JPH06293831A - Chain polyorganosiloxane and its production - Google Patents

Abstract

PURPOSE:To obtain the subject compound having excellent heatresistance and scarcely containing volatile low-molecular siloxane causing environmental pollution by polymerizing a fluorine-containing cyclo}risiloxane, etc., in the presence of a catalyst and removing volatile components from the product. CONSTITUTION:The objective compound of formula IV [X is H or group of formula V (R3 is univalent hydrocarbon group; (q) is 0-3); (m) is 15-4,000; (n) is integer satisfying the formula 0<=n/(n+m)<=0.1] containing <=50ppm of cyclic polysiloxane having a molecular weight of <=3,000 is produced by polymerizing (A) a fluorine-containing cyclotrisiloxane of formula I [R1 is univalent hydrocarbon group; Rf is fluorine-containing group such as group of formula II (R2 is CF(CF3), CF2CF2, etc.; (p) is 1-5)[ or a mixture of the component A and (B) a vinyl-containing cyclotrisiloxane of formula III in the presence of (C) a lithium silanolate catalyst, etc., and purifying the product by heating under reduced pressure and/or extracting with a solvent to remove volatile components.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluorine-containing chain polyorganosiloxane which does not contain a volatile low molecular weight siloxane and is excellent in heat resistance, and a method for producing the same.

[0002]

2. Description of the Related Art Polyorganosiloxane has a low surface tension and a low refractive index and is excellent in properties such as heat resistance, cold resistance, electric insulation, water repellency, releasability, defoaming property and chemical resistance. Therefore, it is used in a wide range of industrial fields. However, with the recent progress of technology, in order to meet higher requirements, development of polyorganosiloxane having various properties is required.

To meet some of these requirements, for example, polyorganosiloxane having a fluorine-containing organic group in the molecule is known. However, most of the fluorine-containing organic groups are 3,3,3-trifluoropropyl groups, and an organopolysiloxane having a longer-chain fluorine-containing organic group has the following formula:

[0004]

[Chemical 7] In the formula, a is an integer of 1 to 3, b is an integer of 1 to 5, c is an integer of 1 or 2, and R represents a divalent fluorine-free organic group having 3 to 10 carbon atoms, Organopolysiloxanes having a fluorine-containing organic group represented by the following formulas have only been known (JP-A-2-219829 and JP-A-2-219830).

However, in the long-chain fluorine-containing organic group represented by the above formula, the bonding portion of --CH ₂ --O--R-- is unstable under high temperature conditions, and thus the heat resistance of polyorganosiloxane is limited. Had the disadvantage.

Further, as a method for producing a polyorganosiloxane having a fluorine-containing organic group such as a long-chain fluoroalkyl group or a fluoropolyether group, cyclotrisiloxane having the fluorine-containing organic group is synthesized and used. Alone or with fluorine-free cyclotrisiloxane such as hexamethylcyclotrisiloxane, concentrated sulfuric acid, activated clay, acid-treated activated clay, alkali metal hydroxide or silanolate, quaternary ammonium hydroxide,
A method of polymerizing in the presence of a catalyst such as quaternary phosphonium hydroxide can be considered. However, in this method, since a depolymerization reaction also occurs, it is difficult to obtain the target polymer in a high yield, and the copolymerization of fluorine-containing cyclotrisiloxane and fluorine-free cyclotrisiloxane is difficult. In this case, it was also difficult to obtain a polyorganosiloxane in which a fluorine-containing organic group was uniformly introduced into each molecule due to the difference in reactivity between the two.

Furthermore, in the above-mentioned production method, in order to cause the depolymerization reaction, cyclic siloxanes and low-molecular chain siloxanes are by-produced in addition to the objective polymer chain siloxane, and in particular, the cyclic siloxane is a trimer. To continuously generate tens of tens. Of these, low-molecular chain siloxanes and cyclic siloxanes having a low degree of polymerization can be removed by heating the polymer under reduced pressure, but removal of 10-mer or more, especially 20-mer or more cyclics is very difficult. Have difficulty. Therefore, the polyorganosiloxane polymer thus obtained is used in the form of an oil, a rubber-like cured product, a coating film, or the like by a known technique, and the cyclic organopolysiloxane contained in the organopolysiloxane is used. Siloxane gradually volatilizes and bleeds from oils, rubber-like cured products, coatings, etc., causing electrical contact troubles in the electric field and surrounding pollution in the construction material field.

As a method for producing a polyorganosiloxane that does not form a low-molecular siloxane or a cyclic siloxane as a by-product, for example, the following formula:

[0009]

[Chemical 8] [In the formula, M is an alkali metal, A is a Si atom or a boron atom, Q ¹ and Q ² are monovalent hydrocarbon groups such as an alkyl group, and u is 1 when A is Si and 1 is A. When boron is 0, v is an integer of 0 to 2], a method of polymerizing hexamethylcyclotrisiloxane and the like using a catalyst represented by (Japanese Patent Publication No. 45-1070) is proposed. U.S. Pat. No. 3,445,426). However, it has been clarified that 400 ppm or more of a 10-mer or more cyclic siloxane is produced even if such a catalyst is used.

Further, a method for producing a monodisperse polyorganosiloxane by homopolymerization of hexamethyltrisiloxane using lithium silanolate or an organic lithium compound as a catalyst, or block copolymerization of hexamethyltrisiloxane and hexaphenyltrisiloxane is also available. Known (Japanese Patent Publication No. 46-27267, EEBostick, ACS PolymerPrep)
rint, 10 (2), 877 (1969), JP-A-1-294738, etc.). However, similarly to the above, this method also inevitably produces a 10-mer or more cyclic siloxane at a ratio of 2000 ppm or more.

Further, a method of removing low-molecular siloxanes and cyclic siloxanes by means of stripping by reduced pressure and heating, solvent extraction, etc. has been carried out (for example, JP-A-64-6930).
(See No. 6), this method improves the purification level, for example, how much of the contained cyclic compounds can be cut, and does not prevent by-products such as cyclic siloxanes.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fluorine-containing chain polyorganosiloxane having excellent heat resistance. Another object of the present invention is to provide a method for producing a fluorine-containing chain polyorganosiloxane that is substantially free of cyclic siloxane and low molecular weight siloxane.

[0013]

According to the present invention, the following general formula (1):

[Chemical 9] [In the formula, R ¹ represents an unsubstituted or substituted monovalent hydrocarbon group, and Rf represents the following formula (1a):

[Chemical 10] Or the following formula _{(1b): C L F 2L} + 1 - (1b) ( wherein, R ² _{is, -CF (CF 3) -,} - CF 2 CF 2
- or -CF (CF ₃₎ CF ₂ - a and, p is 1
5 is an integer of 5 and L is an integer of 1 to 20), and X is a hydrogen atom or the following formula (1
c):

[Chemical 11] (Wherein R ³ is an unsubstituted or substituted monovalent hydrocarbon group, q is an integer of 0 to 3), and m is 15
Is an integer of up to 4000, and n is 0 ≦ n / (n + m) ≦ 0.1
Of a cyclic polysiloxane having a molecular weight of 3,000 or less, and a chain polyorganosiloxane having a content of 50 ppm or less.

According to the present invention, the following general formula (2):

[Chemical 12] (Wherein R ¹ and Rf are the same as above), or the fluorine-containing cyclotrisiloxane and the following general formula (3):

[Chemical 13] (Wherein R ¹ is the same as the above), and a mixture with a vinyl-containing cyclotrisiloxane represented by the formula:

[Chemical 14] [In the formula, R ⁴ and R ⁵ are monovalent organic groups, and M is
Selected from (R ⁶ ) ₄ N, (R ⁶ ) ₄ P and alkali metal atoms (wherein R ⁶ is a monovalent organic group), A is
Represents Si or a boron atom, s is 1 when A is Si, 0 when A is a boron atom, and t is an integer of 0 to 2]. A method for producing a chain polyorganosiloxane represented by the general formula (1), which has a step of subjecting the obtained polymerization product to a heating treatment under reduced pressure and / or a purification treatment by solvent extraction to remove a volatile component, Provided.

Chain Polyorganosiloxane The chain polyorganosiloxane of the present invention is represented by the above general formula (1), and as is clear from the formula,
The linear or polyether perfluoro group represented by Rf is bonded to the Si atom by an ethylene group, and thus has a structure with high thermal stability. The chain polyorganosiloxane uses the fluorine-containing cyclotrisiloxane represented by the general formula (2) and anion ring-opening using a lithium silanolate catalyst or a catalyst represented by the general formula (4). It is produced by polymerization, and depolymerization and rearrangement of siloxane during polymerization are extremely suppressed. Therefore, the perfluoro group represented by Rf in the fluorine-containing cyclotrisiloxane is siloxane 3 in the molecule. The feature is that one is introduced for each unit.

In the above general formula (1), the unsubstituted or substituted monovalent hydrocarbon group R ¹ is, for example, a methyl group,
Alkyl groups such as ethyl, propyl, butyl, pentyl, hexyl, etc., vinyl, allyl, alkenyl such as hexenyl, phenyl, aryl such as tolyl, benzyl, phenylethyl, etc. Aralkyl groups, and groups in which some or all of the hydrogen atoms of these groups have been replaced with halogen atoms, such as chloromethyl groups, 3,3,
Examples thereof include a 3-trifluoropropyl group. Among these, those having 1 to 6 carbon atoms, particularly methyl group, phenyl group and the like are preferable.

Further, Rf is the above formula (1a) or (1b)
Is a fluorine-containing organic group represented by. Specific examples of the fluorine-containing organic group represented by the formula (1a) include the followings.

[0018]

[Chemical 15]

Examples of the fluorine-containing organic group represented by the formula (1b) include CF ₃ −, C ₄ F ₉ −, C ₈ F ₁₇ − and the like.

X is a hydrogen atom or a group represented by the above formula (1c), and in the formula (1c), R ³ is an unsubstituted or substituted monovalent hydrocarbon group such as a methyl group or an ethyl group. , Alkyl groups such as propyl group, vinyl group, allyl group,
Examples include alkenyl groups such as hexenyl group, and groups in which a part of hydrogen atoms of these groups are substituted with halogen atoms, cyano groups, alkoxy groups, etc., such as chloroethyl group, chloropropyl group, cyanoethyl group, methoxyethyl group and the like. be able to. In particular, as R ³ , those having 1 to 8 carbon atoms are preferable among the above.

In the general formula (1), m is 15 to 4000.
And n is an integer satisfying 0 ≦ n / (n + m) ≦ 0.1.

The chain organopolysiloxane of the present invention described above has functional groups such as vinyl group, hydroxyl group and alkoxy group at both ends and side chains, and is addition-cured by using a suitable crosslinking agent and catalyst. The cured product can be formed by a known method such as condensation curing or peroxide curing.

Method for Producing Chain Polyorganosiloxane The chain polyorganosiloxane of the present invention comprises the fluorine-containing cyclotrisiloxane represented by the above general formula (2), or the fluorine-containing cyclotrisiloxane and the above general formula (3). )
It is produced by using a mixture with a vinyl-containing cyclotrisiloxane represented by as a starting material. That is, these raw materials are heated and polymerized in the presence of a lithium silanolate catalyst or a catalyst represented by the above-mentioned general formula (4), and if necessary, a catalyst inactivation treatment and a silylation treatment are carried out, followed by polymerization formation. The chain organopolysiloxane represented by the above general formula (1) can be obtained by purifying the product and removing the volatile components.

(Starting material) n in the general formula (1)
In the case of producing a chain organopolysiloxane in which is 0, the fluorine-containing cyclotrisiloxane of the general formula (2) is used alone as a starting material, and when n is 1 or more. Uses the fluorine-containing cyclotrisiloxane of the general formula (2) and the vinyl-containing cyclotrisiloxane of the general formula (3) as starting materials.

In this manufacturing method, the above formula (2) is used.
It is extremely important to use the fluorine-containing cyclotrisiloxane represented by the formula (1), which effectively suppresses the formation of a 10-mer or more cyclic siloxane during the polymerization using a catalyst such as lithium silanolate. Is a successful one. That is, as described above, when hexamethyltrisiloxane is used as a raw material, a cyclic siloxane having a decamer of 10 or more is produced at a ratio of several hundred ppm or more. It is presumed that the use of the fluorine-containing cyclotrisiloxane represented by the above formula (2) greatly contributes to the suppression of the formation of a cyclic body during polymerization. The reason for this is not exactly clear, but it is considered that this is because the reactivity of the three siloxane bonds in the molecule of the fluorine-containing cyclotrisiloxane is not equivalent.

Therefore, the polymerization product obtained by polymerizing such a fluorine-containing cyclotrisiloxane as a starting material does not substantially contain a 10-mer or more cyclic siloxane, but contains a trace amount thereof. Since the cyclic siloxane and low-molecular-weight siloxane having less than 10 mers are contained in trace amounts, they are easily removed by the purification treatment described later.

In the production method of the present invention, the most preferred examples of the fluorine-containing cyclotrisiloxane represented by the above general formula (2) include those represented by the following formula.

[0028]

[Chemical 16]

The amount of the fluorine-containing cyclotrisiloxane used is such that m in the general formula (1) is in the range described above (15 to 400).
It is set so as to be in the range of 0) according to the polymerization conditions and the like. Further, this fluorine-containing cyclotrisiloxane can be obtained, for example, by subjecting a dichlorosilane compound having a fluorine-containing group corresponding thereto to a disiloxane such as tetramethyldisiloxanediol, as shown in the following formula. Can be manufactured

[0030]

[Chemical 17]

Examples of the dehydrochlorinating agent used here include tertiary amines such as triethylamine and cyclic amines containing no active hydrogen such as pyridine.

The most preferable example of the vinyl-containing cyclotrisiloxane of the formula (3) used in the case of producing a chain organopolysiloxane in which n in the general formula (1) is 1 or more is the following formula. There may be mentioned those represented.

[0033]

[Chemical 18]

The amount of the above-mentioned vinyl-containing cyclotrisiloxane used is such that n in the general formula (1) is in the above-mentioned range, that is, 0 ≦.
The number is set according to the polymerization conditions and the like so that the number satisfies n / (n + m) ≦ 0.1.

(Polymerization catalyst) In the present invention, as the lithium silanolate used as a polymerization catalyst, for example, the following are preferably used.

[0036]

[Chemical 19]

The amount of this lithium silanolate used is not particularly limited and is set according to the degree of polymerization of the target chain organopolysiloxane. Generally, all of the fluorine-containing cyclotrisiloxane of the general formula (2) which is the starting material
It is used in an amount such that the Si atom / catalyst molecule (molar ratio) is about 100 to 10,000.

In the present invention, in addition to the above lithium silanolate catalyst, the catalyst represented by the above general formula (4) can be used. This catalyst is suitable when the above-mentioned fluorine-containing cyclotrisiloxane of the general formula (2) is used alone as a starting material, and in particular, a chain organopolysiloxane (X in the general formula (1) is a hydrogen atom ( That is, it is most preferably used when synthesizing silanol at the terminal).

In the general formula (4), R ^{4 to} R ⁶ which are monovalent organic groups may be the same or different, and examples thereof include alkyl groups such as methyl group, ethyl group, propyl group and octadecyl group, Cycloalkyl groups such as cyclohexyl group, aliphatic unsaturated groups such as vinyl group, allyl group, ethynyl group, aryl groups such as phenyl group, tolyl group, xenyl group, aralkyl groups such as benzyl group, phenylethyl group, and the like. Examples of the group include a group obtained by substituting a part or all of hydrogen atoms of the group with a halogen atom or the like, for example, a chloromethyl group, a chloroethyl group and the like. As the catalyst represented by the general formula (4), the following can be given as examples of catalysts that are particularly preferably used.

[0040]

[Chemical 20]

The polymerization catalyst represented by the above general formula (4) is usually used in an amount of 0.05% by weight or less, particularly 0.001 to 0.02% by weight, based on the fluorine-containing cyclotrisiloxane of the general formula (2). Is desirable.

(Polymerization Conditions) In the present invention, the polymerization reaction using the above-mentioned polymerization catalyst is usually carried out for several minutes depending on the molecular structure of the target chain organopolysiloxane and the kind of the polymerization catalyst. It is carried out by setting the polymerization conditions so that the polymerization time is within 10 hours to several tens hours, preferably within 10 hours. For example, when a lithium silanolate catalyst is used, the polymerization temperature is preferably set to 150 ° C. or lower, and particularly preferably set to 20 to 100 ° C. In particular, the chain-like organopolyene in which X in the general formula (1) is a hydrogen atom is used. 40 to 150 ℃ when siloxane is used,
It is particularly preferable to set the temperature to 60 to 110 ° C. When the catalyst represented by the general formula (4) is used, it is desirable to set the polymerization temperature to a temperature not higher than the decomposition temperature of the catalyst and 25 to 200 ° C, particularly 50 to 150 ° C. No matter which catalyst is used, if the polymerization temperature is too high, the equilibration reaction may increase the production of low molecular weight cyclic compounds, so care must be taken.

The polymerization reaction can be carried out in a non-solvent system or a solvent system, but when the polymerization catalyst of the general formula (4) is used, it is preferably carried out in the presence of a polar solvent. As the polar solvent, acetonitrile, dimethyl sulfone, tetramethylene sulfone, diethyl sulfone, methylpropyl sulfone and the like are preferably used,
The amount used is such that the polymerization catalyst of general formula (4) is sufficiently dissolved. Further, as a solvent that can be used when performing a polymerization reaction using a lithium silanolate catalyst,
Suitable aprotic solvents such as tetrahydrofuran, dioxane, diglyme, and tetraglyme, and fluorine-based and chlorine-based inert solvents such as freon, metaxylene hexafluoride, methylene chloride, and trichloroethane are suitable.

Further, in the case of aiming at a chain organopolysiloxane in which X in the general formula (1) is a hydrogen atom, the polymerization reaction is carried out in the presence of a small amount of water in order to terminate the molecular chain end with a silanol group. It is desirable to do in. In this case, water is mixed with a hydrophilic solvent such as dioxane, diglyme, or THF, and Si / H ₂ O = 20 to 6000 is added to the reaction system.
The concentration may be about (molar ratio).

(Deactivation of catalyst) Since the reaction mixture obtained by the above-mentioned polymerization usually contains a polymerization catalyst, the polymerization product is stabilized by deactivating the polymerization catalyst. Is desirable.

For the deactivation of the catalyst, for example, when lithium silanolate is used as a polymerization catalyst, the catalyst is neutralized by mixing an acidic substance such as dilute hydrochloric acid, dilute sulfuric acid, phosphoric acid, acetic acid or tetrachloroethane. This is easily done by doing. Usually, the amount of the acidic substance used is preferably about 2 to 5 times the amount of the lithium silanolate used. When polymerization is carried out using the catalyst of the general formula (4), heating to a temperature of 200 ° C. or higher, carbon dioxide gas,
The catalyst can be deactivated by adding a weak acid such as acetic acid to the polymerization product.

After the above treatment, the formed salt or excess acidic substance is removed from the polymerization product to give a chain organopolysiloxane terminated with silanol groups, that is, X in the general formula (1) is a hydrogen atom. You get what is.

(Silylation) In the present invention, when the chain organopolysiloxane in which X in the general formula (1) is a triorganosilyl group represented by the formula (1c) is intended, it is obtained as described above. The polymerized product is silylated. This silylation is represented by the following general formula (5):

[Chemical 21] In the formula, R ³ and q are the same as those described above, and Y is a hydrolyzable group.

In the above general formula (5), examples of the hydrolyzable group Y include a halogen atom such as chlorine and an alkoxy group such as methoxy group and ethoxy group. Typical examples of such a silylating agent include the following.

[0050]

[Chemical formula 22] Triorganohalosilanes, etc.

[0051]

[Chemical formula 23] And other triorganoalkoxysilanes.

[0052]

[Chemical formula 24] Such as triorganoacetoxysilane.

[0053]

[Chemical 25] Such as triorganoacyloxysilane.

The amount of the silylating agent used is preferably about 1 to 5 times the molar amount of the catalyst used for the polymerization, and the reaction temperature is 1
0 to 100 ° C. is preferable, and the reaction time is preferably about 2 to 20 hours.

When triorganohalosilane is used among the above silylating agents, the following general formula (6):

[Chemical formula 26] In the formula, it is preferable to use a disilazane compound represented by the following formula in which R ³ and q are the same as above. When this disilazane compound is used in combination, there is an advantage that the silylation can be carried out immediately after the completion of the polymerization without carrying out the above-mentioned neutralization treatment of the polymerization catalyst. In this case, the amount of triorganohalosilane used is 1 to 3 times the molar amount of the catalyst,
The amount of the disilazane compound used is preferably about 1.5 to 4.5 times the mol of the catalyst. The following can be illustrated as a typical thing of such a disilazane compound.

[0056]

[Chemical 27]

(Purification) According to the present invention, purification is carried out after the above-mentioned catalyst inactivation or silylation treatment to remove low-molecular siloxanes such as cyclic siloxanes having a degree of polymerization of less than 10, thereby obtaining the object. The chain organopolysiloxane represented by the general formula (1) can be obtained.

In this purification, the reaction mixture after the above treatment was
It is carried out by heating to 100 ° C. or higher under a reduced pressure condition of 10 ⁻¹ mmHg or lower. In this case, when the target is a chain organopolysiloxane whose molecular chain terminals are triorganosilylated, the heating temperature is preferably in the range of 200 to 300 ° C. Further, when the intended product is a chain organopolysiloxane whose molecular chain ends are silanol groups, the heating temperature is preferably in the range of 100 to 180 ° C. This is because if it is heated to an excessively high temperature, the silanol groups at the ends of the molecular chains will be condensed. In addition, such purification by heating under reduced pressure,
For example, it can be suitably carried out using a thin film type evaporator.

Further, instead of the heating under the above-mentioned reduced pressure condition or in combination therewith, the solvent extraction may be carried out to carry out the purification. Here, the extraction solvent is not particularly limited as long as it dissolves the low-molecular siloxane but does not dissolve the target chain organopolysiloxane and does not break the polymer chain, and various solvents can be used. be able to. Generally, polar solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbon solvents such as toluene and xylene are preferably used. After removing the low-molecular-weight siloxane by solvent extraction, the target chain organopolysiloxane can be obtained by removing the remaining solvent by reducing the pressure.

[0060]

EXAMPLES In the following examples, the viscosity is a value measured at 25 ° C. Example 1 In a 1 liter separa flask equipped with a stirrer, the following formula:

[Chemical 28] 1000 g (1.458 mol) of cyclotrisiloxane represented by

The following formula:

[Chemical 29] 23.2 g (0.0292 mol) of lithium silanolate represented by and tetraglyme 1.0 g are added, and the mixture is placed under a nitrogen atmosphere.
The temperature was raised to 100 ° C. and the reaction was carried out for 5 hours.

Then, the temperature is lowered, and at the temperature of 50 ° C., the following formula:

[Chemical 30] 5.3 g (0.438 mol) of halosilane represented by

The following formula:

[Chemical 31] Then, 12.2 g (0.0657 mol) of disilazane represented by the following formula was added and the mixture was stirred for 2 hours for neutralization and silylation.

Thereafter, vacuum stripping was carried out at 150 ° C., and then salt was filtered to obtain 983 g (viscosity 798 cs) of polysiloxane. This polysiloxane was dissolved in trichlorotrifluoroethane (Freon 113) (concentration 1
%), And when subjected to GPC analysis, the chart of FIG. 1 was obtained. In this chart, peak 1 derived from the polymer
The area of is about 98%.

Next, this organopolysiloxane was mixed with 270
° C., followed by purification through at 1 × 10 ^-4 mmHg in thin-film type molecular distillation apparatus, purified organopolysiloxane 951 g (viscosity 1160
cSt) was obtained. When this purified organopolysiloxane was subjected to GPC analysis in the same manner as described above, G shown in FIG.
A PC chart was obtained. From this chart, it was found that the area of the peak 4 derived from the polymer was 100% and contained almost no cyclic polysiloxane (peaks 2 and 3).

Next, in order to quantify the cyclic polysiloxane, 1.0 g of the produced organopolysiloxane was placed in a glass bottle with a lid.
As an internal standard, 10.0 g of acetone containing 20 ppm of n-decane was added, and after shaking and standing for 24 hours, the cyclic polysiloxane extracted in the acetone layer was detected by a flame ionization detector (FI).
It was 1 ppm or less when detected by D). The measurement conditions are as follows. Equipment used: Shimadzu GC-14A Column: GL capillary column TC-1701 0.53 mm ×
30m temperature raising condition: initial temperature 70 ° C (1 minute), temperature raising rate 15K /
Min, final temperature 270 ℃ (hold 40 minutes)

Furthermore, the purified organopolysiloxane obtained above was subjected to infrared absorption spectrum, ¹ H-NMR spectrum measurement and vinyl group quantification, and the following results were obtained. Infrared absorption spectrum: shown in Fig. 3. Characteristic absorption 1000 to 1130 cm ^-1 (Si-O-Si) 2970, 1260, 810 cm ^-1 (Si-CH ₃ ) 1000 to 1400 cm ^-1 (CF) ¹ H-NMR: (Freon 113 solvent) 0.75 to 1.62 ppm _{(m -CH 2 -Si- 2H) 1.83~2.82} ppm (m -CH 2 -CF 2H) 0.20~0.52 ppm (m -Si- CH 3 15H) vinyl group determination: According to GC-MS. Amount of terminal vinyl group 0.0055mol / 100g (Theoretical value 0.0057mol / 100g)

From the above results, it is recognized that the obtained organopolysiloxane is a chain organopolysiloxane represented by the following average molecular formula:

[Chemical 32]

Example 2 As the fluorine-containing cyclotrisiloxane, the following formula:

[Chemical 33] Using 1000 g (2.203 mol) of the compound represented by the following formula as lithium silanolate:

[0070]

[Chemical 34]

Polymerization reaction was carried out in the same manner as in Example 1 except that 12.4 g (0.02203 mol) of the compound represented by The amount of halosilane used was 4.0 g (0.033 mol) and the amount of disilazane used was 9.2 g (0.0496 g).
Neutralization and silylation were performed in the same manner as in Example 1 except that The polymer obtained was purified in the same manner as in Example 1 to remove the cyclic polysiloxane, and 963 g (3,340 cSt) of organopolysiloxane was obtained. When FID was detected in the same manner as in Example 1, the amount of cyclic polysiloxane was 23 ppm.
It was below.

Further, when the infrared absorption spectrum and ¹ H-NMR spectrum were measured and the terminal vinyl group was quantified, the following results were obtained. Infrared absorption spectrum: shown in Figure 4. Characteristic absorption 1000 to 1130 cm ^-1 (Si-O-Si) 2970, 1260, 810 cm ^-1 (Si-CH ₃ ) 1000 to 1450 cm ^-1 (CF) ¹ H-NMR: (Freon 113 solvent) 0.72 to 1.60 ppm (M -CH ₂ -Si-2H) 1.74 to 2.80 ppm (m -CH ₂ -CF 2H) 0.15 to 0.61 ppm (m -Si- CH ₃ 15H) Amount of vinyl end group Theoretical value 0.0043 mol / 100 g Measured value 0.0042 mol / 100g

From the above results, it is recognized that the obtained organopolysiloxane is a chain organopolysiloxane represented by the following average molecular formula.

[Chemical 35]

Example 3 As the fluorine-containing cyclotrisiloxane, the following formula:

[Chemical 36] Using 1000 g (1.458 mol) of the compound represented by, the following formula as lithium silanolate:

[0075]

[Chemical 37] Polymerization reaction was carried out in the same manner as in Example 1 except that 11.9 g (0.01458 mol) of the compound represented by Also, except that the amount of halosilane used was 2.6 g (0.0219 mol) and the amount of disilazane used was 6.1 g (0.0328 g),
Neutralization and silylation were carried out in the same manner as in Example 1.

The polymer obtained was subjected to solvent extraction several times with 2,000 g of acetone to remove the cyclic polysiloxane, and finally the solvent was distilled off under a reduced pressure condition of 150 ° C./2 mmHg to obtain 938 g (3,570 g). An organopolysiloxane of cSt) was obtained. When FID was detected in the same manner as in Example 1, the amount of cyclic polysiloxane was 1 ppm or less.

Further, when the infrared absorption spectrum and ¹ H-NMR spectrum were measured and the terminal vinyl group was quantified, the following results were obtained. Infrared absorption spectrum: shown in Figure 5. Characteristic absorption 1000 to 1300 cm ^-1 (Si-O-Si) 2970, 1260, 810 cm ^-1 (Si-CH ₃ ) 1000 to 1450 cm ^-1 (CF) ¹ H-NMR: (Freon 113 solvent) 0.77 to 1.73 ppm (M -CH ₂ -Si-2H) 2.03 to 2.87 ppm (m -CH ₂ -CF 2H) 0.02 to 0.70 ppm (m -Si- CH ₃ 15H) Terminal vinyl group content 0.0055 mol / 100 g theoretical 0.0058 mol / 100g

From the above results, it is recognized that the obtained organopolysiloxane is a chain organopolysiloxane represented by the following average molecular formula.

[Chemical 38]

Comparative Example 1 In Example 1, 1000 g (4.505 mol) of hexamethylcyclotrisiloxane was used as the cyclotrisiloxane, and the following formula was used as the lithium silanolate:

[Chemical Formula 39] Polymerization reaction was carried out in the same manner except that 24.9 g (0.045 mol) of the compound represented by was used. Neutralization and silylation were performed in the same manner as in Example 1 except that the amount of halosilane used was 8.1 g (0.0675 mol) and the amount of disilazane used was 18.7 g (0.101 mol).

The polymer obtained was purified in the same manner as in Example 1 to remove the cyclic polysiloxane, and 891 g (2410 cSt) of dimethylpolysiloxane was obtained. When FID was detected in the same manner as in Example 1, 583 ppm of cyclic polysiloxane having a content of 15-mer or more remained.

Example 4 A 1 liter four-necked flask equipped with a stir bar, thermometer and reflux condenser was charged with the following formula:

[Chemical 40] 1000 g (1.46 mol) of cyclotrisiloxane represented by

0.75 g (0.02 mol) of 40% THF solution in water,
Charge 1.0 g of tetraglyme, raise the temperature to 100 ° C, and then use the following formula:

[Chemical 41] 5% THF solution of lithium silanolate represented by 19.2
g (5.4 × 10 ⁻³ mol) was added and the reaction was carried out for 5 hours.

After the reaction, the mixture was cooled to 80 ° C., 8.9 g of tetrachloroethane was added, neutralization was carried out for 3 hours, the salts were filtered off, and the solvent and the like were distilled off under reduced pressure. Furthermore, 150 ° C / 1 ×
When it was passed through a thin film distillation apparatus at 10 ^-5 Torr, it was colorless and transparent, and had an viscosity of 5,286 cSt, a refractive index of 1.3442, a specific gravity of 1.41, and a silanol group content of 0.006 mol / 100 g. A siloxane was obtained.

With respect to the organopolysiloxane obtained above, the amount of cyclic polysiloxane was determined in the same manner as in Example 1. The content was 1 ppm or less.

Further, infrared absorption spectrum and ¹ H-NMR
The spectrum was measured. The measurement results are shown below. Infrared absorption spectrum: A chart is shown in FIG. Characteristic absorption 990 to 1130 cm ^-1 (Si-O-Si) 2970, 1260, 800 cm ^-1 (Si-CH ₃ ) 990 to 1400 cm ^-1 (CF) ¹ H-NMR spectrum δ: 0.75 to 1.60 ppm (m- CH ₂ -Si-2H) 1.83 to 2.83 ppm (m -CH ₂ -CF 2H) 0.21 to 0.52 ppm (m Si-CH ₃ 15H)

From the above results, it is recognized that the obtained organopolysiloxane is a chain organopolysiloxane represented by the following average molecular formula.

[Chemical 42]

Example 5 In a four-necked flask, the following formula:

[Chemical 43] 100 g (0.15 mol) of cyclotrisiloxane represented by

A 40% THF solution of water (0.05 g, 1.1 × 10 ^-3 mol) and tetraglyme (0.1 g) were charged, the temperature was raised to 100 ° C., and the same 5% THF solution of Li silanolate as in Example 4 was added.
0.99 g (2.78 × 10 ^-4 mol) was added and a polymerization reaction was carried out for 5 hours.

After the reaction, the mixture was neutralized with 0.4 g of tetrachloroethane, and the same procedure as in Example 1 was carried out to give a colorless and transparent solution.
There was obtained organopolysiloxane having silanol groups terminated at 8,209 cSt, a refractive index of 1.3444, a specific gravity of 1.41, and a silanol group content of 0.004 mol / 100 g. When the amount of cyclic polysiloxane was determined in the same manner as in Example 1, it was found to be 15
It was ppm.

Furthermore, infrared absorption spectrum and ¹ H-NMR
The spectrum was measured. The measurement results are shown below. Infrared absorption spectrum: A chart is shown in Fig. 7. Characteristic absorption 990 to 1130 cm ^-1 (Si-O-Si) 2970, 1260, 800 cm ^-1 (Si-CH ₃ ) 990 to 1380 cm ^-1 (CF) ¹ H-NMR spectrum δ: 0.77 to 1.73 ppm (m- CH ₂ -Si-2H) 2.03 to 2.87 ppm (m -CH ₂ -CF 2H) 0.02 to 0.70 ppm (m CH ₃ -Si 15H)

From the above results, it is recognized that the obtained organopolysiloxane is a chain organopolysiloxane represented by the following average molecular formula.

[Chemical 44]

Example 6 In a four-necked flask, the following formula:

[Chemical formula 45] Fluorinated cyclotrisiloxane represented by 100 g (0.22
Mol),

A 40% THF solution of water (0.4 g, 8.80 × 10 ^-3 mol) and tetraglyme (0.1 g) were charged, the temperature was raised to 100 ° C., and the same 5% THF solution of Li silanolate as in Example 4 was added.
0.705 g (1.98 × 10 ^-4 mol) was added and the reaction was carried out for 5 hours.

After the reaction, the mixture was neutralized with 0.3 g of tetrachloroethane, and the same procedure as in Example 1 was carried out to give a colorless transparent resin: viscosity
An organopolysiloxane having a terminal silanol group and having a silanol group content of 3,611 cSt, a refractive index of 1.3673, a specific gravity of 1.27, and a silanol group content of 0.009 mol / 100 g was obtained. When the amount of cyclic polysiloxane was determined in the same manner as in Example 1, it was 1 pp.
It was less than m.

Further, infrared absorption spectrum and ¹ H-NMR
The spectrum was measured. The measurement results are shown below. Infrared absorption spectrum: A chart is shown in FIG. Characteristic absorption 990 to 1140 cm ^-1 (Si-O-Si) 2970, 1260, 800 cm ^-1 (Si-CH ₃ ) 990 to 1450 cm ^-1 (CF) ¹ H-NMR spectrum δ: 0.72 to 1.58 ppm (m- CH ₂ -Si-2H) 1.75 to 2.82 ppm (m -CH ₂ -CF 2H) 0.15 to 0.62 ppm (m CH ₃ -Si 15H)

From the above results, it is recognized that the obtained organopolysiloxane is a chain organopolysiloxane represented by the following average molecular formula.

[Chemical formula 46]

Example 7 In a four-necked flask, the same fluorine-containing cyclotrisiloxane as in Example 1 (100 g (0.15 mol), water 0.3 g (0.02 mol), 4 ml of dimethyl sulfoxide, the following formula:

[Chemical 47] Add 1.0 g of the silane compound represented by
When heated for a time, a viscous liquid could be obtained.

When thin film distillation was carried out in the same manner as in Example 4, it was colorless and transparent, had a viscosity of 5,443 cSt, a refractive index of 1.3442 and a specific gravity of 1.
41, a silanol group-terminated organopolysiloxane having a silanol group content of 0.006 mol / 100 g was obtained. When the amount of cyclic polysiloxane was determined in the same manner as in Example 1, it was 23 ppm.

Furthermore, infrared absorption spectrum and ¹ H-NMR
The spectrum was measured. The measurement results are shown below. Infrared absorption spectrum: Characteristic absorption 990 ~ 1140cm ^-1 (Si-O-Si) 2970, 1260, 800 cm ^-1 (Si-CH ₃ ) 990 ~ 1450cm ^-1 (CF) ¹ H-NMR spectrum δ: 0.76 ~ 1.62 ppm (m -CH ₂ -Si-2H) 1.80 to 2.91 ppm (m -CH ₂ -CF 2H) 0.19 to 0.59 ppm (m CH ₃ -Si 15H)

From the above results, it is recognized that the obtained organopolysiloxane is a chain organopolysiloxane represented by the following average molecular formula.

[Chemical 48]

Example 8 A 1 liter separa flask was charged with the following formula:

[Chemical 49] 1000 g (1.458 mol) of cyclotrisiloxane represented by

Pentamethylvinylcyclotrisiloxane
2.27 g (0.00972 mol) The following formula:

[Chemical 50] 7.7 g (0.00972 mol) of lithium silanolate represented by and 1.0 g of tetraglyme were charged, and the mixture was heated to 100 ° C. in a nitrogen atmosphere and reacted for 5 hours.

Then, the temperature was lowered, and at a temperature of 50 ° C., 1.76 g (0.01458 mol) of vinyldimethylchlorosilane and the following formula:

[Chemical 51] Add 4.05 g (0.022 mol) of disilazane represented by
The mixture was stirred for 2 hours and neutralized. After that, vacuum stripping was performed at 150 ° C, and then salt was filtered off.
4,150 cSt) of organopolysiloxane was obtained.

Next, this product was passed through a thin film type molecular distillation apparatus under the conditions of 270 ° C. and 1 × 10 ⁻⁴ mmHg.
15,010 cSt) of organopolysiloxane was obtained. When the amount of cyclic polysiloxane was determined for the above organopolysiloxane in the same manner as in Example 1, the content was
It was 1 ppm or less.

Further, the organopolysiloxane finally obtained above was analyzed by infrared absorption spectrum and ¹ H-NMR.
When the spectrum was measured and the vinyl group was quantified,
The following results were obtained. Infrared absorption spectrum: shown in Figure-9. Characteristic absorption 990 to 1130 cm ^-1 (Si-O-Si) 2970, 1260, 810 cm ^-1 (Si-CH ₃ ) 1000 to 1450 cm ^-1 (CF) ¹ H-NMR (Freon 113 solvent) 0.76 to 1.60 ppm ( _{m -CH 2 -Si- 2H) 1.83~2.81 ppm} (m -CH 2 -CF 2H) 0.21~0.52 ppm (m -CH 3 -Si 15H) vinyl group determination: According to GC-MS.

From the above results, it is recognized that the obtained organopolysiloxane is a chain organopolysiloxane represented by the following average molecular formula.

[Chemical 52]

Example 9 A fluorine-containing cyclotrisiloxane represented by the following formula:

[Chemical 53] The amount of pentamethylvinylcyclotrisiloxane used is 15.5 g, using 1000 g (2.203 mol)
(0.0661 mol),

Further, as lithium siliconate, the following formula:

[Chemical 54] After reacting in the same manner as in Example 8 except that 3.9 g (0.022 mol) of the compound represented by
Neutralize and post-process. The polymer obtained is at 200 ° C., 1
The cyclic polysiloxane was removed by passing through a thin film molecular distillation apparatus under the condition of × 10 ^-4 mmHg. Organopolysiloxane 936
g (3,800 cSt) was obtained. When this was subjected to FID detection in the same manner as in Example 1, the content of cyclic polysiloxane was 15 ppm.

Further, when the infrared absorption spectrum and ¹ H-NMR spectrum were measured and the side chain vinyl group was quantified, the following results were obtained. Infrared absorption spectrum: shown in Fig. 10. Characteristic absorption 1000 to 1130 cm ^-1 (Si-O-Si) 2970, 1260, 810 cm ^-1 (Si-CH ₃ ) 1000 to 1450 cm ^-1 (CF) ¹ H-NMR (Freon 113 solvent) 0.70 to 1.62 ppm ( m-CH ₂ -Si- 2H) 1.75 to 2.80 ppm (m -CH ₂ -CF 2H) 0.14 to 0.63 ppm (m CH ₃ -Si 15H) Side chain vinyl group content 0.0061 mol / 100 g theoretical 0.0065 mol / 100 g

From the above results, it is recognized that the obtained organopolysiloxane is a chain organopolysiloxane represented by the following average molecular formula.

[Chemical 55]

[0111]

The chain polyorganosiloxane of the present invention has the remarkable advantage that the content of the volatile low-molecular-weight siloxane contained as an impurity is suppressed to substantially zero or a remarkably small amount, For example, the molecular weight is 3,000
The content of 0 or less cyclic polysiloxane is 50 ppm or less. Therefore, when this chain polyorganosiloxane is used for various purposes, various problems caused by the presence of volatile low-molecular-weight siloxane, such as electrical contact trouble due to volatilization of low-molecular-weight siloxane from a rubber cured product (especially in the electrical field) ), Problems such as environmental pollution (especially in the field of construction) are effectively avoided.

[Brief description of drawings]

FIG. 1 is a view showing a GPC chart of an organopolysiloxane before purification in Example 1.

FIG. 2 is a view showing a GPC chart of the purified organopolysiloxane of Example 1.

3 is a view showing an IR chart of organopolysiloxane after purification in Example 1. FIG.

4 is a view showing an IR chart of the organopolysiloxane after purification in Example 2. FIG.

5 is a view showing an IR chart of the organopolysiloxane after purification in Example 3. FIG.

6 is a view showing an IR chart of the organopolysiloxane after purification in Example 4. FIG.

FIG. 7 shows an IR chart of the organopolysiloxane after purification in Example 5.

FIG. 8 is a view showing an IR chart of the organopolysiloxane after purification in Example 6.

9 is a view showing an IR chart of the organopolysiloxane after purification in Example 8. FIG.

FIG. 10 is a view showing an IR chart of the organopolysiloxane after purification in Example 9.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Koichi Yamaguchi Inventor Koichi Yamaguchi Matsuida-cho, Usui-gun Gunma No. 1 Hitomi 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Kenichi Fukuda Matsuida-cho, Usui-gun Gunma Daiji Hitomi 1-10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Yoshikazu Saito Matsui-cho, Usui-gun, Gunma Daiji Hitomi 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Kobayashi Nobuyuki 1 Hitomi, Oita, Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (2)

[Claims] 1. The following general formula (1): [In the formula, R ¹ represents an unsubstituted or substituted monovalent hydrocarbon group, and Rf represents the following formula (1a): Or the following formula _{(1b): C L F 2L} + 1 - (1b) ( wherein, R ² _{is, -CF (CF 3) -,} - CF 2 CF 2
- or -CF (CF ₃₎ CF ₂ - a and, p is 1
5 is an integer of 5, L is an integer of 1 to 20), X is a hydrogen atom or the following formula (1c): (Wherein R ³ is an unsubstituted or substituted monovalent hydrocarbon group, q is an integer of 0 to 3), m is an integer of 15 to 4000, and n is 0. ≦ n / (n + m) ≦ 0.1], and a chain polyorganosiloxane having a content of cyclic polysiloxane having a molecular weight of 3,000 or less of 50 ppm or less. 2. The following general formula (2): (Wherein R ¹ and Rf are the same as above), or the fluorine-containing cyclotrisiloxane and the following general formula (3): (Wherein R ¹ is the same as the above), a mixture with a vinyl-containing cyclotrisiloxane represented by the following formula is used as a lithium silanolate catalyst or the following general formula (4): [Wherein R ⁴ and R ⁵ are monovalent organic groups, and M is selected from (R ⁶ ) ₄ N, (R ⁶ ) ₄ P and an alkali metal atom (wherein R ⁶ is a monovalent group. Is an organic group of A), A represents Si or a boron atom, s is 1 when A is Si, is 0 when A is a boron atom, and t is an integer of 0 to 2] Polymerization using the catalyst described above, the resulting polymerized product is subjected to a purification treatment by heating under reduced pressure and / or solvent extraction to remove volatile components. Method for producing organosiloxane.