JPS59152911A - Production of polymeric polyol and polyurethane synthetic resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin having flame retardance and improved heat resistance, by using a polymer polyol obtained by polymerizing a polymerizable monomer at least a part of which is a maleimide, in a polyol. CONSTITUTION:The objective resin is obtained by reacting (A) a polymer polyol obtained by polymerizing polymerizable monomers containing alpha,beta-unsaturated group and composed of a maleimide (preferably N-phenylmaleimide, etc.) as at least a part of the components (preferably a combination of a maleimide and acrylonitrile) in a polyol (preferably polyether polyol, etc.) with (B) a polyisocyanate compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polymer polyol and a polyurethane-based synthetic resin, and particularly relates to a method for producing a polymer polyol and a polyurethane-based synthetic resin, and in particular, a method for producing a polymer polyol containing at least a maleimide in a polyether polyol-based polyol having or not having an unsaturated group. The present invention relates to a polymer polyol obtained by polymerizing a polyurethane monomer, and a method for producing a polyurethane synthetic resin using the same.

It is known to produce polymer-containing polyols, so-called polymer polyols, by polymerizing monomers having polymerizable unsaturated groups (hereinafter referred to as polymerizable monomers) in polyether polyols, polyether ester polyols, polyester polyols, and other polyols. It is. As the polyol, both a polyol having no polymerizable unsaturated group and a polyol having it can be used. Regarding the former polymer polyol, for example, Japanese Patent Publication No. 59-24737, Japanese Patent Publication No. 41-54
Publication No. 73, Special Publication No. 43-22108, Special Publication No. 5
No. 7-5835, Japanese Patent Publication No. 57-6471, and regarding the latter polymer polyol, for example, Japanese Patent Publication No. 4
Publication No. 6-20508,! Japanese Patent Publication No. 51-37228, Japanese Patent Publication No. 52-5459, Japanese Patent Publication No. 52-t3a
Publication No. 34, Special Publication No. 51-40914, Special Publication No. 5
1-40915, JP-A-56-90818, JP-A-56-93724, etc. have detailed explanations of C3, and other types of polymer polyols. -47043 Publication, JP-A-54-6
There are polymer polyols as described in Japanese Patent No. 8894. Polymer polyols are widely used mainly as raw materials for various polyurethane foams, but they can also be used as raw materials for polyurethane synthetic resins such as polyurethane-based elastomers.

The most widely used polymerizable monomer as a polymer polyol is a combination of acrylonitrile and styrene. Polymer polyols obtained using only acrylonitrile are effective in improving the physical properties of polyurethane foams obtained using polymer polyols. However, polymer polyols obtained using only acrylonitrile as a polymerizable monomer have a high viscosity and are inconvenient to handle, so it is customary to use styrene in combination to reduce the viscosity. However, when using acrylonitrile and styrene together, polyurethane raw materials
- The effect of improving the physical properties of the film is not as sufficient as when acrylonitrile alone is used. For example, the hardness of polyurethane foam decreases, making it difficult to reduce the density. Therefore, a polymer polyol with a low viscosity that can produce a polyurethane foam with a hardness comparable to that of a polymer polyol using only acrylonitrile is desired.

On the other hand, polyurethane foam that uses polymer polyols uses polyols that do not contain polymer components. The problem is that it is more flammable than the polyurethane foams used. It is a requirement of the times to make polyurethane foam more flame retardant, and in this respect conventional polymer polyols are inadequate. Polymer polyol v (There are two ways to assess flame retardancy: making the polyol flame retardant and making the polymer component flame retardant.

In order to solve the above problems, the present inventor selected various types of polymerizable monomers for producing polymer polyols, and researched and examined the effectiveness of the resulting polymer polyols as raw materials for polyurethane. As a result, it was found that maleimides are particularly effective as polymerizable heptamers. Although maleimides can be used alone as polymerizable monomers for producing polymer polyols, they are preferably used in combination with other polymerizable monomers. In this case, acrylonitrile is most suitable as the other polymerizable monomer. The present invention relates to a method for producing a polymer polyol using these maleimides. A polymer polyol characterized in that at least a portion thereof is a maleimide.

Maleimides are compounds having the following general formula or derivatives thereof.

A is, for example, an argyl group or an alkylene group, and F is an alkylene group, -5o2-, -5o-, -s-, -o
- etc.), cycloalkyl groups, cycloalkylene groups, etc., and particularly preferred are alkyl groups or alkylene groups having 1 to 4 carbon atoms, and substituted or unsubstituted phenyl groups.

Although n is preferably an integer of 1 to 2 as in A above, 1 is particularly preferred. Further, its derivatives include those in which one or both of the hydrogen atoms bonded to the carbon atoms in the middle-aged saturated bond [7] in the above general formula are substituted with... rogene, argyl group, or other organic group. Maleimides are usually obtained by reacting maleic acid with ammonia or mono- or polyamines. This mono- or polyamine residue is A. Particularly preferred maleimides are those in which n is 1, such as N-phenylmaleimide and N-alkylmaleimide.

Although maleimides can be used alone, it is preferable to use them in combination with other polymerizable heptamers in view of the viscosity of the polymer polyol, the dispersion stability and solubility of the polymer component in the polymer polyol, and so on.

Examples of polymerizable monomers that can be used in combination include acrylonitrile, methacrylonitrile, 2,4-dicyanobutene-1, other cyan group-containing monomers, styrene, α
-Methylstyrene, other styrenic monomers, acrylic esters, methacrylic esters, acrylamide, other acrylic monomers, butadiene, imprene, other diene monomers, other vinyl monomers, vinylidene monomers, olefins, etc. . Particularly preferred are cyan group-containing monomers, acrylic monomers, and styrene monomers, of which acrylonitrile is most preferred.

Maleimides are effective in reducing the viscosity of polymer polyols when used in combination with acrylonitrile (in place of conventional styrene). Moreover, it has less influence on the hardness of polyurethane foam than styrene, and polyurethane foam with high hardness can be obtained. In addition, maleimide polymers impart flame retardancy to polymer polyols, and the higher the proportion thereof in the polymer component, the more effective it is.

On the other hand, in the production of non-7-ohm or microcellular polyurethane elastomers by reaction injection molding, which will be described later, when the polymer polyol of the present invention is used, thermal sagging is lower than that of polyurethane elastomers using conventional polymer polyols. was found to improve. The heat sag property refers to the degree of deformation when held under heating, and the smaller the deformation, the better the heat resistance.

When the polymer polyol of the present invention is used, it is possible to obtain a polyurethane that has lower thermal sag than acrylonitrile-based polymer polyol, which was conventionally considered to have the best physical properties of polyurethane. It will be done. Of course, the effect of improving the flame retardance of the polyurethane elastomer is also maintained as in the case of the above-mentioned foam.

Based on these facts, when maleimides are used in combination with other polymerizable monomers, the proportion of maleimides in the total polymerizable monomers is suitably from 2 to 70% by weight, particularly preferably from 10 to 60% by weight.

The amount of the maleimide polymer or copolymer in the polymer polyol is not particularly limited, but preferably 2 to 60% by weight, particularly 5 to 40% by weight. Further, when a maleimide is used in combination with acrylonitrile, a polymer polyol having a lower viscosity than acrylonitrile alone may be obtained. In combination with acrylonitrile, although this may not be the case in all ranges of combination proportions with acrylonitrile,
The combination ratio is favorable in that a polymer polyol with low viscosity can be obtained compared to acrylonitrile alone. The ratio is such that the maleimide accounts for 15 to 55 parts by weight of all the polymerizable monomers. Further, even if a relatively high viscosity polymer polyol has a high polymer concentration, it can be used after being diluted with another polyol.

Polyols with a high polymer concentration are commercially valuable because they can be used as a masterbatch (they can be diluted and used when producing polyurethane).

As the polyol, various polyols that can be used as raw materials for polyurethane synthetic resins can be used. Examples include polyether polyol, polyester polyol, polyether ester polyol, urethanized polyol, hydroxyl group-carrying hydrocarbon polymer, polycarbonate polyol, and the like. These may be unsaturated polyols having an unsaturated group copolymerizable with the polymerizable monomer, or may be substantially saturated polyols. The hydroxyl value of these polyols is not particularly limited, but 10 to 8[10] is suitable, particularly 20 to 200
, more preferably from 20 to 120. Moreover, the average number of hydroxyl groups in the polyol is preferably 1.7 to 8, particularly preferably 2.0 to 6.0, and more preferably 2.0 to 4.0. A mixture of two or more of these polyols may be used. Particularly preferred polyols include saturated or unsaturated polyether polyols, unsaturated polyester polyols, unsaturated polyether ester polyols having a small amount of ester groups, and unsaturated urethanized polyols.

The saturated polyether polyol is preferably a polyether polyol obtained by adding a cyclic ether to a polyhydric polyester. Typical initiators include polyhydroxy compounds such as polyhydric alcohols and polyhydric phenols, amines such as alkanolamines, and mono- or polyamines. For example, ethylene glycol, propylene glycol, diethylene glycol, cyglobylene glycol, chrycerin, tol. Methylolpropane, pentaerythritol, diglycerin, degistrose, sorbitol, methyl glucoside, sucrose, monoethanolamine, jetanolamine, triethanolamine, diisopropanolamine bisphenol A, phenol-formaldehyde condensate, ethylenediamine, propylenetriamine, Examples include tolylene diamine and diaminodiphenylmethane. The initiator may be a mixture of two or more compounds. Epoxides are preferred as the cyclic ether, but cyclic ethers having four or more negative terms such as tetrahydrofuran may also be used. As the epoxide, an alkylene oxide having 2 to 4 carbon atoms is preferred, but other epoxides, such as), rogen-containing alkylene oxide, styrene oxide, glycidyl ether, and glycidyl ester, may be used alone or in combination with the alkylene oxide. Examples of alkylene oxides having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and butylene oxide, and propylene oxide alone or in combination with ethylene oxide is particularly preferred. When ethylene oxide is used in combination with other alkylene oxides, especially propylene oxide, a polyether polyol having primary hydroxyl groups is obtained if ethylene oxide is added last. In some cases, ethylene oxide can be inserted in the middle of the molecular chain, and separate from these sequential additions, mixed additions such as reacting a mixture of ethylene oxide and propylene oxide can also be performed.

Examples of unsaturated polyols include unsaturated polyether polyols obtained by using an unsaturated epoxide such as allyl glycidyl ether as a part of the epoxide in the above-mentioned polyether polyol production Kb,
Unsaturated polyester polyols obtained by partially using unsaturated polyhydric alcohols or polybasic acids, unsaturated polyether ester polyols and polyether polyols obtained by the reaction of unsaturated polybasic acids and polyether polyols. Unsaturated polyether ester polyols, polyether polyols, unsaturated polyhydric alcohols (and/or unsaturated monoalcohols), and polyisocyanate-1. Examples include unsaturated urethanized polyols obtained by reacting at least six compounds.

The number of unsaturated groups per molecule of these unsaturated polyols is not particularly limited, but on average [1,2
-4 is preferred.

The polymer polyol is obtained by polymerizing the above polymerizable monomer in a polyol.

This polymer polyol can be manufactured by conventional manufacturing methods. For example, a method in which polymerization is carried out while adding a mixture of a radical-generating polymerization initiator and a polymerizable monomer to a polyol, a method in which polymerization is carried out while adding a polymerizable monomer to a polyol containing a polymerization initiator, a method in which a polymerization initiator, a polymerizable A method in which polymerization is carried out while adding a mixture of a polymer and a polyol to a polyol can be used.

The polymerization initiator is not limited to a radical generator, and various compounds that can polymerize a polymerizable monomer having a polymerizable unsaturated group can be used. Polymerization can be carried out by radiation or heat without the need for light. As a polymerization initiator,
Examples include peroxide-based, azo-based, or redox-based polymerization initiators and metal compound catalysts. Examples of commonly used polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, and t-
Alkyl peroxy ester, acetyl peroxide,
Examples include diimpropyl peroxydicarbonate.

The resulting polymer polyol is usually made into an fCC bag product in which residual polymerization initiators are decomposed and unreacted polymerizable monomers are removed.

The polymer polyol obtained by the present invention can be used as is.
Alternatively, it can be diluted with various other polyols and used as a raw material for polyurethane. That is, a polyurethane can be produced by reacting a polyol component containing this polymer polyol with a polyisocyanate component containing a polyisocyanate compound. Polyurethanes include flexible, semi-rigid, or rigid foams, elastomers, microcellular elastomers, paints, adhesives, waterproofing materials, and many others. In particular, the polymer polyol in the present invention is a soft or semi-rigid 7
It is suitable as a raw material for polyurethane synthetic resins, which are ohmic, non-foam, or microcellular elastomers.

The present invention also relates to a method for producing a polyurethane synthetic resin using the polymer polyol, that is, a method for producing a polyurethane synthetic resin using a polyol and a polyisocyanate compound, which includes:
A polyurethane system characterized by using a polymer polyol obtained by polymerizing in a polyol a polymerizable monomer having an α,β-unsaturated group, at least a part of which is a maleimide, as part or all of the polyol. A method for producing synthetic resin.

The polymer polyol in the above-mentioned invention is the polymer polyol of the present invention (b). This polymer polyol can be used alone as a polyol as a raw material for polyurethane synthetic resins, but it can also be used in combination with the polyol of 110. As the diluent polyol (hereinafter referred to as the second polyol), a polyol (hereinafter referred to as the first polyol) that can be used as a medium for producing the polymer polyol described above may be used. 8″!, the second polyol is a saturated polyol within the first polyol,
Polyether polyols that are substantially saturated in I# are preferred. The hydroxyl value of the second polyol is 10 to 200,
In particular, 20 to 120 is preferable, and the hydroxyl value is 1.7 to 8.
In particular, 20 to 6.0, more preferably 2.0 to 4.0. Further, the second polyol may optionally be a low molecular weight polyol. For example, polyhydric alcohols, alkanolamines, and other low molecular weight polyols as chain extenders or crosslinkers may be used. In particular, when producing a polyurethane elastomer, a chain extender or crosslinking agent such as this low molecular weight polyol or other polyamine is usually used. Therefore, polyols used as raw materials for polyurethane synthetic resins are
It is preferable to consist of only the polymer polyol or a combination of the polymer polyol, a second polyol, and at least one type of low molecular weight polyol.

Polyols made of a polymer polyol alone or in combination with a second polyol without using a low molecular weight polyol are suitable as raw materials for flexible polyurethane foam, and polyols made of a combination containing a low molecular weight polyol are suitable for use in polyurethane elastomers or engineered plastics. It is suitable as a raw material for absorbent foams and other semi-rigid polyurethane foams. The molecular weight of the low molecular weight polyol is not particularly limited, but 400 or less, especially 200 or less is light and heavy.

Polyisocyanate compounds used as main raw materials for polyurethane synthetic resins along with polyols include aromatic, aliphatic, alicyclic, and compounds having two or more of these isocyanate groups.For example, tolylene diisocyanate 7 4.4'-diphenylmethane diisocyanate-1, polymethylene polyphenyl isocyanate, xylylene diisocyanate, hexamethylene diisocyanate, inphorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and modifications thereof There are various substances (for example, prepolymer-type modified products, carbodiimide-modified products, trimers, etc.), and these can be used alone or in combination. The amount of the polyisocyanate compound to be used relative to all active hydrogen compounds such as polyols is usually 90 to 130 in terms of isocyanate index, but is not limited thereto.

In addition to the above two main raw materials, polyurethane synthetic resins also contain reaction catalysts, blowing agents, foam stabilizers, crosslinking agents, chain extenders, fillers, ultraviolet absorbers, antioxidants, colorants, and flame retardants depending on the purpose. , internal mold release agents and other additives are used. A reaction catalyst such as a tertiary amine catalyst or an organometallic compound catalyst is usually essential. In the production of polyurethane foam, blowing agents such as low boiling point halogenated hydrocarbon blowing agents and water, and foam stabilizers such as silicone compounds are used. In the production of elastomers, low molecular weight polyvalent active hydrogen compounds (such as the above-mentioned low molecular weight polyols and polyamines) such as chain extenders and crosslinking agents are usually used1, and fibrous fillers such as glass fibers, Powder fillers such as calcium carbonate, silica, clay, and aluminum hydroxide, and tabular fillers such as mica may also be used for the purpose of improving physical properties.

Polyurethane foam usually requires the use of reaction catalysts, blowing agents, and foam stabilizers in addition to the main raw materials of polyols and polyisocyanate compounds. Suitable polyurethane foams include flexible polyurethane foams and semi-rigid polyurethane foams. In the case of semi-rigid foams, chain extenders and crosslinkers such as low molecular weight polyols are often additionally used. In addition to polyurethane foam, Monoke polyurethane elastomers are preferred as polyurethane synthetic resins in the present invention, and particularly preferred are non-7-ohm or microcellular polyurethane elastomers obtained by reaction injection molding.

Polyurethane elastomers produced by reaction injection molding are made of relatively high molecular weight polyols, including polymer polyols,
In particular, a chain extender or crosslinking agent consisting of a high molecular weight polyol and a low molecular weight polyol or polyamine having a hydroxyl value of 15 to 80, particularly 20 to 60, especially a carbon number of 2 to 4.
Polyols consisting of a combination of dihydric alcohols and polyisocyanate compounds, especially di7-functional diylmethane diisocyanate or its modified product, and a reaction catalyst, and in the case of microcellular elastomers, a small amount (usually 20 parts by weight or less) of a blowing agent,
and other additives if necessary. By using the polymer polyol of the present invention in a polyurethane elastomer, as described above, in addition to flame retardancy, heat resistance is improved. Note that the method for producing the polyurethane synthetic resin is not limited to the reaction injection molding method, but may be produced by a one-shot method, a greborimer method, a quasi-full polymer method, or other methods.

Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

Examples 1-7, Comparative Examples 1-6 As shown in Table 1, a 5-ton autoclave was charged with polyether polyol in a predetermined length, and the pressure reduction and nitrogen purge operations were repeated at a predetermined temperature.1. ,,after, the 1st
As described in the table, a mixture of the remaining polyether polyol, a monomer having a polymerizable unsaturated group, and a polymerization initiator was introduced into an autoclave while stirring at a predetermined speed.

Unreacted hexamer was removed under reduced pressure to obtain the desired polymer polyol. As a comparative example, a polymer polyol obtained by rod polymerization of acrylonitrile was also used.
Record in the table.

As is clear from Table 1, the polymer polyol obtained by copolymerizing maleimides has a lower viscosity than the polymer polyol obtained by homopolymerizing acrylonitrile.

Examples 8, 9, 10, Comparative Example 4 Using the polymer polyols produced in Example-1, Example-2, Example-6, and Comparative Example-1 in Table 1, high elasticity 7
Ohm mold foaming was performed.

Polymer polyol 160f, OH value 34.2rNiK
oH/y poly(oxypropylene/oxyethylene) triol 240 f, silicone oil 4.4 f, ) lyethylenediamine dipropylene glycol solution 24 v,
A mixed isocyanate of crude polymethylene polyphenylisocyanate and tolylene diisocyanate (mixed weight ratio 20/80) was mixed into a mixture of 121F water in an amount that gave an index of 105, and the temperature was rapidly controlled to 50°C. Mold (400X400X 100 wa
), and after being left at room temperature for 1 minute, it was taken out to obtain a mold form. The physical properties of this 7 ohm are shown in Table 2.

Examples 8 and 9. The foam of Comparative Example 4 had a LD (form hardness) equal to or higher than that of the foam of Comparative Example 4. On the other hand, the foam of Comparative Example 4 had some defects that appeared to be due to poor mixing. Furthermore, it can be seen that the foams of Examples 8, 9, and 10 have a shorter burning distance and are superior in flame retardancy than the foam of Comparative Example 4.

Table 2 1) According to ASTM D-1692.

Examples 11, 12, 13, Comparative Example 5 Example 1. Example 2. Example 3. Using the polymer polyol obtained in Comparative Example 1, a polyurethane elastomer was molded by RIM molding method, and the physical properties were compared. The results are shown in Table 6.

Table 6 1))-IJ Ethylenediamine dipropylene glycol solution 2) Dibutyltin dilaure-1 6) Modified diphenylmethane diisocyanade Mondur (Mond+ir) manufactured by Mobay Co., Ltd. E-451''4) 1
20°C 1 hour thermal sag distance Examples 11 and 12. It can be seen that the elastomer obtained in No. 15 has less thermal sag at high temperatures than Comparative Example 5, and has excellent heat resistance.

Within the agent 1) Akira Agent Ryo Hagihara -

Claims (1)

[Scope of Claims] 1. In a polymer polyol obtained by polymerizing a polymerizable monomer having an α,β-unsaturated group in a polyol, at least a part of the polymerizable monomer having an α,β-unsaturated group A polymer polyol characterized by being a maleimide. 2. The polymer polyol according to claim 1, wherein the proportion of maleimides in the total polymerizable monomers is 2 to 50% by weight. (5) The polymer polyol according to claim 1, wherein the polymerizable monomer is a combination of maleimides and acrylonitrile. 4. The maleimides are N-phenylmaleimide and N
- The polymer polyol according to claim 1, which is at least one type of argylmaleimide. 5. In a method for producing a polyurethane synthetic resin by reacting a polyol and a polyisocyanate compound, polymerization in which part or all of the polyol has an α,β-unsaturated group, at least a part of which is a maleimide. 1. A method for producing a polyurethane synthetic resin, the method comprising using a polymer polyol obtained by polymerizing a polyurethane monomer in a polyol. The method according to claim 5, wherein the polyurethane-based synthetic resin is polyurethane foam.
5. The method according to claim 5, wherein the polyurethane synthetic resin is a polyurethane elastomer obtained by reaction injection molding.