JP3357110B2 - Method for producing polymer-dispersed polyol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates about the method for producing a polymer-dispersed polyol.

[0002]

BACKGROUND ART in Po Li polyether polyols obtained by polymerization of a monomer having an unsaturated group compounds and mixtures are called polymer-dispersed polyol is used as a raw material for polyurethane foam or polyurethane elastomer.

There are roughly two types of polymer-dispersed polyols, one of which is a polymer-dispersed polyol obtained by polymerizing a monomer in a substantially saturated polyol having no addition- polymerizable unsaturated group. is a polymer-dispersed polyol obtained by copolymerizing polyol and monomers having an addition polymerizable unsaturated group. Both are already commercially available.

The former polymer-dispersed polyols are described, for example, in JP-B-39-24737 and JP-B-47-1.
No. 5108, Japanese Patent Publication No. 43-22108, and the like. Also, the latter polymer-dispersed polyol using an unsaturated polyol is disclosed in JP-B-46-2.
No. 0508, JP-B-46-46556, JP-B-51-37228, JP-B-51-40914, JP-B-59-5608, and JP-B-60-17
No. 372, for example.

[0005]

Polymer-dispersed polyol in order to improve the hardness properties, such as poly urethane foam [0008] is often used. However, a conventional polymer-dispersed polyol is produced by once producing a polyol, using the polyol as a raw material, and polymerizing a monomer having a polymerizable unsaturated group therein. That is, it is necessary to go through two independent polymerization steps to obtain a product called a polymer-dispersed polyol.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and provides a method for producing a monomer having a polymerizable unsaturated group in the presence of a polyether polyol obtained by polymerizing an alkylene oxide. in the method polymerized to produce a polymer-dispersed polyol, the polyether polyol that provides <br/> a method for producing a polymer-dispersed polyol, characterized in that contains a composite metal cyanide complex.

Conventionally, as a method for producing a polymer-dispersed polyol, and again introduced into the reactor polyether port <br/> polyol obtained by purifying removed A alkylene oxide polymerization catalyst after polymerization of alkylene oxides, the polymerization A method of polymerizing a monomer having an unsaturated group in the presence of a polymerization initiator or the like has been widely adopted.

On the other hand, one feature of the present invention is that after polymerizing an alkylene oxide to obtain a polyether polyol, it is possible to continuously produce a polymer-dispersed polyol without performing a step such as purification. is there.

Conventionally, when manufacturing a polyether polyol by polymerizing an alkylene oxide, alkaline catalysts are widely used. However, the alkali catalyst used after this polymerization needs to be neutralized with an acid or treated with an adsorbent, and the alkali catalyst residue after such a process is usually removed by a separation means such as filtration. Therefore, when the polymerization of monomers which have a polymerizable unsaturated group in a conventional manner to precipitate the polymer particles to produce a polymer-dispersed polyol, the polyether polyol used as a raw material already filtration alkali catalyst residue It did not must have been removed by the separating means.

On the other hand, since the double metal cyanide complex used in the present invention has a higher activity than an alkali catalyst, a sufficient polymerization activity can be obtained with 1/10 to 1/100 of the alkali catalyst. It does not necessarily require the removal operation such as an alkali catalyst by the order application.

[0011] introducing a monomer to have a such a high polymerization activity of an alkylene oxide polymerization catalyst used for the first time, subsequent without refining operations polymerizable unsaturated group after obtaining the polyether polyol by polymerizing an alkylene oxide , Ru can be produced a polymer-dispersed polyol in one pot by polymerization.

[0012] Another feature of the present invention is that it can be used as a polymerization catalyst for the monomers that have a polymerizable unsaturated group the double metal cyanide complex. As described above, the double metal cyanide complex is a highly active polymerization catalyst for alkylene oxide.As a result of various studies on the catalytic activity behavior of the double metal cyanide complex by the present inventors,
Even for monomers have a polymerizable unsaturated group as well as alkylene oxide surprisingly been found to have a polymerization activity.

With this discovery, polymer-dispersed polyols can be made by several different methods of manufacture. That method after obtaining the polyether polyol by polymerizing an alkylene oxide, which by polymerizing monomers have a subsequent polymerizable unsaturated group without purification operation to produce a polymer-dispersed polyol using a composite metal cyanide complex, or an alkali catalyst or the like by polymerizing monomers have the alkylene oxide added refining composite metal cyanide complex in the polyether polyol obtained by after the polymerization polymerizable unsaturated group method for producing a polymer-dispersed polyol And the like.

[0014] The shape of port Rimmer dispersed polyol viscosity and the resulting particles, in order to control the size and the like, also has the effect that a combination of radical polymerization catalysts known in the art.

The alkylene oxide is polymerized to form a polyether.
In order to produce a terpolyol, an alkylene oxide is added to an active hydrogen-containing compound such as a polyhydroxy compound or a polyamine. Specifically, glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, dextrose and other polyhydric alcohols, diethanolamine other Al mosquito Noruamin, bisphenol A, phenol - formaldehyde condensates, other polyvalent phenol, ethylenediamine,
Diaminodiphenylmethane and other amines, polyester polyol, polycarbonate polyol, polyoxytetramethylene polyol, polybutadiene- based poly
And all such hydrocarbon polyols, and polyether polyols obtained by adding them to the alkylene oxide with the initiator, which ethylene oxide, propylene oxide, adding butylene oxide, other alkylene oxides.

As a catalyst for polymerizing such an alkylene oxide, for example, diethyl zinc, iron chloride, metal porphyrin, double metal cyanide complex and the like are known, and a double metal cyanide complex catalyst is particularly effective. US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat.
It has been proposed, such as 78459, by-product less unsaturated monols, it is possible to obtain a very high has a molecular weight of polyethers.

[0017] Examples of monomers that have a polymerizable unsaturated group, acrylonitrile, styrene, or alone methacrylic acid ester or acrylic San'e ester may be used in conjunction with them. Further , nitrile monomers such as 2,4-dicyanobutene-1, vinyl ester monomers such as vinyl acetate, diene monomers such as isoprene and butadiene, and other olefins, unsaturated esters, halogenated olefins, vinyl esters and so on. Preferred monomers are nitrile monomers such as acrylonitrile and styrenes.
These monomers Ru cormorants in combination of two or more.

[0018] It is preferable that the amount used of the monomer is particularly LIMITED Lena bur, the polymer concentration of the finally obtained polymer-dispersed polyol is about 5 to 50 wt%. The present invention also feature also that low viscosity polymer-dispersed polyol is obtained high polymer concentrations are suitable for the preparation of the polymer-dispersed polyol of relatively high polymer concentration. Thus, the more preferred polymer concentration of the polymer-dispersed polyol is about 15-45% by weight.

[0019] In the present invention, in the presence of a particle stabilizing agent in order to stably disperse the particles formed by polymerization Ru can also be carried out polymerization. As such a particle stabilizer
For example, acrylic acid residues, methacrylic acid residue, an allyl group, a hydroxy compound having an unsaturated double bond such as maleic acid residue, or glycidyl (meth) both polymerization involving compounds such as acrylate etc. Can be used.

The double metal cyanide complex as described above has a polymerization activity for the monomer to have a polymerizable unsaturated group may be used in combination other polymerization initiator. By supplying such a polymerization initiator to the reactor simultaneously with the monomer,
Monomer polymerization or polymerization initiator-containing polyether
Can or is polymerized by adding monomers to the polyol.

[0021] While preferred radical polymerization catalyst as the polymerization initiator is not limited to radical polymerization catalyst, it is possible to use various compounds capable of polymerizing a monomer having a polymerizable unsaturated group, also optionally Can be polymerized by radiation or heat without using a polymerization initiator. Examples of the radical polymerization catalyst include a peroxide-based, azo-based, or redox-based polymerization initiator and a metal compound catalyst. Specific well radical polymerization catalyst used, for example, azobisisobutyronitrile, benzoyl peroxide, t-alkyl peroxyester, acetyl peroxide Oki shea de, and the like diisopropyl peroxydicarbonate.

The polymerization process of a monomer having a polymerizable unsaturated group, after obtaining the polyether polyol by polymerizing an alkylene oxide in the composite metal cyanide complex, also the presence of a radical polymerization catalyst polymerizable unsaturated in the absence the method of polymerizing <br/> Ru monomer to have a saturated group method, by adding a composite metal cyanide complex in the purified polyether Po <br/> polyol, polymerizing monomers that have a polymerizable unsaturated group Although etc. there Ru, first method of polymer-dispersed polyol in the reaction sequence without purification of the polyether polyol is obtained, further
Is preferable to carry out polymerization in the presence of a radical polymerization catalyst . The reaction temperature is from 80C to 150C , preferably 1C .
It is desirable to carry out at 00 ° C to 120 ° C.

The resulting polymer-dispersed polyol may be as to be used as the polyurethane raw material, such as polyurethane foam, optionally mixed with other polyols is also used as a raw material for polyurethane.

[0024]

By the following examples to illustrate the invention, but the invention is Lena had limited by these examples.

[0025] pressure reactor of Example 1 2 liter molecular weight 1 in glycerine initiated
000 and a polyoxypropylene triol 200g and nitrous <br/> lead hexacyanocobaltate 0.02g addition, 12
0 stirred propylene oxide 800g were fed 2 hours Placing it while at ° C.. After stirring for 1 hour further at subsequent 120 ° C., it was fed a mixture of acrylonitrile 100g of azobisisobutyronitrile 5g on 2 hours Placing <br/> at 120 ° C.. After further stirring at 120 ° C. for 1 hour,
The residual monomer was removed under reduced pressure to obtain a brown-white polymer-dispersed polyol. The viscosity of the reaction 1400c P (25
° C), and the hydroxyl value was 31.0.

[0026] Example 2 3-liter pressure reactor, polyoxypropylene glycol having a molecular weight of 500 with propylene glycol initiator 20
0 g and zinc cyanohexacobaltate 0.05 g were added, and propylene oxide 800
It was supplied g and an ethylene oxide 400g 3 hours or only in. Was continued for an additional 1 hour stirring at 100 ° C., propylene glycol initiated in moles of polyoxypropylene glycol of molecular weight 500 and the tolylene diisocyanate and 2-hydroxyethyl methacrylate ratio of 1: 1: Double bond content was reacted at 1 hydroxy prepolymer 50 g, acrylonitrile 300g, was fed a mixture of styrene 300g and azobisisobutyronitrile scan Ciro nitrile 10g about 3 hours or only with. After further reacting at 100 ° C. for 1 hour, residual monomers were removed under reduced pressure to obtain a white polymer-dispersed polyol. Viscosity 2 800c P reactants, the hydroxyl value was 23.8.

[0027] pressure reactor of Example 3 2 liters of molecular weight 1 in glycerine initiated
0000 polyoxypropyleneoxyethylenetriol and zinc hexacyanocobaltate 0.0
And 5g was added, with stirring at 110 ° C., and reacted for 5 hours to introduce the acrylonitrile 150g methyl methacrylate 150g. Removing residual monomers under reduced pressure,
A brown-white polymer-dispersed polyol was obtained. Reactant viscosity
The 3 500c P, the hydroxyl value was 13.9.

[0028]

The production process of the polymer-dispersed polyol does not require a purification process of the base polyether polyol, and the process can be simplified.

Claims (3)

(57) [Claims] A method for producing a polymer-dispersed polyol by polymerizing a monomer having a polymerizable unsaturated group in the presence of a polyether polyol obtained by polymerizing an alkylene oxide, wherein the polyether polyol is a double metal cyanide A method for producing a polymer-dispersed polyol, which comprises a complex. Wherein the polyether polyol is Ru Oh the double metal cyanide complex in the polyether polyol obtained by polymerizing an alkylene oxide as a catalyst, method for producing a polymer-dispersed polyol according <br/> to claim 1. 3. Polymerization of a monomer having a polymerizable unsaturated group
And carried out in the presence of a radical polymerization catalyst, according to claim 1 or
3. The method for producing a polymer-dispersed polyol according to 2 .