JP3474007B2 - Method for producing organofunctional organosiloxane containing organic functional groups - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an organopolysiloxane containing an organic functional group, and more particularly to an organopolysiloxane containing an organic functional group having a high reaction activity, from a variety of oligomers such as dimers to resins. It relates to a method for producing siloxane. In the case of resin-like powder, these organopolysiloxanes can be made porous, and are useful as a solid for supporting packing materials such as columns, various enzymes and metal compounds, and in the case of oligomers or polymers. Can be used as paint, coating material, encapsulant, electrical insulating material, flame retardant. Further, when these materials contain a compound capable of reacting with the organic functional group of the present invention, the organopolysiloxane of the present invention can be used as a crosslinking agent.

[0002]

2. Description of the Related Art Many proposals have already been made for a method for producing an organic functional group-containing silicon-based powder substance,
For this, a method of co-hydrolysis-polycondensation of tetraalkoxysilane and organoalkoxysilane in the presence of an ammonia catalyst (see JP-A-4-114065), a method of carrying out this reaction in the presence of a hydrofluoric acid catalyst ( See Japanese Unexamined Patent Publication No. 62-166887, Journal of Chemical Society of Japan 19
83 (11), p. 1, 577 to 1,582) and the like are known.

On the other hand, as a method of producing polysilsesquioxane, a method of hydrolyzing and condensing an alkoxysilane such as methyltrimethoxysilane is known. In this case, an acid, a base or a silanol group-containing compound is used. Many methods for use as catalysts have been reported. For example, in JP-A-60-118715, hydrolysis is carried out with an acid catalyst, and then the system is made basic to carry out a condensation reaction. Further, in JP-A-61-854, hydrolysis is carried out using a partial hydrolysis-condensation product of trialkoxysilane as a catalyst.
Conducting condensation reaction.

[0004]

However, for example, in the above method for producing the above-mentioned organic functional group-containing silicon powder,
(1) Uniform dispersion and distribution of organic functional groups (in pores), (2)
Retention of reactive organic functional groups, (3) porosity, (4)
It is known that there is a problem in operability. That is,
With regard to this (1), since it is impossible to uniformly process the pores in the pores by the dry method of spraying the silane coupling agent onto the silicon dioxide powder, the wet method ( It is said that co-hydrolysis is particularly good. Regarding (2), for example, when a silicon powder substance containing a highly active organic functional group such as an epoxy group is produced,
When an acid or alkali catalyst is used, the organic functional group is destroyed and deactivated. As for (3), a method that requires a long time for gelation does not provide a porous material because the silicon-based powder substance is gradually deposited, but
It is known that when HF is used, the gelation is completed in an extremely short time, so that the silicon-based powder substance can be obtained as a porous substance. There is a problem that there are problems.

Further, in the case of producing an epoxy group-containing organopolysiloxane by hydrolyzing and condensing an alkoxysilane containing a functional group having a high reaction activity such as an epoxy group, the above-mentioned technique is as follows. There are drawbacks. (1) In a system containing a large amount of acid (including silanol) or a base catalyst, the epoxy group undergoes electrophilic action by H ⁺ or nucleophilic attack by a base, and easily undergoes ring opening or polymerization, resulting in stable epoxy. You cannot leave the radical. (2) On the other hand, in a system containing a dilute concentration of an acid or base catalyst, the hydrolysis and condensation reactions themselves become difficult to proceed, and the silanol groups generated by the hydrolysis reaction are stabilized, so that the reaction is carried out for a long time. The epoxy group may be ring-opened due to the silanol group exhibiting acidity. (3) In the case of an acid or base catalyst system, a large amount of condensable silanol groups may remain after the completion of the reaction and cause a change over time (for example, thickening or gelation). (4) Since many acidic and basic substances are corrosive substances, technical consideration for corrosion of reactor materials is indispensable, and the safety of acidic and basic substances cannot be said to be high.

As described above, it is difficult to obtain an epoxy group-containing organopolysiloxane which is stable in the epoxy group and does not change with time and is excellent in operability and safety without any problems in the conventional techniques.

Moreover, in order to carry out hydrolysis in a system using an acidic or basic catalyst and leave a certain amount of alkoxy groups, it is necessary to adjust the amount of added water to carry out partial hydrolysis. Since the reaction rate of condensation is slow even in an excess system, the degree of condensation is further lowered when partial hydrolysis is performed, and it is difficult to synthesize a polymer having a desired degree of polymerization as designed.

[0008]

Means for Solving the Problems The present inventor has conducted studies to solve the above-mentioned conventional drawbacks, and as a result, a) an organic functional group-containing alkoxysilane alone or b) an organic functional group-containing alkoxysilane An alkoxy group-containing silane compound, an alkoxy group-containing organopolysiloxane, and a mixture of these silane compounds and at least one compound obtained from a silicone compound obtained by hydrolyzing the organopolysiloxane, with a substantially neutral content. It has been found that various kinds of organopolysiloxanes containing an organic functional group and / or an alkoxy group or a silanol group can be easily produced when hydrolyzed and condensed in the presence of a fluorine compound. Therefore, an object of the present invention is to provide a substantially neutral reaction system which is excellent in operability and stability, and is various organopolysiloxanes containing an organic functional group, which may optionally further contain an alkoxy group or a silanol group. And a method for producing an organopolysiloxane containing the same.

That is, the inventors of the present invention have conducted various studies to develop a method for producing an organopolysiloxane capable of solving the above-mentioned problems of the prior art. As a result, alkoxysilane containing an organic functional group alone or Hydrolyze a mixture of an organic functional group-containing alkoxysilane and an alkoxy group-containing silane compound, an alkoxy group-containing organopolysiloxane and at least one compound selected from these silane compounds and / or silicone compounds obtained from the organopolysiloxane, ( When producing an organofunctional group-containing organopolysiloxane by polycondensation, a substantially neutral fluorine-containing compound as a hydrolysis / condensation catalyst, that is, fluorine-containing silicon containing at least one Si—F bond in the molecule. In the presence of compounds or fluorides, Found reacted in a suitable amount of water or water-containing organic solvent, to be able to obtain an organopolysiloxane from a liquid or oily oligomers having powdery broad state organic functional groups in accordance with the.

When a powdered substance of organofunctional group-containing organopolysiloxane is obtained by the method of the present invention,
1) The functional group can be uniformly dispersed even inside the pores. 2) Since the catalyst used is substantially neutral, it is possible to stably compose a highly reactive organic functional group.
3) When the fluorine-containing compound catalyst used in the present invention is used, H
Since the gelation time is shorter than that of F, the reaction time can be shortened, and further, 4) there is an advantage that the catalyst used is substantially neutral and there is no danger in operation. In this case, it was confirmed that the powder substance obtained was a porous fine solid, and was useful as a column packing material, various enzymes, and a solid for supporting metal compounds.

Further, for example, if an alkoxysilane having an organic functional group having a high reactivity such as an epoxy group is hydrolyzed and condensed in the presence of the above-mentioned fluorine-containing compound catalyst, a group having a high activity such as an epoxy group is damaged. It is possible to obtain an organofunctional group-containing organopolysiloxane that is stably contained without containing. The hydrolysis and condensation proceed rapidly, and by adjusting the amount of water added to the reaction system, the polymer or resin in which the alkoxy groups present in the raw material are completely eliminated, or the alkoxy groups are partially left. Oligomers or polymers can also be obtained. In the case of the former polymer or resin, by adding a monoalkoxysilane during or after hydrolysis, silanol groups remaining in the polymer can be silylated, and the obtained organofunctional group-containing organopolysiloxane is more stabilized. It was found that an organopolysiloxane with almost no change over time can be obtained.

The above object of the present invention is to use a substantially neutral fluorine-containing compound as a hydrolysis / condensation catalyst, and an organopoly group containing an organic functional group represented by the following average composition formula (1). Method for producing siloxane Y _m R ¹ _n Si (OR ² ) _p O _{(4-mnp) / 2} (1) (In the formula, Y is a substituted or unsubstituted alkenyl group, epoxy group, or (meth) acryloxy group. , An amino group, a mercapto group, a hydroxyl group, a siloxy group, an ether group, a ketone group, an ester group or an organic group containing phosphorus, and an organic group containing a poly (vinyl aromatic) unit, a polyether unit and a polyamide unit. that functional group, R1 is at least one substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms, R ² is also atom selected from a hydrogen atom and alkyl and alkenyl groups having 1 to 4 carbon atoms Organic group, m
Is 0 <m ≦ 1, n is 0 ≦ n <2, p is 0 ≦ p ≦ 2, but 0 <m + n + p ≦ 3. ) Is achieved. Incidentally, in the present invention "substantially neutral" in the fluorine-containing compound of not mean that the fluorine-containing compound itself exhibits a substantially neutral as pH, when dissolved in water, F ^- It means a compound in which the counterion of the ion is an ion other than H ⁺ , is a compound in which HF, which is an acid, is neutralized, and may exhibit weak acidity or weak alkalinity.

As a raw material to be hydrolyzed, an organic functional group-containing alkoxysilane represented by the following general formula (2) Y-SiR ¹ _a (OR ² ) _3-a (2) (wherein Y, R ¹ and R ² have the same meanings as described above, and a represents an integer in the range of 0 ≦ a ≦ 2), or an organic functional group-containing silane compound represented by the above general formula (2). An alkoxy group-containing silane compound represented by the following general formula (3), an alkoxy group-containing organopolysiloxane represented by the following general formula (4), a silane compound represented by the following general formula (3) and the following general formula (4) (R ¹ ) _b Si (OR ² ) _4-b (3) R ¹ _c SiO 2 _(4-cd) with a compound selected from a partial or complete hydrolyzate of the alkoxy group-containing organosiloxane of _{^{/ 2 (OR 2) d ......}} (4) ( same respectively wherein, R ^1, R ² above Have the Do meaning, b is an integer satisfying 0 ≦ b ≦ 3, c is a number satisfying 0 ≦ c ≦ 2, d is a positive number satisfying 0.01 ≦ d ≦ 3, provided that 0.
01 ≦ c + d ≦ 3. ) Is used.

In particular, Y in the formula (1) is an epoxy group- containing organic compound.
Those having a group or a (meth) acryloxy group- containing organic group are preferable because they have various uses because of their high reactivity.

The present invention has been completed based on the above findings. The present invention will be described in more detail below. The present invention is a method for producing an organofunctional group-containing organopolysiloxane of the above composition formula (1), which comprises using a substantially neutral fluorine-containing compound as a hydrolysis catalyst. Enter.

As a raw material, an organic functional group-containing alkoxysilane represented by the following general formula (2) Y-SiR ¹ _a (OR ² ) _3-a (2) (wherein Y is substituted or unsubstituted) Alkenyl group, epoxy group, (meth) acryloxy group, amino group, mercapto group, hydroxyl group, siloxy group, ether group, ketone group, ester group and organic group containing a phosphorus atom respectively, and (vinyl aromatic) repeating unit A group selected from organic groups each containing an ether repeating unit and an amide repeating unit, R ¹ is at least one carbon atom having 1 to 1 carbon atoms.
8 is a substituted or unsubstituted hydrocarbon group, R ² is a hydrogen atom and an atom or an organic group selected from an alkyl group and an alkenyl group having 1 to 4 carbon atoms, and a is an integer in the range of 0 ≦ a ≦ 2. ) Is used alone, or an organic functional group-containing silane compound represented by the general formula (2), an alkoxy group-containing silane compound represented by the following general formula (3), and a general formula (4) below. At least one compound selected from a partial or complete hydrolyzate of the alkoxy group-containing organopolysiloxane represented and the silane compound of the following general formula (3) and the alkoxy group-containing organosiloxane of the following general formula (4) (R ¹ ) _b Si (OR ² ) _4-b (3) R ¹ _c SiO 2 _{(4-cd) / 2} (OR ² ) _d (4) (wherein R ¹ , R ² has the same meaning as described above, b is an integer satisfying 0 ≦ b ≦ 3, c is a number satisfying 0 ≦ c ≦ 2, d is a positive number satisfying 0.01 ≦ d ≦ 3, and 0 .01 ≦ c + d ≦ 3) in the presence of the fluorine-containing compound, and (heavy) To condense.

The group containing an unsubstituted or substituted alkenyl group represented by Y in the organoalkoxysilane of the general formula (2) is a lower alkenyl group having 2 to 10 carbon atoms, for example, -CH = CH ₂ ,-. CH ₂ CH = CH ₂ , CH ₂ = C
H (CH _{2) 4} - and the _{like, -, CH 2 = CH (} CH 2) 8
It may be substituted with a halogen atom such as fluorine. Similarly, examples of the epoxy group-containing organic group include those represented by the following formula.

[0018]

[Chemical 1]

Specific examples of such an epoxy group-containing organic group include the following.

[0020]

[Chemical 2]

Examples of the organic group containing a (meth) acryloyl group include those represented by the following general formula.

[0022]

Embedded image ^{_{CH 2 = CHCOOR 4 - CH 2}} = C (CH 3) HCOOR 4 - ( wherein, R ⁴ is a divalent hydrocarbon group having 1 to 8 carbon atoms.)

Examples of the amino group-containing organic group include those represented by the following general formula.

[0024]

Embedded image H ₂ NR ⁵ —, R ⁶ HNR ⁵ —, R ⁷ ₂ NR ⁵ — (In the formula, R ⁵ has a carbon number of 1 to which an NH group may be present.
10 alkylene groups, R ⁶ and R ⁷ each have 1 to 10 carbon atoms.
10 represents an alkyl group, a phenyl group or a benzyl group. )

Specific examples of the amino group-containing organic group include the following. _{H 2 N (CH 2) 3} -, C 6 H 5 NH
_{(CH 2) 3 -, H} 2 N- (CH 2) 10 -C 6 H 5 CH 2 NH
_{(CH 2) 3 -, CH} 3 NH (CH 2) 3 -, - (CH 2) 3
N (CH3) ₂

The mercapto group-containing organic group is specifically-
A C ₃ H ₆ SH and _{-C 2 H 4 -C 6 H 4} -CH 2 SH.

The hydroxyl group-containing organic group is represented by —R ⁸ —OH (wherein R ⁸ is an alkylene group having 3 to 10 carbon atoms).

As the siloxy group-containing organic group, those represented by the following general formula are exemplified.

[0029]

[Chemical 5]

As a specific example, —O—Si (CH ₃ ) ₃ ,
_{-O-SiH (CH 3) 2} , -O-Si (CH 3) 2 -CH
_{= CH 2, -O-Si (} CH 3) 2 C 6 H 5, -O- (Si
_{(CH 3) 2 O) 10} -Si (CH 3) 3, -O- (Si (C
_{H 3) 2 -O) 20 -Si} (OCH 3) 3 and the like.

The organic group containing an ether group is represented by the general formula R ¹⁰
A group represented by —O—R ¹¹ — (in the formula, R ¹⁰ has 1 carbon atom).
An alkyl group or an alkenyl group of 10 to R ¹¹
Is an alkylene group having 1 to 10 carbon atoms containing an ether bond. As a specific organic group, CH ₂ ═C (CH ₃ ) —
_{OCH 2 CH 2 O (CH 2} ) 3 -, CH 2 = CH-CH 2 -O
_{CH 2 CH 2 -O- (CH 2} ) 3 - , and the like.

The organic group containing a ketone bond has the general formula R ¹² C
(O) is a group represented by CR ¹³ — (in the formula, R ¹² is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ¹³ is an alkylene having 2 to 10 carbon atoms which may contain a carboxylic acid residue). A specific ketone bond-containing group is a group represented by the following chemical formula 6.

[0033]

[Chemical 6]

The ester group-containing organic group is represented by the general formula R ¹⁴ C
Specific examples of the group represented by OO- (wherein R ¹⁴ is an alkyl group or an alkenyl group having 1 to 18 carbon atoms) include C ₁₇ H ₃₅ -COO.
_{- (CH 2) 3 -,} CH 2 = CH- (CH 2) 15 -COO-
(CH ₂ ) ₃ −.

The organic group containing phosphorus is a group represented by the following general formula. _{- (CH 2) n -P (} R 15) (R 16) ( wherein, a monovalent hydrocarbon R ^15, R ¹⁶ are each a saturated or unsaturated having 1 to 6 carbon atoms, n represents 1 to 10 Is an integer.)

The organic group containing a (vinyl aromatic) repeating unit is a group or a polymer portion having a repeating unit represented by the following general formula.

[0037]

[Chemical 7]

[0038] The group having an ether repeating unit of the general formula _{- (C m H 2m -O)} n - repeating unit is a group or a polymer moiety having a (wherein m = 1 to 4 of, n = 2 to 1 0.0 × 10 ³ )

The organic group having an amide repeating unit is
Polycapramide repeating unit, polyhexamethylene adipamide repeating unit, polyhexamethylene sebacamide repeating unit, poly-ω-aminoheptanoic acid repeating unit, poly-ω-aminononanoic acid repeating unit, etc.,
The degree of polymerization is about 2 to 1.0 × 10 ³ .

In the above formulas, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and specifically, --CH
_{3, -CH 2 CH 3, -CH} 2 CH 2 CH 3, -CH (C
_{H 3) 2, -CH 2 CH} 2 CH 2 CH 3, -CH (CH 3) C
_{H 2 CH 3, -CH 2 CH} (CH 3) CH 3, -C (CH 3)
_{3, -C (CH 3) 2} -CH 2 CH 3, -C 6 such as H ₅ and the like, and these groups may be substituted with a halogen atom or the like.

R ² is a hydrogen atom, a lower alkyl group or a lower alkenyl group. Particularly, the lower alkyl group has 1 to 5 carbon atoms, and the lower alkenyl group has 2 carbon atoms.
Are mentioned those 5, specifically, -H, -CH _3, -
_{CH 2 CH 3, -CH 2 CH} 2 CH 3, -CH (CH 3) 2,
_{-CH 2 CH 2 CH 2 CH 3} , -CH (CH 3) CH 2 C
_{H 3, -CH 2 CH (CH} 3) CH 3, -C (CH 3) 3, -
_{CH = CH 2, -CH 2 CH} = CH 2, -C (CH 3) = C
H _{2 and the} like are exemplified. These groups H may be substituted with a halogen atom or the like.

Further, a in the general formula (2) is an integer of 0-2. These specific compounds will be exemplified.

CH ₂ = CHSi (OCH ₃ ) ₃ , CH ₂ = C
_{HSi (CH 3) (OCH 3} ) 2, CH 2 = CHSi (OC
_{H 2 CH 3) 3, CH} 2 = CHSi (CH 3) (OCH 2 CH
₃ ) ₂ , CH ₂ = CHCH ₂ Si (OCH ₃ ) ₃ , CH ₂ = C
_{HCH 2 Si (CH 3) (} OCH 3) 2, CH 2 = CHSi
(OCH ₂ CH ₃ ) ₃ , CH ₂ = CHCH ₂ Si (CH ₃ )
(OCH ₂ CH ₃ ) ₂ , CH ₂ = CH (CH ₂ ) ₄ Si (OC
_{H 3) 3, CH 2 =} CH (CH 2) 4 Si (CH 3) (OCH
₃ ) ₂ CH ₂ = CH (CH ₂ ) ₄ Si (OCH ₂ CH ₃ ) ₃ , CH
_{2 = CH (CH 2) 4} Si (CH) 3 (OCH 2 CH 3) 2,
_{CH 2 = CH (CH 2)} 8 Si (OCH 3) 3, CH 2 = C
H (CH ₂ ) ₈ Si (OCH ₂ CH ₃ ) ₃ , CH ₂ = CHO
(CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ = CHO (C
H ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ ,

[0044]

[Chemical 8]

[0045]

[Chemical 9]

[0046]

[Chemical 10]

[0047]

[Chemical 11]

[0048]

[Chemical 12]

[0049]

[Chemical 13]

[0050]

[Chemical 14]

[0051]

[Chemical 15]

[0052]

[Chemical 16]

[0053]

[Chemical 17]

[0054]

[Chemical 18]

[0055]

[Chemical 19]

HS (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , HS
(CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , HS (CH ₂ ) ₃ S
_{i (CH 3) (OCH 3} ) 2, HS (CH 2) 3 Si (C
_{H 3) (OCH 2 CH 3} ) 2, CH 3 O (CH 2 CH 2 O) 10
(CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₃ O (CH ₂ CH
₂ O) ₁₀₀ (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ ,

[0057]

[Chemical 20]

[0058]

[Chemical 21]

(C ₆ H ₅ ) ₂ P (CH ₂ ) ₂ Si (OCH ₃ )
_{3, (C 6 H 5)} 2 P (CH 2) 2 Si (OCH 2 CH 3) 3,
_{(C 6 H 5) 2 P} (CH 2) 3 Si (OCH 3) 3, (C
₆ H ₅ ) ₂ P (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , (C
_{H 3) 2 N (CH 2} ) 3 Si (OCH 3) 3, (CH 3) 2 N
(CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , (CH ₃ CH ₂ CH ₂
CH ₂ ) ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , (CH ₃ CH _{2
CH 2 CH 2) 2 N (} CH 2) 3 Si (OCH 2 CH 3) 3,

H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (O
CH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OC
_{H 2 CH 3) 3, H} 2 N (CH 2) 2 NH (CH 2) 3 Si (C
_{H 3) (OCH 3) 2} , H 2 N (CH 2) 2 NH (CH 2) 3 S
_{i (CH 3) (OCH 2} CH 3) 2, H 2 N (CH 2) 6 NH
(CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₆ NH
(CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , H ₂ N (CH ₂ ) _{2
NHCH 2 -C 6 H 4 - (} CH 2) 2 Si (OCH 3) 3, H 2
_{N (CH 2) 2 NHCH 2} -C 6 H 4 - (CH 2) 2 Si (O
_{CH 2 CH 3) 3, H} 2 N (CH 2) 2 NH (CH 2) 2 NH
(CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH
(CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , H _{2
N-C 6 H 4 -Si (} OCH 3) 3, H 2 N-C 6 H 4 -Si
(OCH ₂ CH ₃ ) ₃ ,

CH ₂ ═C (CH ₃ ) OCH ₂ CH ₂ O (CH
₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ ═C (CH ₃ ) OCH ₂ C
_{H 2 O (CH 2) 3} Si (OCH 2 CH 3) 3,

[0062]

[Chemical formula 22]

[0063]

[Chemical formula 23]

CH ₃ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,
_{CH 3 NH (CH 2) 3} Si (OCH 2 CH 3) 3, (CH 3
O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ S
i (OCH ₃ ) ₃ , (CH ₃ CH ₂ O) ₃ Si (CH ₂ ) ₃ N
H (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ ,
_{(CH 3 O) 3 Si (} CH 2) 3 NH (CH 2) 3 Si (OC
_{H 3) 3, (CH 3} CH 2 O) 3 Si (CH 2) 3 NH (C
H ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ ,

[0065]

[Chemical formula 24]

[0066]

[Chemical 25]

[(CH ₃ ) ₃ SiO] -Si (OC
_{H 3) 3, [(CH} 3) 3 SiO] 2 -Si (OCH 3) 2,
_{[(CH 3) 3 SiO]} 3 -SiOCH 3, [(CH 3) 3 S
_{iO] -Si (OCH 2 CH 3} ) 3, [(CH 3) 3 Si
_{O] 2 -Si (OCH 2 CH} 3) 2, [(CH 3) 3 SiO]
_3- SiOCH ₂ CH ₃ ,

The above-mentioned organic functional group-containing alkoxysilanes can be used alone or as a mixture, but when used in a mixture, it is preferable to use a mixture with those having the same kind of functional group.

Of the above-mentioned organic groups, groups containing hydrogen atom groups and phosphorus groups respectively exist in the final product, polyorganosiloxane, and act as reactive groups, while the groups having polymer repeating units are reactive groups. When a polyorganosiloxane rather than a functional group is used as a composition for use with another resin, for example, the polyorganopolysiloxane having the repeating unit has a function of remarkably improving the compatibility with other resins.

Among various organic functional group-containing alkoxysilanes of the formula (2), functional group-containing alkoxysilanes containing an epoxy group or a (meth) acryloxy group are particularly preferable. Examples of the epoxy group include γ-glycidoxypropylmethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 2- [3,4-epoxycyclohexyl] ethyltrimethoxysilane and 2- [3,4-epoxycyclohexyl. ] Ethylmethyldiethoxysilane is preferable, and as the functional group-containing alkoxysilane containing a (meth) acryloyl group, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane. And γ-acryloxypropylmethyldimethoxysilane are preferred.

In the present invention, the organofunctional group-containing organopolysiloxane of formula (1) can be obtained by subjecting the organofunctional group-containing alkoxysilane to a hydrolysis / condensation reaction in the presence of a fluorine-containing compound catalyst. A) an alkoxy group-containing silane compound represented by the general formula (3), (b) an alkoxy group-containing disiloxane represented by the general formula (4), and (c)
It can be used in combination with at least one compound selected from those obtained by polymerizing the above silane compound and / or the above disiloxane compound by hydrolysis.

In the general formula (3), the groups represented by R ¹ and R ² are the same as those exemplified in connection with the formula (2), and b is 0, 1, 2, 3 or an integer. Is. Therefore, the alkoxysilane of the general formula (3) represents mono-, di-, tri- and tetraalkoxysilanes. At least one of these alkoxysilanes can be used depending on the purpose described later. Specific examples of these alkoxysilanes are shown below.

[0073]

[Chemical formula 26]

[0074]

[Chemical 27]

[0075]

[Chemical 28]

[0076]

[Chemical 29]

[0077]

[Chemical 30]

[0078]

[Chemical 31]

[0079]

[Chemical 32]

[0080]

[Chemical 33]

[0081]

[Chemical 34]

[0082]

[Chemical 35]

[0083]

[Chemical 36]

Next, the organosiloxane of the general formula (4) will be exemplified.

[0085]

[Chemical 37]

[0086]

[Chemical 38]

[0087]

[Chemical Formula 39]

[0088]

[Chemical 40]

[0089]

[Chemical 41]

Further, a silicone compound which is obtained by hydrolyzing the silane compound of the general formula (3) and the alkoxy group-containing disiloxane of the general formula (4) to form a polymer can also be used.
In this case, the silane compound and the alkoxy group-containing disiloxane are used in a molar ratio of 100: 1 to 1: 100, and the degree of polymerization may be a polymer or resin up to about 1 × 10 ³ .

The structure of this silicone polymer is linear,
It may be branched, annular or a combination thereof. Moreover, as those other than the above, for example, among those commercially available as silicone resins, the number of carbon atoms is 1 to 1.
Those containing 4 alkoxy groups can also be used. In this case, the above-mentioned commercially available silicone resin can be used as the alkoxy group-containing silicone of the present invention even if it partially contains a silanol group.

Further, in the present invention, a silicone resin having only a silanol group at the terminal can be used in combination if necessary. Such a resin is, for example, a trade name KR-2.
82 and KR-311 are available from Shin-Etsu Chemical Co., Ltd.

These alkoxy group-containing silanes,
When the alkoxy group-containing siloxane and / or the silicone compound is used, they can be used alone or as a mixture of two or more kinds.

As mentioned above, the at least one organic functional group-containing alkoxysilane represented by the general formula (2) can be used alone, but is mixed with the alkoxy group-containing silane, the alkoxy group-containing organosiloxane and / or the silicone compound. In that case, the mixing ratio is not particularly limited. Preferably, the proportion of the organic functional group-containing alkoxysilane is 0.1 to 100% by weight, more preferably 1
~ 100% by weight. That is, when the mixing ratio is less than 0.1% by weight, the organic functional groups are not uniformly distributed in the final organopolysiloxane, and the compatibility and reactivity are poor, which is not preferable. If the type and amount of the alkoxy group-containing silane, alkoxy group-containing disiloxane and / or silicone compound used in the above range, the amount of the catalyst and the amount of water for hydrolysis are appropriately adjusted, a desired form, that is, a powder solid. An oily or liquid organofunctional group-containing organopolysiloxane can be obtained.

In the above-mentioned alkoxy group-containing silane, alkoxy group-containing disiloxane and / or silicone compound, the alkoxy group is used as a hydrolyzable group, but the same applies even if another hydrolyzable group such as an oxime group is used. Although such results can be obtained, the alkoxy group-containing silane and siloxane described above are used in the present invention from the viewpoints of reactivity, availability of raw materials, economy, and the like. Incidentally, typical, the oxime group can be used may be exemplified _{-0-N = (CH 3)} -CH 2 CH 3.

Next, the fluorine-containing compound, which is the hydrolysis / condensation catalyst, which is a feature of the present invention will be described.

As the fluorine-containing compound used in the present invention, either a fluorine-containing inorganic salt compound containing a quaternary ammonium salt compound or a fluorine-containing inorganic or organic compound having at least one Si-F bond in the molecule may be used. Can be done.

Examples of the fluorine-containing inorganic salt compound include:
Fluorine-containing salt compounds of Group 1A elements such as LiF, NaF, KF, CsF, BeF ₂ , MgF ₂ , CaF ₂ , Sr
Fluorine-containing salt compounds of 2A group elements such as F ₂ and BaF ₂ ,
Fluorine-containing salt compounds of 3B group elements such as BF ₃ , AlF ₃ , GaF ₃ , InF ₃ , TiF ₄ , CuF ₂ , ZnF ₄ ,
Fluorine-containing salt compounds of metal elements such as SnF ₄ , PdF ₃ , SbF ₃ , CrF ₃ and YF ₃ , LaF ₃ , CeF ₃ , Pr
F ₃ , NdF ₃ , SmF ₃ , EuF ₃ , GdF ₃ , TbF ₃ ,
Examples thereof include lanthanoid-based fluorine-containing salt compounds such as DyF ₃ , HoF ₃ and ErF _3, and hydrates thereof may be used. Further, the above-mentioned fluoride salt compound may be supported on silica gel or alumina. Also,
As the fluorinated quaternary ammonium salt compound,
2 can be illustrated.

[0099]

[Chemical 42]

Organic compounds include FSi (O
CH ₃ ) ₃ , FSi (OCH ₂ CH ₃ ) 3, FSi (OCH ₂
CH ₂ CH ₃ ) ₃ , FSi (OCH ₂ CH ₂ CH ₂ CH ₃ ) ₃ ,
F ₂ Si (OCH ₃ ) ₂ , F ₂ Si (OCH ₂ CH ₃ ) ₂ , F ₂
Si (OCH ₂ CH ₂ CH ₃ ) 2, F ₂ Si (OCH ₂ CH ₂
CH ₂ CH ₃ ) ₂ , F ₃ SiOCH ₃ , F ₃ SiOCH ₂ C
H ₃ , F ₃ SiOCH ₂ CH ₂ CH ₃ , F ₃ SiOCH ₂ CH ₂
Specific examples thereof include CH ₂ CH _{3 and the} like, but S
A polysiloxane or a polysilane compound may be used as long as it contains an i-F bond. As the inorganic compound type, SiF ₄ , Na ₂ SiF ₆ , (NH ₄ ) ₂ SiF _{6 and the} like can be mentioned as specific examples.

Of these, in view of cost, solubility in solvents, operability and safety, in the present invention, NaF, KF, (C ₄ H ₉ ) ₄ N ⁺ F ⁻ , Na ₂ SiF are used.
₆ is preferable, more preferably NaF, KF, (C ₄ H
₉ ) ₄ N ⁺ F ⁻ , and KF and (C ₄ H ₉ ) ₄ N ⁺ F ⁻ are the most preferable.

The fluorine-containing compound may be added directly to the hydrolysis raw material, or may be added after dilution with water or an organic solvent. The addition amount of the fluorine-containing compound in the present invention is such that the molar ratio of Si atoms present in the entire alkoxy group-containing organosilicon compound to be hydrolyzed and F in the fluorine-containing compound used is 1: 0.00001 to 1: 2. It is preferable that the molar ratio of Si: F is 1: 0.001.
˜1: 0.1. The molar ratio of F is 0.0000
When it is lower than 1, the effect as a catalyst is not so great and the reaction takes a long time. Moreover, the properties of the resulting organofunctional group-containing organopolysiloxane are not very good. On the other hand, if the molar ratio exceeds 2, the pot yield may decrease, resulting in high cost.

The amount of water used for hydrolysis determines the degree of polymerization of the raw material organic functional group-containing silane, alkoxysilane, siloxane compound and / or silicone compound.
For example, when the alkoxysilane raw material used is a monomer having one silicon atom, in order to obtain an organopolysiloxane containing at least an organic functional group consisting of Z silicon atoms, from 1 mol of the alkoxysilane raw material ( Z-1) / Z mol of water may be used during the hydrolysis reaction. The amount of water used for the hydrolysis reaction is 1 mol or more,
That is, when used in an equimolar amount or more with the alkoxysilane raw material, it becomes a resin body with many branched structures, the type of raw material used,
A powdery organopolysiloxane is obtained depending on the amount of the catalyst.

In the production method of the present invention, organic solvents such as alcohols, ethers, esters and ketones may be used, if necessary. Specific examples of these organic solvents include methyl alcohol, ethyl alcohol, 1-
Alcohols such as propyl alcohol and 2-propyl alcohol, ethers such as diethyl ether and dipropyl ether, esters such as methyl acetate, ethyl acetate and ethyl acetoacetate, acetone, diethyl ketone and methyl ethyl ketone. And ketones such as methyl isobutyl ketone. Further, a nonpolar solvent such as hexane, benzene, toluene, xylene may be used together with the above solvent. In the present invention, especially methyl alcohol
It is preferable to use alcohols such as alcohol and ethyl alcohol.

The amount of the solvent used is 10% as the starting alkoxysilane.
It is 0 to 1000 parts by weight with respect to 0 parts by weight. More preferably, it is 0 to 500 parts by weight. The amount of solvent is 100
If the amount exceeds 0 parts by weight, the reactor and the like must be enlarged, and the pot yield also decreases, which is economically disadvantageous. If the amount of the solvent is less than 20 parts by weight, the reaction system may not be uniform. In this sense, it is preferable to use a solvent together.

As an actual reaction operation for carrying out the present invention, a predetermined amount of a predetermined amount is added to a mixed system of an alkoxysilane as a raw material for hydrolysis reaction, siloxane, etc., a fluorine-containing compound used as a catalyst, and an organic solvent. It is preferable to add water or an organic solvent diluent diluted with water dropwise.

The fluorine-containing compound as the catalyst may be added to the aqueous system. It is not preferable to reverse the order of addition such as adding the mixed system to water or a water-diluted organic solvent, because the reaction system tends to gel.

The (co) hydrolysis / condensation reaction is carried out at 0 ° C to 100 ° C.
It may be carried out in the range of 20 ° C, and particularly preferably in the range of 20 ° C to 80 ° C. Although the temperature rises when water and a fluorine-containing compound catalyst are added to the organic functional group-containing silane,
Usually, the above range is not exceeded, so the reaction may be continued as it is. The hydrolysis and condensation reactions are performed under stirring,
Usually, it may be aged in the above temperature range for 0.1 to 10 hours.

Since the fluorine-containing compound catalyst used in the present invention remarkably accelerates the (co) hydrolysis / condensation reaction, the added water is completely consumed, and most of the silanol groups do not remain. An organopolysiloxane compound having a structure as designed can be obtained. Moreover, as described in Examples, unlike the hydrolysis using an acid or alkali catalyst, the functional group in the organic functional group-containing silane is not impaired by the hydrolysis or condensation reaction.
After the reaction, the used catalyst is removed, but by-product alcohol
The solvent may be distilled off and then filtered off, or the organic solvent system having a high hydrophobicity may be changed and then washed with water. The trace amount of water in the product is
A known post-treatment method such as volatilizing the solvent after removing with a desiccant or azeotropic dehydration can be employed.

By the above operation, the organofunctional group-containing organopolysiloxane of the average compositional formula (1) is obtained, but the reaction conditions, the amount of water to be added, the organic functional group-containing silane of the formula (2), the formula A powdery resin, an oily polymer and a liquid oligomer can be obtained depending on the kind and the addition amount of the silane (3) containing no organic functional group, the siloxane of the formula (4) and / or the silicone compound. These different forms of organopolysiloxane will be described.

The amount (mol) of water used for hydrolysis needs to be 50 times or less mol of all the alkoxy groups (mol) in the raw material. If it exceeds this, the pot yield decreases, and in this system, which is economically disadvantageous, the alkoxy group may almost disappear and a trace amount of OH group may remain. If necessary, it is possible to remove a trace amount of OH groups by reacting with monoalkoxysilane. In particular, if the amount of catalyst is reduced, it is possible to intentionally leave OH groups. In this case, since the amount of catalyst is small, the condensation rate becomes slow and the reaction requires a long time. Since residual OH groups generally tend to deteriorate the product, it is better to reduce them as much as possible except intentionally leaving them. For that purpose, after the condensation reaction, a monoalkoxysilane is added to the system in which the organofunctional group-containing organopolysiloxane is generated and hydrolyzed, or a monoalkoxysilane is added after the hydrolysis to cause a reaction, and the OH group becomes It is silylated and is virtually absent from the final product. The amount of monoalkoxysilane used for silylation is not particularly limited,
Preferably, the molar ratio of the monoalkoxysilane and the organic functional group alkoxysilane alone or the mixture thereof with the alkoxysilane having at least dialkoxysilane, the siloxane, and / or the silicone compound is 0.01: 3 to 1: 1.
3, more preferably 0.1: 1 to 1: 1. On the other hand, if the amount of water is less than 1/2 times the molar amount, the alkoxy group remains.

As described above, since the degree of polymerization of the raw material alkoxysilane or the like depends on the amount of water, the degree of polymerization of the organofunctional group- and alkoxy group-containing organopolysiloxane of the present invention is from a dimer of two Si atoms to a Si atom. Number 1 x 10 ⁴
It is possible to produce an organopolysiloxane having a wide range of polymerization degrees up to a resin. The conditions for producing oligomers, polymers and resins, particularly powdery resins, are described below.

Derived from the organofunctional group-containing silane of the formula (2) and, if necessary, the alkoxysilane of the formula (3), the alkoxysiloxane of the formula (4) and / or the compound of the formula (3) or the formula (4). When a (poly) condensation reaction is carried out in the presence of a fluorine-containing compound which is less than 1/2 times the molar amount of the alkoxy group in the residual raw material and is substantially neutral, using a silicone Dimer having both alkoxy groups
To a polymer having about 10,000 Si atoms can be easily synthesized simply by adjusting the amount of water. In particular, an oligomer having a Si number of up to about 10 is useful and preferable as a cross-linking agent, a kind of silane coupling agent, and a modifier for an organic resin.

Y of the organopolysiloxane represented by the composition formula (1) having both an organic functional group and an alkoxy group
Is an epoxy group-containing organic group, and one in which p is in the range of 1 ≦ p ≦ 2 is particularly preferable. Similarly, those in which Y is a (meth) acryloxy group are also useful because of their reactivity.

In the case of an organopolysiloxane having both an organic functional group and an alkoxy group, when the organofunctional group-containing alkoxysilane is also used, the silane of the formula (3) is mono,
Any of di, tri, and tetra can be used alone or in combination of two or more kinds, and the siloxane of the formula (4) can be used alone or in combination, and can also be combined with the silane of the above formula (3). It can be used. In this case, the silane of the formula (3), the siloxane of the formula (4) and / or the silicone compound can be used in combination with the organic functional group-containing silane of the formula (2) in an amount of 0 to 99.9% by weight. it can. When the amount of the organic functional group-containing silane of the formula (2) is 0.1% by weight or less, the amount of the organic functional groups present in the obtained organopolysiloxane becomes too small, and the effect cannot be expected. Preferably, the amount of the organic functional group-containing silane used is 1.0% by weight or more.

Next, the amount of water used for hydrolysis (mol)
A case will be described in which the amount is in the range of 1/2 to 50 times the moles of all alkoxy groups in the raw material. In this case, no oligomer can be obtained and theoretically no alkoxy group should remain, but depending on the reaction time, the amount of catalyst, and the amount of water,
Some alkoxy groups or silanol groups may remain.

Instead of using the above-mentioned powdery silicone compound, a silane of the formula (3) and / or a siloxane of the formula (4) and an organofunctional group-containing alkoxysilane are used in the form of a powdery organofunctional group-containing organopolysiloxane. In order to reliably obtain siloxane, 70% by weight or more of a raw material having an alkoxy group of trialkoxy or more of the total raw material is used, and the amount of water for hydrolysis is 1-fold as a molar ratio to the alkoxy group in the total raw material 5
It should be 0 times. When it is less than this ratio, solid polyorganosiloxane can be obtained, but it is difficult to obtain a powdery product as a lump.

In order to improve the compatibility of all the above-mentioned liquid organofunctional group-containing organopolysiloxane oligomers and polymers obtained in the present invention with other resins, the phenyl group in the alkoxysilane described above is used. It is preferable to mix and react an alkoxysilane containing Further, the inclusion of the phenyl group increases the refractive index. In this case, the phenyl group / Si molar ratio is preferably 0.01: 1 to 0.9: 1. The molar ratio is 0.
When it is lower than 1: 1, the refractive index is not sufficiently improved, and when the molar ratio exceeds 0.9: 1, the target substance may not become liquid. More preferably, the phenyl group / Si molar ratio is 0.3: 1 to 0.7: 1. Alternatively, if an organic functional group-containing alkoxylane having a repeating polymer unit is used, the compatibility with other resins is improved.

Next, preferred and more limited embodiments of the present invention will be further described. According to this aspect, the general formula (R ¹ ) _b Si (OR ² ) _4-b (wherein R ¹ is an unsubstituted or substituted alkyl group, an organic group containing at least one of a phenyl group, and R ² is hydrogen). Atom, an atom or a group selected from an alkyl group having 1 to 4 carbon atoms and an alkenyl group, and b is an integer of 0 to 3), and an organoalkoxysilane represented by the general formula Y-SiR ¹ _a (OR ² ) _{3 -a} (wherein R ¹ and R ² are the same as above, Y is a substituted or unsubstituted alkenyl group, epoxy group, (meth) acryloxy group, amino group, mercapto group, hydroxyl group, siloxy group,
A group selected from an organic group containing an ether, a ketone, an ester, a phosphorus compound, an organic group containing a poly (vinyl aromatic), a polyether, and a polyamide, and a is an integer of 0 to 2. )
And an organoalkoxysilane represented by
The reaction is carried out in water or a water-containing organic solvent in the presence of a fluorine-containing silicon compound containing at least one Si—F bond or a fluoride catalyst to give a compound of the general formula Y _m R ¹ _n Si (OR ² ) _p O _{(4- mnp) / 2} (where R ¹ , R ² and Y are the same as above, and m, n and p are 0 <
m <1, 0 <m + n + p <2. (3) A method for producing an organic functional group-containing silicon-based powder substance is provided, which comprises obtaining an organic functional group-containing silicon total powder substance represented by (4).

R ¹ of this embodiment is an organic group containing at least one of the above-mentioned unsubstituted or substituted alkyl group and phenyl group shown in relation to the general composition formula (1), and R ² is also related to the general composition formula. Described as hydrogen atom, having 1 to 4 carbon atoms
Is an alkyl group or an alkenyl group.

Another preferred embodiment is the following epoxy group and group
Method for producing organopolysiloxane containing lucoxy group
Is the law. That is, the existence represented by the following general formula (2 ')
Functional group-containing alkoxysilane Y-SiR¹ _a(OR²)_3-a  ... (2 ') (In the formula, Y has a substituted or unsubstituted epoxy group.
Organic group, R¹Is a substituted or unsubstituted hydrocarbon having 1 to 8 carbon atoms
Organic group selected from elementary groups, R²Is hydrogen, having 1 to 4 carbon atoms
Atom or organic group selected from alkyl group and alkenyl group
Is. In addition, a is an integer represented by 0 ≦ a ≦ 2.
It ), Or an epoxy group-containing group represented by the above general formula.
Lucoxysilane and an alcohol represented by the following general formula (3 ')
Represented by a silane compound containing a coxyl group and the following general formula (4 ')
Organopolysiloxane containing alkoxy groups (R¹)_bSi (OR²)_4-b  ... (3 ') R¹ _cSiO_(4-cd)_{/ 2}(OR²)_d   ... (4 ') (In the formula, b is an integer satisfying 0 ≦ b ≦ 3, and c is 0 ≦ c ≦ 2
Is a positive number that satisfies, and d is a positive number that satisfies 0.01 ≦ d ≦ 3
0.01 ≦ c + d ≦ 3 is satisfied. ) Is fluorinated
Characterized by partial hydrolysis and condensation in the presence of a compound
The following general formula (1 ') Y_mR¹ _nSi (OR²)_pO_{(4-mnp) / 2}  ...... (1 ') (In the formula, 0 <m ≦ 1, 0 ≦ n <2, 0 <p ≦ 2, 0 <m
It is a positive number that satisfies + n + p ≦ 3. ), Represented by
Organopolysiloxane containing xy and alkoxy groups
It is a manufacturing method of Sun.

In the above general formula (1 ′), p is 1 ≦ p ≦
It is preferable that the number satisfy the range of 2. further,
The number of moles of water used for hydrolysis is preferably less than 1/2 of the number of moles of alkoxy in the raw material before hydrolysis. Preferably, the epoxy-containing alkoxysilane used in the above production method is γ-glycidoxypropyltrimethoxysilane or 2- [3,4-epoxycyclohexyl] ethyltrimethoxysilane. More preferably, the fluorine-containing compound is KF.

Yet another preferred embodiment is an epoxy group-containing organopolysiloxane represented by the following general formula (5). ^{_{Y m R 1 n Si (OR}} 2) p (OH) q O (4-mnpq) / 2 ...... (5) ( wherein, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon having 1 to 8 carbon atoms , R ² is a hydrogen atom, a lower alkyl group or a lower alkenyl group), Y is an organic group containing an epoxy group, and 0 <m ≦ 10 <n ≦ 10 0 ≦ p <10 <q <0.1 0 <m + n <2

When the epoxy group-containing organopolysiloxane of the above formula (5) is hydrolyzed with an epoxy group-containing alkoxysilane to produce an epoxy group-containing organopolysiloxane, a Si--F bond is incorporated into the molecule as a hydrolysis catalyst. It is manufactured by a method characterized by using at least one fluorine-containing silicon compound or a fluorinated salt. In the above method, it is preferable to add the monoalkoxysilane during or after the hydrolysis of the epoxy group-containing organopolysiloxane.
Thereby, the amount of residual OH groups can be adjusted appropriately.

Further, according to a preferred embodiment, the following general formula (2 ″) Y—SiR ¹ _a (OR ² ) _3-a (2 ″) (wherein R ¹ is a substituent having 1 to 8 carbon atoms). Or an organic group selected from unsubstituted hydrocarbon groups, R ² is a hydrogen atom, a lower alkyl group or a lower alkenyl group, Y is an organic group having an epoxy group, and a is 0, 1 or 2.). Epoxy group-containing alkoxysilane or this epoxy group-containing alkoxysilane and the following general formula (3 ″) (R ¹ ) _b Si (OR ² ) _4-b (3 ″) (wherein R ¹ and R ² are as described above). Has the same meaning as
0, 2 or 3. ) A mixture of tetra, tri or dialkoxysilane represented by the following general formula _{^{(4 ") R 1 3 SiO}} (OR 2) ...... (4") ( wherein, similar to R ^1, R ² above And a monoalkoxysilane represented by the formula (1) are hydrolyzed in the presence of a fluorine-containing silicon compound or a fluoride salt containing at least one Si—F bond in the molecule. Provided is a method for producing a group-containing organopolysiloxane.

Further, the following general formula (2 ″) Y—SiR ¹ _a (OR ² ) _3-a (2 ″) (wherein R ¹ is a substituted or unsubstituted hydrocarbon having 1 to 8 carbon atoms). An organic group selected from the group, R ² is a hydrogen atom, a lower alkyl group or a lower alkenyl group, Y is an organic group having an epoxy group, and a is 0, 1 or 2. This epoxy group-containing alkoxysilane and the following general formula (3 ″) (R ¹ ) _b Si (OR ² ) _4-b (3 ″) (wherein R ¹ and R ² have the same meanings as described above). And b is
0, 2 or 3. ) Is hydrolyzed with a tetra-, tri-, or dialkoxysilane mixture in the presence of a fluorine-containing silicon compound or a fluoride salt containing at least one Si—F bond in the molecule, and then the following general formula ( _{^{4 ") R 1 3 SiO (}} OR 2) ...... (4") ( wherein, R ^1, R ² is characterized by reacting a mono-alkoxy silane represented by.) of as defined above Provided is a method for producing an epoxy group-containing organopolysiloxane. The epoxy-containing organic groups of the above formulas (2 ′) and (2 ″) are shown below.

[0127]

[Chemical 43]

[0128]

[Chemical 44]

Further, represented by the equations (3 ′) and (3 ″),
The tetra, tri and dialkoxysilanes are as follows.

[0130]

[Chemical formula 45]

[0131]

[Chemical formula 46]

Specific monoalkoxysilanes of the formulas (4 ') and (4 ") are shown below.

[0133]

[Chemical 47]

[0134]

EXAMPLES The present invention will be specifically described below by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples. Example 1 0.17 g (3 mmol) of KF, 261 g of water (14.7)
(Mol) was placed in a 500 ml reactor equipped with a stirrer, a thermometer, and a condenser, and mixed by stirring. Next, 23.5 g (150 mmol) of tetramethoxysilane and 36.5 g (15) of γ-glycidoxypropyltrimethoxysilane were added.
(0 mmol) was added dropwise at room temperature over 3 minutes, and after the completion of the dropwise addition, the mixture was stirred at room temperature for 1 minute. The colorless and transparent reaction liquid changed to a white gel, and the mixture was further stirred at room temperature for 1 hour. After stirring, it is filtered with a pressure filter, distilled water,
Then, wash with acetone, and use a vacuum dryer at 80 °.
When the solvent was removed by treatment with C and 10 mmHg for 4 hours, 31.8 g of a γ-glycidoxypropyl group-containing silicon-based powder substance was obtained with a yield of 93%.

The γ-glycidoxypropyl group-containing silicon-based powder substance is extremely porous with a bulk specific gravity of 0.27 g / cm ³ and a specific surface area of 715 m ² / g.
When the PMAS- ¹³ C-NMR spectrum was measured,
The chart shown in FIG. 1 was obtained, in which the presence of δ44.5 ppm and 51.5 ppm derived from the epoxy group was observed, and no peaks due to the decomposition products were observed. It was confirmed that the content was stable without any problem [see FIG. 6: chart of γ-glycidoxypropyltrimethoxysilane as a raw material],
About this, when a color reaction was carried out by the sodium thiosulfate method [Experimental Chemistry Course, sequel 5, Qualitative confirmation method of organic compounds (above), p.518 (Maruzen Co., Ltd.)], a red color was obtained. It was confirmed that it was retained.
In addition, about this by the methyl Grignard method ≡
When the Si—OH group was quantified (≡Si—OH as methane gas), it was found to be 19.6 mg equivalent / g, and as a result of microanalysis, it was found that the carbon content was 30.7 wt%. From what I found, this is

[0136]

[Chemical 48]

It was confirmed to be the one shown by.

Example 2 0.09 g of (NH ₄ ) ₂ SiF _{6 was used as} KF in Example 1.
When the reaction was performed in the same manner as in Example 1 except that the amount was (0.5 mmol), the reaction liquid changed to a white gel after 1 minute from the completion of the dropping. Therefore, when the same treatment as in Example 1 was performed below, γ -The yield of the glycidoxypropyl group-containing silicon-based powder material was 89%, and 30.4 g was obtained, which was porous with a bulk specific gravity of 0.28 g / cm ³ and a specific surface area of 702 m ² / g. Met.

The CPMAS- ¹³ C-NMR spectrum of this product was measured in the same manner as in Example 1, and it was confirmed that the epoxy group was safely contained without being damaged. When a color reaction similar to that in Example 1 was performed, a red color was exhibited. Also, for this
Quantitative analysis of Si-OH group showed that it was 21.3 m.
As a result of microanalysis, g equivalent / g was found to contain carbon in an amount of 30.3 wt.

[0140]

[Chemical 49]

It was confirmed to be the one shown by.

Example 3 The reaction was carried out in the same manner as in Example 1 except that the water in Example 1 was 223.2 g (12.4 mol) of water and 40.8 g (1.38 mol) of methanol. After 5 minutes, the reaction liquid changed to a white gel, so that the same treatment as in Example 1 was performed, and 31.6 g of a γ-glycidoxypropyl group-containing silicon-based powder substance was obtained at a yield of 93%. However, this was an extremely porous powder having a bulk specific gravity of 0.29 g / cm ³ and a specific surface area of 680 m ² / g.

Example 4 23.5 g (150 mmol) of tetramethoxysilane and 36.5 of γ-glycidoxypropyltrimethoxysilane.
g (150 mmol) was placed in a 500 ml reactor equipped with a stirrer, a thermometer, and a condenser, and the mixture was stirred and mixed. Then, KF 0.17 g (3 mmol) was added to water 264 g (14.
When the solution dissolved in 667 mol) was added dropwise, the reaction liquid changed to a white gel immediately after the completion of the addition, and therefore the same treatment as in Example 1 was performed. As a result, the silicon-based powder substance containing γ-glycidoxypropyl group was 3% at a yield of 99%.
3.7 g was obtained, which has a bulk specific gravity of 0.31 g / cm.
³ , a porous powder having a specific surface area of 667 m ² / g.

Example 5 The same procedure as in Example 1 was carried out except that 22.6 g (96.0 mmol) of γ-glycidoxypropyltrimethoxysilane and 36.6 g (240 mmol) of tetramethoxysilane were used as the alkoxysilanes. When the reaction was carried out by the reaction, the reaction solution changed into a white gel one minute after the completion of the dropping, so that the same treatment as in Example 1 was carried out. As a result, the γ-glycidoxypropyl group-containing silicon-based powder substance was obtained in a yield of 99% and 30%.
This was an extremely porous powder having a bulk specific gravity of 0.17 g / cm ³ and a specific surface area of 780 m ² / g.

Comparative Example 1 36% of a catalyst and 30.4 g of an aqueous hydrochloric acid solution (HCl: 300
Mmol) and 244.6 g (13.589 mol) of water, the reaction was carried out in the same manner as in Example 1, and the reaction solution became a white gel 5 hours after the completion of the dropping. Processed as in Example 1. As a result, 29.2 g of a silicon-based powder substance could be obtained with a yield of 86%, which had a bulk specific gravity of 0.86 g / cm ³ and a specific surface area of 14
3 m ² / g of CPMAS- ¹³ C of this
When the -NMR spectrum was measured, the chart as shown in FIG. 2 was obtained, but in this product, the peaks derived from the epoxy group disappeared and the peaks derived from the decomposed products thereof were δ 64.6 ppm and 71.0 ppm. It was confirmed to exist.

Example 6 22.2 g (15 g) of vinyltrimethoxysilane was added to γ-glycidoxypropyltrimethoxysilane in Example 1.
(0 mmol) except that the reaction was carried out in the same manner as in Example 1 to cause a reaction, and the reaction solution immediately changed to a white gel after completion of the dropping, so the same treatment as in Example 1 was carried out. As a result, 20 g of a vinyl group-containing silicon-based powder substance could be obtained with a yield of 96%, but this product had a bulk specific gravity of 0.2.
It was an extremely porous powder having a specific surface area of 7 g / cm ³ and 550 m ² / g.

Then, FT-IR measurement was performed on this powder, and the chart shown in FIG. 3 was obtained. This chart shows the presence of a vinyl group at 1,604 cm ^-1 due to a peak due to C = C stretching. Was confirmed, but this vinyl group was purple in the color reaction by the potassium permanganate method [Experimental Chemistry Lecture, Sequel 5, Qualitative Confirmation Method for Organic Compounds (above), p.132 (Maruzen Co., Ltd.)]. It was also confirmed by the decolorization of the liquid. In addition, about this, as a result of quantitative analysis of ≡Si—OH group, this was 31.4 mg equivalent / g,
As a result of microanalysis, it was confirmed to contain 16.7% by weight of carbon. Therefore, this vinyl group-containing silicon-based powder substance is represented by the formula (CH ₂ ═CH) _0.49 (OH) _0.13 SiO _1.69. It was confirmed to be a thing.

Example 7 33.6 g (1) of γ-glycidoxypropyltrimethoxysilane in Example 1 was substituted with styryltrimethoxysilane.
The reaction was performed in the same manner as in Example 1 except that the amount was 50 mmol), and the reaction liquid changed to a white gel 5 minutes after the completion of the dropping. Therefore, the same treatment as in Example 1 was performed.
As a result, 27.3 g of a styryl group-containing silicon-based powder substance was obtained with a yield of 84%, which had a bulk specific gravity of 0.4.
It was an extremely porous powder having a specific surface area of 410 m ² / g and 0 g / cm ³ .

Then, FT-IR measurement was carried out on this powder, and the chart shown in FIG. 4 was obtained. This chart shows C = C expansion and contraction at 1,603 cm ^-1 and 678c.
The presence of a styryl group was confirmed because a peak based on the C-H out-of-plane angular plane of monosubstituted benzene was observed at m ^-1 . In addition, when a color reaction was carried out using the potassium permanganate method (supra), the purple liquid was desorbed, confirming the presence of an styryl group.
This was 24.2 mg equivalent / g in the Si-OH group quantitative analysis.
In those results of microanalysis, since it was found that the carbon is contained 41.9 wt%, this compound of formula _{(CH 2 = CH-C 6} H 5) 0.46 (HO) 0.15 SiO 1.695 Was confirmed.

Example 8 Reaction was carried out by the same procedure as in Example 1 except that 37.3 g (150 mmol) of γ-methacryloxypropyltrimethoxysilane was used as the γ-glycidoxypropyltrimethoxysilane in Example 1. As a result, the reaction liquid changed to a white gel one minute after the completion of the dropping.
When treated in the same manner as above, 28.7 g of a silicon-based powder substance was obtained with a yield of 80%, which had a bulk specific gravity of 0.4.
It was a porous powder having a specific surface area of 4 g / cm ³ and a specific surface area of 386 m ² / g.

Then, FT-IR measurement was performed on this powder, and the chart shown in FIG. 5 was obtained.
The presence of a γ-methacryloxypropyl group was confirmed from the fact that a peak due to C = O stretching was observed at 1,718 cm ^-1 . This was the coloration by the potassium permanganate method (supra). It was also confirmed by the fact that the liquid that was purple in the reaction was decolorized. Moreover, about this ≡Si-O
It was found by H group quantitative analysis that this was 16.5 mg equivalent / g, and as a result of microanalysis, it contained 32.6% by weight of carbon.

[0152]

[Chemical 50]

It was confirmed to be a γ-methacryloxypropyl group-containing silicon powder substance represented by:

Example 9 γ-glycidoxypropyltrimethoxysilane in Example 1 was replaced with aminopropyltrimethoxysilane 26.9.
When the reaction was carried out in the same manner as in Example 1 except that the amount was changed to g (150 mmol), the reaction liquid changed to a white gel immediately after the completion of the dropping. Therefore, the same treatment as in Example 1 was performed. 80% rate of silicon powder substance is 20.4
g was obtained, which had a bulk specific gravity of 0.5 g / c
It was m ³ and had a specific surface area of 410 m ² / g and was porous.

Then, a Rimini test [Experimental Chemistry Lecture, Sequential 5, Method for Qualitative Confirmation of Organic Compounds (bottom), p. 1,044 (Maruzen Co., Ltd.)] with primary amine was carried out on this powder. It was confirmed that an amino group was present in this, and this was ≡S
As a result of quantitative analysis of i-OH group, this was 40.3 mg equivalent /
As a result of a microanalysis with g, it was found that the carbon content was 19.2% by weight, and therefore, this product had an amino acid represented by the formula [H ₂ N (CH ₂ ) ₃ ] _0.45 (HO) _0.20 SiO _1.675. It was confirmed to be a propyl group-containing silicon-based powder substance.

Example 10 γ-glycidoxypropyltrimethoxysilane in Example 1 was replaced with mercaptopropyltrimethoxysilane 2
When the reaction and treatment were carried out in the same manner as in Example 1 except that the amount was 9.5 g (150 mmol), the reaction liquid changed to a white gel immediately after the completion of the dropping. Therefore, the same treatment as in Example 1 was carried out. 82% yield with 2 silicon-based powder substances
5.8 g was obtained, which has a bulk specific gravity of 0.37 g / c.
It was m ³ and was porous with a specific surface area of 520 m ² / g.

Next, a color reaction by the sodium nitroproside method [Experimental Chemistry Lecture, sequel 5, Method for qualitative confirmation of organic compounds (bottom) p.1,170 (Maruzen Co., Ltd.)] was performed on this powder. Since it had a purple-red color, it was confirmed that a mercapto group was present in this, and the ≡Si—OH group of this product was quantitatively analyzed to find that it was 32.
It was 6 mg equivalent / g, and as a result of microanalysis, it was found that the carbon content was 18.4% by weight. Therefore, this substance had the formula [HS (CH ₂ ) ₃ ] _0.48 (HO) _0.18 SiO 2. It was confirmed to be a mercaptopropyl group-containing silicon-based powder substance represented by _1.67 .

Example 11 100 g of γ-glycidoxypropyltrimethoxysilane
(424 mmol) and 100 g (3.12 mol) of methanol were put into a 500 ml reactor equipped with a stirrer, a thermometer and a cooler, and mixed with stirring. KF 0.5g (9
(4 mmol) dissolved in 45.8 g (2.54 mol) of water was added dropwise at room temperature over 3 minutes. After dropping, 4
The internal temperature rose to 4 ° C. After stirring for 2 hours at room temperature as it was, 8.8 g (84 mmol) of trimethylmethoxysilane was added dropwise over 1 minute, and subsequently stirred for 2 hours. Then, the ester adapter was attached to the reactor, 200 g of toluene was added, and methanol was distilled off while heating. After cooling the reaction solution, the aqueous layer and the organic layer were separated, and the organic layer was washed 3 times with water. Glauber's salt was added to the washed reaction solution to remove water, and then toluene was removed by an evaporator to obtain 75.8 g of a transparent viscous liquid substance.

This transparent viscous liquid substance has a viscosity of 1316.
It was 8 cp (25 ° C.), a refractive index of 1.4669 (25 ° C.) and an epoxy equivalent of 153.

When ¹³ C-NMR measurement of this substance was carried out, the result was as shown in FIG. The difference is clear when compared with the ¹³ C-NMR spectrum of γ-glycidoxypropyltrimethoxysilane in FIG. From this result, it can be seen that trimethylsilylation treatment is performed since the peak is at δ1.021 ppm. Further, since no peak derived from the methoxy group, which should be observed at δ50.361 ppm, is not seen at all, it can be seen that the methoxy group has completely disappeared. Furthermore, since the peaks of δ43.208 ppm and δ50.040 ppm derived from the epoxy group are seen and no peaks other than those observed in the raw material epoxysilane have newly appeared, the epoxy group is contained without being damaged. It turned out that it was done.

The results of ²⁹ Si-NMR measurement are shown in FIG. From this result, the molar ratio of each unit was as follows.

[0162]

[Chemical 51]

From the above results, it was confirmed that this substance was an epoxy group-containing liquid polysilsesquioxane represented by the following formula.

[0164]

[Chemical 52]

Example 12 100 g of γ-glycidoxypropyltrimethoxysilane
(424 mmol), trimethylmethoxysilane 8.8
g (84 mmol) and 100 g of methanol (3.12).
500 ml equipped with stirrer, thermometer and cooler
It was put in the reactor of and mixed with stirring. KF 0.5g here
A solution of (9 mmol) in 45.8 g (2.54 mol) of water was added dropwise at room temperature over 3 minutes. After the dropping was completed, the internal temperature rose to 43 ° C. After stirring for 2 hours at room temperature, an ester adapter was attached to the reaction apparatus, 200 g of toluene was added, and methanol was distilled off while heating. After cooling the reaction solution, the aqueous layer and the organic layer were separated, and the organic layer was washed 3 times with water. Glauber's salt was added to the washed reaction solution to remove water, and then toluene was removed by an evaporator to obtain 81.0 g of a transparent viscous liquid substance.

This transparent viscous liquid substance has a viscosity of 826.0.
cp (25 ° C.), refractive index 1.4634 (25 ° C.), epoxy equivalent 143.

As a result of ²⁹ C-NMR measurement performed in the same manner as in Example 11, the molar ratio of each unit was as follows.

[0168]

[Chemical 53]

From the above results, it was confirmed that this substance was an epoxy group-containing liquid polysilsesquioxane represented by the following formula.

[0170]

[Chemical 54]

Example 13 KF 0.5 g (9 mmol), water 45.8 g (2.54)
Mol) and 100 g (3.12 mol) of methanol were put into a 500 ml reactor equipped with a stirrer, a thermometer and a condenser, and mixed with stirring. 100 g (424 mmol) of γ-glycidoxypropyltrimethoxysilane was added dropwise thereto over 8 minutes. After the dropping was completed, the internal temperature rose to 36 ° C. After stirring for 2 hours at room temperature as it was, 8.8 g (84 mmol) of trimethylmethoxysilane was added dropwise over 1 minute, and subsequently stirred for 2 hours. Thereafter, the same treatment as in Example 11 was carried out to obtain 76.0 g of a transparent viscous liquid substance.

This transparent viscous liquid substance has a viscosity of 1103.
2 cp (25 ° C.), refractive index 1.4653 (25 ° C.), epoxy equivalent 153.

As a result of ²⁹ C-NMR measurement performed in the same manner as in Example 11, the molar ratio of each unit was as follows.

[0174]

[Chemical 55]

From the above results, it was confirmed that this substance was an epoxy group-containing liquid polysilsesquioxane represented by the following formula.

[0176]

[Chemical 56]

0.5 g (9 mmol) of KF was added to (NH ₄ ) ₂
The reaction and treatment were conducted in the same manner as in Example 11 except that 0.27 g (1.5 mmol) of SiF ₆ was used to obtain 76.3 g of a transparent viscous liquid substance.

This transparent viscous liquid substance has a viscosity of 1301.
6 cp (25 ° C.), refractive index 1.4670 (25 ° C.), epoxy equivalent 153.

As a result of ²⁹ C-NMR measurement performed in the same manner as in Example 11, the molar ratio of each unit was as follows.

[0180]

[Chemical 57]

From the above results, it was confirmed that this substance was an epoxy group-containing liquid polysilsesquioxane represented by the following formula.

[0182]

[Chemical 58]

Example 15 100 g of γ-glycidoxypropyltrimethoxysilane
(424 mmol), fluorotriethoxysilane 1.6
4 g (9 mmol) and 100 g of methanol (3.12)
500 ml equipped with stirrer, thermometer and cooler
It was put in the reactor of and mixed with stirring. 45.8g of water here
(2.54 mol) was added dropwise at room temperature over 3 minutes. After the dropping was completed, the internal temperature rose to 38 ° C. After stirring as it is at room temperature for 2 hours, 8.8 g of trimethylmethoxysilane
(84 mmol) was added dropwise over 1 minute, followed by stirring for 2 hours. After that, the same process as in Example 11 was performed to obtain 7
5.8 g of transparent viscous liquid substance was obtained

This transparent viscous liquid substance has a viscosity of 138.2.
It was 5 cp (25 ° C.), a refractive index of 1.4501 (25 ° C.) and an epoxy equivalent of 152.

As a result of ²⁹ Si-NMR measurement performed in the same manner as in Example 11, the molar ratio of each unit was as follows.

[0186]

[Chemical 59]

From the above results, it was confirmed that this substance was an epoxy group-containing liquid polysilsesquioxane represented by the following formula.

[0188]

[Chemical 60]

Example 16 γ-glycidoxypropyltrimethoxysilane 63.7
g (270 mmol), phenyltrimethoxysilane 3
5.7 g (180 mmol) and 100 g of methanol
(3.12 mol) was put into a 500 ml reactor equipped with a stirrer, a thermometer and a condenser, and mixed by stirring. KF here
A solution prepared by dissolving 0.5 g (9 mmol) in 48.6 g (2.70 mol) of water was added dropwise at room temperature over 3 minutes.
After the dropping was completed, the internal temperature rose to 47 ° C. After stirring for 2 hours at room temperature, trimethylmethoxysilane 9.4 was added.
g (90 mmol) was added dropwise over 1 minute, followed by stirring for 2 hours. After that, the same process as in Example 11 was performed to obtain 6
1.7 g of transparent viscous liquid substance was obtained.

This transparent viscous liquid substance has a viscosity of 6771.
It was 1 cp (25 ° C.), a refractive index of 1.4958 (25 ° C.), and an epoxy equivalent of 140.

As a result of ²⁹ Si-NMR measurement performed in the same manner as in Example 11, the molar ratio of each unit was as follows.

[0192]

[Chemical formula 61]

From the above results, it was confirmed that this substance was an epoxy group-containing liquid polysilsesquioxane represented by the following formula.

[0194]

[Chemical formula 62]

Example 17 γ-Glycidoxypropyltrimethoxysilane 33.0
g (140 mmol), phenyltrimethoxysilane 6
5.4 g (330 mmol) and 100 g of methanol
(3.12 mol) was put into a 500 ml reactor equipped with a stirrer, a thermometer and a condenser, and mixed by stirring. KF here
0.55 g (9.4 mmol) was added to water (50.8 g, 2.8 mmol).
What was melt | dissolved in 2 mol) was dripped at room temperature over 3 minutes. After the dropping was completed, the internal temperature rose to 46 ° C. After stirring as it was for 2 hours at room temperature, 9.4 g (90 mmol) of trimethylmethoxysilane was added dropwise over 1 minute, and subsequently stirred for 2 hours. Thereafter, the same treatment as in Example 11 was carried out to obtain 76.3 g of a transparent viscous liquid substance.

This transparent viscous liquid substance has a viscosity of 1867.
7.5 cp (25 ° C), refractive index 1.5206 (25
C.) and the epoxy equivalent was 131.

As a result of ²⁹ Si-NMR measurement performed in the same manner as in Example 11, the molar ratio of each unit was as follows.

[0198]

[Chemical formula 63]

From the above results, it was confirmed that this substance was an epoxy group-containing liquid polysilsesquioxane represented by the following formula.

[0200]

[Chemical 64]

Example 18 Example 1 except that the water was 7.6 g (424 mmol).
The reaction and treatment were conducted in the same manner as in 1 to obtain 85.2 g of a transparent viscous liquid substance.

This transparent viscous liquid substance has a viscosity of 972 cp.
(25 ° C), the refractive index was 1.4651 (25 ° C), and the epoxy equivalent was 159.

As a result of ²⁹ Si-NMR measurement performed in the same manner as in Example 11, the molar ratio of each unit was as follows.

[0204]

[Chemical 65]

From the above results, it was confirmed that this substance was an epoxy group-containing liquid polysilsesquioxane represented by the following formula.

[0206]

[Chemical formula 66]

Comparative Example 2 100 g of γ-glycidoxypropyltrimethoxysilane
(424 mmol) and 100 g (3.12 mol) of methanol were put into a 500 ml reactor equipped with a stirrer, a thermometer and a cooler, and mixed with stirring. 45.8 g of a 5% NH ₃ aqueous solution was added dropwise thereto at room temperature over 3 minutes. After the dropping was completed, the internal temperature rose to 33 ° C. After stirring for 2 hours at room temperature as it is, 8.8 g of trimethylmethoxysilane (84 g)
(Mmol) was added dropwise over 1 minute, followed by stirring for 2 hours. After that, an ester adapter was attached to the reaction apparatus, 200 g of toluene was added, and methanol was distilled off while heating. During the distillation of methanol, the epoxy group was opened, and the system gelled.

Comparative Example 3 45.8 g of 5% aqueous NH ₃ solution was added to 45.8 g of 5% aqueous hydrochloric acid solution.
The reaction was performed in the same manner as in Comparative Example 2 except that g was used. After that, an ester adapter was attached to the reaction apparatus, 200 g of toluene was added, and methanol was distilled off while heating. During the distillation of methanol, the epoxy group was opened, and the system gelled.

Comparative Example 4 45.8 g of 5% NH3 aqueous solution was added to 0.61% hydrochloric acid aqueous solution 4
The reaction was performed in the same manner as Comparative Example 2 except that the amount was 5.8 g.
Then, the same treatment as in Example 11 was carried out to obtain 48 g of a transparent viscous liquid substance. This transparent viscous liquid substance has a viscosity of 2
23.1 cp (25 ° C), refractive index 1.4450 (25
℃).

The result of ¹³ C-NMR measurement of this substance is shown in FIG. As a result, a peak derived from a methoxy group is observed at δ 47.332 ppm, which indicates that the hydrolysis is incomplete. Δ43.19 derived from an epoxy group
Since the peak of δ50.104 ppm was decreased to 5 ppm, and the peak which was not found in the raw material γ-glycidoxypropyltrimethoxysilane was appeared at δ71.056 ppm to δ64.445 ppm, the epoxy group was damaged. I also understand that.

Comparative Example 5 The reaction was carried out in the same manner as in Comparative Example 2 except that 45.8 g of 5% NH ₃ aqueous solution was changed to 45.8 g of 0.2% ammonia aqueous solution. Then, the same treatment as in Example 11 was carried out to obtain 68 g of a transparent viscous liquid substance. This transparent viscous liquid substance has a viscosity of 452.7 cp (25 ° C.) and a refractive index of 1.4642 (2
5 ° C.).

The results of ¹³ C-NMR measurement of this substance are shown in FIG.
Shown in. As a result, a peak derived from a methoxy group is observed at δ47.453 ppm, which indicates that the hydrolysis is incomplete. Δ43.2 derived from epoxy group
The peak at δ60.096 ppm decreased to 06 ppm,
Moreover, since the peaks that were not found in the starting material γ-glycidoxypropyltrimethoxysilane appeared at δ64.532 ppm and at δ70.996 ppm, it can be seen that the epoxy group is damaged.

Example 19 A 1-liter reactor equipped with a stirrer, a thermometer, a condenser and a nitrogen inlet tube was charged with 236.3 g (1.00 mol) of γ-glycidoxypropyltrimethoxysilane and 100 g of methanol. , Stirred at room temperature and mixed. 0.58 g (0.01 mol) of KF and 14.4 of water were added to the resulting mixture.
When a solution prepared by mixing and dissolving 100 g (0.80 mol) and 100 g of methanol was added dropwise at room temperature over 10 minutes, the temperature of the system, which was 26 ° C. before the start of dropping, rose to 38 ° C. After completion of the dropwise addition, the reaction solution, which was stirred at room temperature for 1 hour, was directly analyzed by ¹³ C-NMR.
No alcoholic carbon other than the peaks derived from methanol and γ-glycidoxypropyltrimethoxysilane was observed. From this, it was confirmed that the ring opening of the epoxy ring did not occur.

When analyzed by ²⁹ Si-NMR, the silane component was hydrolyzed and condensed, and
To 70 parts in sequence, 14 mol%, 36 mol%, 41
It was found that the composition had changed to an oligomer having a composition ratio of mol% and 9 mol%.

[0215]

[Chemical formula 67]

[0216]

[Chemical 68]

[0217]

[Chemical 69]

(However, X in Chemical formulas 67 to 69 represents a hydrogen atom or a methyl group.)

[0219]

[Chemical 70]

From the above results, it is considered that 91% by weight of the water added for hydrolysis was converted into a siloxane bond, so that the hydrolysis and condensation reactions in this reaction system were confirmed to be fairly fast. When the reactor containing the above reaction solution was heated to distill off methanol, and the reaction solution was cooled and then filtered to remove the salt of the catalyst, 189.5 g of a slightly yellow transparent liquid was obtained. . The yield was 95.0%.
The obtained liquid has a viscosity of 60.7 cs (25 ° C), a specific gravity of 1.164 (25 ° C) and a refractive index of 1.4544 (25 ° C).
C.) and epoxy equivalent were 200.8 (g / mol, theoretical value 199.2).

From these results, the obtained substance is a partially hydrolyzed oligomer of γ-glycidoxypropyltrimethoxysilane having an average composition represented by the following chemical formula 71 as expected from the mixing ratio of the raw materials. It was confirmed.

[0222]

[Chemical 71]

Infrared absorption spectrum of the obtained liquid (Fig. 1
1), ¹³ C-NMR spectrum (FIG. 12), ²⁹ Si-N
From the results of the MR spectrum (FIG. 13) and the ¹ H-NMR spectrum (FIG. 14), it was confirmed that ring opening of the epoxy group did not occur at all.

[0224] absorption of IR epoxy group: 1254cm ^-1, 910cm ^-1, 8
Absorption of 20 cm ⁻¹ Si—O—Si group: 1104 cm ⁻¹ Si—OCH ₃ group absorption: 2841 cm ⁻¹ , 1198c
The analysis results of m ⁻¹ , 1104 cm ^{−1 13} C-NMR spectrum are as shown in Table 1.

[0225]

[Table 1]

[0226]

[Chemical 72]

The analysis results of ²⁹ Si-NMR spectrum are as shown in Table 2.

[0228]

[Table 2]

The results shown in Table 2 show that the reaction product is represented by the following chemical formula 73 and agrees well with the designed compound represented by the chemical formula 71, and the water used for hydrolysis is completely consumed. It indicates that the condensation reaction is also completed.

[0230]

[Chemical formula 73]

The analysis results of the ¹ H-NMR spectrum are shown in Table 3.
As shown in.

[0232]

[Table 3]

From the results shown in Table 3, the structure is presumed to be represented by the following Chemical formula 74, which is in good agreement with the designed compound represented by the chemical formula 70, and the water used for hydrolysis is completely It means that the condensation reaction has been completed.

[0234]

[Chemical 74]

Example 20 A hydrolysis / condensation reaction was carried out in the same manner as in Example 19 except that the amount of water added was changed to 8.0 g (0.50 mol). Is 14.2cs
(25 ° C.), specific gravity 1.126 (25 ° C.), refractive index 1.4434 (25 ° C.), and epoxy equivalent 214.
A colorless and transparent liquid having an average composition represented by the following 75 of 1 (g / mol, theoretical value 213.3) was obtained. The yield was 200.5 g, and the yield was 94.1%.

[0236]

[Chemical 75]

The results of infrared absorption spectrum, ¹ H-NMR spectrum and ²⁹ Si-NMR spectrum analysis are also as follows:
It supported the above structure.

Example 21 The alkoxysilanes used were 118.2 g (0.50 mol) of γ-glycidoxypropyltrimethoxysilane and 99.0 g (0.50 mol) of phenyltrimethoxysilane.
Except that the mixed system was changed to 5.0 ml (0.005 mol) of tetrabutylammonium fluoride (1.0 M THF solution) was used as a catalyst, and the average of the following Chemical Formulas 76 was the same as in Example 19. It is expressed by the composition formula, the viscosity is 59.2 cs (25 ° C.), and the specific gravity is 1.174 (25
C.), a refractive index of 1.4846 (25.degree. C.), and an epoxy equivalent of 362.1 (g / mol, theoretical value 360.8),
172.3 g of a slightly yellow transparent liquid was obtained. Yield is 95.5%
Met.

[0239]

[Chemical 76]

The results of infrared absorption spectrum, ¹ H-NMR spectrum and ²⁹ Si-NMR spectrum analysis were also
It supported the above structure.

Example 22 197.1 g of the alkoxysilane used was 2- [3,4-epoxycyclohexyl] ethyltrimethoxysilane.
(0.80 mol) and diphenyldimethoxysilane 48.
202.0 g of a slightly yellow transparent liquid represented by the average composition formula of the following Chemical Formula 77 was obtained in exactly the same manner as in Example 19 except that the mixed system was changed to 9 g (0.20 mol). The yield is 97.
It was 1%.

[0242]

[Chemical 77]

The viscosity of this substance is 608.5 cs (25
℃), specific gravity 1.153 (25 ℃), refractive index 1.50
22 (25 ° C.), and epoxy equivalent of 275.1 (g /
And the theoretical value was 273.0). The results of infrared absorption spectrum, ¹ H-NMR spectrum and ²⁹ Si-NMR spectrum analysis also supported the above structure.

Example 23 The alkoxysilanes used were 8,2.8 g (0.30 mol) of 9,10-epoxydecyltrimethoxysilane and 3,3.
3,3-trifluoropropyltrimethoxysilane 15
In the same manner as in Example 19 except that the mixed system was changed to 2.7 g (0.70 mol) and the water used for the hydrolysis reaction was changed to 12.6 g (0.70 mol), the following 78 198.5 g of a colorless transparent liquid represented by the average composition formula was obtained. The yield was 97.7%.

[0245]

[Chemical 78]

The viscosity of this substance is 29.8 cs (25
℃), specific gravity 1.162 (25 ℃), refractive index 1.41
52 (25 ° C), and the epoxy equivalent is 661.3 (g /
And the theoretical value was 677.3). The results of infrared absorption spectrum, ¹ H-NMR spectrum and ²⁹ Si-NMR spectrum analysis also supported the above structure.

Example 24 The alkoxysilane used was γ-glycidoxypropyltrimethoxysilane 177.2 g (0.75 mol), γ
-Glycidoxypropylmethyldimethoxysilane 11.
While changing to a mixed system of 0 g (0.05 mol) and 1,3-dimethyltetramethoxydisiloxane 22.6 g (0.10 mol), the addition amount of water was 12.6 g (0.7
Hydrolysis / condensation reaction was performed in exactly the same manner as in Example 19 except that the amount was changed to 0 mol), and then methanol was distilled off.

Next, 300 g of toluene was added, and washing with water using 200 g of a 10% by weight sodium sulfate aqueous solution was performed 3 times.
This was repeated to remove the KF of the catalyst. Further, when toluene was distilled off under reduced pressure, 167.9 g of a colorless and transparent liquid represented by the average composition formula of the following Chemical Formula 79 was obtained. 94% yield
Met.

[0249]

[Chemical 79]

The viscosity of this substance is 107.6 cs (25
℃), specific gravity 1.170 (25 ℃), refractive index 1.45
62 (25 ° C), and the epoxy equivalent is 223.5 (g /
And the theoretical value was 223.4). The results of infrared absorption spectrum, ¹ H-NMR spectrum and ²⁹ Si-NMR spectrum analysis also supported the above structure.

Comparative Example 6 (Acid Hydrolysis) KF was not used, and the amount of water used in the hydrolysis was 0.1.
The substance obtained in exactly the same manner as in Example 24 except that 1N hydrochloric acid was used, had a viscosity of 11.3 cs (25 ° C.), a specific gravity of 1.116 (25 ° C.), and a refractive index of 1.4530 ( Two
5 ° C.), and the epoxy equivalent was 252.5 (g / mol). The yield was 197.6 g, and the yield was 110.6.
%Met. Since the epoxy equivalent when the hydrolysis reaction is 0% is 261.5 (g / mol), the above results indicate that the hydrolysis / condensation reaction has hardly progressed.

Comparative Example 7 (Acid Hydrolysis) 1N hydrochloric acid was used in place of 0.1N hydrochloric acid,
Other than changing the reaction to take place under the return of methanol,
The viscosity of the substance obtained in exactly the same manner as in Comparative Example 6 was 13.
9 cs (25 ° C.), specific gravity 1.121 (25 ° C.), refractive index 1.4232 (25 ° C.), and epoxy equivalent 26
It was 5.4 (g / mol). The yield is 195.1.
g, the yield was 109.2%. Thus, by increasing the concentration of hydrochloric acid, the hydrolysis / condensation reaction slightly proceeded as compared with the case of Comparative Example 6, but it is clear that the destruction of the epoxy group also partially occurred.

Comparative Example 8 (Basic Hydrolysis) The reaction was carried out in the same manner as in Comparative Example 6 except that 1N ammonia water was used instead of 0.1N hydrochloric acid. However, when the methanol was distilled off, the inside of the system gelled and the target substance could not be obtained.

Example 25 248.4 g (1.00 mol) of γ-methacryloxypropyltrimethoxysilane was used instead of the mixed system of γ-glycidoxypropyltrimethoxysilane, and tetrabutylammonium fluoride was used instead of KF. 1 ml of 1M THF solution (0.001 mol) and water 14.4 g
(0.80 mol) was used and synthesized in the same manner as in Example 24. The obtained substance has a viscosity of 120.0 cs (25 ° C.),
Specific gravity 1.114 (25 ° C), refractive index 1.4629 (25
It was a slightly yellow transparent liquid exhibiting the characteristics of (° C.). Yield 10
The yield was 5.8 g and the yield was 97.5%. ^{From the 1} H-NMR spectrum, it was found that the methacryl group was completely retained and the methoxy group remained almost as set.

The analysis results of ¹ H-NMR spectrum are shown in Table 4.
Shown in.

[0256]

[Table 4]

From the results in Table 4, the reaction product is estimated to have the following structure.

[0258]

[Chemical 80]

Example 26 The amount of water added was 15.4 g (0.86 mol) and KF
When a hydrolysis / condensation reaction was carried out in the same manner as in Example 19 except that the amount of was 5 × 10 ⁻⁵ mol, the clay at 25 ° C. was 49.9 cs (25 ° C.) and the specific gravity was 1. 163
(25 ° C.), a refractive index of 1.4551 (25 ° C.), an epoxy equivalent of 192.7 (g / mol, theoretical value 196.9) and an OH amount of 0.70 wt% were obtained. ¹ H-N
From the result of the MR spectrum analysis, the obtained substance was an organopolysiloxane having the following structural formula.

[0260]

[Chemical 81]

[0261]

As described above, according to the method of the present invention, (1) a substantially neutral fluorinated compound, that is, Si
Since a fluorine-containing silicon compound or a fluorinated salt compound containing at least one --F bond in the molecule is used, the final polyorgano can be stably maintained even during the reaction without damaging an organic functional group having a high reaction activity, such as an epoxy group. It can be contained in siloxane. (2) Since this catalyst has a fast hydrolysis and condensation reaction, the alkoxy groups in the raw material are easily hydrolyzed according to the amount of added water, and a wide range of products such as organopolysiloxane powders, polymers and oligomers can be obtained easily and stably. To be (3) Since this catalyst is substantially neutral, it does not damage the reaction equipment, and since it is less dangerous like acids and bases, it is excellent in operability and safety. When the obtained organopolysiloxane is a powder, it is porous and has a small bulk density in which functional groups are dispersed even inside the pores, and it is used as a column packing material, various enzymes, and a carrier for metal compounds. , The polymer is a liquid that is compatible with both organic and inorganic and is a scientifically extremely stable liquid.
It is useful as an additive for paints, sealants, electrical insulation agents, and flame retardants. Furthermore, the oligomer is a cross-linking agent for various curing systems,
It is useful as a modifier for organic resins.

[Brief description of drawings]

FIG. 1 is a CPMAS- of a γ-glycidoxypropyl group-containing organopolysiloxane powder substance obtained in Example 1.
It is a figure showing a ¹³ C-NMR spectrum diagram.

2 is a CPMAS- ¹³ C-NMR spectrum diagram of the organopolysiloxane powder substance obtained in Comparative Example 1. FIG.

3 is an FT-IR chart of the vinyl group-containing organopolysiloxane powder material obtained in Example 6. FIG.

FIG. 4 is an FT-IR chart of the styryl group-containing organopolysiloxane powder material obtained in Example 7.

FIG. 5: FT-I of γ-methacryloxypropyl group-containing organopolysiloxane-based powder substance obtained in Example 8
It is an R chart.

FIG. 6 is a CPMAS- ¹³ C-NMR spectrum diagram of γ-glycidoxypropyltrimethoxysilane used in Example 1.

FIG. 7 shows a ¹³ C-NMR spectrum diagram of the epoxy group-containing organopolysiloxane obtained in Example 11.

8 is a ²⁹ Si-NMR spectrum diagram of the epoxy group-containing organopolysiloxane obtained in Example 11. FIG.

FIG. 9 is a ¹³ C-NMR spectrum diagram of the epoxy group-containing organopolysiloxane obtained in Comparative Example 4.

FIG. 10 shows a ¹³ C-NMR spectrum diagram of the epoxy group-containing organopolysiloxane obtained in Comparative Example 5.

11 is an infrared absorption spectrum of the epoxy group-containing oligomer obtained in Example 19. FIG.

FIG. 12 is a ¹³ C-NMR spectrum of the epoxy group-containing oligomer obtained in Example 19.

FIG. 13 is a ²⁹ Si-NMR spectrum of the epoxy group-containing oligomer obtained in Example 19.

FIG. 14 is a ¹ H-NMR spectrum of the epoxy group-containing oligomer obtained in Example 19.

Continuation of front page (56) Reference JP-A-2-107638 (JP, A) JP-A-59-129230 (JP, A) JP-A-59-108033 (JP, A) JP-A-3-147840 (JP , A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 77/00-77/62

Claims (8)

(57) [Claims] 1. A lower Symbol average composition formula _{^{(1) Y m R 1 n}} Si (OR 2) p O (4-m-n-p) / 2 ...... (1) ( in the formula, Y is a substituted or non A substituted alkenyl group, an epoxy group, a (meth) acryloxy group, an amino group, a mercapto group, a hydroxyl group, a siloxy group, an ether group, a ketone group, an ester group and an organic group containing phosphorus and a (vinyl aromatic) repeating unit, A group selected from organic groups each containing an ether repeating unit and an amide repeating unit, R ¹ is at least ^one substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms, R ² is a hydrogen atom and 1 carbon atom To an atom or an organic group selected from an alkyl group and an alkenyl group, m is 0 <m ≦ 1, and n is 0 ≦ n <
2, p is O containing 0 ≦ p ≦ 2, where 0 <m + n + p ≦ 3 organic functional group represented by a number) respectively satisfying
A method for producing luganopolysiloxane, comprising:
An alkoxysilane containing an organic functional group represented by Y-SiR1a (OR2) 3-a (2) (wherein Y, R1 and R2 have the same meanings as described above, respectively ).
And a represents an integer in the range of 0 ≦ a ≦ 2. ) Or above
Organic functional group-containing silane compound represented by the general formula (2)
And an alkoxy group-containing sila represented by the following general formula (3)
Compound, containing an alkoxy group represented by the following general formula (4)
Organopolysiloxane and / or the following general formula (3)
Containing a silane compound and an alkoxy group represented by the following general formula (4)
Partial or complete hydrolysis with organopolysiloxane
Mixture with at least one compound selected from the compounds (R1) bSi (OR2) 4-b ... (3) R1cSiO (4-cd) / 2 (OR2) d ... (4) (wherein , R1 and R2 have the same meanings as above.
Where b is an integer that satisfies 0 ≦ b ≦ 3, and c is 0 ≦ c ≦ 2.
The addition number, d is a positive number satisfying 0.01 ≦ d ≦ 3, provided that 0.
01 ≦ c + d ≦ 3) as a hydrolysis / condensation catalyst
Hydrolysis and polycondensation in the presence of neutral fluorine-containing compounds
A method for producing an organopolysiloxane containing an organic functional group, which comprises : 2. The organopolycarbonate according to claim 1, wherein the number of moles of water used for hydrolysis is less than 1/2 times the total number of moles of alkoxy groups contained in all raw materials before hydrolysis.
Method for producing roxane . 3. In the general formula (1), p is 1 ≦ p.
≦ a 2, a manufacturing method of the organopolysiloxane of claim 2. Wherein said general formula (1), Y is an epoxy group-containing organic group, the manufacturing method of the organopolysiloxane according to any one of claims 1 to 3. 5. The number of moles of water used for hydrolysis is less than 1/2 of the total number of moles of alkoxy groups contained in all raw materials before hydrolysis, and the organopolysiloxane has epoxy groups and alkoxy groups. The method for producing an organopolysiloxane according to claim 4 , which is a group-containing oligomer. Wherein said general formula (1), Y is (meth) acryloxy group-containing organic group, claims 1 to 3
Method for producing organopolysiloxane according to one something Re of. 7. The number of moles of water used for hydrolysis is less than 1/2 of the total number of moles of alkoxy groups contained in all raw materials before hydrolysis, and the organopolysiloxane is (meth) acryloxy. A group-containing oligomer,
7. The method for producing an organopolysiloxane according to item 6 . 8. In the general formula, 0 <m + n + p <
There 2, an organic functional group-containing organopolysiloxane obtained is a powder, method for producing the organopolysiloxane of the placing serial to claim 1.