Polysilanes and process for preparation of same

Details Polysilanes and process for preparation of same Polysilanes and process for preparation of same

1999-07-08

2001-07-03

Moore, Margaret G. (Department: 1712)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From silicon reactant having at least one...

C528S010000, C528S049000, C528S025000, C556S430000, C556S449000

Reexamination Certificate

active

06255430

ABSTRACT:

TECHNICAL FIELD
The present invention relates to novel polysilanes regarded important as starting materials for engineering plastics such as modified polycarbonates, as materials for resists or as materials for electrophotographic photoreceptors, and to a process for preparing the same.
BACKGROUND ART
Investigations have been made on the use of engineering plastics, e.g. polycarbonate, as a material for hard coat. In fact, some of such plastics have been in actual use. However, bisphenol A polycarbonate is not satisfactory in hardness and has been modified to increase the hardness.
The polysilanes having phenol groups at both ends according to the present invention can be used as a starting material for producing a polycarbonate or polyester having a polysilane skeleton in the main chain. Thus, when the polysilane of the invention is used, a polycarbonate or the like with improved hardness can be prepared and a more useful material for hard coat can be provided. Further the obtained polycarbonate or the like with a polysilane skeleton has a photosensitive property and a charge-transporting property derived from the polysilane and is usable as a new type of hard coat material showing an optoelectronic function.
However, no research has been conducted on such polysilanes with phenol groups at both ends which are useful in producing a modified polycarbonate or the like. No process for preparing the polysilanes is known.
Further it is needless to say that a process was unknown for preparing such polysilanes having phenol groups at both ends wherein the degree of polymerization of polysilane is controlled and phenol groups are introduced at both ends in order to produce a modified polycarbonate or the like having properties optimal for various applications as a hard coat material.
DISCLOSURE OF THE INVENTION
An object of the present invention is to provide a novel polysilane which is important as a starting material for engineering plastics such as modified polycarbonates, as a material for resists or as a material for electrophotographic photoreceptors.
Another object of the invention is to provide a process for preparing such novel polysilane.
In view of the foregoing situation of the prior art, the inventors of this invention conducted extensive research and found out a process for preparing the desired polysilane by reacting a polysilane having halogen atoms at both ends with a Grignard reagent prepared by reacting magnesium with a hydroxyl-protected halogenated phenol or a hydroxyl-protected halogenated phenol derivative, followed by deprotection.
The inventors also discovered a process for preparing a polysilane having phenol groups at both ends in a manner to control the degree of polymerization in the polysilane moiety, the polysilane being useful in producing a modified polycarbonate having properties optimal for various applications as a hard coat material, the process comprising conducting an electrode reaction using a specific metal as the anode or a reduction reaction using a specific metal in the presence of a specific lithium salt and a specific halogenated metal to give a polysilane having halogen atoms at both ends.
According to the present invention, there are provided the following polysilanes having phenol groups at both ends and processes for preparing the same.
1. A polysilane represented by the formula (1)
wherein R is hydrogen atom, alkyl group, aryl group, alkoxy group, amino group or silyl group; R's may be the same or at least two of them may be different from each other; each hydroxyl group is in the p-position or m-position; and n is 2 to 10,000.
2. The polysilane as defined in item 1, wherein n is 5 to 8,500.
3. The polysilane as defined in item 1, wherein n is 13 to 8,500.
4. A process for preparing a polysilane having phenol groups at both ends which is represented by the formula (1)
wherein R is hydrogen atom, alkyl group, aryl group, alkoxy group, amino group or silyl group; R's may be the same or at least two of them may be different from each other; each hydroxyl group is in the p-position or m-position; and n is 2 to 10,000, the process comprising the steps of (a) conducting the Grignard reaction between (i) a polysilane having halogen atoms at both ends which is represented by the formula (2)
wherein R and n are as defined above; and X is halogen atom, and (ii) a Grignard reagent prepared by reacting magnesium with a hydroxyl-protected halogenated phenol represented by the formula (3)
wherein R
1
is hydroxyl-protecting group, and represents alkyl group, alkoxyalkyl group, silyl group, acyl group, alkylthioalkyl group or alkylsulfoxy group; protected hydroxyl group is in the p-position or m-position; and X
1
is halogen atom, thereby producing a polysilane represented by the formula (4)
wherein R, R
1
, the position of protected hydroxyl group and n are as defined above although variant depending on the starting materials; and (b) reacting the polysilane of the formula (4) with an acid.
5. The process for preparing a polysilane having phenol groups at both ends as defined in item 4, the process being characterized in that the polysilane having halogen atoms at both ends which is represented by the formula (2)
wherein R is hydrogen atom, alkyl group, aryl group, alkoxy group, amino group or silyl group; R's may be the same or at least two of them may be different from each other; n is 2 to 10,000; and X is halogen atom, is produced by subjecting to an electrode reaction a dihalosilane represented by the formula (5)
wherein m is 1 to 3; R is hydrogen atom, alkyl group, aryl group, alkoxy group, amino group or silyl group; 2 R's in the case of m=1, 4 R's in the case of m=2, or 6 R's in the case of m=3 may be the same or at least two of them may be different from each other; and X is halogen atom, using Mg or a Mg-based alloy as the anode, a lithium salt as a supporting electrolyte and an aprotic solvent as a solvent with or without use of a halogenated metal as a current carrying aid.
6. The process for preparing a polysilane having phenol groups at both ends as defined in item 4, the process being characterized in that the polysilane having halogen atoms at both ends which is represented by the formula (2)
wherein R is hydrogen atom, alkyl group, aryl group, alkoxy group, amino group or silyl group; R's may be the same or at least two of them may be different from each other; n is 2 to 10,000; and X is halogen atom, is produced by reducing a dihalosilane represented by the formula (5)
wherein m is 1 to 3; R is hydrogen atom, alkyl group, aryl group, alkoxy group, amino group or silyl group; 2 R's in the case of m=1, 4 R's in the case of m=2, or 6 R's in the case of m=3 may be the same or at least two of them may be different from each other; and X is halogen atom, using Mg or Mg-based alloy in an aprotic solvent in the presence of a lithium salt and a halogenated metal.
7. A polysilane represented by the formula (6)
wherein R is hydrogen atom, alkyl group, aryl group, alkoxy group, amino group or silyl group; R's may be the same or at least two of them may be different from each other; Y is CH
2
, C
2
H
4
, C
3
H
6
, C
4
H
8
, O or S; each hydroxyl group is in the p-position or m-position; and n is 2 to 10,000.
8. The polysilane as defined in item 7, wherein n is 5 to 8,500.
9. The polysilane as defined in item 7, wherein n is 13 to 8,500.
10. A process for preparing a polysilane having phenol groups at both ends which is represented by the formula (6)
wherein R is hydrogen atom, alkyl group, aryl group, alkoxy group, amino group or silyl group; R's may be the same or at least two of them may be different from each other; Y is CH
2
, C
2
H
4
, C
3
H
6
, C
4
H
8
, O or S; each hydroxyl group is in the p-position or m-position; and n is 2 to 10,000, the process comprising the steps of (a) conducting the Grignard reaction between (i) a polysilane having halogen atoms at both ends which is represented by the formula (2)
wherein R and n a

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