene and reduced to a pressure of 10 μm using the casting method.
When a film was prepared and analyzed by infrared absorption spectrum, it was confirmed that it contained vinylsilyl groups. Next, 10 g of this poly-p-vinylphenyldimethylvinylsilane and 0.05 g of 2,4-dichlorobenzoyl peroxide were dissolved in 150 ml of toluene, and a film with a pressure of 10 μm was made by the casting method at room temperature. When crosslinked at ℃ for 30 minutes, this film became a very strong three-dimensional polymer and was no longer completely insoluble in toluene. Example 2 62 g of chloromethyldimethylvinylsilane obtained by Grignard reaction of vinyl bromide Grignard reagent and chloromethyldimethylchlorosilane in a conventional manner was charged into a 500 ml flask, and 59 g of sodium methacrylate and dimethylformamide were added to the flask.
100 ml and 2 ml of pyridine were added, and the mixture was heated and reacted at 80°C for 3 hours with stirring. After that, the reaction solution was cooled and poured into 500ml of water, and the separated organic layer was distilled under reduced pressure.

[Formula] 74g was obtained. Next, 20 g of this methylene vinyl dimethyl methacrylate silane was dissolved in 300 ml of anhydrous toluene under a nitrogen stream, and then 3.6 ml of a diethyl ether solution of 3.3 mole ^-1 phenylmagnesium bromide (C ₆ H ₅ MgBr) was added. The mixture was polymerized for 6 hours with stirring at 5° C. under a nitrogen stream. This viscous liquid was poured into methanol 1 and the polymer was precipitated and separated, washed and dried to obtain 13 g of a white polymer. This polymer was once again dissolved in toluene, and a film with a thickness of 5 μm was produced by a casting method. When this film was analyzed using an infrared spectrum, it was found that there was a large absorption at 3080 cm ^-1 , confirming that vinylsilyl groups remained.
When this film was then irradiated for 3 minutes under reduced pressure using an ultra-high pressure mercury lamp (365 nm, 110 W/m ² ), it became a very strong film and was insoluble in toluene. Also,
When analyzed by infrared absorption spectrum, it was 3080cm ^-1
It was confirmed that the absorption of 20% disappeared, and the vinyl groups were crosslinked to form a three-dimensional polymer. Example 3 3-chloropropylmethylphenylvinylsilane obtained by Grignard reaction of bromobenzene Grignard reagent and 3-chloropropylmethylvinylchlorosilane according to a conventional method Place 30g and 25g of sodium acrylate in a 500ml flask, and add 50ml of dimethylformamide to this.
and 2 ml of pyridine were added, and the mixture was heated and reacted at 80°C for 3 hours. After that, the reaction solution was cooled, 300ml of water was added, and the separated organic layer was distilled under reduced pressure. Obtained 21g. Next, 100 g of water, 3 g of hydroxypropyl methylcellulose, 0.1 g of oleyl alcohol, 0.1 g of gelatin, 4 g of propylene methylphenyl vinyl acrylate, 8 g of vinyl chloride, and 0.05 g of benzoyl peroxide were placed in one autoclave, and suspended at 60°C for 10 hours under nitrogen. A cloudy copolymerization was carried out. After the reaction, after filtering, washing and drying,
11 g of a vinyl chloride-propylene acrylate methyl phenyl vinyl silane copolymer was obtained. When this polymer was analyzed by infrared absorption spectrum,
There was an absorption at 3080 cm ^-1 , confirming that vinyl groups remained. Next, after dissolving 10 g of this copolymer in 100 ml of tetrahydrofuran, 2 g of dimethylsiloxane (average degree of polymerization 10) having hydro groups at both ends and a 2% butanol solution of chloroplatinic acid were added.
After adding 0.3ml, use the casting method to create a thickness of 200μ.
After making the film, a crosslinking reaction was carried out at 120°C for 15 minutes. This film was strong and flexible. It was confirmed that this film was no longer soluble in tetrahydrofuran and had become a three-dimensional polymer. Examples 4 to 5 6 g of p-vinylphenyldimethylvinylsilane synthesized in exactly the same manner as in Example 1 was purified under high vacuum using a (C ₆ H ₅ ) ₃ CLi-LiBr mixed purification agent. It was purified using a living anionic polymerization method under high vacuum using 1.2 × 10 ^-4 mol of n-BuLi as an initiator and a reaction temperature of -78 °C using cumyl cesium (Cum-Cs) as a solvent. Polymerization was carried out for 2 hours using 100 ml of tetrahydrofuran. After the polymerization was completed, the contents were poured into methanol, and the resulting polymer was separated by precipitation, washed, and dried to obtain a white polymer. The glass transition point (Tg), number average molecular weight (Mn), and weight average molecular weight (Mw) of the obtained polymer were measured by GPC, membrane osmotic pressure method, and light scattering method. The results are shown in Table 1, and the GPC curve is shown in Figure 1.

[Table] The results of IR spectrum analysis of all of the obtained polymers showed that they contained ≡Si-CH=CH ₂ . A film with a thickness of 10 μm was made as a toluene solution by the casting method, and it was heated using a high-pressure mercury lamp (110 W/m ^{2 ).} , 365 nm) for 1 minute, a strong film insoluble in toluene was obtained.

[Brief explanation of the drawing]

FIG. 1 shows the GPC elution curve of poly(4-vinylphenyldimethylvinylsilane) polymerized at -78°C in THF using n-BuLi and Cum-Cs as initiators.

Claims (1)

[Claims] 1. General formula (In the formula, V is an organic group having a polymerizable ethylenic double bond, R ¹ and R ² are an alkyl group or phenyl group having 1 to 4 carbon atoms, n is a number from 0 to 3, where n = 0 (where V is not a vinyl group) is subjected to radical polymerization using a peroxide or an azo compound as a catalyst,
By anionic polymerization using a Grignard reagent as an initiator or anionic polymerization using an alkali metal compound of a hydrocarbon in a tetrahydrofuran solvent as an initiator, the vinyl silyl group remains and the ethylenic double bond in the organic group V is preferentially polymerized. 1. A method for producing a silicon atom-containing organic polymer compound, which comprises causing a reaction.