JP2512606B2 - Chlorinated cyclic dialkyl siloxane and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel chlorinated cyclic dialkylsiloxane and a method for producing the same.

(Problems to be Solved by Conventional Techniques and Inventions) Polyvinyl chloride resin (hereinafter abbreviated as PVC) has been applied to various fields because of its inexpensive and balanced physical properties. Recently, various improvements have been made by blending this PVC with various polymers in order to further enhance its physical properties and functions. Modification of PVC by blending with a silicone resin has already been carried out, for example, improvement of antifogging property of agricultural PVC film by addition of silicone oil (Japanese Patent Publication No. 63-12498, Japanese Patent Publication No. 59-39463, Japanese Patent Publication No. 53337/533), improvement of PVC thermal stability by the addition of silicone containing α-mercaptoester groups (Japanese Patent Laid-Open No. Sho 63-5)
No. 234054) is known.

The present inventors have conducted various studies on the effect of adding polydimethylsiloxane to PVC for the purpose of improving PVC. As a result, it has been found that the addition of polydimethylsiloxane to PVC improves the hot fluidity, which is a drawback of PVC. However, at this time, it was also clarified that polydimethylsiloxane significantly slowed down the gelation rate of PVC when kneaded with PVC, that is, significantly lowered the processability.

As described above, polydimethylsiloxane has a drawback of deteriorating the processability of PVC in spite of having an excellent ability as a flow improver of PVC. Therefore, it has the same effect of improving the fluidity of PVC as polydimethylsiloxane,
In addition, the appearance of a polysiloxane as a flowability improving agent for PVC, which has a better processability when kneading with PVC than that of adding polydimethylsiloxane, has been strongly desired.

(Means for Solving the Problems) The inventors of the present invention have conducted extensive studies to solve the above problems, and newly synthesized a compound obtained by chlorinating a cyclic dialkylsiloxane having a specific alkyl chain. PVC
The effect of addition to the above was investigated. As a result, the PVC added with the compound of the present invention is similar to the PVC added with polydimethylsiloxane.
It has been found that it has a fluidity at the same time as that of the above-mentioned, and has a workability superior to that of PVC to which polydimethylsiloxane is added, and has proposed the present invention.

That is, the present invention provides the following general formula [I] , And the number of chlorine atoms and hydrogen atoms contained in the molecule are m and n, respectively, Is 0.005 to 0.8 and is a chlorinated cyclic dialkyl siloxane.

In the general formula [I], R ¹ and R ² are an alkyl group having 5 to 16 carbon atoms which may be substituted with a chlorine atom. When the carbon number is less than 5, the fluidity improving effect is small, and when the carbon number exceeds 16, the synthetic yield of the compound of the present invention is lowered, which is not preferable. As the alkyl group having 5 to 16 carbon atoms, specifically, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl Groups. As will be described later, these alkyl groups have a number of chlorine atoms and hydrogen atoms contained in the chlorinated cyclic dialkylsiloxane of the present invention which are m and n, respectively, It is substituted with chlorine atoms so that (hereinafter referred to as chlorination degree) is in the range of 0.005 to 0.8. Accordingly, in the above general formula [I], the alkyl group having 5 to 16 carbon atoms which may be substituted with a chlorine atom represented by R ¹ and R ² is represented by the following general formula.

−C _x H _{2x + 1-y} Cl _y The substitution position of the chlorine atom is the same as in the production method b) of the compound of the present invention to be described later. In the method of adding dichlorosilane to a chlorinated olefin, followed by hydrolysis and condensation, substitution of chlorine as a chlorinated olefin as a raw material is performed. When the one with a clear position is used, it can be identified from the raw material. On the other hand, when the method of chlorinating a cyclic dialkylsiloxane as in the method a) for producing a compound of the present invention described below is adopted, chlorine atoms are randomly introduced, so that the substitution position of chlorine atoms is strictly determined. it is difficult to, ¹³ C-nuclear magnetic resonance spectrum (hereinafter, abbreviated as ¹³ C-NMR) makes it possible to some extent determine the number and partial structures of the chlorine atoms in R ¹ and R ^2. That is, when the degree of chlorination is about 0.025, the number of chlorine atoms contained in the chlorinated alkyl group is 0 or 1, and only one chlorine atom is contained. Presence of Cl unit can be confirmed. When the degree of chlorination is about 0.075, there are multiple chlorinated alkyl groups. Cl units will be included, No units can be seen. When the degree of chlorination further reaches about 0.16, chlorinated alkyl groups Units will be included.

The alkyl group having 5 to 16 carbon atoms which may be substituted with a chlorine atom represented by R ¹ and R ² in the general formula (I) is
The number of carbon atoms, the number of substituted chlorine atoms and the substitution position may be the same or different, and a plurality of R ¹ and R ² present in one molecule are each R ¹ and each R ^The number of carbon atoms, the number of substituted chlorine atoms, and the substitution position may be the same or different between the ^two .

1 in the general formula [I] is 3 or 4. l is 2
The compounds below and 5 or more are difficult to synthesize.

The chlorinated cyclic dialkyl siloxane of the present invention has the following formula, where the numbers of chlorine atoms and hydrogen atoms contained in the molecule are m and n, respectively: (Chlorination degree) is in the range of 0.005 to 0.8. Chlorination degree is 0.
When it is less than 005, the fluidity-improving effect is exhibited, but it is not preferable because the processability-improving effect is not observed, and when the chlorination degree exceeds 0.8, the processability-improving effect is exhibited but the fluidity-improving effect is exhibited. Is not preferable because it is not observed.
In order for both the workability improving effect and the fluidity improving effect to be exhibited in a well-balanced manner, the above chlorination degree is 0.01 to 0.8.
The range is more preferably 0.03 to 0.5.

The structure of the compound of the present invention can be confirmed by the following method.

(1) Measurement of infrared absorption spectrum (hereinafter abbreviated as IR) When the IR of the chlorinated cyclic dialkylsiloxane of the present invention is measured, absorption based on an aliphatic carbon-hydrogen bond appears at around 3,000 to 2,850 cm ^-1. . Furthermore, when the chlorinated cyclic dialkyl siloxane is a cyclic trimer, it becomes 1,005 cm ^-1 ,
Also, when it is a cyclic tetramer, absorption due to the bond to Si-O appears at 1,080 cm ^-1 .

(2) Elemental analysis By performing elemental analysis of the chlorinated cyclic dialkylsiloxane of the present invention, the weight percentage of carbon, hydrogen and chlorine can be found.

^{(3) 13 C-NMR 13} C-NMR of the chlorinated cyclic dialkyl siloxane of the present invention
When the low magnetic field is expressed as positive with respect to tetramethylsilane, absorption of carbon in the side chain appears around 10 to 40 ppm. In addition, carbon with one chlorine atom bonded around 40 to 70 ppm Is carbon with two chlorine atoms bound around 70-100 ppm Absorption appears. Further, from the behavior of the absorption peak splitting appearing in the vicinity of 40 to 70 ppm, it is contained in the side chain chlorinated alkyl group of the chlorinated cyclic dialkylsiloxane of the present invention represented by the general formula [I]. Information about the number of Cl units is obtained.

Further, when the chlorinated cyclic dialkylsiloxane of the present invention is produced by the production method a) described later, it is 10 to 40 ppm.
From the position of the absorption peak appearing in the vicinity and the integrated intensity of the peak, it can be confirmed that cleavage of the alkyl group did not occur during the chlorination reaction.

(4) ²⁹ Si-nuclear magnetic resonance spectrum (hereinafter ²⁹ Si-NM
Abbreviated as R) ²⁹ Si-NM of the chlorinated cyclic dialkyl siloxane of the present invention
When measured as R, a single peak due to silicon of a siloxane cyclic trimer or a siloxane cyclic tetramer appears between −9 and −23 ppm when expressed in terms of tetratylsilane standard and low magnetic field as positive.

From the results of IR and ²⁹ Si-NMR, it is confirmed that the chlorinated cyclic dialkylsiloxane of the present invention has a cyclic structure.

(5) Gel Permeation Chromatography (hereinafter abbreviated as CPC) When GPC of the chlorinated cyclic dialkylsiloxane of the present invention is measured, absorption appears in a molecular grade of 5,000 to 7,000.

The method for producing the novel chlorinated cyclic dialkylsiloxane of the present invention is not particularly limited. Two typical manufacturing methods are described below.

(1) General formula [II] A method for producing a chlorinated cyclic dialkylsiloxane represented by the above general formula [I] by chlorinating a cyclic dialkylsiloxane represented by

The compound represented by the above general formula [II] can be obtained by the following method.

General formula [III] R'CH = CH ₂ [III] By reacting dichlorosilane with the same or different olefin represented by the following formula using chloroplatinic acid as a catalyst: [IV] Is obtained, and then the compound represented by the general formula [IV] is brought into contact with water or hydrochloric acid.

The reaction between the olefin represented by the general formula [III] and dichlorosilane is generally carried out without a solvent, but the presence of a solvent does not matter. The amount of chloroplatinic acid used as a catalyst is preferably in the range of 1 to 10 ^-8 mol with respect to 1 mol of dichlorosilane. Also, the reaction temperature is generally -20 ° C to 200 ° C.
Chosen from.

In the reaction of the compound represented by the general formula [IV] and water or hydrochloric acid, the reaction ratio of these is not particularly limited,
Generally, the range of 10: 1 to 1:10 (molar ratio) is preferable. In this reaction, it is generally preferable to use an organic solvent. Examples of the solvent suitably used as the solvent include ethers such as diethyl ether, diisopropyl ether and di n-butyl ether; ketones such as diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and cyclohexanone; benzene, toluene, There are aromatic or aliphatic hydrocarbons such as xylene, hexane, heptane, petroleum ether, chloroform, methylene chloride and ethylene chloride or halogenated hydrocarbons, and polar non-aqueous solutions such as ethers and ketones are particularly preferable. Also, two or more kinds of solvents may be mixed and used.

The reaction temperature is generally selected from the range of 0 to 100 ° C.

In this reaction, the structure of the compound that gives the reaction time is determined. That is, in the compound represented by the general formula [II], the compound of l = 3 can be obtained in a good yield by setting the reaction time to within 2 hours and the compound of l = 4 to the reaction time of 48 hours or more.

In addition, a by-product may be generated in this reaction, and when this by-product inhibits the subsequent reaction, it is preferable to remove the by-product by a method such as solvent extraction or distillation.

Next, a method for producing the chlorinated cyclic dialkylsiloxane of the present invention by chlorinating the compound represented by the general formula [II] thus obtained will be described.

As the chlorination method, any method can be used without particular limitation as long as it can chlorinate an alkyl group.

Although the chlorination agent is not particularly limited, a method of using chlorine gas in a solvent and chlorinating in the presence of a radical initiator or by light is generally used.

The solvent used in this chlorination reaction is not particularly limited as long as it dissolves or suspends the compound represented by the general formula [II], but generally, carbon tetrachloride,
Halides of aliphatic hydrocarbons such as tetrachloroethylene, chloroform, and chlorofluorocarbons are preferred.

At this time, the concentration of the compound represented by the general formula (II) is 0.1
The range may be up to 80% by weight, but the range is preferably 1 to 50% by weight.

Further, in this chlorination reaction, in order to generate chlorine radicals, a radical initiator is generally added or light is irradiated. Examples of suitable radical initiators include peroxides such as t-butyl peroxide, benzoyl peroxide, and acetyl peroxide; t-butyl peracetate, t-butyl perbenzoate, and perphenylacetic acid. peresters such as t-butyl; or
Examples thereof include azo compounds such as phenylazotriphenylmethane and azoisobutyronitrile. At this time, the amount of the radical initiator is 0 with respect to the compound represented by the general formula [II].
It may be in the range of 1 to 50% by weight, but is preferably in the range of 1 to 10% by weight.

The flow rate of chlorine gas in this chlorination reaction varies depending on the scale of the reaction, but if expressed as a chlorine flow rate per mole of the compound represented by the general formula (II), 0.001 to 100 mol / min.
The range of 0.01 to 1 mol / min is preferable in consideration of the reaction time and the reaction efficiency of chlorine.

The reaction temperature may be in the range of 0 to 200 ° C., but 20 to 100 ° C.
The range of ° C is preferred.

The reaction time may be determined according to the amount of chlorine contained in the chlorinated cyclic dialkylsiloxane of the present invention to be produced.
When the reaction temperature and the chlorine flow rate are in the above-mentioned preferred ranges, chlorine reacts almost quantitatively.

b) The second method for producing the chlorinated cyclic dialkyl siloxane of the present invention is represented by the general formula [V] And contacting bischloroalkyldichlorosilane with water or hydrochloric acid.

The compound represented by the above general formula [V] can be obtained by the following method.

General formula [VI] C _n H _2n-x Cl _x [VI] And reacting the same or different olefins having terminal carbon-carbon double bonds with dichlorosilane using chloroplatinic acid as a catalyst.

At this time, the compound represented by the general formula [VI] may be the same or different, but the chlorination degree of the obtained chlorinated cyclic dialkylsiloxane is in the range of 0.005 to 0.8, The chlorine content of the compound represented by [VI] may be determined.

In addition, this method is a method for obtaining a compound represented by the general formula [IV] from a compound represented by the general formula [III] in the method a) for producing the chlorinated cyclic dialkylsiloxane of the present invention. The same can be done.

Using the compound of the general formula [V] thus obtained as a raw material, the chlorine of the present invention can be obtained in the same manner as that for obtaining the compound of the general formula [II] from the compound of the general formula [IV]. A modified cyclic dialkyl siloxane can be obtained.

(Effect) The chlorinated cyclic dialkyl siloxane of the present invention has a unique effect of improving the processability during PVC kneading while maintaining the PVC fluidity improving effect of polydimethylsiloxane. Further, at this time, the heat resistance and the rigidity of the PVC are not reduced. This effect is obtained not only for PVC but also for thermoplastic resins in general, but is particularly remarkable for PVC or chlorinated vinyl chloride resin (hereinafter referred to as CPVC).

The compounds of the present invention can be used alone or in combination with other physical property modifiers such as stabilizers and inorganic fillers in thermoplastic resins. At this time, the compounding amount of the compound of the present invention is:
The amount may be in the range of 0.05 to 50 parts by weight based on 100 parts by weight of the thermoplastic resin, but is preferably in the range of 0.1 to 20 parts by weight in consideration of operability.

Specifically, when 3 parts by weight of polydimethylsiloxane is added to PVC, the resin flow rate is 2 × 10
^-3 ml / s temperature (hereinafter referred to as fluidization temperature) is 18
° C and flowability is improved. And the general formula [I]
In which R ¹ and R ^{2 have} a carbon number of 8 and l is 3 and a chlorination degree of 0.16 is PV
When 3 parts by weight is added to C, the fluidization temperature hardly changes as compared to the case where 3 parts by weight of polydimethylsiloxane is added to PVC, and PV measured by plastography
The gelling time of C is shortened to about 1/17, and the workability is greatly improved. Furthermore, the PVC beat cut softening temperature and tensile elastic modulus at this time do not change as compared with the case where polydimethylsiloxane is added.

Such a peculiar effect is an effect peculiar to the chlorinated cyclic dialkyl siloxane of the present invention, as is apparent from the comparison of Examples and Comparative Examples described later. Therefore, the chlorinated cyclic dialkyl siloxane of the present invention is a compound useful as a fluidity improver for thermoplastic resins.

(Examples) Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

The physical properties of the resins shown in Examples and Comparative Examples were evaluated by the following methods.

(1) Fluidity In the measurement of a high-level flow tester by the temperature raising method performed under the following conditions, the fluidity at the temperature (fluidization temperature) at which the resin flow rate becomes 2 × 10 ^-3 (ml / s) It was evaluated as an index.

Conditions: Die hole diameter 1 mmφ, die thickness 10 mmt Heating rate 4 ° C./min (2) Workability The gel time measured by a plastograph performed under the following conditions was evaluated as an index of workability.

Conditions: Set temperature 180 ° C, residual heat time 5 minutes Resin amount 61g, rotor rotation speed 30r.pm (3) Thermal stability Approximately 1cm x 2cm plate specimens of 1mm thickness are required in a gear oven of 190 ° C. And the test piece was taken out with time. The color of the removed test piece was compared with a Lovibond disk according to the Gardner scale to determine the time until black was obtained. The time until this black color was obtained was evaluated as an index of the thermal stability of the resin.

(4) Tensile modulus JIS K7113 (5) Beakt softening temperature JIS K7206 Method B Production example 1 226 g of 1-octene in isopropyl alcohol solution of chloroplatinic acid (H ₂ PtCl ₆ 1 × 10 ^-4 mol / isopropyl alcohol)
0.1 ml) was added. After heating this liquid to 30 ° C., 101 g of cyclosilane was introduced over 5 hours to react 1-octene with dichlorosilane to obtain 327 g of a liquid reaction product.

Methyl isobutyl ketone (hereinafter abbreviated as MIBK) 500 ml of 1 and 3N hydrochloric acid aqueous solution was heated to 60 ° C. To this mixed solution, 327 g of the reaction product of 1-octene and dichlorosilane obtained in the above operation was added with stirring for about 5 minutes, and 60
Stirring was continued at 30 ° C. for 30 minutes to carry out hydrolysis. After cooling to room temperature, the MIBK layer was taken out and washed with pure water until neutral. After removing MIBK, acetone 1 and methyl alcohol 1 were added to the reaction product. Heat to 50 ° C and 10
The mixture was stirred for minutes, cooled to room temperature, and allowed to stand to separate into two layers. The lower layer was taken out and dried under reduced pressure to obtain 189 g of a reaction product. The compounds by various measurement results below, hexa octyl cyclotrisiloxane was confirmed that a (hereinafter, abbreviated as OctD _3).

(1) IR 3000cm ^-1 carbon aliphatic to ~2850cm ^-1 - absorption based on hydrogen bonding, specific to the cyclic trimer of siloxane 1005cm ^-1 Si
Absorption due to -O bonds appears.

(2) ¹ H-NMR (tetramethylsilane standard, low magnetic field was expressed as positive.) Si—CH ₂ — (CH ₂ ) ₆ —CH ₃ absorption at 0.56 ppm, Si—CH ₂ — absorption at 0.88 ppm _{Si-CH 2 - (CH 2} ) 6 absorption of -CH ₃ of -CH _3, 1.29Ppm the _{Si-CH 2 - (CH 2} ) 6 -CH ₃ of - (CH _{2) 6}
-Absorption appears.

(3) ²⁹ Si-NMR (tetramethylsilane standard, low magnetic field expressed as positive) At -10.7 ppm, absorption based on a single cyclic siloxane appears.

(4) GPC The w of this compound was 820 and n was 820.

(5) Elemental analysis The elemental analysis for this compound was 70.93 wt% carbon, 12.42 hydrogen.
wt%, the theoretical value of OctD ₃ is 71.04 wt% carbon, hydrogen
It was in good agreement with 12.67 wt%.

The structures of the products in the following production examples were also determined by the same method as described above.

Production Example 2 In Production Example 1, 170 g of 1-olefin was used.
The same operation as in Production Example 1 was carried out except that hexene was used to obtain 148 g of a reaction product. Its elemental analysis value was 67.15% by weight of carbon and 12.18% by weight of hydrogen, which agreed well with the theoretical values of hexahexylcyclotrisiloxane of 67.23% by weight of carbon and 12.22% by weight of hydrogen. The molecular weight of the product was measured by GPC and found to be 640 for both w and n. Further consideration of ^{IR, 1 H-NMR, 29} Si-NMR , etc. results of instrumental analysis of the product hexa hexyl cyclotrisiloxane was confirmed that a (hereinafter, abbreviated as HexD _3).

Production Example 3 To 228 g of 1-hexadecene was added 0.05% isopropyl alcohol solution of chloroplatinic acid having the same concentration as used in Production Example 1.
ml was added. After heating this solution to 30 ° C, dichlorosilane
50 g was introduced in 3 hours and 1-hexadecene was reacted with dichlorosilane to obtain 278 g of a reaction product.

500 ml of an aqueous solution of MIBK1 and 3N hydrochloric acid was heated to 90 ° C. To this mixed solution, 278 g of the reaction product of 1-hexadecene and dichlorosilane obtained by the above operation was added with stirring for about 5 minutes. After 90 minutes, take out the MIBK layer and keep it about 60 until neutral.
Washed with warm water of at least ℃. When the MIBK layer was cooled to room temperature, a solid was precipitated. The solid was separated by filtration and dried under reduced pressure to obtain 197 g of a solid product. Elemental analysis value of this product was 77.59 wt% carbon.
%, Hydrogen 13.36 wt%, which is the logical value of hexahexadecylchlorotrisiloxane, carbon 77.65 wt%, hydrogen 13.44
Good agreement with wt%. The molecular weight of this product measured by GPC was 1,500 and n was 1,500. Further consideration of ^{IR, 1 H-NMR, 29} Si-NMR , etc. results of instrumental analysis of the product hexa hexadecyl cyclotrisiloxane was confirmed that a (hereinafter, abbreviated as HexdD _3).

Production Example 4 After cooling 300 ml of n-hexane to 0 ° C., 101 g of dichlorosilane was introduced. To this solution was added 0.1 ml of an isopropyl alcohol solution of chloroplatinic acid having the same concentration as in Production Example 1. 112 g of 1-octene was added dropwise over 3 hours while maintaining the temperature in the reactor between 0 ° C and 8 ° C. Then change the temperature in the reactor
While maintaining the temperature at 20 ° C to 30 ° C, 84 g of 1-hexene was added dropwise over 3 hours. After completion of the reaction, n-hexane was removed, and 297 g of a reaction product of 1-hexene and 1-octene with dichlorosilane was removed.
Obtained.

MIKB1 and 500 ml of a 3N aqueous hydrochloric acid solution were heated to 60 ° C. To this mixed solution, 297 g of the reaction product of 1-hexene and 1-octene obtained by the above operation and dichlorosilane was added under stirring for about 5 minutes to carry out hydrolysis. The MIBK layer was taken out and washed with pure water until it became neutral. After removing the MIBK,
Acetone 1 and methanol 1 were added to the reaction product. It was heated to 50 ° C. and stirred for 10 minutes. Upon standing, it separated into two layers. The lower layer was taken out and dried under reduced pressure to obtain the reaction product 16
I got 7g. The elemental analysis value of this product was 69.28 wt% carbon and 12.38 wt% hydrogen, and the theoretical value of 1,3,5-trihexyl-1,3,5-trioctylcyclotetrasiloxane was carbon.
It was in good agreement with 69.36 wt% and hydrogen 12.47 wt%. Moreover, when the molecular weight of this product was measured by GPC, w was 740,
n was also 740. Considering the results of IR, ¹ H-NMR and ²⁹ Si-NMR together, this compound is 1,3,5-trihexyl-1,
3,5-tritoctylcyclotetrasiloxane (hereinafter referred to as Hex
OctD ₃ ).

Production Example 5 The same procedure as in Production Example 1 was carried out except that the olefin used in Production Example 1 was 170 g of 1-hexene, and the time for hydrolyzing the reaction product with dichlorosilane was 72 hours. Obtained 150 g. The elemental analysis value of this product was 67.18 wt% carbon and 12.21 wt% hydrogen, and the theoretical value of octahexyltetrasiloxane was 67.2%.
It was in good agreement with 3 wt% and hydrogen 12.22 wt%. The molecular weight of this product was measured by GPC and found to be 860 for both w and n. Also, in IR, a cyclic tetramer of Si-O at 1080 cm ^-1
A peak due to binding appeared. Further, in ²⁹ Si-NMR, a single peak based on silicon of the cyclic tetramer appeared at −21.9 ppm. In addition, it was confirmed that the product was octahexyl tetrasiloxane (hereinafter abbreviated as HexD ₄ ) in consideration of ¹ H-NMR results and the like.

Production Example 6 Reaction product 19 was prepared by the same procedure except that the olefin used in Production Example 5 was changed to 226 g of 1-octene.
1 g was obtained.

By the same confirmation method as in Production Example 5, it was confirmed that this was octaoctyltetrasiloxane (hereinafter abbreviated as OctD ₄ ).

Example 1 40 g of OctD ₃ obtained in Production Example 1, 0.4 g of azobisisobutyronitrile (hereinafter abbreviated as AIBN) and 500 m of carbon tetrachloride.
Chlorine gas was blown into the solution consisting of 1 while stirring at 70 ° C. at a flow rate of 60 Ncc / min to carry out a reaction for 1 hour. After completion of the reaction, the reaction solution was concentrated and developed with an excess amount of methanol with stirring, and then the stirring was stopped and the mixture was allowed to stand still to separate into two layers. At this time, unreacted AIBN is extracted into the methanol layer. The lower layer product was separated and dried under reduced pressure to obtain 43.3 g of a chlorinated product which was a viscous liquid at room temperature. The structure of this product was confirmed by the following method.

(1) Absorption based on aliphatic carbon-hydrogen bond appears at IR 3,000 to 2,850 cm ^-1, and absorption based on Si-O bond of cyclic trimer appears at 1,005 cm ^-1 .

(2) ²⁹ Si-NMR (tetramethylsilane standard, low magnetic field was expressed as positive) At -10.8 ppm, a single peak attributed to silicon in the cyclic trimer appears. From the results of IR and ²⁹ Si-NMR, it is confirmed that the product maintains the siloxane cyclic trimer structure even after the chlorination reaction.

(3) ¹³ C-NMR (tetramethylsilane standard, low magnetic field was expressed as positive) As shown below, absorptions corresponding to those of various carbons appear.

Chemical shift of carbon atoms in which the only bonded atoms are hydrogen atoms (a) 16.8 ppm (b) 23.3 ppm (c) 32.3 ppm (d) 29.7 ppm (e) 29.7 ppm (f) 34.0 ppm (g) 22.8 ppm (h) 14.1 ppm Further, since no absorption attributed to carbon other than the above (a) to (h) appeared around 10 to 40 ppm, the side chain in the general formula [II] during the chlorination reaction It is confirmed that cleavage of the alkyl group has not occurred.

Chemical shift of carbon atom with one chlorine atom bonded (a) 50.5ppm (b) 58.0ppm (c) 65.0ppm (d) 63.0ppm (g) 58.0ppm (h) 44.4ppm Is confirmed to depend randomly on the carbon position of the side chain alkyl group.

(4) GPC Both w and n of this product were 910.

(5) Elemental analysis result The elemental analysis result of this product is chlorine 11.60 wt%, carbon 63.
It was 00 wt% and hydrogen 10.91 wt%. From this result, it is confirmed that the chlorination degree of this product is 0.03.

Examples 2 to 9 The reaction was carried out in the same procedure as in Example 1 under the conditions shown in the table below. The results are shown in Table-1.

The structures of these substances were confirmed by the same method as in Example 1.

Example 10 To 52.3 g of 5-chloro-1-pentene was added 0.03 ml of an isopropyl alcohol solution of chloroplatinic acid having the same concentration as that used in Production Example 1. After the solution was heated to 30 ° C., 25 g of dichlorosilane was introduced in 90 minutes, and 5-chloro-1-pentene was reacted with dichlorosilane to obtain 77 g of a reaction product.

500 ml of an aqueous solution of MIBK1 and 3N hydrochloric acid was heated to 60 ° C. To this mixed solution, 77 g of the reaction product obtained in the above operation was added with stirring for about 3 minutes. After 30 minutes, the MIBK layer was taken out after cooling to room temperature and washed with pure water until neutral. After removing MIBK, acetone 1 and methyl alcohol 1 were added to the reaction product. The mixture was heated to 50 ° C., stirred for 10 minutes, cooled to room temperature, and allowed to stand to separate into two layers. The lower layer was taken out and dried under reduced pressure to obtain 44.3 g of a reaction product.

The elemental analysis value of this product is as follows: chlorine 27.75 wt%, carbon 47.03
wt.%, hydrogen 7.88wt%, the theoretical value of hexa (5-chloropentyl) cyclotrisiloxane chlorine 27.78wt.
%, Carbon 47.05 wt% and hydrogen 7.90 wt%. From this result, it can be seen that the chlorination degree is 0.09. The molecular weight of this product was measured by GPC and found to be 760 for both w and n. Further, IR, ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-
In consideration of the results of instrumental analysis such as NMR, it was confirmed that the product was hexa (5-chloropentyl) cyclotrisiloxane.

Example 11 3 g of tin stabilizer (TVS1320, Nitto Kasei Co., Ltd.) and Hoechst wax OP to 100 g of PVC (SA800B, No. 1 PVC Sales Co., Ltd.)
0.2 g (manufactured by Hoechst), 0.1 g hoechst wax E (manufactured by Hoechst) and 3 g of the chlorinated cyclic dialkyl siloxane obtained in Example 4 were added and mixed. When the gelation time was measured using 61 g of the obtained mixed powder, the gelation time was 52 seconds.

The mixed powder obtained in the same manner was kneaded with a roll machine at 165 ° C. for 5 minutes. When a fluidization temperature was measured with a flow tester using a part of this, the fluidization temperature was 178 ° C. Furthermore, after preheating this roll kneaded material at 180 ° C. for 5 minutes,
Pressing was performed at 180 kgG / cm ² for 5 minutes at the same temperature to obtain a molded plate having a thickness of 1 mm. When a rectangle of about 1 cm × 2 cm was cut out from the obtained molded plate and subjected to an oven test at 190 ° C., the time required for blackening was 110 minutes. The tensile modulus is 295 kg.
It was f / mm ² and the Beecut softening temperature was 77.4 ° C. Examples 12 to 20 In Example 11, the chlorinated cyclic dialkylsiloxane obtained in Example 4 was changed to the chlorinated cyclic dialkylsiloxane shown in Table 2. The gelation time, the fluidization temperature, the time required for blackening, the tensile modulus of elasticity and the bead cut softening temperature were examined in the same manner except that they were changed. The results are shown in Table 2 including Example 11.

Example 21 To 100 g of CPVC (HA-24K manufactured by Tokuyama Sekisui Kogyo Co., Ltd.), 3 g of a tin stabilizer (Nitto Kasei TVS1320) and 5 g of the chlorinated cyclic dialkylsiloxane obtained in Example 4 were added and mixed. When the gelation time of this mixed powder was measured, the gelation time was 2 minutes and 10 seconds. Further, this mixed powder was kneaded with a roll machine at 180 ° C. for 5 minutes. When a fluidization temperature was measured with a flow tester using this part, the fluidization temperature was 188 ° C.
Met. Further, the roll kneaded product was preheated at 185 ° C. for 5 minutes and then pressed at the same temperature for 5 minutes at a pressure of 180 kgG / cm ² , and the bead cut softening temperature was measured. As a result, the bead cut softening temperature was 112.1 ° C. .

Examples 22 to 26 In Example 21, the fluidization temperature, bead cut softening temperature and gelling time were measured in the same manner except that the chlorinated cyclic dialkyl siloxane to be added was changed to the chlorinated cyclic dialkyl siloxane shown in Table 3. did. Example results
It is shown in Table 3 including 21.

Comparative Example 1 The gelation time and the fluidization temperature were measured in the same manner as in Example 11 except that the added chlorinated cyclic dialkylsiloxane was changed to w4,000 polydimethylsiloxane. As a result, the gelation time was 15 minutes and 24 seconds, and the fluidization temperature was 172 ° C. The tensile elastic modulus was 290 kgf / mm ² , and the Vicat softening temperature was 77.5 ° C.

Comparative Example 2 The time required for blackening was examined in the same manner as in Example 11 except that the chlorinated cyclic dialkylsiloxane to be added was changed to the chlorinated cyclic polydimethylsiloxane described below. It was 20 minutes.

The chlorinated cyclic polydimethylsiloxane used in this comparative example was Thermochimica Acta, 13
(1975) 100-104, hexamethylcyclotrisiloxane (Shin-Etsu Silicone LS-8120)
Chlorination was carried out by directly blowing chlorine gas to the mixture, carbon tetrachloride was added, and residual chlorine and hydrogen chloride in the product were removed by distillation together with carbon tetrachloride.

The chlorine content of this chloride cyclic dimethylsiloxane was 37 wt% (corresponding to a chlorination degree of 0.2).

Comparative Example 3 A mixed powder of CPVC and a stabilizer was obtained in the same manner except that the chlorinated dialkylsiloxane added in Example 21 was changed to w17,000 polydimethylsiloxane. When the gelation time of this mixed powder was measured, gelation did not occur under the above conditions. Further, kneading was tried with a roll machine at 180 ° C. However, gelation did not occur and molding was impossible.

[Brief description of drawings]

FIG. 1 shows the ¹³ C-NMR spectrum of the chlorinated cyclic dialkylsiloxane of the present invention obtained in Example 1.

Claims (4)

(57) [Claims] 1. A general formula , And the number of chlorine atoms and hydrogen atoms contained in the molecule are m and n, respectively, A chlorinated cyclic dialkyl siloxane having a ratio of 0.005 to 0.8. 2. General formula The method for producing a chlorinated cyclic dialkylsiloxane according to claim (1), characterized in that the cyclic dialkylsiloxane represented by (5) is chlorinated. 3. General formula The method for producing a chlorinated cyclic dialkylsiloxane according to claim (1), characterized in that the bischloroalkyldichlorosilane represented by the formula (1) is brought into contact with water or hydrochloric acid. 4. A fluidity improver comprising the chlorinated cyclic dialkyl siloxane according to claim (1).