WO2001068737A1

WO2001068737A1 - Polyorganosiloxane and process for producing the same

Info

Publication number: WO2001068737A1
Application number: PCT/JP2001/002078
Authority: WO
Inventors: Kiichi Kawabata; Youichi Kimae
Original assignee: Chisso Corporation
Priority date: 2000-03-17
Filing date: 2001-03-15
Publication date: 2001-09-20
Also published as: JP4977816B2

Abstract

A polyorganosiloxane having a polyoxyalkylene segment introduced at one end thereof. The polyorganosiloxane can be evenly mixed with an ingredient capable of undergoing a reaction, such as polyaddition or polycondensation, with a diol-containing polysiloxane, and has satisfactory solubility in polar solvents.

Description

Specification

TECHNICAL FIELD The present invention relates to a polyorganosiloxane and a method for producing the same.

The present invention relates to a novel polyorganosiloxane having a terminal diol group and a method for producing the same. Background art

Conventionally, polyorganosiloxanes having a diol group at one end have undergone ring-opening polymerization of cyclotrisiloxanes using an organolithium compound or lithium silanolate as a polymerization initiator, and a termination having a SiH bond at the end. The reaction is stopped with an agent, and the product is produced by a hydrosilylation reaction between the obtained polysiloxane having a terminal SiH bond and a diol having an aryl group. JP-A-63-161013 and JP-A-2-60935 disclose a method for producing a polysiloxane having a diol group at one end. Its applications include a polyurethane resin composition, a magnetic recording medium using the same, synthetic leather (Japanese Patent Laid-Open No. 3-167212), and a resin composition for coating an optical fiber (Japanese Patent Laid-Open No. 5-720) 183) are known.

When such a polyorganosiloxane having a diol group at one end is used, for example, as a polyaddition component of a polyurethane or a polycondensation component of a polyester, that is, as a part of a diol component for producing a polyurethane or a polyester. As a result, a darafto polymer having a polyorganosiloxane chain as a branch is obtained, and a polymer having excellent surface properties such as water repellency, abrasion resistance and lubricity is obtained. Since the polysiloxane chain is chemically bonded to the polymer main chain in the graph polymer obtained by such polyaddition and polycondensation, it can be simply added to conventional polymers such as polyurethane and polyester. Unlike those that are blended with polysiloxane No problem of bleeding out.

However, the polyorganosiloxane having a diol group at one end may not be mixed uniformly during the polyaddition reaction with the corresponding diisocyanate or the polycondensation reaction with the dicarboxylic acid. It was difficult to make a graph with some diisocyanates and dicarboxylic acids. Further, when the molecular weight of the polyorganosiloxane having a diol group at one end is increased, the obtained resin solution becomes cloudy. Due to such cloudiness, applications where transparency is required are limited, and if left undisturbed, cloudy substances will settle out, resulting in a non-uniform resin solution. This was undesirable due to variations in performance.

These disadvantages are caused by the fact that dialkylpolysiloxane, which constitutes most of the conventional polyorganosiloxane having a diol group at one end, is insoluble in polar substances such as water and alcohol. For this reason, development of a polyorganosiloxane having a diol group at one end and having compatibility with polar substances such as alcohol is desired.

An object of the present invention is to eliminate the drawbacks of conventional polyorganosiloxanes having a diol group at one end. That is, a polyorganosiloxane having a one-terminal diol group, which can be uniformly mixed with a component capable of reacting with a diol-containing polysiloxane, such as polyaddition or polycondensation, and has good solubility in a polar solvent, and the like. Decide to provide a manufacturing method. Disclosure of the invention

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by introducing a polyoxyalkylene moiety into a molecular chain, a diol group at one end having compatibility with various polar solvents and monomers has been obtained. Polio with They have found that luganosiloxane can be obtained, and have completed the present invention.

The polyorganosiloxane having a terminal diol of the present invention is as follows:

Indicated in paragraph (I).

(I) General formula (1)

[Wherein, RR ² , R ³ , R ⁴ and R ⁵ are a linear or branched alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 4 to 10 carbon atoms. Or an aryl-containing group having 6 to 12 carbon atoms; n is a number of 1 or more, m is a number of 0 or more, and (n + m) is an average molecular weight of polyxanxane segment of 300 to 80. X is an alkylene group having 2 to 20 carbon atoms; Y is _OCH ₂ CH ₂ —, one OCH (CH ₃ ) CH ₂ — or one OCH ₂ CH

(CH ₃ ) —; p is a number satisfying the average molecular weight of the polyoxyalkylene segment (Y _p ) of 150 to 2000; Ζ is 1 to 20 carbon atoms. An alkylene group having 4 to 10 carbon atoms or a cycloalkylene group having 4 to 10 carbon atoms or an arylene-containing group having 6 to 20 carbon atoms; S and Τ each represent an alkyl having 1 to 20 carbon atoms. And a cycloalkylene group having 4 to 10 carbon atoms or an arylene group having 6 to 12 carbon atoms. ]

A polyorganosiloxane having a terminal dial having a number average molecular weight of 50,000 to 1,000, represented by the following formula:

The method for producing the polyorganosiloxane having a terminal diol of the present invention is shown in the following items (II) to (IV).

(II) a polyoxyalkylene / polyorganosiloxane block copolymer having one terminal hydroxyl group (provided that polyoxyalkylene And a polyisocyanate having an average molecular weight of 150 to 200,000 and a polyorganosiloxane moiety of 300 to 800,000). To form a urethane bond, thereby producing a polyorganosiloxane intermediate having one terminal isocyanate group, and reacting the intermediate with diolamine to form a diol group at one end. A method for producing a polyorganosiloxane having a terminal diol having a number average molecular weight of 500 to 1000, characterized in that a polyoxyalkylene'polyorganosiloxane block copolymer having the same is obtained.

(I I I) General formula (2)

A hydroxyl group-containing polysiloxane represented by the general formula (3)

O ^ C = NZ—— N ^ = C = 0 ( ³ )

A general formula (4) formed by reacting a diisocyanate represented by the following formula with or without a catalyst:

(Four)

A polyorganosiloxane intermediate having one terminal isocyanate group represented by the general formula (5)

Is reacted with a diol amine represented by the general formula (1) (1)

For producing a polyorganosiloxane having a terminal diol having a number average molecular weight of 500 to 100 000

[Here, the definitions of R ¹ R ² , R ³ , R ⁴ , R ⁵ , n, m, (n + m), X, Y, p, Z, S, and T are the same as described above. ].

(IV) The polysiloxane having a terminal hydroxyl group has a polyorganosiloxane having a terminal SiH bond having an average molecular weight of 300 to 800 and a polyoxysiloxane having an alkenyl group having an average molecular weight of 150 to 2000. The process for producing a polyorganosiloxane having a terminal diol according to any one of the above (II) and (III), which is a block copolymer obtained by a hydrosilylation reaction with an alkylene. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a ¹ H-NMR spectrum of the polyorganosiloxane having a terminal diol group of Example 1.

FIG. 2 is an IR spectrum of the polyorganosiloxane having a terminal diol group of Example 1. BEST MODE FOR CARRYING OUT THE INVENTION

The general formulas (1), (2) and (4) of the present invention will be specifically described.

R ¹ , R ² , R ³ , R ⁴ and R ⁵ include methyl, ethyl, n-propynole, i-propynole, n-butynole, i-butynole, s-butynole, t-butyl, pentizole Linear or branched alkyl groups having 1 to 20 carbon atoms, such as neopentyl, hexynole, heptyl, octyl, nonyl, decyl, pendecyl, dodecyl; cyclopentyl, cyclopentyl Cycloalkyl group having 4 to 10 carbon atoms such as hexyl or the like; aryl-containing group having 6 to 12 carbon atoms such as feninole, tonorenole, xylyl, ethynolephenine, benzinole, and phenethyl Is raised.

Preferred R ま, R ² , R ³ , R ⁴ and R ⁵ include groups such as methyl, ethyl, propyl, butyl, phenyl and the like.

X is ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, otatamethylene, nonamethylene, decamethylene, pendecamethylene, dodecamethylene, tetradecamethylene, 2-methylethylene, 2-methyltomethylene Carbon, such as dimethylene, 2-methinoletramethylene, 2-methinolepentamethylene, 2-methinolehexamethylene, 2-methylheptamethylene, 2-methylotatamethylene, 2-methylnonamethylene, 2-methyldecamethylene, and 2-methyldecamethylene An alkylene group having 2 to 20 atoms is exemplified.

Preferred X includes ethylene, trimethylene, and 2-methylethylene, and more preferably trimethylene.

Z is methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, otamethylene, nonamethylene, decamethylene, pendecamethylene, dodecamethylene, tetradecamethylene, 2-methylethylene, 2 -Methyl trimethylene, 2-methylinoletramethylene, 2-methylinopentamethylene, 2-methylhexamethylene, 2-methylheptamethylene, 2-methylotatamethylene, 2-methylnonamethylene, 2-methyldecamethylene, 2-methyl Alkylene groups having 1 to 20 carbon atoms such as dexcamethylene; cycloalkylene groups having 4 to 10 carbon atoms such as cyclohexylene groups; phenylene, diphenylene, Naphthylene, Tolylene, Xylylene, Tetramethi Xylylene, methylenebis (4 — phenyl socyanate) {MD I}, the residue of the 2,41-tolylene diisocyanate {TDI}, excluding the isocyanate group, 3-isocyanatomethyl-3,5,5 — An arylene-containing group having 6 to 20 carbon atoms, such as a residue of trimethylcyclohexyl isocyanate (IPDI) excluding the isocyanate group, may be mentioned.

Preferred Z includes hexamethylene, tolylene, xylylene, methylenebis (4-phenylisocyanate) {MD I}, and 2,4-isocyanate group of tolylene diisocyanate {TDI} Residues excluding 3 — isocyanatomethyl-1,3,5,5 — trimethylcyclyl are the residues excluding the isocyanato group of the mouth hexylisocyanate (IPDI).

S and T are methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, pendenemethylene, dodecamethylene, tetradecamethylene, respectively. Methylethylene, 2-methyltrimethylene, 2-methyltetramethylene, 2_methylpentamethylene, 2-methynolehexamethylene, 2-methynoleheptamethylene, 2-methylenoctamethylene, 2-methynolenamethylene, 2 —Alkylene group having 1 to 20 carbon atoms, such as methyldecamethylene and 2_methyldenecamethylene; arylene group having 6 to 12 carbon atoms, as in the above examples; 4 to 10 carbon atoms And the like.

Preferred S and T include ethylene and trimethylene.

n is a number of 1 or more, m is a number of 0 or more, and (n + m) is a number satisfying the average molecular weight of the polysiloxane segment of 300 to 800, preferably 500. 3300 000, more preferably 100 000 to 150 000. Y _p represents a polyoxyalkylene segment; Y represents one OCH ₂ CH ₂ —, one OCH (CH ₃ ) CH ₂ — or one OCH ₂ CH (CH ₃ ) —, and p represents a polyoxyalkylene segment. It is a number that satisfies the average molecular weight of 150 to 200,000, preferably 150 to 500,000, and more preferably 200 to 100,000.

As shown in the following Scheme A, the method for producing a polysiloxane having a diol group at one end of the present invention comprises a polyorganosiloxane having a hydroxyl group at one end represented by the general formula (2) and a polyorganosiloxane having a hydroxyl group at one end represented by the general formula (3). The polyorganosiloxane intermediate having one terminal isocyanate group represented by the general formula (4) (hereinafter sometimes referred to as a terminal NCO group-containing silicone) is obtained by the addition reaction with the diisocyanate to be obtained. An addition reaction between the intermediate and the diolamine represented by the general formula (5) yields a polysiloxane having a diol group at one end represented by the general formula (1).

More specifically, referring to Scheme A, a polysiloxane containing a terminal hydroxyl group (2) and a diisocyanate (3) are reacted with NCO / OH 2 in a solvent in the presence of a catalyst at a reaction temperature of 5 ° C to 2 ° C. The reaction is carried out at 5 ° C. to obtain a silicone having a terminal NCO group (4) as a reaction intermediate, and the intermediate is further reacted with diolamine (5). By-products resulting from the reaction between the excess isocyanate (3) and diolamine (5) are distilled off from the reaction solution to obtain the polyorganosiloxane (1) having a terminal diol group of the present invention.

More specifically, referring to Scheme A, the terminal NCO group-containing silicone (4) is, as described above, a compound having a hydroxyl group-containing polysiloxane (2) and a diisocyanate (3) in NCO / OH. ≥ 2, obtained by reacting in a solvent in the presence of a catalyst at a reaction temperature of 5 ° C to 25 ° C.

This reaction is basically a reaction between the —OH group of the polysiloxane having a terminal hydroxyl group (2) and one NCO group of the diisocyanate (3), that is, a reaction that forms a so-called urethane bond. In addition to the terminal NCO group-containing silicone (4) generated in this reaction, a dimer is also formed as a by-product, in which one NCO group of (4) is further reacted with the —OH group of (2). You. When NC OZO H is 2 or more, the reaction intermediate (4) is advantageously formed. The excess diisocyanate (3) can be removed by methanol washing using the difference in solubility between the main product and the polyorganosiloxane having a terminal diol group (1) after completion of the entire reaction in the present scheme. There is no strong reason to set an upper limit for NCO / OH, but common sense NC It does not make much sense to react under conditions where O / OH exceeds 4. If NCO / OH is smaller than 2, it is not preferable because a dimer obtained by further reacting the terminal hydroxyl group-containing polysiloxane (2) with the terminal NCO group-containing silicone (4) is produced as a by-product.

The reaction temperature is preferably 25 ° C or lower, more preferably 5 ° C to 15 ° C, in order to suppress the by-product of the dimer. At this temperature, it takes a long time to produce the silicone containing terminal N—C〇 groups (4), so that it is preferable to add a catalyst to accelerate the reaction.

If the silicone containing terminal NCO groups (4) is stored without being used in the reaction, it is desirable not to add a catalyst in order to minimize the activity of the isocyanate group, which is easily affected by moisture.

However, the use of a catalyst in the subsequent reaction of the terminal NCO group-containing silicone (4) with the diolamine (5) does not pose any problem.

As a catalyst used in such an addition reaction, a known catalyst can be used.

Typical of such addition reaction catalysts are an inorganic acid, an ester of phosphoric acid or boric acid, or an acid catalyst such as ρ-toluenesulfonic acid, triethylamine, N-methylmorpholine, N —Ethylmorpholin, N, N—Dimethylbenzylamine, N, N′—Dimethylpiperazine, N, N, N ′, N′—Tetramethylethylenediamine, N, N, N ′ , N'-tetramethylhexamethylenediamine, N, N, N ', N ", N" monopentamethylethylethylene triamine, hexamethylenetetramamine, etc. Cobalt naphthenate, lead naphthenate, zinc naphthenate, stannous chloride, stannic chloride, tri-n-butyltin acetate, trimethyltin hydroxide, tetraoctyl titanate , Dibutyl tin Raure door, Okuchiru tin, Okuchiru acid cobalt, such as antimony trichloride Such metal complexes. These may be used alone or in combination of two or more.

The amount of such an addition reaction catalyst used is not particularly limited as long as it does not decrease the selectivity of the reaction and is an amount for obtaining an economical reaction rate. In consideration of the effect on the selectivity of the reaction and the economic efficiency, it is preferably 500 ppm or less with respect to the terminal hydroxyl group-containing polysiloxane (2).

A reaction solvent is not necessarily required in each reaction in the production method of the present invention, but an appropriate solvent may be used as necessary. The amount of the reaction solvent used is not particularly limited, and depends on the practitioner of the present invention. Generally, since the viscosity of the terminal hydroxyl group-containing polysiloxane (2) is high, a solvent is added for the purpose of lowering the viscosity of the reaction solution and completing the reaction sufficiently.

Such a solvent must be one that does not inhibit the reaction, and may be a hydrocarbon solvent such as hexane or heptane, an aromatic hydrocarbon solvent such as benzene, toluene, or xylene, dimethyl ether, tetrahydrofuran. And ether solvents such as dioxane, halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride, and ester solvents such as ethyl ethyl carbonate. These solvents can be used alone or in combination.

Some diolamines (5) are soluble only in polar solvents such as tetrahydrofuran, and it is considered preferable to use a polar solvent as a reaction solvent in order to make the reaction uniform. The reactivity of the isocyanate group is so high that it is safe to use non-polar solvents that are heterogeneous.

It is desirable that these solvents do not contain impurities which react with the diisocyanate (3) or the silicone containing a terminal NCO group (4), ie, alcohols, primary and secondary amines, and carboxylic acids. New The diisocyanate represented by the general formula (3) can be obtained as a commercial product. For example, toluene diisocyanate, diphenyl methane diisocyanate, naphthalene diisocyanate, triazine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, p-phenylene diisocyanate, transcyclohexane diisocyanate , Xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethyl xylylene diisocyanate, and the like.

Scheme A describes the reaction between a silicone containing terminal NCO groups (4) and diolamine (5). This reaction is a reaction that forms a so-called urea bond, which is obtained by selectively reacting the isocyanato group of (4) with the second amino group of diolamine (5). Since the reaction rate of the hydroxyl group and the second amino group with respect to the isocyanate group is much higher in the second amino group, the reaction can be performed as NCO / NH 1. By collecting a few g of the reaction solution, adding a predetermined amount of dibutylamine and titrating with a dilute hydrochloric acid solution, the isocyanate content in the reaction solution can be determined. What is necessary is just to react an equivalent or more of diolamine (5) with respect to this isocyanate content.

Finally, the by-product of the reaction between the excess diisocyanate (3) and diolamine (5) is distilled off from the reaction solution to obtain the polyorganosiloxane (1) having a terminal diol group of the present invention.

The diolamine represented by the general formula (5) can be obtained as a commercial product, and includes diethanolamine, dimethanolamine, dipropanolamine and the like.

The terminal hydroxyl group-containing polysiloxane represented by the general formula (2) can be produced, for example, by the following method.

As shown in scheme (B), the hydrogen atom bonded to S i The hydroxyl group-containing polysiloxane (2) is obtained by a hydrosilylation reaction between the polyorganosiloxane (6) and the polyalkylene (7) having an alkenyl group.

Scheme (B):

(6)

(2) (where RR ² , R ³ , R ⁴ , and R ⁵ are the same as those described above for X, Y, p, n, m, and (n + m); It is an anorecenyl group having 20.)

The reaction of the above scheme (B) is a hydrosilylation reaction carried out in the presence of a catalyst, and a catalyst generally used for a hydrosilylation reaction can be used. As the catalyst, a transition metal catalyst can be used, and specific examples thereof include platinum, rhodium, iridium, ruthenium, palladium, molybdenum, and manganese. These are forms of so-called homogeneous catalysts that dissolve in solvents, forms of supported catalysts supported on carbon, silica, etc., and forms of catalyst systems using phosphine diamine, potassium acetate, etc. as co-catalysts. Both can be adopted.

A solvent is not necessarily required in the reaction of the scheme (B), but an appropriate solvent may be used if necessary. With such a solvent The reaction must be one that does not hinder the reaction, such as hydrocarbon solvents such as hexane and heptane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; and solvents such as getyl ether, THF, and dioxane. Examples thereof include halogenated hydrocarbon solvents such as tellurium solvents, methylene chloride, and carbon tetrachloride, phenolic solvents such as methanol, ethanol, and pronoanol, and water. These solvents can be used alone or in combination.

Although the reaction temperature of the hydrosilylation reaction is not particularly limited, it is usually carried out at a temperature lower than the boiling point of the reaction solvent. When no reaction solvent is used, the reaction can be performed at 0 to 250 ° C, but it is preferable to perform the reaction at 20 to 120 ° C in consideration of economy and the like.

The polyoxyalkylene having an alkenyl group represented by the general formula (7) can be obtained as a commercial product. For example NOF Co., Ltd. "Interview two Ox P KA- 5 0 0 1" ( X '= § Li _{_{le, Y = _ OCH 2 CH 2}} -, average molecular weight 2 0 0 poly ethylene glycol monomethyl A Li "Uniox P KA-502" (, = aryl, = -OCH ₂ CH ₂ _, polyethylene glycol monoaryl ether with an average molecular weight of 400); "Uniox P KA—5003 ”(X, = aryl, Y = — OCH ₂ CH ₂ —, average molecular weight 450 MW polyethylene glycol),“ Uniox P KA— 50 0 4 "(X '= § Li _{_{le, Y = - OCH 2 CH 2}} _, average molecular weight 7 5 0 of port triethylene glycidyl copolymers Noremono a Li Noreetenore);" Yuniokkusu PKA - 5 0 0 5 "( X' = _{_{Arinore, Y = - OCH 2 CH 2}} -, average molecular weight 1 5 0 0 poly ethylene glycidyl Konoremono a Li ether); "Interview two safe P KA 5 0 1 4 "(X ' = § Li _{le, Y = - OCH (CH 3} ) CH 2 - or a _{_{OCH 2 CH (CH 3) -}} , average molecular weight 1 5 0 0 poly pro Pirenguri glycol monomethyl A Li ether ) Example

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

Toluene, methanol and n-hexane described in the examples used reagents manufactured by Kishida Chemical Co., Ltd. Toluene range isocyanate used a reagent manufactured by Tokyo Chemical Industry Co., Ltd. Diethanolamine used a reagent from Kanto Chemical Co., Ltd. Polyoxyethylene having an aryl group at one terminal is manufactured by Nippon Oil & Fats Co., Ltd. using "UNIOX PKA-501" (average molecular weight: 200), "UNIOX PKA-50002" (average molecular weight). Molecular weight: 400) and "UNIOX PKA—500-4" (average molecular weight: 750) were used.

The water content was measured according to JIS K 0668 (Method for measuring water content of chemical products).

Number average molecular weight and dispersity were measured by gel permeation chromatography (GPC).

The detector is a UV detector and the mobile phase is tetrahydrofuran.

Ο The equivalent weight was determined by the following formula using a titration method in which a sample was acetylated with acetic anhydride and excess acetic anhydride was back titrated.

Ο Evaluation (mg g K O HZ g) = (A— B) / s X f X 2 8.05

O H equivalent = 5 6.l ZO H value X 1 0 0 0

{Where A is the blank test drop volume (m 1), B is the main test drop volume (ml), f is the KOH factor, and s is the sample volume (g). } Example 1

(a1) Preparation of terminal hydroxyl group-containing polysiloxane (2):

Attach a porcelain stirrer, cooling tube, and thermometer to a 500-milliliter three-necked flask, and add 100 g of polydimethylsiloxane having a number average molecular weight of 500,000 having terminal SiH bonds. Number average molecule with an aryl group at one end 13 g of polyoxyethylene and 170 g of Tonolen in a quantity of 400 were measured, and the temperature was raised to 80 ° C., and 11 μl of a platinum catalyst solution was added. The reaction was carried out at 80 ° C for 4 hours. Cool the reaction mixture, add 210 g of methanol, extract unreacted polyoxyethylene and remove the methanol layer.Twice twice, then evaporate the solvent and volatiles from the toluene layer under reduced pressure using an evaporator. As a result, 87 g of a pale yellow transparent liquid product was obtained.

The OH equivalent of this product was 450. Analysis of this product by IR or the like confirmed that it was a block copolymer composed of polydimethylsiloxane having an average molecular weight of 50,000 and polyoxetylene having an average molecular weight of 400.

(b1) Production of polyorganosiloxane (1) having a terminal diol group:

Attach a porcelain stirrer, a cooling tube, and a thermometer to the four-necked flask of 300 milliliters, and add the above-mentioned (a1) polydimethylsiloxane 'polyoxyethylene block copolymer 100 g, Toluylene range isocyanate 4.7 g (NCO / OH-2.4) and THF 100 g. This liquid was below 1 0 ° C, dibutyltin dilaurate a 5 wt% toluene solution of rate 0. 1 9 9 g (7 X 1 0- 4 eq ZO H) was charged and the reaction temperature 1 0 ° C The following reaction was performed for 5.5 hours.

The N CO content of 202 g of the reaction solution was 1.15 wt%. Based on the NCO content of the obtained reaction solution, 4.15 g (NCO / NH = 0.8) of diethanolamine was added thereto, and the reaction was carried out overnight. The obtained reaction solution was transferred to a NASFRASCO, and THF was distilled off by an evaporator and concentrated. The concentrated solution was placed in a 1-liter separating funnel, to which 550 g of methanol and 50 g of toluene were added to carry out a separating operation to remove the methanol layer containing one component of oligomeric. The volatile components in the toluene layer were distilled off under reduced pressure to obtain 94 g of a transparent wax-like polymer.

The number average molecular weight (Mn) of this polymer in terms of polystyrene is 57 The dispersity (MwZMn) is 1.2 and the OH equivalent is 180. FIG. 1 shows the ¹ H-NMR spectrum of this polymer, and FIG. 2 shows the IR spectrum.

The integral ratio of the dimethylpolysiloxane portion to the polyoxyethylene portion of the ¹ H-NMR spectrum was 97: 8, and the calculated molecular weight ratio of the dimethylpolysiloxane portion to the polyoxyethylene portion was 93: 7. It is. This molecular weight ratio is equivalent to 500: 400.Thus, this polymer is composed of a polydimethylsiloxane segment having an average molecular weight of 500, and a polyoxyethylene segment having an average molecular weight of 400. The block copolymer was identified as a polyorganosiloxane having a terminal diol group having a diol-containing group {(in the formula (1), Z is toluylene, S = T = —CH ₂ CH ₂ —}) at one end. Was.

Example 2

(a2) Preparation of polysiloxane containing terminal hydroxyl group (2):

Attach a stirrer, condenser, and thermometer to a 500-milliliter three-necked flask, and add 200 g of polydimethylsiloxane with an average molecular weight of 500,000 having terminal SiH bonds. 12 g of polyoxyethylene having an average molecular weight of 200 having a terminal aryl group and 70 g of toluene were heated, the temperature was raised to 80, and 40 μl of a platinum catalyst solution was added and reacted for 5 hours. . Cool the reaction solution, add 65 g of methanol, extract unreacted polyoxyethylene and remove the methanol layer.Twice twice, then evaporate the solvent and volatiles from the toluene layer under reduced pressure using an evaporator. As a result, 203 g of a colorless and transparent liquid product was obtained.

The OH equivalent of this product was 380. This product is composed of polydimethylsiloxane with an average molecular weight of 500 and polyoxyethylene with an average molecular weight of 200 from IR, NMR, GPC, etc. It was confirmed that it was a block copolymer.

(b2) Production of polyorganosiloxane (1) having a terminal diol group:

Attach a porcelain stirrer, a cooling tube, and a thermometer to the three-necked three-neck flask of 300 milliliters, and obtain the polydimethylsiloxane / polyoxyethylene block copolymer 1 obtained in (a2) above. 0 g, Tolu Rangey Socyanate 5.5 g (NC OZO H = 2.4) and Tetrahydrofuran (THF) 100 g were added. In an ice bath was below 1 0 ° C, a 5 wt% toluene solution of the jib Chiruchinjira Ure preparative 0. 2 3 lg (7 X 1 0_ 4 eq ZO H) was charged, maintaining the reaction temperature below 1 0 ° C The reaction was performed for 6 hours.

The N CO content of the reaction solution (153 g) was 1.33 wt%. Based on the NCO content of the obtained reaction solution, 4.15 g (NCO / NH = 0.8) of jetanolamine was added to the reaction solution, and the reaction was carried out overnight. The obtained reaction solution was transferred to an eggplant flask, and THF was distilled off using an evaporator, followed by concentration. The concentrated solution was placed in a 1-liter separatory funnel, and 500 g of methanol and 50 g of toluene were added thereto. The mixture was separated, and the methanol layer containing the oligomer component was removed. The volatile components of the toluene layer were distilled off under reduced pressure to obtain 93.7 g of a transparent waxy polymer.

This polymer had a polystyrene-equivalent number average molecular weight (Mn) of 540, a dispersity (MwZMn) of 1.2, and an OH equivalent of 170,000. The integral ratio of the dimethylpolysiloxane portion to the polyoxyethylene portion in the ¹ H-NMR spectrum of this polymer was 45: 2, and the calculated molecular weight ratio of the dimethylpolysiloxane portion to the polyoxyethylene portion was calculated from this. Is 9 6: 4. This molecular weight ratio corresponds to 50,000: 200.

From the above, this polymer is a polydimethylsiloxane segment having an average molecular weight of 500,000 and a polyoxyethylene having an average molecular weight of 200,000. In the block copolymer consisting of a segment, a diol-containing group {(in the formula (1), Z is toluylene and S = T = —CH ₂ CH ₂ —} at the one end, a polymer having a terminal diol group having a terminal diol group. It was identified as an organosiloxane.

Example 3

(a3) Preparation of terminal hydroxyl group-containing polysiloxane (2):

Attach a stirrer, cooling tube, and thermometer to the three millimeter flask of 500 milliliters, and obtain 200 g of polydimethylsiloxane having a number average molecular weight of 100,000 with terminal SiH bond, 200 g, piece 6 g of polyoxyethylene having a number average molecular weight of 200 having a terminal aryl group and 70 g of toluene were added, the temperature was raised to 80 ° C., and 40 μl of a platinum catalyst was added and reacted for 5 hours. The reaction solution was cooled, 65 g of methanol was added to extract unreacted polyoxyethylene, and the methanol layer was removed.After three times, the solvent and volatile components were distilled off from the toluene layer under reduced pressure using an evaporator. As a result, 188 g of a colorless transparent liquid product was obtained.

The OH equivalent of this product was 970. According to IR, NMR, GPC, and the like, this product was found to be a block copolymer composed of polydimethylsiloxane having an average molecular weight of 1000 and polyoxyethylene having an average molecular weight of 200. confirmed.

(b3) Production of polyorganosiloxane having terminal diol group (1):

Attach a porcelain stirrer, a cooling tube, and a thermometer to a 300-milliliter four-necked flask, and add 100 g of the block copolymer obtained in (a3) above, toluene range isocyanate 2 15 g (NCO / OH-2.4) and 100 g of THF were added. The charge was below 1 0 ° C, dibutyltin dilaurate rate 5 wt%% toluene solution 0. 0 9 1 g (7 X 1 0- 4 eq ZOH) bets were placed, and the reaction temperature 1 5 ° C The reaction was maintained for 7.5 hours. The NCO content of 200 g of the reaction solution was 0.62 wt%. Based on the NCO content of the obtained reaction solution, 1.89 g (NC 0 / NH = 0 to 8) of diethanolamine was added thereto, and the reaction was carried out overnight. The obtained reaction solution was transferred to an eggplant-shaped flask, and THF was distilled off using an evaporator, followed by concentration. The concentrated solution was placed in a 1-liter separating funnel, and 65 g of methanol and 250 g of toluene were added thereto to carry out a separating operation to remove the methanol layer containing the oligomer component. The volatiles in the toluene layer were distilled off under reduced pressure to obtain 94 g of a slightly yellow highly viscous liquid polymer {polyorganosiloxane (1) having a terminal diol group).

The refractive index of this polymer is 1.4082, the water content is 69900 ppm, the number average molecular weight (Mn) in terms of polystyrene is 1330000, and the dispersity (Mw / Mn) is 1.1, OH equivalent is 5300. The integral ratio of the dimethylpolysiloxane portion and the polyoxyethylene portion in the ¹ H-NMR spectrum of this polymer was 110: 2, and the calculated molecular weight of the dimethylpolysiloxane portion and the polyoxyethylene portion was calculated from this. The ratio is 98: 2. This molecular weight ratio corresponds to 1000: 200.

Based on the above, this polymer has a diol at one end of a block copolymer consisting of polydimethylsiloxane segment having a number average molecular weight of 1000 and polyoxyethylene segment having a number average molecular weight of 200. In the containing group {Formula (1), Z was confirmed to be toluylene and a polyorganosiloxane having a terminal diol group having S = T = —CH ₂ CH ₂ —}.

Example 4

(a4) Preparation of terminal hydroxyl group-containing polysiloxane (2):

Attach a porcelain stirrer, condenser, and thermometer to a three-neck flask of 500 milliliters, and add 100 g of polydimethylsiloxane with a number average molecular weight of 100,000 having terminal SiH bonds. , Number-average number with an aryl group at one end 6 g of polyoxyethylene having a molecular weight of 400 and 160 g of tonoleene were added, the temperature was raised to 80 ° C, 65 μl of a platinum catalyst was added, and the reaction was carried out at 80 ° C for 20 hours. .

The reaction mixture was cooled, 140 g of methanol was added to extract unreacted polyoxyethylene, and the methanol layer was removed.Twice twice, and then the solvent and volatiles were removed from the toluene layer using an evaporator. After distilling off, 98 g of a brown transparent liquid product was obtained. The OH equivalent of this product was 112.000. According to IR, NMR, GPC, etc., this product is a block copolymer composed of polydimethylsiloxane having an average molecular weight of 100,000 and polyoxyethylene having an average molecular weight of 400. confirmed.

(b4) a polyorganosiloxane having a terminal diol group (1)

Attach a porcelain stirrer, a cooling tube, and a thermometer to a 300-milliliter four-necked flask, and add 100 g of the block copolymer obtained in (a4) above, and toluene range isocyanate 1 9 g (NCO / OH = 2.4) and 100 g of tetrahydrofuran were added. The charge liquid in an ice bath to below 1 0 ° C, Jibuchiruchinjira © a rate 5 wt% Toruen solvent solution of 0. 0 7 9 2 g (7 X 1 0- 4 eq Ζθ H) were charged, reaction The reaction was maintained for 7 hours while maintaining the temperature at 10 ° C or less. Further, the reaction was carried out at room temperature (20 to 25 ° C) for 10 hours.

The NCO content of 200 g of the reaction solution was 0.54 wt%. Based on the NCO content of the obtained reaction solution, 1.63 g (NCO / NH = 0.8) of diethanolamine was added, and the reaction was carried out overnight. The obtained reaction solution was transferred to an eggplant-shaped flask, and THF was distilled off using an evaporator, followed by concentration. The concentrate was placed in a 1-liter separatory funnel, and 300 g of methanol and 250 g of n-hexane were added thereto, followed by liquid separation. The methanol layer containing the oligomer components was removed. The volatile components of the hexane layer were distilled off under reduced pressure to obtain 96 g of a slightly yellow highly viscous liquid polymer.

The refractive index of this polymer is 1.4082, the water content is 280 ppm, the polystyrene equivalent number average molecular weight (Mn) is 13700, and the dispersity (Mw / Mn) is 1 2. The 〇H equivalent is 4900. The integral ratio of the dimethylpolysiloxane portion to the polyoxyethylene portion in the iH-NMR spectrum of this polymer was 99: 3, and the dimethylpolysiloxane portion and the polyoxetylene portion calculated from this were 9: 3. Has a molecular weight ratio of ₉

7: 3. This molecular weight ratio corresponds to 1000: 300. Based on the above, this polymer was added to one end of a block copolymer consisting of polydimethylsiloxane segment having a number average molecular weight of 1000 and polyoxyethylene segment having a number average molecular weight of 400. In the diol-containing group {(formula (1), Z is toluylene, and a polyorganosiloxane having a terminal diol group having S = T = —CH ₂ CH ₂ —} has been identified.

The polyorganosiloxane having a diol group at one end of the present invention is used as a copolymer component such as polyurethane and polyester, and can be uniformly mixed with a corresponding copolymer component such as dicarboxylic acid and diisocyanate. And good solubility in polar solvents. Therefore, unlike a conventional polyorganosiloxane having a diol group at one terminal, a resin solution having a high molecular weight does not become cloudy or a cloudy substance precipitates, resulting in an uneven resin solution. This is probably because the molecular chain has a polyoxyalkylene segment.

Claims

The scope of the claims

[Wherein, RR ² , R ³ , R ⁴ and R ⁵ are a linear or branched alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 4 to 10 carbon atoms. Or an aryl-containing group having 6 to 12 carbon atoms; n is 1 or more, m is 0 or more, and (n + m) is an average molecular weight of polysiloxane segment of 300 to X is an alkylene group having 2 to 20 carbon atoms; Y is one OCH ₂ CH ₂ —, one OCH (CH ₃ ) CH ₂ — or one OCH _{2 is} CH (CH ₃ ) —; p is a number satisfying the average molecular weight of polyoxyalkylene segment (Y _p ) of 150 to 2000; Ζ is 1 to 20 carbon atoms An alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms or an arylene-containing group having 6 to 20 carbon atoms; 1-2 0 alkylene group having the consequent Roaruki Renmotoma other having 1 0 4 carbon atoms are Ariren group having 1 two 6 carbon atoms. ]

A polyorganosiloxane having a terminal polyol having a number average molecular weight of 50,000 to 1,000, represented by the following formula:

2. Polyoxyalkylene / polyorganosiloxane block copolymer having one terminal hydroxyl group (provided that the average molecular weight of the polyoxyalkylene moiety is 150 to 2000, the average molecular weight of the polyorganosiloxane moiety is A polysiloxane having a terminal isocyanate group by reacting a polysiloxane having a terminal hydroxyl group comprising a polysiloxane having a terminal hydroxyl group and a diisocyanate to form a urethane bond. An organosiloxane intermediate is formed, and the intermediate is reacted with a diol amine. To obtain a polyoxyalkylene 'polyorganosiloxane-oxane block copolymer having a diol group at one end, and having a number average molecular weight of 500 to 100,000. A method for producing a polyorganosiloxane having a diol.

3. General formula (2)

(2)

A hydroxyl group-containing polysiloxane represented by the general formula (3)

0 = C ^ = NZN ^ = C ^ = 0 ( ³ )

S OH

HN (5)

The diol amine represented by T- ■ OH is reacted to form a compound of the general formula (

A terminal diol having a number average molecular weight of 50,000 PROCESS FOR PRODUCING POLY ORGANO SILOXANE HAVING OLE

[Wherein, RR ² , R ³ , R ⁴ and R ⁵ are a linear or branched alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 4 to 10 carbon atoms. Or an aryl-containing group having 6 to 12 carbon atoms; R ⁶ is a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms or a carbon atom having 6 to 1 carbon atoms. N is an aryl-containing group having two; n is 1 or more, m is a number of 0 or more, and (n + m) is an average molecular weight of the polysiloxane segment from 500 to 100,000. X is an alkylene group having 2 to 20 carbon atoms; Y is one OCH ₂ CH ₂ —, — OCH (CH ₃ ) CH ₂ — or — OCH ₂ CH (CH ₃ ) And p is a number satisfying the average molecular weight of the polyoxyalkylene segment (Y _p ) of 150 to 20000.

Ζ is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms or an arylene-containing group having 6 to 20 carbon atoms; S and Τ Is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms or an arylene group having 6 to 12 carbon atoms, respectively.

] ο

4. The terminal hydroxyl group-containing polysiloxane has a polyorganosiloxane having a number average molecular weight of 300 to 800 and having a terminal SiH bond and an alkenyl group having a number average molecular weight of 150 to 2000. 4. The process for producing a polyorganosiloxane having a terminal diol according to claim 2, which is a block copolymer obtained by a hydrosilylation reaction with polyoxyalkylene having the same.