JPS604213B2 - Internal mold release agent for polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to organopolysiloxanes, and more particularly to organopolysiloxane fluids containing phenyl groups.

Conventionally, most phenyl group-containing organopolysiloxanes have been comprised of three types of silicone polymers.

These three types include a polymer that has a phenyl group and a methyl group on the same silicon atom as in '1l; Polymers containing methyl groups and '
It is a polymer consisting of phenyl group-containing units chain-terminated with 3'trimethylsilyl units. Examples of the first type of polymer include those having a structure as represented by the formula (where Ph is a phenyl group and generally x=0.0$ to x=y). It will be done.

Illustrative examples of the second type of polymer include the formula (where Ph is a phenyl group and generally x=0
．． 05y or x=y).

A third type of polymer is one having a structure as represented by the formula (where Ph is a phenyl group).

In this case, the length of the polymer extends to about 23 units in terms of the number of phenyl group-containing units. Technical and commercial problems are associated with these conventional silicone fluids for a variety of reasons. For example, the first of the silicone fluids described above must be manufactured from starting materials derived from the expensive Grignard process (e.g., methylphenyldichlorosilane), while other subordinate structure-related polymers are processed. I have the above problem. For example, polymers containing both diphenylsiloxy and dimethylsiloxy units have been found to be extremely volatile, and furthermore, such polymers cannot be manufactured to the low viscosity states currently desired. It is a karma. The uses of silicone polymers such as those described above, depending on their molecular weight and structure, are of course wide-ranging and are known.

Examples include lubricants for plastics, heat-resistant grease components, and general machine oils. More specifically, the use of phenyl group-containing organopolysiloxane fluids as internal mold release agents for polycarbonates has become prominent in recent years.

In this regard, for example, US Pat. No. 3,751,519
Please refer to the specification. However, conventional phenyl group-containing organopolysiloxane fluids have low solubility in polycarbonates and are therefore not completely satisfactory for use in polycarbonates. Additionally, the addition of conventional phenyl-containing organopolysiloxane fluids has typically compromised the clarity and properties typically desired for polycarbonate products. Such a shortcoming of the prior art is that the formula (where Ph is a phenyl group, and R
is a group selected from a hydrogen atom, a trimethylsilyl group, and a mixture thereof, and x and y are about 7 to about 80
This is overcome by the phenyl group-containing organopolysiloxane fluids of the present invention, which are characterized in that they have a basic structure of: (by weight) having a value sufficient to give a phenyl group content of %.

The novel phenyl group-containing organopolysiloxane fluid represented by formula (1) above is produced by solvent hydrolysis of diphenyldichlorosilane and dimethyldichlorosilane.

Generally, such solvent hydrolysis methods begin by preparing a mixture of diphenyldichlorosilane, dimethyldichlorosilane, and a water-immiscible organic solvent. As the organic solvent that is immiscible with water, any organic solvent can be used as long as it is inert to the hydrolysis reaction during hydrolysis and dissolves water scales to enable their separation.
More specifically, suitable organic solvents include benzene toluene xylene, esters such as butyl acetate,
Ethyl acetate and the like, and ethers such as diethyl ether, dioxane and the like. A preferred organic solvent is toluene. The amount of organic solvent used can vary over a wide range, but is generally within the range of about 10 to about 55 percent (by weight) of the total amount of the organohalogenosilane mixture;
It is also preferably about 25% (by weight). For purposes of this invention, the weight ratio of diphenyldichlorosilane to dimethyldichlorosilane in the organohalogenosilane mixture undergoing hydrolysis is from about 1.5:1 to about 4:1. Still preferably, the weight ratio of diphenyldichlorosilane to dimethyldichlorosilane is about 3:1. The above organohalogenosilane mixture in an organic solvent is
Then, about 20 to about 85q0, preferably about 60 to about 65
It is mixed with pre-heated water.

The addition at that time is about 60 to about 85 CO, preferably about 75
This is done slowly, for example, over a period of about 1 to about 2 hours, while maintaining a temperature of ˜85 qo. After settling the hydrolysis mixture thus obtained, the lower aqueous acid phase is separated and disposed of. The remaining organic phase is washed several times, for example with 15% sodium hydroxide solution, until the HCI content is below about 1 cap. At this point,
Water is azeotropically removed from the hydrolysis mixture at a temperature not exceeding about 115°C. The remaining material (hereinafter referred to as hydrolyzate) is a mixture of linear siloxanes (chain-terminated with diphenylsilanol units), cyclic siloxanes, and organic solvents. The hydrolyzate is then saturated with anhydrous ammonia and then trimethylchlorosilane is slowly added. Such trimethylchlorosilane acts as a chain terminator, resulting in the substitution of silanol groups with trimethylsiloxy units. The amount of trimethylchlorosilane used varies with the desired degree of silanol group substitution. For purposes of this invention, trimethylchlorosilane is about 9.9% of the total weight of the hydrolyzate.
It is used in a proportion of 5 to 25.5% (by weight). More specifically, for polycarbonate additives, the amount of trimethylchlorosilane chain terminator used is about 11.4% to 19% (by weight) of the total weight of the hydrolyzate, so that for the fluid it is about 12% to 19% (by weight) of the total weight of the hydrolyzate. A trimethylsiloxy unit content of approximately 21% (by weight) is obtained. After stirring for about 1 hour, the mixture is washed, for example with 15% sodium hydroxide solution, and the lower aqueous phase is separated and discarded.

The remaining organic phase is washed, for example with sodium hydroxide solution, and then the organic solvent and residual crab water are heated to about 150°C.
and stripping at a temperature of, for example, 25 to 3 m Hg under vacuum. The remaining phenyl group-containing organopolysiloxane fluid has the formula (1) above.
In the formula, x and y are approximately 40
with a value such as to give a phenyl group content of ~80% (by weight). Such phenyl group-containing organopolysiloxane fluids are particularly suitable as internal mold release agents for polycarbonates because they are highly soluble in polycarbonates and yet maintain the desired transparency of the polycarbonates. For such purposes, x and y generally have values of about 3 to 10. A sufficient amount of trimethyl to obtain a high phenyl group content, low volatility organopolysiloxane fluid that is within the scope of the present invention and is particularly suitable as a base stock for any mechanical or hydraulic phenyl silicone fluid. By using chlorosilane, the phenyl-containing organopolysiloxane fluids described above are completely chain terminated.

The fluid, which is almost completely chain terminated with trimethylsiloxy units, is then subjected to an equilibration step. That is,
The fluid is mixed with potassium hydroxide and then heated to about 180 oo for about 1-2 hours. If desired, trimethylchlorosilane chain terminator may be added during equilibration. Stripping the mixture at a temperature of about 250 to 300 °C and under high vacuum (3 to 5 feet of Hg) produces a high phenyl content, low volatility organopolysiloxane of formula (1) above. A fluid is obtained. In that case, x has a value of about 3 to 10 and y also has a value of about 3 to 10, and the phenyl group content is about 40
~80 (weight)%. Included within the scope of the invention,
Moreover, in order to obtain a phenyl group-containing organopolysiloxane fluid that is particularly suitable as a component of machine oil and heat-resistant grease, it is necessary to completely chain-stop the fluid by adding a sufficient amount of trimethylchlorosilane, while also using The hydrolysis process continues.

The mixture thus obtained is equilibrated for about 1 hour at a temperature of about 180-200 oo by use of potassium hydroxide. During the equilibration, a sufficient amount of Octamethylcyclotetrasiloxane and a material containing trimethylsiloxy units (eg, cyclic decamethyltetrasiloxane) are added. A preferred equilibration step involves first equilibrating the octamethylcyclotetrasiloxane and the material containing trimethylsiloxy units, then adding the phenyl-containing organopolysiloxane fluid, and then continuing equilibration for about 3 hours. The equilibrated mixture thus obtained is subjected to stripping at a temperature of about 280 DEG C. and under very high vacuum (e.g. 3-5 willow Hg). The fluids described above as being particularly useful as internal templates for polycarbonates may be further modified to obtain fluids that are particularly useful for transparent and controlled density greases. That is, sufficient octamethylcyclotetrasiloxane is added to reduce the phenyl group content to about 30% (by weight), and the resulting mixture is then equilibrated and stripped as described above. . As is obvious to those skilled in the art, when the phenyl group-containing organopolysiloxane fluid of the present invention represented by the above formula (1) is compared with conventional fluids, the fluid of the present invention mainly contains diphenylsiloxy units. It is distinctive in that it contains directly attached trimethylsiloxy chain termination units.

This fact explains the advantageous solubility properties of the fluids of the invention in polycarbonates and the other advantageous properties mentioned above. Polycarbonates intended to be used in combination with the internal mold release agent comprising the phenyl group-containing organopolysiloxane fluid of the present invention include aromatic polycarbonates produced by the reaction of a dihydric phenol with a carbonate ester precursor. can be mentioned.

The reaction mixture may also contain small amounts of other additives and varying amounts of reactive monomer components. Furthermore, it may also contain copolymers of two or more dihydric phenols. Specifically, examples of dihydric phenols that can be used for the preparation of polycarbonates contemplated herein include bis(4-hydroxyphenyl)
Methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane.

Pan, 4,4-bis(4-hydroxyphenyl)butane, 2,2-pis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-
Dihydric phenol ethers such as 3,5-dibromophenyl)propane, e.g. bis(4-hydroxyphenyl)
ether, bis(3,5-dichloro-4-hydroxyphenyl) ether, dihydroxydiphenyl such as p,p'-dihydroxydiphenyl, 3,3-dichloro4,4'-dihydroxydiphenyl, dihydroxyarylsulfone such as bis (4-hydroxyphenyl) sulfone, bis(3,5-dimethyl-4-hydroxyphenyl) sulfone, etc., dihydroxybenzenes such as resorcinol, hydroquinone, etc., halogen- and alkyl-substituted dihydroxybenzenes such as 1.
4-dihydroxy-2-chlorobenzene, 114-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, etc., as well as dihydroxydiphenyl sulfoxide such as bis(4-hydroxyphenyl) sulfoxide, bis(3,5-dibromo 4
-hydroxyphenyl) sulfoxide and the like. Various other dihydric phenols can also be used to obtain polycarbonates, but they are described in U.S. Pat.
83F3028365 and 3153008. Of course, if a copolymer is desired rather than a homopolymer in the production of the aromatic polycarbonate of the present invention, two or more types of dihydric phenols may be used, or dihydric phenols and glycols, hydroxyl groups or acid groups may be used. It is also possible to use end-stopped polyesters or copolymers with diboric acid. The carbonate ester precursor used in the production of the above polycarbonate is as follows:
phosgene, dibromocarbonyl, jodocarbonyl,
Bishaloformates of dihydric phenols (e.g. bischloroformates such as hydroquinone, bisphenol A) and bishaloformates of glycols (e.g. bischloroformates such as ethylene glycol, neobentyl glycol, polyethylene glycol)
can be mentioned.

Preferred aromatic polycarbonates within the scope of this invention are those prepared by the reaction of phosgene with 2,2-bis(4-hydroxyphenyl)propane (commonly referred to as "bisphenol A").

The production of such polycarbonates is generally carried out in the presence of an acid acceptor, and the acid acceptor may be either an organic compound or an inorganic compound.

Suitable organic acid acceptors are tertiary amines, examples of which include materials such as pyridine, triethylamine, dimethylaniline, tributylamine, and the like. The inorganic acid acceptor can also be any of alkali metal or alkali metal hydroxides, carbonates, bicarbonates, and phosphates. In the production of polycarbonate, phenol, cyclohexanol, methanol, p
Molecular weight modifiers such as -tert-butylphenol, p-bromophenol, etc. may also be used.

The phenyl group-containing organopolysiloxane fluid of the present invention represented by the above formula (1) can be easily mixed with an aromatic polycarbonate by any suitable method.

Since the phenyl group-containing organopolysiloxane fluid of the present invention is compatible and highly soluble in polycarbonate, complete mixing is easily achieved and separation is not a concern. Therefore, when producing injection molded pellets, the polycarbonate and fluid may be premixed or may be fed separately to the feed hopper of the extruder. The phenyl group-containing organopolysiloxane fluid of the present invention provides an excellent mold release effect even in a small amount during molding of a composition.

The amount of such fluid used is generally from about 0.01% to about 2.0% (by weight), preferably from about 0.1% to about 1.0% (by weight), based on the weight of the polycarbonate. Note that even if the phenyl group-containing organopolysiloxane fluid of the present invention is present, the desired transparency of the polycarbonate will not be lost. To enable those skilled in the art to better understand how to practice the present invention. Examples are shown below.

These examples are intended to illustrate the practice of the invention and are not intended to limit the scope of the invention. Example 1 This example illustrates the preparation of a phenyl group-containing organopolysiloxane fluid that falls within the scope of formula (1) above and is particularly suitable as an internal mold release agent for aromatic polycarbonates.

57.7 parts (by weight) of diphenyldichlorosilane, 19.2 parts (by weight) of dimethyldichlorosilane, and 2 parts by weight of toluene.
3.1 parts (by weight) were mixed in a container.

On the other hand, an amount of water equal to about 1 part of the total weight of the logeran was heated to about 60-6 ro in a separate container. Then, a mixture of organohalogenosilane and toluene was slowly added to the water. During that time, hawking continued and the overflow was maintained at approximately 75-85'C. After the completion of the addition, the sashiko Hishigo Kowatatto Gayafune textile was visited.

The lower aqueous acid phase was separated and discarded. The organic phase was washed twice with 15% sodium hydroxide solution and then tested for HCI content. This HCI content is required to be 10 legs or less. Water was removed simultaneously at temperatures not exceeding 115°C.

Enough anhydrous ammonia is added to saturate the remaining water scales, and then 12.7 g of trimethylchlorosilane (
parts) were added. At this time, care was taken to ensure that ammonia was not lost. 55q of such mixture
Ammonium chloride was removed by washing with water after incubation for approximately 1 hour at o. The lower aqueous acid phase was separated and discarded. The organic phase is washed until approximately neutral with a 15% sodium hydroxide solution, and then the remaining water and toluene are washed at a temperature of about 150 oo and about 20
It was removed by stripping under a vacuum of ~3 Hg. The remaining phenyl group-containing organopolysiloxane fluid has a structure represented by the above formula (1), and has a phenyl group content of 68.85% (by weight) and a trimethylsiloxy unit content of 16% (by weight). Was. This material is particularly suitable as an internal mold release agent for polycarbonates. Example 2 This example illustrates the preparation of a phenyl group-containing organopolysiloxane fluid that falls within the scope of formula (1) above and is particularly suitable as a heat resistant grease component and machine oil.

About 1.6 parts (by weight) of decamethyltetrasiloxane chain terminator and 41.8 parts (by weight) of octamethylcyclotetrasiloxane were added to 56.65 parts (by weight) of the phenyl group-containing organopolysiloxane fluid produced in Example 1.
part was added.

After adding 600 platefuls of potassium hydroxide pellets into the reaction vessel, the mixture was equilibrated at 180 oo for about 3 hours.

The reaction mixture was subjected to stripping at a temperature of up to about 280 qo and under high vacuum (eg 3-5 willow Hg). The remaining phenyl group-containing organopolysiloxane fluid has a structure represented by the above formula (1), and has a phenyl base content of 39% (by weight) and 1
It had a trimethylsiloxy unit content of 8% (by weight). Example 3 This example illustrates the preparation of a phenyl group-containing organopolysiloxane fluid that falls within the scope of formula (1) above and is particularly suitable as a transparent grease component.

57.6 parts (by weight) of octamethylcyclotetrasiloxane were added to 42.4 parts (by weight) of the phenyl group-containing organopolysiloxane fluid produced in Example 1.

After adding 60 grams of potassium hydroxide pellets, the mixture was equilibrated at 180°C for 2 hours.

The refractive index was then adjusted by adding octamethylcyclotetrasiloxane or a phenyl group-containing organopolysiloxane fluid to adjust the amount of phenyl groups. After the desired refractive index was obtained, the mixture was cooled to 4000 °C, Fuller's earth was added, and then filtered through Celi 545, a diatomer sold by Johns-Manville. It was. The mixture was stripped at a temperature of about 250 qo and under high vacuum (eg, 3 Yanagi Hg), leaving the desired clear grease components. The thus obtained phenyl group-containing organopolysiloxane fluid had a structure represented by the above formula (1) and had a phenyl group content of 30% (by weight). Example 4 The following general formula was prepared by hydrolyzing diphenyldichlorosilane and dimethyldichlorosilane and chain-terminating the resulting silanol polymer by reaction with hexamethyldisiloxane in the presence of acid-treated clay. A polysiloxane fluid with a high phenyl content (>65% by weight) was prepared having the following formula, where Me represents a methyl group and Ph represents a phenyl group.

This fluid was a polysiloxane of the type contemplated by this invention and was designated SFI179. The fluid is a trimethylsiloxane chain-terminated diorganopolysiloxane in which the terminal trimethylsiloxy units are bonded to diphenylsiloxy units. Equilibrating the above SFI179 polymer with a basic catalyst (KOH) and adding chain termination to produce a trimethylsiloxy chain-terminated polysiloxane in which a significant portion of the diorganosiloxy units attached to the terminal units are dimethylsiloxy. Another high phenyl content (greater than 65% by weight) polysiloxane fluid was prepared by.

That is, this second polysiloxane fluid was a mixture of a polysiloxane of the above formula and a polysiloxane of the following general formula, and was named SF1271.

1% by weight of SFI 179 was added to bisphenol-A polycarbonate powder to form a molding composition;
Pushed out with q○.

The extrudate was transparent. 1% by weight of SF1271 was similarly added to the bisphenol-A polycarbonate powder and the resulting composition was extruded at 30,000.

The extrudate was cloudy and had a white milky color. Furthermore,
Due to the non-uniform shape of the extrudate, SF12
It was found that 71 was causing trouble in the adjustment of extrusion molding. This example shows that when certain high phenyl loading polysiloxanes of the present invention are added to polycarbonate compositions, conventionally cloudy, opaque polycarbonate molded articles such as those obtained with other polysiloxane additives are obtained. It takes a lot not to give up.

Embodiments of the present invention are shown below. l x and y have sufficient combined values to provide a phenyl group content of about 40 to about 80% (by weight), and R is about 12 to 21% (by weight)
2. The phenyl group-containing organopolysiloxane fluid of claim 1, which is a mixture of hydrogen atoms and trimethylsilyl groups sufficient to provide a trimethylsiloxy unit content of . 2. The phenyl of claim 1, wherein 2 x and y have a total value sufficient to provide a phenyl base content of about 40 to about 80% (by weight), and substantially all of R is trimethylsilyl groups. Group-containing organopolysiloxane fluid.

3 x and y have sufficient combined values to provide a phenyl group content of about 38% to about 48% (by weight), and the viscosity is 2.
50 qo is about 100 to 200 centistokes,
The phenyl group-containing organopolysiloxane fluid according to claim 1.

4 x and y have a total value sufficient to provide a phenyl base content of about 68% (by weight) and the trimethylsiloxy unit content is about 16% (by weight).
The fenyl group-containing organopolysiloxane fluid described above.

5 The phenyl group-containing organopolysiloxane fluid has a content of about 0% based on the weight of the aromatic polycarbonate.
．． 3. The polycarbonate composition of claim 2, wherein the polycarbonate composition is present in a proportion of from 0.01% to about 2.0% (by weight). 6 The aromatic polycarbonate has phosgene and 2,2-bis(4-
is a reaction product with hydroxyphenyl)propane,
The poIJ carbonate composition according to claim 2 or the preceding item.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, Ph is a phenyl group, and R is a group selected from a hydrogen atom, a trimethylsilyl group, and a mixture thereof, Also, x and y are about 7 to about 80% (by weight)
a phenyl group-containing organopolysiloxane fluid having a total value sufficient to provide a phenyl group content of
Internal mold release agent for polycarbonate.