JPS59207922A - Lactone-siloxane block copolymer composition and its production - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent compatibility with a number of organic polymers, and useful as an additive for polymer, by copolymerizing a lactone compound to a specific organopolysiloxane having terminal hydroxyl group. CONSTITUTION:The objective composition having a weight average molecular weight of 1,000-100,000, composed of the unit of formula III and the unit of formula IV, and having the content of formula II of 20-99% can be prepared by mixing (A) an organosiloxane of formula I (m is 3-1,000; R is 1-18C alkyl, aryl, vinyl or aralkyl) with (B) the lactone compound of formula II (n is 4-6; R' is H, 1-12C alkyl, aryl, aralkyl or alkoxy) in the presence or absence of (C) an ester exchange catalyst, and copolymerizing the components under stirring at 50-200 deg.C. EFFECT:The composition gives an organic polymer having excellent surface smoothness, gloss, impact strength, mold releasability, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a lactone-siloxane block copolymer composition useful as a polymer additive and a method for producing the same.

More specifically, the present invention relates to a block copolymer composition obtained by copolymerizing a lactone compound to an organopolynoroxane having a terminal hydroxyl group, and a method for producing the same.

Additives are often added to organic polymer compounds to improve their mechanical properties and functionality. In particular, organic siloxane compounds have many properties such as low surface tension, good thermal stability, wide usable temperature range, good oxidation stability, and good insulation properties, so they are often used as additives for organic polymer compounds. has been used as.

However, in general, organic siloxane compounds have poor compatibility with organic polymer compounds, and if the former is a liquid compound, it oozes onto the surface of the molded product, dissipates from the surface by contact, etc. It is difficult to maintain the surface properties of a molded article constant over a period of time. It is difficult to uniformly mix solid organosiloxane compounds, such as crosslinked silicone rubber, with organic polymer compounds.

Polyalkylsiloxanes having long-chain alkyl groups have been considered, but the organic polymer compounds to which they can be added are limited to polyolefins, and they have the disadvantage that their addition reduces thermal stability.

As a block copolymer of polyalkylsiloxane compound and polyester, for example, Macromolecules magazine (M
acromolecules) Volume 1O No. 6 (19
Synthesis of poly(hexamethine/sebacate)-poly(dimethylsiloxane) block copolymer is reported on page 1197 of '/'i1 year). However, this copolymer is synthesized by a condensation reaction between polydimethylsiloxane, which has chlorine or dimethylamino groups at both ends, and polyhexamethylene separated glycol, which has hydroxyl groups at both ends. It is necessary to remove it from the system. Furthermore, the bonding form between the polyester part and the polysiloxane part is also different from that of the copolymer of the present invention.

Japanese Patent Publication No. 4B-411'i' also describes a siloxane-polyester block copolymer produced by a similar method.

Furthermore, Japanese Patent Publication No. 50-39643 discloses a new composition containing a lactone-silicone block copolymer.

This is a copolymer composition obtained by polymerizing lactone using an unsaturated oloalcohol as an initiator, and adding polyalkylnoylone loxane to the unsaturated groups of the resulting polyester. It differs from the copolymer of the present invention in the bonding form between the siloxane part and the polyester part.

That is, in order to obtain a polyester-polysilgythane copolymer using conventional techniques, it was necessary to use a condensation reaction or a two-step reaction. Also, the bonding form between the polyester part and polysiloxane part of the copolymer is =S
i OOHz- or =Si-OH20H2-
This was due to D-0-0- (D is a 211-valent hydrocarbon group).

The present inventor has synthesized a polyester-polysiloxane compound by employing an organopolysiloxane having a terminal hydroxyl group as an initiator for the polymerization reaction of a lactone compound, and the bonding form between the two polymer parts is =Si-0- 0
The present invention was achieved by discovering that it is a novel 1 copolymer based on -.

As is clear from the above description, the purpose of the present invention is to develop a novel lactone that has excellent compatibility with a wide variety of organic polymer compounds.
An object of the present invention is to provide a siloxane copolymer composition and a method for producing the same.

The lactone-siloxane copolymer composition of the present invention is as follows (
11% The composition described in (2) or (3)K, and the manufacturing method of the present invention is the method described in (4) or (5).

The organopolysiloxane represented by the same or different alkyl, aryl, aralkyl or vinyl group is treated with the general formula (where n=4-6; R ' is a hydrogen group or a carbon number of 1 to 1
The content of the former is 20 to 99% and the weight average molecular weight is 1,00.
0-100,000 lactone-siloxane block copolymer composition.

(2) The block copolymer composition according to item (1) above, wherein the organopolysiloxane is polydimethylsiloxane.

(3) The block copolymer composition according to item (1) or (2) above, wherein the lactone compound is 8-caprolactone.

(4) Using an organopolysiloxane represented by general formula (1) as an initiator, a lactone compound represented by general formula (It) is mixed in the presence or absence of a transesterification catalyst, and the mixture is heated at 50 to 200°C. A method for producing a bilactone-siloxane block copolymer composition in which a lactone compound is added under stirring to an organopolysiloxane having a weight average molecular weight of 20-99% and a weight average molecular weight of 1000-100,000.

(5) Adding 0.001 to 1 tin salt of an organic acid or alkyl titanate as a transesterification catalyst (
4) Manufacturing method.

The organopolysiloxane used in the present invention is represented by the general formula (1) above. Specific examples include organopolysiloxanes having the same substituents such as polydimethylsiloxane, polydiethyl 70xane, polydipropylsiloxane, polydiisopropylsiloxane or polydiphenylsiloxane, or different types such as polymethylvinylsiloxane and polymethylisopropylsiloxane. These include compounds consisting of substituents, copolymers consisting of a plurality of these structural units, and the like.

If the degree of polymerization of the organopolysiloxane is too small, dehydration condensation reaction will easily occur between siloxanes during the lactone-siloxane block copolymerization reaction, and if m in formula (1) is too large, the active hydrogen concentration in the copolymerization reaction will be reduced. This is not preferable because it reduces the chance of block copolymerization reaction. The preferred range is 3<m<1000. The lactone compound used in the present invention has the above general formula (I
I) is what I am made to do. Preferred lactone compounds include δ-valerolactone, 6-caprolactone, ζ-enantholactone, etc. in which all R's are hydrogen groups, and ξ-caprolactone and its substituted products are particularly preferably used. Specific examples of substituted caprolactones include monomethyl-6-caprolactone, monoethyl-C-caprolactone, monoprobil-6-caprolactone, monoisogropyru-e-caprolactone, and monobutyl-6-caprolactone.
Examples include monoalkyl-substituted products such as 8-caprolactone, dialkyl-ε-caprolactone or trialkyl-e-caprolactone having the same or different substituents. Alkyl substituted products such as δ-valerolactone and ζ-enantholactone can also be made into desired copolymers by the method of the present invention.

These organopolysiloxanes and lactone compounds can be used as commercially available products, but copolymers with higher molecular weight can be obtained by using sufficiently dehydrated products.

Even when the organopolysiloxane and lactone compound used in the present invention are mixed, they do not become uniformly soluble IK but separate into two layers.

However, if the stirring is continued, a cloudy liquid will be formed and the reaction will proceed.

Although the reaction proceeds without a catalyst, it proceeds more efficiently with the use of a catalyst.

The catalyst used in the present invention is preferably a conventional transesterification catalyst, and alkoxides, carbonates, or oxides of alkali and alkaline earth metals such as zinc oxide, antimony oxide, germanium oxide can be used. However, tin salts of organic acids such as tin 2-ethylhexanoate and the general formula Ti (OR') a (wherein R' represents the same or different alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms) Alkyl titanates represented by q# are preferred. Specific examples of alkyl titanates include tetrabutyl titanate, nato2 ether titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, nato2
Examples include isobutyl titanate, tetratertiary butyl titanate, diisopropyl diptyltitanate, etc. - By increasing the amount of the catalyst added, the reaction can be completed more quickly than K, but if the amount added is increased too much, the formation of polystyrene! - This is not preferable because it causes coloring. KO in reaction solution
, OO1 to 11 are sufficient, or the more preferred amount is 001 to 0.5%. The reaction is 2 chtons! The ring-opening polymerization of - proceeds, and step 11 is carried out until it is completely completed. According to the method of the present invention, K requires several hours to several tens of hours to complete the reaction. The charging ratio of the organopolysiloxane and the lactone compound is set almost equal to the desired composition ratio of the copolymer.

The reaction proceeds at room temperature, but heating increases the temperature to 50-300°C.
It is preferable to maintain the If the reaction temperature is increased too much, it may cause coloring of the product, so the more preferable reaction temperature is 50 to 200°C. The selection of reaction temperature should be determined by the charge ratio of organopolysiloxane and lactone compound. Even if the charging ratio of both is the same, if production is carried out in a so-called batch process, the reaction rate will be higher at the beginning of the reaction than at the end of the reaction because the concentration of lactone monomer is higher. Therefore, starting the reaction at a relatively low temperature at the initial stage and gradually increasing the reaction temperature as the reaction progresses is effective in controlling the reaction rate and shortening the reaction time at high temperatures that cause product coloration.

The reaction mechanism in the production method of the present invention is not necessarily fully elucidated;
1150-39648.08F3169945 etc. and Interscience Publishers, Inc.
terscience Publisher) Published (
Encyclopedia op Polymer Science and Technology (1969)
peaia of I'olymer 5science
The role of alcohols, amines, etc. in the ring-opening polymerization of lactone compounds using alcohols, amines, etc. as initiators, as described in ana TeChrlOIOgy) Vol. 11, p. It is presumed that polysiloxane is responsible for this. That is, it is thought that the hydrogen of the terminal silanol group attacks the lactone compound, a ring-opening addition reaction occurs as described below, and the addition reaction proceeds sequentially due to the terminal hydrogen.

As it should be done, the result is A as shown below.
When a BA type block copolymer is produced, it becomes K.

It is thought that the reaction described above takes place predominantly, but depending on the reaction conditions, for example, if the molecular weight of the organopolysiloxane is small and the mixing ratio of the organopolysiloxane to the gallactone compound is large, the terminals in the reaction solution may be It is expected that as the silanol concentration increases, a condensation reaction will occur between the cinnols due to dehydration. Therefore, it is desirable to avoid such reaction conditions, and the upper limit of the content of organopolysiloxane in the copolymer of the present invention is also taken into consideration from this point of view.

In addition, dehydration condensation reaction between 1CHR-OH or -0HR-OH and -81-OH, which are the growth terminals of the polymerization reaction, is also considered a possibility, but under the reaction conditions of the present invention, it is not the dominant reaction. do not have. As the reaction progresses, the viscosity of the liquid increases and the power required for stirring increases. A solvent can also be used to avoid this phenomenon. Toluene, xylene, etc., which are good solvents for the produced copolymer and both raw materials, are examples of preferred solvents.

When the reaction is completed, the trace amount of unreacted lactone monomer remaining is heated to 150 to 200°C, melted, and then coercively distilled.
It is preferably removed under reduced pressure of QtmHf or less over a period of 0.5 to several hours. If the copolymer to be produced is solid and a large amount of solvent is used, the reaction solution is transferred to several times the volume of a non-solvent such as alcohol (e.g. methanol, -ol) to precipitate the produced polymer, and then It can also be dried separately.

As described above, the production method of the present invention involves two steps of reaction.
The method is characterized by the synthesis of a lactone-siloxane block copolymer, and by using a catalyst, the reaction can be completed in a short period of time and in high yield. Since the reaction proceeds through a ring-opening addition reaction, there are no condensation products to be removed, and there is no particular need to remove catalyst residue after the reaction is completed; the product can be obtained by simply removing a trace amount of remaining unreacted supernatant. I can do it. Although it is possible to use a reaction solvent,
This use can be avoided by selecting an appropriate agitation device. As described above, the present invention can provide an economical and efficient manufacturing method.

The copolymer of the present invention obtained as described above is a white to pale yellow, odorless solid.

It has the appearance of a sticky cake or viscous liquid. The higher the content of the lactone compound in the copolymer, the harder the polymer becomes solid, but as the organopolysiloxane content increases, the copolymer becomes softer and eventually becomes a sticky cake or viscous liquid. Also, regarding the molecular weight, the higher the molecular weight, the easier it is to assume a solid form, and as the molecular weight decreases, the properties become closer to liquid.

The ratio of lactone compounds in the copolymer of the present invention is 2
0 to 99% by weight. The lower limit is determined by the above-mentioned problems during the reaction and also by the decrease in compatibility with the organic polymer compound, which is one of the objectives of the copolymer of the present invention. The upper limit is the minimum amount necessary to maintain the properties of the organopolysiloxane.

The block copolymer of the present invention has a weight average molecular weight of 4ooo
The following can also be synthesized, but from the viewpoint of stability of organopolysiloxane, the weight average molecular weight is
The above copolymers can be synthesized more stably. Regarding the high molecular weight side, it is theoretically possible to obtain a high molecular weight product by using a raw organopolysiloxane with a large molecular weight and increasing the proportion of lactone compound added, but in reality, the weight The average molecular weight was about 100,000. If a higher purity raw material can be obtained, it may become possible to obtain a block copolymer with an even higher molecular weight.

The eye-catching copolymer of the present invention obtained as described above can be uniformly mixed with many organic polymer compounds.

For example, polyvinyl chloride, polyvinylidene chloride.

As a type of plasticizer, polyolefins such as polyethylene, polypropylene, IPR, polystyrene, S
BR, polypa 2 methyl styrene 7, As copo 17-+r,
Styrene-based copolymers such as styrene=M M A co-M combination, PET% PBT.

Polyesters such as unsaturated polyester and aliphatic polyester, nylon 6, nylon 6-6, nylon 6-1
0, vinyl polymers such as polyvinyl butyral, polyvinyl formal, polyethyl vinyl ether, polyvinyl acetate, methacrylic esters such as PMMA, acrylic esters such as polymethyl acrylate, polyethyl acrylate, polyethylene oxide, The copolymer of the present invention gives a uniform molded product regardless of the amount added to an organic polymer compound such as polyethers such as polypropylene oxide.

Since the copolymer of the present invention has an organopolysiloxane segment and a polyester segment in the molecule, it has higher compatibility with an organic polymer compound than the polyether segment (K) as described above, and at the same time has a high compatibility with both the organopolysiloxane and the polyester. Characteristics can be imparted to organic polymer compounds.

Organopolysiloxane segments have properties such as low surface tension, good oxidation stability, and thermal stability, and when added to organic polymer compounds, they improve surface smoothness, surface gloss, and impact resistance, as well as improve molding properties. Contributes to improved mold releasability of the cylinder.

On the other hand, as mentioned above, polyester segments have good compatibility with many organic polymer compounds, and when added to them, they impart plasticity, improve gloss, optical surface smoothness, and improve impact resistance. , imparts thread properties that improve dyeability to polyolefin fibers. For example, when the copolymer of the present invention is mixed with a chlorine-containing polymer such as PVO, the polyester segment acts as a plasticizer and becomes plasticized and softened, and at the same time, the characteristics of the organo-organoboric xane segment are also added to make the surface smooth and smooth. Provides a polymer composition with good gloss.

When the copolymer of the present invention is added to a polyolefin and the molded product is a film, its surface exhibits good gloss and exhibits anti-blocking properties. When the molded article is a fiber, it exhibits a smooth surface, a reduced coefficient of friction, and good dyeability with disperse dyes. Alternatively, although polyolefins without polar groups generally have poor compatibility with inorganic fillers, the compatibility can be improved by adding the copolymer of the present invention to a mixture of the two. It can be expected to have various effects as an additive. Which of the aforementioned properties imparted to the organic polymer compound is strongly expressed can be adjusted by controlling the composition of the lactone-siloxane copolymer and the composition added to the organic polymer compound.

The present invention will be explained in detail below using Examples and Application Examples, but the present invention is not limited thereto.

Example 1 500 with stirrer, thermometer and condenser connected
-200 6-caprolactone in a three-necked flask? And polydimethylsiloxane 1002, which is terminated with hydroxyl groups at both ends and has a weight average molecular weight of 200, is taken and stirred in a nitrogen atmosphere. Gradually raise the reaction temperature to 9 after 30 minutes.
When the temperature reached 0°C, 0.5f of tin 2-ethylhexanoate was added as a catalyst. After another 20 minutes, the reaction temperature was raised to 140°C, and the reaction was carried out at 140-150°C for 4 hours. Thereafter, the pressure was reduced to 1 waHyK at this temperature for 2 hours to remove unreacted 8-capro2chton. The resulting viscous polymer became a brittle solid upon cooling. Weight average molecular weight8. :LOO 2942 copolymers having a mesi p-xane content of 338% were obtained. A portion of the produced polymer was extracted with n-pentane, which is a good solvent for polydimethylsiloxane and a non-solvent for poly-caprolactone, and the results are shown in Figure 1.

From this result, it is clear that a block copolymer was produced.

Example 2 Using the same equipment and method as in Example 1, polydimethylsiloxane 20f1 and tetrabutyl titanium (20f1 and tetrabutyl titanate) having a weight average molecular weight of 900 and terminated with hydroxyl groups at both terminals of ε-cablockton 1801 were prepared. B f t - Mix and stir. 90℃ after 30 minutes and 150℃ for another 15 minutes.
The reaction temperature was raised to 150-160°C for 5 hours. 1++++H at this temperature after the reaction is completed
The pressure was reduced to yK and maintained for 1.5 hours to remove unreacted ε-caprolactone from the system. Rigid and brittle copolymer is 195f
Obtained. The weight average molecular weight was 8,300 and the polydimethylsiloxane content was 9.6%.

From the extraction results in Table 1, it is clear that a block copolymer was produced.

Example 3 Using the same apparatus and method as in Example 1, 150f of 8-caprolactone, 150f of polydimethylsiloxane terminated with hydroxyl groups at both ends and having a weight average molecular weight of '7.200, and 0.3f of tetranepropyl titanate were mixed and stirred. . The reaction temperature was raised to 90°C in 165 hours, and after 0.5 hours, the reaction temperature was raised to 120°C.
The reaction was carried out at 30°C for 3 hours. Then at this temperature for 5 hours 1
jll) ipVC was applied under reduced pressure to remove unreacted C-caprolactone. A white cake-like copolymer 291 having a weight average molecular weight of 12,000 and a polydimethylsiloxane content of 50.1 was obtained.

From the extraction results in Table 1, it is clear that a block copolymer was produced.

Actual flow side 4 Using the same equipment and method as in Example 1, e-caprolactone 902 and polydiethylsiloxane 210, which is terminated with hydroxyl groups at both ends and has a weight average molecular weight of 3,700? and 0.8 t of tetralinepropyl titanate were mixed and stirred. The temperature was raised to 90°C in 1 hour, and 1 in another 0.5 hours.
The reaction temperature was increased to 30°C, and 4
Allowed time to react. Unreacted ε-capro2 chtone is 1 絽H
2 was kept at this temperature for 2 hours under reduced pressure and removed.

A viscous liquid copolymer having a weight average molecular weight of 4.400 and a polydiethylsiloxane content of 70.2% was obtained.

n-Pentane is also a &i medium for polydiethylsiloxane, and from the extraction results in Example 1, it is clear that a block copolymer is produced.

Example 5 E-cabrolactone 2 was prepared using the same apparatus and method as in Example 1.
90 terminated with hydroxyl groups at both ends, polydimethylsiloxane 102 with a weight average molecular weight of 7.200, O-xylene 60t1 catalyst tetrabutyl titanate as solvent)
1. of was mixed and stirred. The temperature was raised to 90° C. in 0.5 hours and then to 120° C. in 0.5 hours, and the reaction was carried out at 120 to 130° C. for 8 hours. The reaction product was washed with a large amount of methanol to remove the solvent xylene and unreacted 6-caprolactone. From the solid reaction product to the liquid component t-F
120~13cm under a nitrogen stream.
The remaining liquid component was removed from the melted polymer component by pressing IIIHfKtj at 0° C. for 2 hours.

The obtained copolymer was a pale yellow solid with a weight average molecular weight of 54,000° and a polydimethylsiloxane content of 3.2%, with a yield of 294? Met. From the extraction results of Cloth 1, it is clear that a block copolymer is produced.

Example 6 Using the same apparatus and method as in Example 1, 6-caprolactone 10011 was terminated with hydroxyl groups at both terminals and the weight average molecular weight was '7. OOO polydimethylsiloxane 60
t, 1 Oclr of O-xylene as a solvent, and 0.5 t of tetrainglovir titanate were mixed and stirred. The temperature was raised to 90°C in 1 hour and 120°C in 0.5 hours.
The reaction was carried out at ~135°C for 10 hours. The reaction product was washed with a large amount of methanol to remove the solvent xylene and unreacted 8-caprolactone, and then heated at 50°C under a nitrogen stream.
Heat and melt at 120-130°C for 1 hour at 1wxHf.

The pressure was reduced to 1 mHyic, and the remaining solvent etc. were distilled off over 2 hours. A solid copolymer 153f having a weight average molecular weight of 92.000 and a polydimethylsiloxane content of 38.3% was obtained. From the extraction results of Shishi 1, it is clear that a block copolymer is produced.

Example 7 Using the same apparatus and method as in Example 1, 80 f 6-cabrolactone, 120 t of polydimethylsiloxane terminated with hydroxyl groups at both ends and having a weight average molecular weight of 4 OOOO, and 0.02 t of tet-2-butyl titanate were mixed and stirred. Raise the temperature to 150℃ in 1 hour, then further increase the temperature to 150-160℃
The reaction was carried out at ℃ for 24 hours. Unreacted 6-capro2chton was removed by reducing the pressure to 1WIifK and then keeping it at this temperature for 2 hours. A liquid copolymer 183f with a weight average molecular weight I4400 polydimethylsiloxane content of 64.8% was obtained. From the extraction results in Table 1, it is clear that a block copolymer was produced.

Example 8 Using the same apparatus and method as in Example 1, 60 f of δ-valerolactone, 120 t of polydimethylsiloxane terminated with hydroxyl groups at both ends and having a weight average molecular weight of 3,200, and 0.1 lt of nat-2-butyl titanate were mixed and stirred. The temperature was raised to 160°C in 2 hours, and the reaction was carried out at 160-1°C for 20 hours.

Unreacted 6-caprolactone was removed under reduced pressure of 1 HfK and kept at this temperature for 2 hours. Weight average molecular weight 3,900
．． A liquid copolymer 171t with a polydimethylsiloxane content of 6α3- was obtained. n-pentane is also a non-solvent for poly-δ-valley 2 ctone, and from the extraction results in Table 1 it is clear that a block copolymer is produced.

Comparative Example 1 Polydimethylsiloxane 100 terminated with hydroxyl groups at both ends and having a weight average molecular weight of 3,200 in Example IK
In place of t, polydimethylsiloxane 10 is terminated with trimethylsiloxy groups at both ends and has a weight average molecular weight of 3,800.
The same method of apparatus and raw materials were used except that 0f was used and the reaction time at 140 to 150°C was changed to 6 hours. The 290 tons of polymer produced was non-uniform, with a viscous liquid believed to be polydimethylsiloxane adhering to the solid polymer.

A portion of this polymer was extracted with n-pentane, and an analysis of each sample revealed that the extract was liquid polydimethylsiloxane, and the extraction residue was a solid homopolymer of poly-C-caproctone. there were.

Comparative Example 2 Polydimethylsiloxane 150 terminated with both terminal hydroxyl groups and having a weight average molecular weight of 7.200 in Example 3
The same apparatus method was used, except that polydimethylsiloxane 150R, which was terminated with trimethylsiloxy groups at both ends and had a weight average molecular weight 'i' of 400, was used instead of f, and the reaction time at 120-130°C was changed to 5 hours. and raw materials. The produced 286t polymer was non-uniform as in Comparative Example 1. Same as Comparative Example 1, n
- As a result of extraction with pentane, the ttt-form polydimethylsiloxane extraction residue was a solid poly ε-caprolactone O homopolymer.

Table 1 n-pentane extraction results *1 For solid polymers (Examples 1, 2..3, 5.
6) was extracted for 24 hours using a Soxhlet extractor.

In the case of liquid polymer (Example 4.'7.8), it was mixed with n-pentane and extracted using a separating funnel.

*2 The metal content of the organopolysiloxane segment in the copolymer was analyzed by infrared absorption spectrum.

Next, the effect when the copolymer composition of the present invention is mixed with an organic polymer compound will be specifically explained.

Application Example 1.2 and Control Example 1 Effect of addition to polyvinyl chloride 1.0 part by weight of varicum stearate and 0.5 part by weight of zinc stearate were mixed as stabilizers to 100 parts by weight of polyvinyl chloride with a degree of polymerization of 1300. Furthermore, in order to examine its performance as a plasticizer, 90 parts of the copolymer of the present invention was added and kneaded in an 8-inch barrel at 160°C for 10 minutes.

This mixture was heated in a steam press: 1) Preheated at 0°C for 3 minutes, pressurized at 100Kt/- for 2 minutes at 170°C, cooled (water-cooled) 3
Thickness: 20m due to pressing conditions of 1100F/-min.
A test piece was molded.

Tensile test was carried out using the method of J-8-6723, and J-5
Hardness was measured using 4-6301. Note that instead of the copolymer of the present invention, poly-C-caprolactone (
Weight average molecular weight 10,000) t-90 parts were mixed, a test piece was prepared in the same manner, and the intelligence measurement was performed. The results are shown as Control Example 1. The copolymer of the present invention is homogeneously mixed with polyvinyl chloride to form a smooth and glossy surface condition, and furthermore, as is clear from the results in Table 2, there is a significant decrease in 100 thymodulus and hardness. Plasticizing effect Application examples 3 and 4 and control example 2 Additive effect on polypropylene 2 parts by weight of the copolymer of the present invention were blended with 100 parts by weight of crystalline polypropylene having a melt flow rate (MFR) of 11.4, and after blending 0.02 g of 3,5-di-t-butyl-4-hydroxytoluene (abbreviated as BHT) was added to the composition, and the mixture was kneaded and granulated using an extruder at a resin temperature of 200°C.

All of the obtained pellets had good surface condition and gloss, and formed a homogeneous mixture. Using this pellet, physical properties were measured by the following method.

The test piece was created by Custom Scientific Inc.
Min-Ma manufactured by fic instruments)
It was molded using a x molding machine at a resin temperature of 200°C.

The tensile test was performed using a Min-Max tensile testing machine manufactured by the same company at 25° C. and a tensile rate of 23.067 minutes.

The tensile impact test was conducted at 25°C using a Min-Max impact tester manufactured by the same company.

Surface gloss was measured according to ASTM D523 method.
A 1 ml sheet of i'OX'i'oi was used.

These measurement results are listed in Table 3iC.

3 Effect of addition to polypropylene As shown in 3, by adding a small amount of the copolymer of the present invention to polypropylene, the tensile impact strength and surface gloss could be significantly improved.

Application Examples 5 and 6 and Control Example 3 Effect of Addition on Polyglobylene-Filler System MFR 70 parts by weight of crystalline polypropylene of R4,5, 30 parts by weight of white Merck with an average particle size of 10μ and 0.02 parts by weight of heat The stabilizer BIT was mixed, and 3 parts by weight of the copolymer of the present invention were further blended, and the mixture was granulated using an extruder at a resin temperature of 200°C. Table 4 shows the physical property values measured using a Min-Max tester.

As shown in Table 4, it is clear that the copolymer of the present invention improves the compatibility between polypropylene and talc and significantly increases its elongation at break and tensile impact strength.

Amendment to the above procedure April 27, 1989 Director-General of the Japan Patent Office Kazuo Wakasugi Patent Application No. 82251-2, Title of the Invention 2 Chton-siloxane block co-vertical composition and method for producing the same & Relationship with the case of the person making the amendment Patent applicant 3-6-32 Nakanoshima, Kita-ku, Osaka-shi, Osaka (530)
(207) Chin Co., Ltd. Representative Sada Nogi Yutun Agent 2-8-1 Shinjuku, Shinjuku-ku, Tokyo (160) & Date of amendment order (voluntary amendment) α Number of inventions increased by amendment 11 Amendment Detailed explanation of the invention in the subject application and specification (a) Contents of the amendment (1) In the title column indicating the applicable regulations in the application documents, [
(Patent application pursuant to the proviso to Article 38 of the Patent Act)" is inserted.

(2) Insert "Number of inventions stated in claims a: 2" before the column "λ Inventor" in the application.

(3) In the third line from the bottom of the 29th line of the specification, "C-caprolactone" is corrected to "δ-valerolactone."

(4) In the third to second lines from the bottom of page 33 of the same J#, "shown as a control example" is corrected to "shown in Table 2 together with the results of application examples 1 and 2 as a control example."

(5) In lines 5 and 6 of Circular 35, "Custom Scientific Instruments" is corrected to "Custom Scientific Instruments."

that's all 207-

Claims (1)

[Scope of Claims] (In the formula, m=3 to 1000: R represents the same or different alkyl group, aryl group, aralkyl group, or vinyl group having 1 to 1 carbon atoms) , in the presence or absence of a transesterification catalyst, a compound of the general formula (where n = 4 to 6; R' has a hydrogen group or a carbon number content of 20 to 99%, and a weight average molecular weight of 1000 to IOQ , 000 lactone-siloxane block copolymer composition. (3) The block copolymer composition according to claim +1) or (2), wherein the lactone compound is ε-caprolactone. (4) In the presence or absence of a transesterification catalyst, an organopolysiloxane represented by the general formula (or vinyl group tl-) is used as an initiator to react with the general formula (where n=4 to 6; R' is hydrogen). group or carbon number 1-1
2 (representing the same or different alkyl group, aryl group, acylkyl group, or alkoxy group) are mixed and heated at 50 to 200°C.
A lactone-siloxane block copolymer composition having a characteristic amount of 20 to 99% and a weight average molecular weight of 1000 to 100,000 is prepared by copolymerizing a lactone compound with organopolysiloxa 7 while stirring. Manufacturing method. (5) The production method according to claim (4), wherein 0.001 to 1% of a tin salt of an organic acid or an alkyl titanate is added as a transesterification catalyst.