JP2593155B2 - Method for producing silane-modified polymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a modified polymer having excellent reactivity (functionality) treated with silane (silicon hydride compound). Specifically, the present invention relates to a method for producing a polymer containing a silyl group or the like containing a Si—H bond.

[Problems to be solved by conventional technology and invention]

In recent years, the development of highly functional polymers has been remarkable, and a large number of polymers having various physical properties have been produced. Not only hydrocarbon (organic) polymers but also inorganic polymers have made remarkable progress. Many polymers containing silicon are known,
Starting with silicones with Si-O bonds as the main chain, Si-C
Polycarbosilanes having a bond as a main chain, polysilanes having a Si-Si bond as a main chain, and polyolefins having a vinyltrialkoxysilane as a component of a monomer are commercially produced.

An object of the present invention is to provide a method for modifying a conventional carbon-based polymer compound to produce a highly functional polymer compound.

[Means and actions for solving the problems]

The present inventors have worked for many years to develop polymers with new functions unprecedented, and as a result, have excellent reactivity
With the idea of introducing a Si-H bond into a conventional hydrocarbon-based polymer, the present invention could be completed.

That is, according to the present invention, C = C, C≡C, C =
O, C = N, N = C = O, C≡N, C-Cl, A polymer compound containing at least one of O—H and N—H bonds is represented by the general formula Si _n H _{2n + 2} (where n is 1, 2,
3 or 4. A method for producing a modified polymer, characterized by treating with a silicon hydride compound represented by the formula (1):

 Hereinafter, the present invention will be described in detail.

In the present invention, the polymer compound used for the modification includes CＣC, C≡C, C ＝ O, CＮN, N ＝ C in the molecule.
= 0, C≡N, C-Cl, It contains at least one of O—H and N—H bonds. That is, all of these bonds cause an addition reaction with a silicon hydride compound described later, and a silyl group having a Si—H bond can be easily introduced into the polymer compound by the reaction. Specific examples of the polymer compound include polyacrylate Polymethyl methacrylate Polyacrylonitrile Polycyanoacrylate Polyacrylamide Polyacrylic hydrochloric acid Polyvinyl acetate Polyvinyl alcohol (popal) PVC Polyvinyl pyrrolidone Polybutadiene Polychloroprene Polyethylene imine (Permiston C) CH ₂ CH ₂ NH _n phenolic resin, urea resin, melamine resin, guanamine resin, aniline resin, sulfoamide resin, modified xylenol resin, ketone resin, polyester resin, amide resin, furan resin, polyurethane resin , Polyurea resin,
Polymeric repeating units containing the bond specified in the present invention, such as epoxy resins, copolymers containing these polymer repeating units in the molecule, or high as seen in epoxy resins Those containing the bond specified in the present invention at the terminal of the molecular compound are exemplified. However, in the above chemical formula, R represents an alkyl group. M represents an alkali metal atom.

Next, the silicon hydride compound is represented by the general formula Si _n H _{2n + 2} (where n is 1, 2, 3 or 4), and specifically, SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ and Si ₄ H ₁₀ . Among them, SiH ₄ ,
Si ₂ H ₆ is particularly preferred. These silicon hydride compounds have been rapidly growing in recent years for semiconductor gases.
It is expected that this trend will further evolve, and that these hydrides will be mass-produced and available at lower cost.

The method of treating the above-mentioned polymer compound with a hydrogen silicon compound is not particularly limited in the present invention, and may be changed depending on the type of a bond or the type of a silicon hydride compound of the polymer compound to be treated. For example, the following method can be adopted as the processing method.

(1) A method in which a gaseous or liquid silicon hydride compound is introduced into a solution in which a polymer is dissolved in a solvent and brought into contact with the solution.

(2) A method in which a gaseous or liquid silicon hydride compound is introduced into and contacted with a liquid polymer (in some cases, heated and melted) without a solvent.

(3) A method in which a gaseous or liquid silicon hydride compound is introduced into a polymer in a slurry state and brought into contact with the polymer.

(4) A method in which a gaseous or liquid silicon hydride compound is introduced into a polymer in a solid (preferably, powder) state and brought into contact with the polymer.

In addition, since the reaction conditions of the bond of the polymer compound according to the present invention and the silicon hydride compound differ depending on the type of the bond, the above-mentioned treatment conditions must further consider these reaction conditions. For example, C = C, C≡C, C≡N
In the case of treating a polymer compound having a bond, heat treatment (usually at a temperature in the range of 300 to 700 ° C.), radicals such as benzoyl peroxide, cumene peroxide, di-t-butyl peroxide, azobisbutyronitrile, etc. Initiator,
Fe (CO) ₅ , Co (CO) ₈ , L ₂ Ni (olefin) (L is PΦ ₃ , PR ₃ (Φ is a phenyl group, R is an alkyl group)), L ₂ NiCl ₂ , L ₃ RhCl, L ₄ Pd, L ₂ PdCl ₂ , L ₄ Pt, H ₂ Pt
Cl ₆ · 6H ₂ O, may be employed a technique such as with Group VI to Group VIII transition metal complexes, such as Pt / C. Also, C = O, C
ＮN, N ＝ C ＝ O bond, ZnCl _2, etc. in addition to the Group VI to VIII transition metal complex;
catalyze u, alkali, amines, etc., and in the case of N—H bond, catalyze alkali metal alkylamide, etc. In the case of bonding, the object of the present invention can be achieved by high-temperature treatment. The reaction by the treatment is considered to proceed, for example, by the following formula in the case of SiH ₄ .

Further, the silyl group or the like in the present invention is at least one
SiH having a Si-H bond, etc., not only -SiH ₃ but also SiH ₂ in which the remaining Si-H bond has reacted in the above reaction formula,
-SiH is also included. The same applies to the case of Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H ₁₀ . These silyl groups and the like are stable in the air and can be stored for a long period of time. The temperature at which silyl groups and the like are oxidized in the air is relatively high and is usually about 150 ° C.

The reactive polymer compound containing a Si—H bond obtained according to the present invention can impart various functions by using a highly reactive Si—H bond. For example, the physical properties of polymer compounds, especially surface properties, can be freely improved by improving dyeing properties, adhesion, water repellency, improving paintability, or adding other low-molecular or high-molecular compounds using Si-H bonds. Can be changed to The possibility of application of the polymer compound of the present invention, such as crosslinking by oxygen oxidation, foaming, and hardening the surface, is extremely wide for those and others.

〔Example〕

 Hereinafter, the present invention will be described with reference to examples.

[Example 1] 300 ml of a toluene solution of polybutadiene having an average molecular weight of about 100,000 (polymer concentration: 0.3 g / ml), and Pt (P
Φ ₃ ) ₄ (Φ is a phenyl group) was charged to a 1.0 g, 500 ml autoreave. Then the temperature of the autoclave is set to 100 ° C
, And SiH ₄ was injected under pressure of about 20 kg / cm ² abs and reacted for 18 hours. After completion of the reaction, the reaction solution was poured into methanol to precipitate and recover a polymer.

The Si content in the polymer was 2.7% by weight. Also, about 587 ml by heating 10 g of this polymer with NaOH aqueous solution
The generation of H ₂ gas, further by IR spectra 850-9
50 cm ^-1, confirming absorption by Si-H bonds to 2100~2200cm ^-1. This polymer is stable in air,
No weight increase due to combustion of -H bonds was observed.

[Example 2] Polymethyl methacrylate having an average molecular weight of about 600,000 was added to 6
0 g, 300 ml of toluene, RuCl ₂ (PΦ ₃ ) ₃ as a catalyst
1.0 g, 500 ml were charged into an autoclave. Thereafter, the temperature of the autoclave was set to 100 ° C, and the temperature was set to about 20 kg / cm ² a.
SiH ₄ was injected under the pressure of bs and reacted for 10 hours. After completion of the reaction, the reaction solution was poured into methanol to precipitate and recover a polymer.

The amount of Si in the polymer was 1.8% by weight. Also polymer 1
The generation of H ₂ gas of about 373ml by a heat treatment with aqueous NaOH to 0g, 850~950c further by IR spectrum
Absorption at m ^-1 and 2100 to 2200 cm ^-1 was confirmed by Si-H bonds. This polymer is stable in air and has a Si-H
No weight increase was observed due to the burning of the bond.

Example 3 Powder of polyvinyl alcohol having an average molecular weight of about 50,000
70 g, xylene 300 ml, metal sodium 1.2 g, 500 ml
In an autoclave. After that, the temperature of the autoclave was set to 40 ° C, and the pressure was increased to about 20 kg / cm ² abs.
press-fitting the iH _4, was allowed to react for 5 hours. After completion of the reaction, the reaction solution was treated with acetic acid to recover a polymer.

The Si content in the polymer was 9.7 wt%. Also polymer 1
About 983 ml of H ₂ by heat treatment of 0 g with an aqueous NaOH solution.
Gas generation, 800-1000c by IR spectrum
Absorption at m ^-1 and 2100 to 2200 cm ^-1 was confirmed by Si-H bonds. This polymer is stable in air and has a Si-
No weight increase due to H-bond combustion was observed.

Example 4 Polyacrylonitrile powder having an average molecular weight of about 80,000
100 g, 300 ml of toluene, 1.7 g of Co ₂ (CO) ₈ and 500 ml of autoclave were charged. Thereafter, the temperature of the autoclave was set to 70 ° C., and the pressure was increased to about 20 kg / cm ² abs.
₄ was injected and reacted for 18 hours. After completion of the reaction, the polymer was recovered by filtration.

The Si content in the polymer was 6.1% by weight. Also polymer 1
About 550 ml of H ₂ by heating 0 g with an aqueous NaOH solution.
Gas generation, 800-1000c by IR spectrum
Absorption at m ^-1 and 2100 to 2200 cm ^-1 was confirmed by Si-H bonds. This polymer is stable in air and has a Si-
No weight increase due to H-bond combustion was observed.

Example 5 An autoclave of 100 g of 6-nylon having an average molecular weight of about 20,000, 300 ml of toluene, 2 g of Li and 500 ml was charged.
After that, set the temperature of the autoclave to 0 ° C,
Si ₂ H ₆ was charged under a pressure of ² kg / cm ² abs and reacted for 2 hours.

After the reaction, the amount of Si in the polymer was 0.9% by weight.
The generation of H ₂ gas of about 160ml by heating the polymer 10g with aqueous NaOH, further 800～1000Cm ^-1 by IR spectrum confirmed the absorption by Si-H bonds to 2100~2200cm ^-1. This polymer is stable in air,
Up to 140 ° C., no weight increase due to combustion of the Si—H bond was observed.

〔The invention's effect〕

The present invention modifies a conventional carbon-based polymer compound and introduces a highly reactive Si-H bond into the polymer compound, and provides a method for producing a highly functional reactive polymer compound. It is. Silicon hydride compounds used as modifiers are SiH ₄ , Si ₂ H _6, etc. These have been mass-produced as semiconductor gases in recent years and have become available at low cost.

The polymer compound according to the present invention can be used in various ways, and it is also possible to add another low-molecular or high-molecular compound using a Si-H bond, for example, to improve water repellency, improve paintability, The range of applications, such as foaming, crosslinking, surface hardening, and adhesion, is extremely wide.

Claims (1)

(57) [Claims] (1) In the molecule, C 分子 C, C≡C, C ＝ O, C =
N, N = C = O, C≡N, C-Cl, A polymer compound containing at least one of O—H and N—H bonds is converted to a compound of the general formula Si _n H _{2n + 2} (where n is 1,
2, 3 or 4. A method for producing a modified polymer, characterized by treating with a silicon hydride compound represented by the formula: