WO2011114788A1

WO2011114788A1 - Method for producing lactone-modified single-terminal silicone polyol, and urethane resin composition

Info

Publication number: WO2011114788A1
Application number: PCT/JP2011/052086
Authority: WO
Inventors: 善之小田; 弘須崎; 西村　勝英; 晶子雨宮
Original assignee: Dic株式会社
Priority date: 2010-03-19
Filing date: 2011-02-02
Publication date: 2011-09-22
Also published as: TW201139511A

Abstract

Disclosed is a method for producing a silicone polyol, which has a normally-distributed molecular weight distribution, a low molecular dissociation, and a polysiloxane chain in a side chain, and which is suitable for use as a polyurethane resin starting material having little unreacted primary hydroxyl groups that have not reacted with lactones. Specifically, provided is a silicone polyol which can be used as a polyurethane resin starting material for one-shot molding. The method for producing a lactone-modified single-terminal silicone polyol involves ring-opening polymerizing a lactone monomer with 5 to 10 moles of an organo polysiloxane, which has two primary hydroxyl groups at one terminal and a molecular weight of 2000 to 4000 and which does not have a reactive group at the other terminal, per one primary hydroxyl group at the temperature of 80 to 140°C and in the presence of a catalyst.

Description

Method for producing lactone-modified one-end type silicone polyol and urethane resin composition

The present invention relates to a method for producing a lactone-modified one-end type silicone polyol and a urethane resin composition.

In recent years, organopolysiloxane compounds have excellent interfacial properties such as low friction, thermal stability, water repellency, antifoaming, and releasability, so that the performance of synthetic resins such as paints and molded products can be improved. For example, modifiers such as dimethylpolysiloxane, methylphenylpolysiloxane, reactive group-containing dimethylpolysiloxane, and polyether-modified organopolysiloxane are added and used.

However, these materials have insufficient compatibility with the resin or have insufficient heat resistance, so the range of use has been limited. Therefore, a lactone-modified organopolysiloxane compound in which a lactone is added to an addition reaction product of polysiloxane and glycerol monoallyl ether has been proposed for the purpose of improving these drawbacks. (Patent Document 1)
However, in this product, the lactone reacts with a plurality of hydroxyl groups of glycerin monoallyl ether and has a plurality of polylactone chains to increase the crosslinking structure, and the primary hydroxyl group and the secondary hydroxyl group coexist and the reactivity varies. It was difficult to use as a raw material for polyurethane resins. Furthermore, development of a polysiloxane chain-containing polyol (hereinafter referred to as a silicone polyol) that can be used as a raw material for a polyurethane resin has been desired.

Japanese Unexamined Patent Publication No. 03-6230

An object of the present invention is to provide a silicone having a polysiloxane chain in the side chain which is suitable as a raw material for a polyurethane resin having a normal molecular weight distribution, a low molecular weight deviation rate, and a low unreacted primary hydroxyl group that has not reacted with lactones. It exists in the manufacturing method of a polyol, and exists in the silicone polyol which can be especially used as a polyurethane resin raw material for one shot molding.

As a result of diligent research on a method for producing a silicone polyol for polyurethane resin having a normal molecular weight distribution and a small number of unreacted primary hydroxyl groups, the present inventors have found that a specific polysiloxane is produced at a specific temperature in the presence of a catalyst. The inventors have found that an excellent silicone polyol can be obtained as a polyurethane elastomer raw material, and have completed the present invention.

That is, in the present invention, a lactone monomer is present at a temperature of 80 to 140 ° C. in an organopolysiloxane having a molecular weight of 1000 to 4000 having two primary hydroxyl groups at one end and no reactive group at the other end. The present invention provides a process for producing a lactone-modified one-end type silicone polyol for a urethane raw material characterized by 5 to 10 moles of ring-opening addition polymerization per primary hydroxyl group, and a urethane resin composition using the same. .

The present invention provides a ring-opening addition polymerization of a specific amount of a lactone monomer at a specific temperature to an organopolysiloxane having two primary hydroxyl groups at one end of a specific molecular weight and no reactive group at the other end. As a one-shot molding polyurethane resin raw material, it is possible to produce a silicone polyol having a normal molecular weight distribution, a low molecular weight deviation rate, and a low unreacted primary hydroxyl group remaining without reacting with lactones. Useful.

The organopolysiloxane used in the present invention has a molecular weight of 1000 to 4000 having two primary hydroxyl groups at one end and no reactive group at the other end, and preferably has a molecular weight of 2000 to 4000. . The hydroxyl value is preferably 20 to 60 mgKOH / g, and the acid value is preferably 0.5 mgKOH / g or less. When the molecular weight is larger than 4000, the reaction between the lactone monomer and the organopolysiloxane does not proceed well, resulting in two peaks, which is not preferable because unreacted primary hydroxyl groups increase. On the other hand, if it is less than 1000, the effect of organopolysiloxane such as low friction cannot be imparted to the urethane resin.

Examples of the lactone monomer used in the present invention include β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, γ-crotonolactone, and preferably ε-caprolactone. The lactone monomer is subjected to ring-opening addition polymerization of 5 to 10 moles per primary hydroxyl group. Preferably, 8 moles of lactone monomer are added and polymerized to two primary hydroxyl groups on one side of the organopolysiloxane. Is. If the lactone monomer is less than 5 moles per primary hydroxyl group of the organopolysiloxane, the amount of unreacted primary hydroxyl groups will increase, and it will not be normal distribution and will have a shoulder, which is not preferable. . On the other hand, when the amount is more than 10 moles, the viscosity of the obtained resin becomes high and handling properties are inferior.

The production conditions of the lactone-modified one-end type silicone polyol are produced by carrying out in the system at a temperature of 80 to 140 ° C. in the presence of a catalyst. More preferably, it is 80 to 120 ° C.
When the temperature in the system is lower than 80 ° C., the reaction rate becomes slow and a long-time synthesis is required. When the temperature in the system is higher than 140 ° C., organopolysiloxane having two primary hydroxyl groups at one end and no reactive group at the other end decomposes, and the desired lactone-modified one-end type silicone A polyol cannot be obtained.

The catalyst to be used is preferably a tin-based catalyst, and particularly preferably butyltin tris-2-ethylhexanoate. At that time, the concentration of the catalyst in the system is preferably 100 to 500 ppm.

In order to produce a lactone-modified one-end type silicone polyol, an organopolysiloxane having a molecular weight of 1000 to 4000 having two primary hydroxyl groups at one end and no reactive group at the other end and a catalyst are charged into a reaction vessel. Then, the temperature in the system is set to 80 to 140 ° C., and the lactone monomer is charged in a nitrogen gas atmosphere so as to be 5 to 10 mol per hydroxyl group of the organopolysiloxane, preferably 6 to 24 hours, more preferably 8 The reaction is performed for ˜15 hours, and the reaction is terminated when the nonvolatile content becomes 99.5% by mass or more. Thereafter, the silicone polyol may be taken out.

The urethane resin composition of the present invention is a urethane resin molded product by reacting with the polyisocyanate by mixing the modified piece-terminated silicone polyol and other polyol components to form a polyol component. In that case, it is good also as a urethane prepolymer beforehand, and polyisocyanate, a polyol, and a chain extender may be formed in one shot.

The polyisocyanate used in the present invention is usually used for a polyurethane resin. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, or a mixture thereof, m- or p-phenylene diisocyanate. P-xylene diisocyanate, ethylene diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, diphenylmethane-4,4′-diisocyanate, 3,3′-dimethyl-diphenylmethane-4,4-biphenylene Diisocyanate, 3,3-dichloro-4,4-biphenylene diisocyanate, 4,4-biphenylene diisocyanate or 1,5-naphthalene diisocyanate, tolidine diisocyanate, ifosolone diisocyanate Sulfonates, cyclohexane diisocyanate, toluidine diisocyanate, crude diphenylmethane diisocyanate, and diphenylmethane diisocyanate are triphenylmethane triisocyanate and their various derivatives. Moreover, the urethane prepolymer whose terminal which made the following polyol and one of the said polyisocyanates react is an isocyanate group is also mentioned.

Other polyols include known polyether polyols, polycarbonate polyols, or ordinary polyester polyols, that is, those having an ester bond by condensation reaction of polyhydric alcohol and polyhydric carboxylic acid in the presence of a catalyst. It is. The polyol preferably has a molecular weight of 500 to 5000, particularly preferably 1000 to 3000, as determined from the hydroxyl value.

The chain extender is preferably a low molecular weight linear diol or diamine compound having 2 to 10 carbon atoms. Typical examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 2,2′-dimethyl-1,3-propanediol. , Diethylene glycol, 1,5 pentamethylene glycol, 1,6-hexamethylene glycol, cyclohexane 1,4-diol, cyclohexane-1,4 diol, cyclohexane-1,4 dimethanol, or the like; ethylenediamine, 1, 6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, 1, - propanediamine, diethylenetriamine, triethylenetetramine, 3,3'-dichloro-amine compounds such as, and hydrazine, hydrazine such as acid hydrazide. In particular, 1,4-butanediol and trimethylolpropane are preferable.

The urethane resin composition of the present invention can be produced by a conventionally known polyurethane production method, for example, a one-shot method, a prepolymer method or a quasi-prepolymer method, and further, bulk polymerization, solution polymerization, emulsion polymerization, emulsion polymerization, etc. Can be used. The production method may be a conventionally known method, such as a slab method, a double conveyor method, a hot cure method, a cold cure method, a RIM method, molding by an open mold, an integral molding with a composite material, an on-site construction method, a spray method, a casting method. Methods such as injection, coating, and impregnation can be used. In the production, the polyisocyanate and the polyol are preferably reacted at a molar ratio (NCO / (OH + NH ₂ )) of 0.8 to 1.1, more preferably 1.0 to 1.05. Moreover, a well-known urethanization catalyst, surfactant, another adjuvant, etc. can be used in the addition amount generally used when manufacturing urethane.

Furthermore, the urethane composition of the present invention can be added with an antioxidant, an ultraviolet absorber, a hydrolysis inhibitor, a filler, a colorant, a reinforcing agent, a release agent, a flame retardant and the like, if necessary. Furthermore, other thermoplastic polyurethane elastomers and other general-purpose thermoplastic resins such as ABS resin, AS resin, vinyl chloride resin, polyamide and the like can be added within a range not impairing the effect of the urethane resin composition according to the present invention. . The composition of the present invention may contain various additives selected from surfactants, catalysts, stabilizers, and pigments.

The urethane composition of the present invention can be used as a thermoplastic elastomer (TPU), a thermosetting elastomer (TSU), an aqueous polyurethane resin, a radical curable urethane resin, a molding material, an adhesive, an adhesive, a paint, a foam, It can be used for polyurethane products in all fields such as sealing agents and photo-curable resins. Specific applications include three-dimensional molded products such as yarns, films, sheets, belts, hoses, rolls, tires, anti-vibration materials, packings, and shoe soles, as well as artificial leather, synthetic leather, soft / hard foams, and textile materials. It can be used in many fields such as industrial materials, electrical and electronic materials, optical materials, medical materials, and civil engineering materials.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, “part” and “%” in the sentence are based on mass.

Example 1 (Synthesis of lactone-modified one-end type silicone polyol)
Organo with two primary hydroxyl groups at one end of the following structural formula and no reactive group at the other end in a 1 liter four-necked flask equipped with a nitrogen inlet tube, thermometer, cooling tube, and stirring device Charge 500 parts of polysiloxane (hydroxyl value: 41.1 mg KOH / g, acid value: 0.05 mg KOH / g), 335 parts of ε-caprolactone, 0.250 part of butyltin tris-2-ethylhexanoate as a reaction catalyst, and pass through nitrogen. The reaction was carried out at 100 ° C. for 13 hours. (Non-volatile content (NV) was appropriately measured for the reaction end point, and the end point was determined when NV was 99.5% or higher.) After reaction for 13 hours, NV reached 99.7%, so the resin was removed from the flask. I took it out. The reaction product had a hydroxyl value of 24.4 mg KOH / g, an acid value of 0.55 mg KOH / g, and a white solid at room temperature (25 ° C.), and a transparent liquid resin at 100 ° C. The molecular weight distribution by GPC measurement showed a normal distribution, and the proportion of the unreacted primary hydroxyl group of the organopolysiloxane by C13 NMR measurement was 5% (that is, the primary hydroxyl group reacted with ε-caprolactone was 95%).

Examples 2-4
Synthesis was performed in the same manner as in Example 1 except for the number of parts and the synthesis conditions shown in Table 1.

Comparative Examples 1-7
Synthesis was performed in the same manner as in Example 1 except for the number of parts and the synthesis conditions shown in Table 1.

The resins obtained in the above Examples and Comparative Examples were measured for the non-volatile content, hydroxyl value, acid value, molecular weight deviation rate, ratio of unreacted primary hydroxyl groups, and molecular weight distribution by GPC measurement by the following methods.

<Nonvolatile content>
A 1 g sample was placed in a metal petri dish, 5 ml of toluene was added, and the remaining amount after drying at 107.5 ° C. for 1 hour was determined.
Nonvolatile content (%) = (BC) / (AC) × 100
However, A: Metal Petri dish + Mass of the sample before drying (g)
B: Mass of the metal petri dish + sample after drying (g)
C: Mass of metal petri dish

<Hydroxyl value>
An acetylating agent consisting of acetic anhydride and pyridine was added to the sample, and then acetylated at 115 ° C. for 1 hour. Next, water was added to decompose excess acetic anhydride into acetic acid, acetone and toluene were added, and then neutralization titration was performed using N / 2 potassium hydroxide ethyl alcohol solution.
Hydroxyl value (mgKOH / g) = (BT) × F × 28.05 / S + AN
B: Drop amount of N / 2 potassium hydroxide ethyl alcohol in the blank test (ml)
T: Drop amount of N / 2 potassium hydroxide ethyl alcohol in this test (ml)
F: Potency of N / 2 potassium hydroxide ethyl alcohol S: Sampling amount (g)
AN: Acid value of the sample

<Acid value>
The sample was dissolved by adding a neutral solvent (toluene / methanol), and then neutralized with 0.1N potassium hydroxide ethyl alcohol.
Acid value (mgKOH / g) = V × F × 5.661 / S
V: Drop amount of 0.1N potassium hydroxide ethyl alcohol (ml)
F: Potency of 0.1N potassium hydroxide ethyl alcohol S: Sampling amount (g)

<Molecular weight deviation rate>
The target molecular weight determined by calculation from the hydroxyl value of the one-end diol type organopolysiloxane, the acid value, and the molar ratio of ε-caprolactone / one-end diol type organopolysiloxane,
The deviation rate was determined from the experimental molecular weight obtained by calculation from the hydroxyl value and acid value of the obtained resin.
Molecular weight deviation rate (%) = (Target molecular weight−Experimental molecular weight) / Target molecular weight × 100
However, molecular weight = 56100 × 2 / (hydroxyl value + acid value)

<Ratio of unreacted primary hydroxyl group>
A sample was dissolved in deuterated chloroform, and ¹³ C-NMR was measured by a conventional method. It was calculated from a peak appearing at 65.5 ppm (corresponding to carbon adjacent to the unreacted primary hydroxyl group) and a peak appearing at 62.0 ppm (carbon adjacent to the primary hydroxyl group reacted with lactone).
Unreacted primary hydroxyl group ratio (%) = 65.5 ppm peak area / (65.5 ppm peak area + 62.0 ppm peak area) × 100

<Molecular weight distribution by GPC measurement>
The sample was dissolved in tetrahydrofuran (THF) (0.4% solution) and subjected to gel permeation chromatography analysis. The shape of the obtained chart was evaluated.
[Measurement conditions] Eluent: THF Column: TSKgel flow rate: 1.0 ml / min
Column: TSKgelG5 ・ 4 ・ 3 ・ 2 Detector: RI

Example (production of urethane elastomer sheet)
(Synthesis of urethane prepolymer)
484.1 parts of 4,4-diphenylmethane diisocyanate was placed in a 2 liter flask, and 1000 parts of polylite OD-X-640M (polyester polyol molecular weight of DIC 2000) and 50.1 parts of the lactone-modified one-end type silicone polyol of Example 1 were added. The mixture was mixed and reacted at 70 ° C. for about 5 hours under a nitrogen atmosphere to obtain a silicone-containing urethane prepolymer having an NCO equivalent of 525.

(Creation of urethane elastomer)
400 parts of a silicone-containing urethane prepolymer adjusted to 80 ° C. and 32.6 parts of a 70/30 (weight ratio) mixture of 1,4 butanediol / trimethylolpropane were mixed and cast in a centrifugal molding machine at 140 ° C. After curing under conditions of × 1 hour, secondary curing was performed under conditions of 110 ° C. × 16 hours to obtain a 2 mm thick urethane elastomer sheet. Although the obtained sheet was slightly cloudy, a tough sheet having a transparent feeling was obtained.

Claims

A lactone monomer is added to an organopolysiloxane having a molecular weight of 2000 to 4000 having two primary hydroxyl groups at one end and no reactive group at the other end in the presence of a catalyst at a temperature of 80 to 140 ° C. A process for producing a lactone-modified one-end type silicone polyol, which comprises 5 to 10 moles of ring-opening addition polymerization per unit.
The method for producing a lactone-modified one-end type silicone polyol according to claim 1, wherein the catalyst is a tin-based catalyst.
The method for producing a lactone-modified one-end type silicone polyol according to claim 2, wherein the tin-based catalyst is butyltin tris-2-ethylhexanoate.
2. The process for producing a lactone-modified one-end type silicone polyol according to claim 1, wherein the concentration of the catalyst in the system is 100 to 500 ppm.
The process for producing a lactone-modified one-end type silicone polyol according to claim 1, wherein the lactone monomer is ε-caprolactone.
The method for producing a lactone-modified one-end type silicone polyol according to claim 1, wherein the lactone-modified one-end type silicone polyol is obtained by adding lactone monomer to each of the two primary hydroxyl groups on one side of the organopolysiloxane by 8 moles.
A polyurethane resin composition comprising the lactone-modified one-end type silicone polyol according to claim 1.
A lactone monomer is added to an organopolysiloxane having a molecular weight of 2000 to 4000 having two primary hydroxyl groups at one end and no reactive group at the other end in the presence of a catalyst at a temperature of 80 to 140 ° C. A process for producing a lactone-modified one-end type silicone polyol, which comprises 5 to 10 moles of ring-opening addition polymerization per unit.
The method for producing a lactone-modified one-end type silicone polyol according to claim 1, wherein the catalyst is a tin-based catalyst.
The method for producing a lactone-modified one-end type silicone polyol according to claim 2, wherein the tin-based catalyst is butyltin tris-2-ethylhexanoate.
3. The method for producing a lactone-modified one-end type silicone polyol according to claim 1, wherein the concentration of the catalyst in the system is 100 to 500 ppm.
The process for producing a lactone-modified one-end type silicone polyol according to claim 1, wherein the lactone monomer is ε-caprolactone.
The method for producing a lactone-modified one-end type silicone polyol according to claim 1, wherein the lactone-modified one-end type silicone polyol is obtained by adding lactone monomer to each of the two primary hydroxyl groups on one side of the organopolysiloxane by 8 moles.
A polyurethane resin composition comprising the lactone-modified one-end type silicone polyol according to claim 1.