JP2004143441A - Method for producing rigid foamed synthetic resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide lightweight rigid foam having excellent adhesion and dimensional stability, by using water as a foaming agent. <P>SOLUTION: This method for producing the rigid foam comprises reacting a polyol compound with a polyisocyanate compound together with water, etc., wherein a polyol mixture which contains a polyoxyethylene polyol produced by subjecting only ethylene oxide to ring-opening addition polymerization by the use of at least one kind selected from a group comprising aliphatic amines and alicyclic amines as an initiator and having a hydroxy value of 150-800 mgKOH/g is used as the polyol compound, water is used as the foaming agent, and further a fluorine-containing compound expressed by the formula: R<SP>f</SP>-O-(A-O)<SB>n</SB>-R (R<SP>f</SP>is a 2-27C fluorine-containing organic residue; and n is 1-100) is used. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to a method for producing a rigid foam synthetic resin. More specifically, the present invention relates to a method for producing a rigid foamed synthetic resin such as a rigid polyurethane foam characterized by using a relatively large amount of water as a foaming agent.

Production of rigid foamed synthetic resins (hereinafter referred to as rigid foam) such as rigid polyurethane foam and rigid polyisocyanurate foam by reacting a polyol compound and a polyisocyanate compound in the presence of a foaming agent or the like is widely performed. ing. Here, various compounds are known as a foaming agent for producing a rigid foam. Previously, low-boiling fluorine-containing compounds have been mainly used. However, considering the burden on the environment, it is desirable to reduce the use of fluorine-containing compounds. Therefore, in order to reduce the amount of use, techniques for using a large amount of water as a blowing agent have been studied. When a large amount of water is used, a relatively lightweight rigid foam can be obtained at low cost.

However, when a rigid foam is produced using a large amount of water, since the compatibility between the polyol compound and water is generally not so high, water is likely to be sufficiently dispersed and not easily dissolved in the polyol compound. As a result, the reaction between water and the polyisocyanate compound does not proceed sufficiently, and as a result, it is difficult to reduce the density of the rigid foam produced. In particular, when producing a rigid foam in a low temperature environment, it is difficult to control the density of the rigid foam low. Specifically, particularly when manufacturing a rigid foam by spray foaming at a construction site in winter, temperature control is difficult, and the density of the manufactured rigid foam cannot be controlled low. Further, when the density of the rigid foam is lowered by using a large amount of water, there arises a problem that the obtained rigid foam tends to shrink.

In addition, the low compatibility between water and the polyol compound results in a decrease in compatibility and miscibility between the polyisocyanate compound and the mixed liquid (polyol system liquid) of the polyol compound, water, and other additives. . As a result, it is difficult to form fine bubbles uniformly during the production of the rigid foam, and cell roughness and striped patterns are likely to appear in the obtained rigid foam.

In addition, rigid foams produced using a large amount of water increase the proportion of urea bonds formed by the reaction of water and polyisocyanate compounds, making the resulting foams brittle, thus reducing the adhesiveness of the rigid foams. There is a problem of doing.

Among these problems, a polyoxyalkylene polyol produced using piperazines such as 1- (2-aminoethyl) piperazine as an initiator is used as a method for producing a lightweight rigid foam using a large amount of water. Has been proposed (see, for example, Patent Documents 1 and 2).

Also, it is known to add a specific fluorine-containing compound in order to suppress the generation of voids in the rigid foam and improve the heat insulation performance of the foam (see, for example, Patent Document 3).

JP-A-6-87943 JP-A-8-100044 JP 60-199015 A

However, the techniques proposed in Patent Documents 1 and 2 etc. do not sufficiently solve the problem that the obtained rigid foam tends to shrink. Moreover, in the technique known by patent document 3 etc., the problem of shrinkage | contraction of the rigid foam in the case of using much water is not recognized.

That is, the present invention solves the problem of shrinkage of the rigid foam when a large amount of water is used as described above, uses water as a foaming agent, is lightweight, excellent in adhesiveness, and hardly shrinks, and has good mechanical properties. An object of the present invention is to provide a method for producing a rigid foam, which is capable of producing a rigid foam and having excellent raw material storage stability.

In the method for producing a rigid foam synthetic resin by reacting a polyol compound and a polyisocyanate compound in the presence of a fluorine-containing compound represented by formula 1, a foaming agent, a foam stabilizer and a catalyst, There is provided a method for producing a rigid foam synthetic resin, comprising using a polyol mixture containing the following polyol (A) and having a hydroxyl value of 100 to 700 mgKOH / g and using water as a foaming agent. However, the polyol (A) is produced by ring-opening addition polymerization of only ethylene oxide using at least one selected from the group consisting of aliphatic amines and alicyclic amines as an initiator, and has a hydroxyl value of 150 to 800 mgKOH. / G of polyoxyethylene polyol.

(In Formula 1, R ^f is a fluorine-containing organic group having 2 to 27 carbon atoms, n is an integer of 1 to 100, and A is an alkylene group having 2 to 4 carbon atoms in the straight chain part of the bond, A in the formula when A is 2 to 100 may be the same or different, and R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an acyl having 1 to 18 carbon atoms. Group.)

Here, it is preferable to use piperazine as an initiator of the polyol (A). Moreover, it is preferable that the said polyol mixture contains the following polyol (BA) and / or polyol (BB). However, the polyol (BA) is a polyoxyalkylene polyol having a hydroxyl value of 100 to 700 mgKOH / g, produced by ring-opening addition polymerization of alkylene oxide using an aromatic compound as an initiator. The polyol (BB) is a polyester polyol having a hydroxyl value of 100 to 700 mgKOH / g, produced by polycondensation of a monomer containing an aromatic compound. Here, it is preferable to use at least one selected from the group consisting of a Mannich condensation product, diaminotoluene and bisphenol A as an initiator for the polyol (BA). Furthermore, the fluorine-containing compound is preferably represented by Formula 1a.

However, in Formula 1a, ^Rf is a C2-27 fluorine-containing organic group, k and m are the integers of 1-99 each independently, and k + m is 2-100.

According to the present invention, it has become possible to produce a rigid foam that uses water as a foaming agent and is lightweight, excellent in adhesiveness, hardly contracted, has a good appearance, and has good mechanical properties. Moreover, it is excellent also in the storage stability of a raw material.

In the method for producing a rigid foam of the present invention, a rigid foam synthetic resin is produced by reacting a polyol compound and a polyisocyanate compound in the presence of a foaming agent, a foam stabilizer and a catalyst. The details will be described below.

(Polyol compound)
In the present invention, the polyol (A) is produced by ring-opening addition polymerization of only ethylene oxide using at least one selected from the group consisting of aliphatic amines and alicyclic amines as an initiator and having a hydroxyl value of 150. It is a polyoxyethylene polyol which is ˜800 mg KOH / g. By using this polyol (A), the dissolution stability of water and the polyol compound is improved, the reactivity of water and the polyisocyanate compound is also improved, and an effect such that a lower density rigid foam can be produced is obtained. It is done.

The initiator used for producing the polyol (A) is at least one selected from the group consisting of aliphatic amines and alicyclic amines. Here, as the initiator, an alicyclic amine is more preferable. Examples of the aliphatic amine include alkylamines and alkanolamines. Examples of alkylamines include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetraamine. Examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, 1-amino-2-propanol, and aminoethylethanolamine.

Examples of alicyclic amines include piperidines, piperazines, pyrrolidines, etc., piperazines are particularly preferred, and piperazines substituted with aminoalkyl groups are most preferred. Piperazine has a high effect as a catalyst for promoting the urethane bond formation reaction, and by using it as an initiator of the polyol (A), an effect of increasing the reactivity at the time of producing the rigid foam can be obtained. Examples of piperidines include 1- (2-aminoethyl) piperidine. Examples of piperazines include piperazine, N-aminomethylpiperazine, 1- (2-aminoethyl) piperazine and the like. Examples of pyrrolidines include 1- (2-aminoethyl) pyrrolidine.

Further, only ethylene oxide is used as the alkylene oxide used for the production of the polyol (A). By using only ethylene oxide, the affinity between the polyol (A) and water is improved, and the dissolution stability of water and polyol is improved. Further, by using only ethylene oxide, the hydroxyl group of the polyol (A) becomes a primary hydroxyl group, the reactivity of the polyol (A) is increased, and the adhesiveness is improved.

The hydroxyl value of the polyol (A) is 150 to 800 mgKOH / g, preferably 250 to 700 mgKOH / g. When the hydroxyl value of the polyol (A) is within the above range, the compatibility between the polyol compound and water can be secured, the reactivity of the polyol compound can be increased, and the adhesiveness of the rigid foam can be easily secured, which is preferable. Moreover, 2-8 are preferable and, as for the average functional group number of a polyol (A), 2-6 are more preferable. Here, the average number of functional groups means the average number of active hydrogen atoms in the initiator.

In the polyol mixture used in the present invention, the proportion of the polyol (A) is preferably 5 to 95% by mass, and more preferably 15 to 80% by mass. If the proportion of the polyol (A) is less than 5% by mass, the adhesive property of the rigid foam tends to deteriorate, such being undesirable. Moreover, when the ratio of a polyol (A) exceeds 95 mass%, it becomes difficult to obtain the strength of a rigid foam, which is not preferable.

In the present invention, the polyol mixture preferably contains a polyol (BA) and / or a polyol (BB). By using this polyol (BA) and / or polyol (BB), flame resistance can be imparted to the resulting rigid foam.

In the present invention, the polyol (BA) is a polyoxyalkylene polyol having a hydroxyl value of 100 to 700 mgKOH / g, produced by ring-opening addition polymerization of alkylene oxide using an aromatic compound as an initiator.

As the initiator used for the production of polyol (BA), an aromatic compound is used, but at least one selected from the group consisting of Mannich condensation products, diaminotoluene and bisphenol A is preferably used. Here, the aromatic compound means a compound having an aromatic ring. Here, the aromatic ring may be a ring composed of only carbon atoms or a ring containing atoms (heteroatoms) other than carbon atoms such as nitrogen atoms. Examples of the ring consisting of only carbon atoms include a benzene ring and a naphthalene ring. Examples of the ring containing an atom other than a carbon atom include a pyridine ring. However, the presence or absence of a heteroatom in these rings is not considered.

The aromatic compound may be a condensed compound or a non-condensed compound. The condensation compound includes a Mannich condensation product, which is a reaction product of phenols, alkanolamines and aldehydes, a resol-type initial condensate obtained by condensation-bonding phenols with an excess of formaldehyde in the presence of an alkali catalyst. Examples include a benzylic type initial condensate reacted in a non-aqueous system when synthesizing a type initial condensate, a novolak type initial condensate obtained by reacting excess phenols with formaldehyde in the presence of an acid catalyst, and the like. The molecular weight of these initial condensates is preferably about 200 to 10,000. In the above, examples of phenols include phenol, nonylphenol, cresol, bisphenol A, resorcinol, and examples of aldehydes include formalin and paraformaldehyde. Examples of non-condensable compounds include polyphenols such as bisphenol A and resorcinol, diaminotoluene, diethyldiaminotoluene, diaminodiphenylmethane, and the like.

Also, examples of the alkylene oxide used for the production of the polyol (BA) include ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, and styrene oxide. Of these, propylene oxide and ethylene oxide are preferred.

The hydroxyl value of the polyol (BA) is 100 to 700 mgKOH / g, preferably 200 to 600 mgKOH / g. When the hydroxyl value of the polyol (BA) is within the above range, it is preferable because sufficient flame retardancy can be imparted while maintaining the mixing property of the polyol compound. Moreover, 2-8 are preferable and, as for the average functional group number of a polyol (BA), 2-6 are more preferable.

In the present invention, the polyol (BB) is a polyester polyol having a hydroxyl value of 100 to 700 mgKOH / g produced by polycondensation of a monomer containing an aromatic compound. That is, as a monomer used for producing this polyol (BB), a diol having an aromatic ring or a dicarboxylic acid having an aromatic ring is used. Examples of the diol having an aromatic ring include a diol obtained by adding ethylene oxide to bisphenol A. Examples of the dicarboxylic acid having an aromatic ring include phthalic acids such as terephthalic acid. The hydroxyl value of the polyol (BB) is 100 to 700 mgKOH / g, preferably 200 to 600 mgKOH / g. When the hydroxyl value of the polyol (BA) is within the above range, it is preferable because sufficient flame retardancy can be imparted while maintaining the mixing property of the polyol compound.

In the polyol mixture used in the present invention, the total ratio of the polyol (BA) and the polyol (BB) is preferably 7 to 90% by mass, and more preferably 20 to 70% by mass. If the total ratio of the polyol (BA) and the polyol (BB) is within the above range, an appropriate flame retardancy can be imparted to the obtained rigid foam, and other mechanical properties and the like are not impaired. Moreover, there is no restriction | limiting in particular in the ratio of a polyol (BA) and a polyol (BB).

In the present invention, a polyol mixture containing the above-described polyol (A) and having a hydroxyl value of 100 to 700 mgKOH / g is used as the polyol compound. Here, the hydroxyl value of the polyol mixture is 100 to 700 mgKOH / g, but preferably 150 to 600 mgKOH / g. When the hydroxyl value is within this range, a rigid foam having good physical properties can be obtained.

As the above-mentioned polyol mixture, polyol (A), optionally polyol (BA) and / or polyol (BB) described above may be mixed, and other active hydrogen-containing compounds may be mixed and used together. . Here, other active hydrogen-containing compounds include polyols, polyhydric phenols, and polyamines. The polyols that may be used in combination here are any polyols other than polyol (A), polyol (BA), and polyol (BB).

Examples of the polyhydric phenols that may be used in combination include compounds having a phenolic hydroxyl group among the initiators used in the production of the polyol (BA) described above, specifically, Mannich condensation products, resol type initial condensations. Products, benzylic type initial condensates, novolak type initial condensates, bisphenol A, resorcinol and the like. Examples of polyamines that may be used in combination include aliphatic amines, alicyclic amines used as initiators for the production of polyol (A), and aromatic amines used as initiators for the production of polyol (BA). Is mentioned. Examples of the aromatic amines include diaminotoluene, diethyldiaminotoluene, diaminodiphenylmethane, and the like.

(Fluorine-containing compounds)
The fluorine-containing compound in the present invention is represented by Formula 1. R ^f is a fluorine-containing organic group having 2 to 27 carbon atoms. Examples of the fluorine-containing organic group include a polyfluoroalkyl group having 2 to 27 carbon atoms or a group containing an oxygen atom or a nitrogen atom between the carbon-carbon bonds of the polyfluoroalkyl group (hereinafter, these groups are referred to as R ^f0 . ) Is preferred. The R ^f0 group is particularly preferably a polyfluoroalkyl group having 2 to 27 carbon atoms.

The R ^f0 group is a C ^1-22 polyfluoroalkyl group (hereinafter referred to as R ^fB group) (B portion) which may have an oxygen atom or a nitrogen atom, and a linear or branched alkylene group (C portion). It consists of The R ^fB group is a group in which two or more hydrogen atoms in the alkyl group are substituted with fluorine atoms or a group containing an oxygen atom or a nitrogen atom between the carbon-carbon bonds of the group, and the former is preferred. The number of carbon atoms in R ^fB group is 1 to 16 are preferred, particularly preferably 4 to 16, especially 6 to 14 are preferred. R ^fB number of fluorine atoms in the group, if expressed in ^{(R fB} fluorine atoms group) / ^(hydrogen atom in the alkyl group of the same number of carbon atoms corresponding to ^{R fB} group) × 100 (%), 60% or more is preferable, and 80% or more is particularly preferable. The R ^fB group preferably has a linear structure or a branched structure, and particularly preferably has a linear structure. In the case of a branched structure, the branched portion is preferably a short chain having about 1 to 3 carbon atoms and is present at the terminal portion of the R ^fB group.

The R ^fB group is preferably a perfluoroalkyl group or a group containing an oxygen atom or a nitrogen atom between the carbon-carbon bonds of the group (hereinafter referred to as an R ^FB group). The R ^fB group is preferably a perfluoroalkyl group. Moreover, the thing of a linear structure is preferable. The R ^FB group is a group in which substantially all of the hydrogen atoms are substituted with fluorine atoms. The number of carbon atoms of R ^FB group is 1 to 16 preferably, 6 to 14 are particularly preferred. The R ^FB group is preferably a group having a linear structure represented by F (CF ₂ ) m- (m is an integer of 1 to 16). m is preferably 4 to 16, and particularly preferably 6 to 14.

A linear ^RFB group is obtained by telomerization of C ₂ F ₅ I with tetrafluoroethylene. The ^RFB group having a branched structure can be obtained by oligomerizing a fluorine-containing monomer such as tetrafluoroethylene or hexafluoropropylene with a catalyst such as KF or CsF. The R ^FB group containing an oxygen atom can be obtained by ring-opening polymerization of hexafluoropropylene oxide.

The fluorine-containing compound may be a mixture of two or more compounds having different R ^fB group carbon numbers. In ^particular, the number of carbon atoms in ^{R fB} group is a main component 6-14 of the fluorine-containing ^compound, a mixture the average carbon number of the ^{R fB} group is 8-10 are preferred.

The C moiety in the R ^f0 group is a linear or branched alkylene group having 1 to 5 carbon atoms. The number of carbon atoms in the C moiety is preferably 2, 3 or 4, and particularly preferably 3 or 4. Most preferably, the C moiety is an alkylene group having 3 carbon atoms. The fluorine-containing compound when the C moiety is an alkylene group having 3 carbon atoms is a compound having excellent chemical stability and heat resistance.

Examples of the C moiety include ethylene group, trimethylene group, tetramethylene group, propylene group [—CH ₂ CH (CH ₃ ) —], butylene group [—CH (CH ₃ ) CH ₂ CH ₂ —, —CH ₂ CH ( CH ₃ ) CH ₂ —, —CH (CH ₃ ) CH (CH ₃ ) —] and the like.

N in the fluorine-containing compound represents an integer of 1 to 100, preferably 2 to 50, particularly preferably 2 to 15. The fluorine-containing compound of the present invention may be a mixture of two or more compounds having different n, and even in that case, the average value of n is preferably in the range of 1 to 50, more preferably 2 to 30, In particular, it is preferably in the range of 2-15.

A in the fluorine-containing compound (formula 1) is an alkylene group having 2 to 4 carbon atoms in the straight chain part of the bond, and the hydrogen atom of the alkylene group is substituted with an aromatic hydrocarbon group or an alkoxy group. Also good. The carbon number of the straight chain portion between the bonds refers to the carbon number of the straight chain structure portion including the two carbon atoms having a carbon atom having a bond at both ends.

The A, an ethylene group, a propylene group, 1,2-butylene group, 2,3-butylene group, tetramethylene _{group, -CH (C 6 H 5)} CH 2 -, - CH (CH 2 OR 1) CH 2 -Etc. are mentioned. An alkylene group having 2 to 4 carbon atoms is preferable, and an ethylene group, a propylene group, or a tetramethylene group is particularly preferable. However ^{R 1} is a hydrocarbon group having 1 to 10 carbon atoms, as ^{R 1} is a methyl group, a butyl group or a 2-ethylhexyl group, preferred.

When n is 2 to 100, A in Formula 1 may be the same or different. When they are different from each other, A is preferably two or three, particularly preferably two. One or two kinds of A in the fluorine-containing compound are preferably present, and particularly, two kinds of ethylene group and propylene group are preferably present.

The (A-O) _n moiety in Formula 1 is preferably a structure formed by a ring-opening addition reaction of a cyclic ether described later, and includes oxyethylene, oxypropylene, oxy (1,2-butylene), oxy (2,3-butylene), oxy (isobutylene), oxy (trimethylene), oxy (1 or 2-methyltrimethylene), oxy (phenoxymethylethylene), oxy (tetramethylene), oxy (phenylethylene), oxy ( Alkoxyethylene) and the like, and a structure in which two or more selected from these are connected. Of these, the (A-O) _n moiety in Formula 1 is preferably an oxyalkylene group or a polyoxyalkylene group, particularly preferably a polyoxyalkylene group, and particularly preferably a polyoxyethylene group or a polyoxypropylene group. Furthermore, the (AO) _n moiety in Formula 1 preferably has a structure in which one or more oxyethylene groups and one or more oxypropylene groups are linked in a block or random manner.

(AO) The _n portion is preferably formed by a ring-opening addition reaction of a cyclic ether. The cyclic ether is preferably a compound containing a 3- to 5-membered cyclic ether group having one oxygen atom in the ring, and particularly preferably a compound (monoepoxide) having one 3-membered cyclic ether group. Further, the cyclic ether is preferably an alkylene oxide having 2, 3 or 4 carbon atoms.

Specific examples of the cyclic ether include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, oxetane, methyl oxetane, phenyl glycidyl ether, tetrahydrofuran, styrene oxide, and alkyl glycidyl ether. Can be mentioned. Examples of the alkyl glycidyl ether include methyl glycidyl ether, butyl glycidyl ether, (2-ethylhexyl) glycidyl ether, and the like.

Preferred cyclic ethers are ethylene oxide, propylene oxide, and tetrahydrofuran. A formed by the ring opening of tetrahydrofuran is a tetramethylene group. One or more cyclic ethers can be used, and two or more cyclic ethers are preferably used. When using 2 or more types of cyclic ether, the mixture of 2 or more types of cyclic ether may be used for reaction simultaneously, and 2 or more types of cyclic ether may be used for reaction sequentially.

R in the fluorine-containing compound represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an acyl group having 1 to 18 carbon atoms. As an alkyl group, a C1-C5 alkyl group is preferable, and especially a methyl group, an ethyl group, n-propyl group, n-butyl group, and n-pentyl group are preferable. As the acyl group, an acyl group having 1 to 10 carbon atoms is preferable, and an acyl group having 1 to 6 carbon atoms is particularly preferable. R is preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom.

As the fluorine-containing compound represented by Formula 1, a case where R is a hydrogen atom, n is 2 to 100, and A is an alkylene group having 2 to 4 carbon atoms is preferable. Furthermore, as the fluorine-containing compound represented by the formula 1, a compound represented by the formula 1a is preferable.

However, the symbols in Formula 1a have the following meanings, and the sequence of (CH ₂ CH ₂ O) and [CH ₂ CH (CH ₃ ) O] is random regardless of the order, even in blocks. May be. A block is preferred. R ^f has the same meaning as in formula 1. k and m are each independently an integer of 1 to 99, and k + m is 2 to 100. k and m are each independently preferably 1 to 30, particularly preferably 2 to 10. k + m is preferably from 2 to 60, particularly preferably from 4 to 20. Further, k ≧ m is preferable.

Specific examples of the fluorine-containing compound (Formula 1) include, but are not limited to, the following compounds. However, in the following compounds, the portion corresponding to the R ^fB group may have a linear structure or a branched structure, and a linear structure is preferred. Moreover, when the polyoxyalkylene chain containing 2 or more types of oxyalkylene groups exists, the connection method may be a block or random. The (C ₃ H ₆ O) moiety represents an oxypropylene group and indicates [CH (CH ₃ ) CH ₂ O] or [CH ₂ CH (CH ₃ ) O]. The (C ₄ H ₈ O) moiety indicates (CH ₂ CH ₂ CH ₂ CH ₂ O) which is a ring-opened product of tetrahydrofuran. The fluorine-containing compounds in the present invention can be used alone or in combination of two or more.

The fluorine-containing compound of the present invention is preferably synthesized by subjecting the fluorine-containing hydroxy compound represented by Formula 2 to a ring-opening addition reaction with a cyclic ether.

(In Formula 2, R ^f has the same meaning as in Formula 1).

For example, as a method for synthesizing a fluorine-containing hydroxy compound (R ^FB CH ₂ OH) when the R ^fB group in R ^{f of} Formula 2 is an R ^FB group and the C moiety has 1 carbon, Perfluoroalkyl iodine (R ^FB I) obtained in step 1 was added with ethylene to give an alkali treatment to give perfluoroalkyl ethylene (R ^FB CH═CH ₂ ), and then the perfluoroalkyl ethylene was oxidized to perfluoroalkanecarboxylic acid. (R ^FB COOH), and a method obtained by further reducing perfluoroalkanecarboxylic acid with NaBH ₄ or the like.

As a synthesis method of the fluorine-containing hydroxy compound [R ^FB (CH ₂ ) ₂ OH] in the case where the R ^fB group in R ^{f of} Formula 2 is an R ^FB group and the C moiety has 2 carbon atoms, the above R An example is a method in which ethylene is inserted into ^FB I to form R ^FB (CH ₂ ) ₂ I, and then the terminal iodine atom is replaced with a hydroxyl group.

As a synthesis method of the fluorine-containing hydroxy compound [R ^FB (CH ₂ ) ₃ OH] in the case where the R ^fB group in R ^{f of} Formula 2 is an R ^FB group and the C moiety has 3 carbon atoms, the above R After a ^R FB _{CH 2} cHICH 2 OH is added allyl alcohol ^FB I, and a method of replacing a hydrogen atom iodine atom with a reducing agent.

^{R fB} group in the ^{R f} of formula 2 is ^{R FB} group, the fluorine-containing hydroxy compound where the carbon number of the C moiety is 4 as a method for synthesizing _{^{[R FB (CH 2) 4}} OH] is the ^{R FB} A method may be mentioned in which 3-buten-1-ol is added to I to give [R ^FB CH ₂ CHI (CH ₂ ) ₂ OH], and then the iodine atom is replaced with a hydrogen atom with a reducing agent.

In addition, as a method for synthesizing R ^fB CH ₂ CH ₂ CH ₂ (OH) CH ₃ , which is an isomer of the fluorine-containing hydroxy compound [R ^FB (CH ₂ ) ₄ OH] when the C moiety has 4 carbon atoms. The above-mentioned method includes a method in which the above R ^FB CH═CH ₂ is obtained by adding a predetermined radical initiator in a large amount of ethanol solvent and stirring while heating, and adding ethanol by radical addition reaction. As a method for synthesizing R ^FB (CH ₂ ) ₅ OH when the C moiety has 5 carbon atoms, 4-penten-1-ol is added to R ^FB I and [R ^FB CH ₂ CHI (CH ₂ ) is added. ₃ OH] and then a method of substituting iodine atoms with hydrogen with a reducing agent.

Next, the fluorinated hydroxy compound (formula 2) obtained by the above method is subjected to a ring-opening addition reaction with a cyclic ether. When two or more kinds of cyclic ethers undergo ring-opening addition reaction, they may be mixed and reacted, or may be reacted sequentially. In the case where only one kind of cyclic ether is used, in the case where two or more kinds are used, they may be charged all at once or may be gradually added to the reaction system.

The amount of fluorine-containing hydroxy compound (formula 2) charged varies depending on the amount of cyclic ether compound added, but it is preferable to charge 1/10 or more of the reactor internal volume in consideration of the stirring conditions of the reactor. Considering volumetric efficiency in particular, it is desirable that the volume ratio be 80 to 95% after adding cyclic ether.

The ring-opening addition reaction is preferably carried out in the presence of a catalyst. As the catalyst, an alkali metal catalyst, an acid catalyst, and a metal complex catalyst are preferable, and an acid catalyst and a metal complex catalyst are particularly preferable. Examples of the alkali metal catalyst include KOH, NaOH, CsOH, and a three-way catalyst composed of NaBH ₄ / NaI / I _2. Examples of the acid catalyst include BF _3. Examples of the metal complex catalyst include zinc hexacyanocobaltate. Examples include double metal cyanide complexes such as ether and / or alcohol complex catalysts.

When the ring-opening addition reaction is carried out under strongly alkaline conditions, a side reaction in which HF is eliminated at the R ^f portion may occur. Therefore, when an alkali metal catalyst is used, a mild alkaline catalyst NaBH ₄ / It is preferable to use a three-way catalyst consisting of NaI / _{I 2.} In addition, when an acid catalyst is used, if the acidity of the catalyst is too strong, a side reaction in which HF is eliminated at the R ^f portion may occur. Therefore, in order to suppress this deHF reaction, dilute as necessary. It is preferable to use a solvent. Examples of the diluent solvent include ether solvents such as glyme, diglyme, triglyme, and methyl-tert-butyl ether.

The reaction temperature of the cyclic ether ring-opening addition reaction is preferably -20 to 180 ° C, particularly preferably 0 to 130 ° C. When a diluting solvent is used and the diluting solvent is a diluting solvent having a low boiling point, the reaction is preferably performed at a temperature lower than (boiling point of solvent + 20 ° C.) in consideration of an increase in internal pressure.

A compound obtained by subjecting a fluorinated hydroxy compound (formula 2) to a ring-opening addition reaction of a cyclic ether is a fluorinated compound (formula 1) when the terminal is a hydroxyl group (R is a hydrogen atom), and the terminal hydroxyl group Various properties can be adjusted by modifying (for example, esterification or alkylation).

Esterification is preferably carried out by reacting an organic carboxylic acid, an organic carboxylic acid ester or an organic carboxylic acid anhydride. Examples of organic carboxylic acids include monovalent carboxylic acids such as acetic acid, propionic acid, butanoic acid, 2-ethylhexanoic acid (octylic acid), 3,5,5-trimethylhexanoic acid (isononanoic acid), oleic acid, and stearic acid. Examples of organic carboxylic acid esters include esters of the above monovalent carboxylic acids and low-boiling alcohols. Examples of organic carboxylic acid anhydrides include acetic anhydride, propionic anhydride, butanoic anhydride, and n-anhydride. And monovalent carboxylic acid anhydrides such as butyric acid.

In the esterification, the above-mentioned organic carboxylic acid, organic carboxylic acid ester or organic carboxylic acid anhydride is added to the fluorine-containing compound (formula 1) in the case where the terminal is a hydroxyl group (R is a hydrogen atom). It is preferable to carry out by stirring while heating in the presence, followed by dehydration, dealcoholization, or removal of unreacted acid. The catalyst is preferably a trace acid catalyst such as paratoluenesulfonic acid or sulfuric acid, or an alkali catalyst such as potassium hydroxide or sodium hydroxide.

Alkylation includes a method of reacting with monohaloalkyl under a strong alkali condition, a method of using dialkyl sulfuric acid, and the like, but a reaction using an alkylating agent such as alkyl sulfuric acid is preferred from the viewpoint that the elimination reaction of HF can be suppressed.

The fluorine-containing compound (formula 1) obtained by the various reactions described above may be subjected to acid treatment using sulfuric acid, phosphoric acid or the like, or adsorption treatment using synthetic magnesium silicate, activated clay, activated carbon, or the like, if necessary. It is preferable to purify it to have a high purity.

The addition amount of the fluorine-containing compound is preferably 0.01 to 1 part by mass, particularly preferably 0.01 to 0.4 part by mass with respect to 100 parts by mass of the total amount of the polyol and the polyisocyanate compound.

(Foaming agent)
In the present invention, water is used as the foaming agent. As the blowing agent, a low boiling point hydrocarbon compound, a low boiling point fluorine-containing compound, and an inert gas can be used in combination. The amount of water used as the foaming agent is preferably 1 to 15 parts by mass, particularly preferably 2 to 13 parts by mass with respect to 100 parts by mass of the polyol compound. When the amount of water used is less than 1 part by mass, the obtained rigid foam is not preferred because it is difficult to lighten. Moreover, when there is much usage-amount exceeding 15 mass parts, the miscibility of water and a polyol compound tends to deteriorate, and it is not preferable.

Examples of the low boiling point hydrocarbon compound include butane, pentane, hexane, and cyclohexane. Examples of the low boiling point fluorine-containing compound include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1, 1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,2,2-tetrafluoroethyl difluoromethyl ether (HFE-236pc), 1,1,2,2-tetrafluoroethyl methyl ether (HFE-254pc), 1,1,1,2,2,3,3-heptafluoropropyl methyl ether (HFE-347mcc) and the like. Examples of the inert gas include air, nitrogen, carbon dioxide gas and the like.

(Polyisocyanate compound)
In the present invention, the polyisocyanate compound is not particularly limited, but aromatic, alicyclic and aliphatic polyisocyanates having two or more isocyanate groups; mixtures of two or more of the above polyisocyanates; And modified polyisocyanates obtained by modifying. Specific examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (common name: crude MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI), and the like. These polyisocyanates or their prepolymer-modified products, nurate-modified products, urea-modified products, carbodiimide-modified products, and the like. Of these, TDI, MDI, crude MDI, or modified products thereof are preferred.

The amount of the polyisocyanate compound used is represented by 100 times the number of isocyanate groups with respect to the total number of active hydrogens in the polyol compound and other active hydrogen compounds (usually, the value represented by this 100 times is referred to as the isocyanate index). ~ 300 is preferred. Here, in the urethane prescription which mainly uses a urethanization catalyst as a catalyst, the usage-amount of a polyisocyanate compound is an isocyanate index | exponent, 50-140 are preferable and 60-130 are more preferable. Moreover, in the isocyanurate prescription which mainly uses the catalyst which accelerates | stimulates the trimerization reaction of an isocyanate group as a catalyst, the usage-amount of a polyisocyanate compound is an isocyanate index, 120-300 are preferable and 150-250 are more preferable.

(catalyst)
The catalyst used in the present invention is not particularly limited as long as it is a catalyst that promotes the urethanization reaction. Examples thereof include tertiary amines such as triethylenediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N′-tetramethylhexamethylenediamine; and organometallic compounds such as dibutyltin dilaurate. Moreover, you may use together the catalyst which accelerates | stimulates the trimerization reaction of an isocyanate group, and carboxylic acid metal salts, such as potassium acetate and potassium 2-ethylhexanoate, etc. are mentioned. When spray foaming is employed as a method for producing a rigid foam, an organic metal catalyst such as lead 2-ethylhexanoate is preferably used in combination in order to complete the reaction in a short time. As for the usage-amount of a catalyst, 0.1-10 mass parts is preferable with respect to 100 mass parts of polyol compounds.

(Foam stabilizer)
In the present invention, a foam stabilizer is used to form good bubbles. Examples of the foam stabilizer include silicone foam stabilizers and fluorine-containing compound foam stabilizers. Although the usage-amount of a foam stabilizer may be selected suitably, 0.1-10 mass parts is preferable with respect to 100 mass parts of polyol compounds.

(Other ingredients)
In the present invention, any compounding agent can be used in addition to the above-described polyol compound, polyisocyanate compound, foaming agent, catalyst, and foam stabilizer. Compounding agents include fillers such as calcium carbonate and barium sulfate; anti-aging agents such as antioxidants and UV absorbers; flame retardants, plasticizers, colorants, anti-fungal agents, foam breakers, dispersants, discoloration prevention Agents and the like.

(Foaming device)
As a manufacturing method of the rigid foam of the present invention, normal hand foaming or a foaming apparatus may be used. As the foaming apparatus, either a high pressure foaming apparatus or a low pressure foaming apparatus can be used. The reaction conditions may be appropriately selected, but the reaction temperature is preferably 0 to 50 ° C, more preferably 15 to 45 ° C.

As the method for producing the rigid foam of the present invention, spray foaming is particularly preferable. This is because high reactivity can be obtained by using the polyol (A). Various methods for producing by spray foaming are known. Of these, airless spray foaming is preferred, in which the compounded liquid is mixed and foamed by a mixing head. Here, spray foaming is a foaming method in which a polyol system solution and a polyisocyanate compound are reacted while sprayed, and the reaction is completed in a short time by selecting a catalyst or the like. Spray foaming is often employed when constructing hard foam insulation on walls, ceilings, etc. at construction sites. Spray foaming has advantages such as manufacturing rigid foams directly at the construction site, thus reducing the construction cost, and being able to construct even on uneven construction surfaces. Specific construction examples include heat insulating materials for condominiums, office buildings, prefabricated refrigerated warehouses, etc. In recent years, they are also being used as heat insulating materials for highly airtight detached houses.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Of the following examples, Examples 1-31 represent production examples of rigid polyurethane foam, and Examples 32-61 represent production examples of rigid urethane-modified polyisocyanurate foam. However, Examples 1-8, 13-18, 22-27, 32-39, 44-49 and 53-58 are Examples, Examples 9-12, 19-21, 28-31, 40-43, 50-52 And 59 to 61 represent comparative examples. Moreover, the unit of the numerical value of the part which showed prescription in the table | surface is a mass part. The raw materials used in Examples and Comparative Examples are as shown in each table, and the details are as follows.

(Polyol compound)
Polyol A1: A polyoxyethylene polyol having a hydroxyl value of 350 mgKOH / g, obtained by reacting only ethylene oxide as an alkylene oxide using ethylenediamine as an initiator.
Polyol A2: A polyoxyethylene polyol having a hydroxyl value of 350 mgKOH / g, obtained by reacting only ethylene oxide as alkylene oxide using 1- (2-aminoethylpiperazine) as an initiator.
Polyol BA1: A polyoxyethylene polyol having a hydroxyl value of 280 mgKOH / g, obtained by reacting only ethylene oxide as an alkylene oxide using bisphenol A as an initiator.
Polyol BA2: polyoxyethylene having a hydroxyl value of 350 mgKOH / g and a proportion of oxyethylene groups of 25% by mass, obtained by mixing and reacting ethylene oxide and propylene oxide as alkylene oxide using diaminotoluene as an initiator Polyoxypropylene polyol.
Polyol BB1: Polyoxyethylene polyol having a hydroxyl value of 250 mgKOH / g, obtained by polycondensation of diethylene glycol and terephthalic acid.
Polyol Y1: Polyoxypropylene polyol having a hydroxyl value of 760 mgKOH / g, obtained by reacting only propylene oxide as an alkylene oxide using ethylenediamine as an initiator.
Polyol Y2: A polyoxypropylene polyol having a hydroxyl value of 350 mgKOH / g, obtained by reacting only propylene oxide as an alkylene oxide using ethylenediamine as an initiator.
Polyol Y3: Polyoxypropylene polyol having a hydroxyl value of 350 mgKOH / g, obtained by reacting only propylene oxide as alkylene oxide using 1- (2-aminoethylpiperazine) as an initiator.
Polyol Z1: Polyol having a hydroxyl value of 300 mgKOH / g, obtained by reacting only propylene oxide as alkylene oxide using a mixture of sucrose and glycerin as the initiator (mixing ratio is 1.5: 1 by mass). Oxypropylene polyol.

(Fluorine-containing compounds)
Compound F1: with a fluorine-containing compound _{C 8 F 17 CH 2 CH 2} CH (CH 3) OH 12 carbon atoms as an initiator, a catalyst as a composite metal cyanide complex catalyst (a zinc hexacyanocobaltate / glyme complex catalyst) A compound having an average molecular weight of 1000, which is produced by ring-opening addition polymerization of a mixture of propylene oxide and ethylene oxide having a mass ratio of 50:50 and corresponding to a compound having n of about 10 in Formula 1.
Compound F2: Fluorine-containing compound having 10 carbon atoms C ₆ F ₁₃ CH ₂ CH ₂ CH (CH ₃ ) OH is used as an initiator, and a _double metal cyanide complex catalyst (zinc hexacyanocobaltate / glyme complex catalyst) is used as a catalyst. A compound having an average molecular weight of 800, which is produced by ring-opening addition polymerization of a mixture of propylene oxide and ethylene oxide having a mass ratio of 50:50, corresponding to a compound having n of about 8 in Formula 1.

(Foaming agent)
Blowing agent 1: HFC-245fa.
Foaming agent 2: HFC-365mfc.
Blowing agent 3: HFC-134a.
Foaming agent 4: cyclopentane.

(Examples 1-31)
The polyols shown in Tables 1 to 3 were mixed and used. The foaming agents shown in Tables 1 to 3 were used. The following foaming agent, catalyst, foam stabilizer and flame retardant were added to and mixed with the polyol mixture and the foaming agent to obtain a polyol composition. As the catalyst, N, N-dimethylcyclohexylamine (trade name: Kaulizer No. 10, manufactured by Kao Corporation) was used. The amount used was such that the gel time was 25 seconds. As the foam stabilizer, 1.5 parts by mass of a silicone foam stabilizer (trade name: SH-193, manufactured by Toray Dow Corning Silicone) was used. As the flame retardant, 10 parts by mass of tris (2-chloropropyl) phosphate (trade name: TMCPP, manufactured by Daihachi Chemical Co., Ltd.) was used. As the polyisocyanate compound, polymethylene polyphenyl polyisocyanate (trade name: MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd.) was used. The amount of polyisocyanate compound used was set to 110 in terms of isocyanate index.

The polyol composition and the polyisocyanate compound were mixed at a liquid temperature of 20 ° C., and placed in a wooden box having a length of 200 mm × width of 200 mm × height of 200 mm to produce a rigid polyurethane foam by foaming.

(Examples 32-61)
The polyols shown in Tables 4 to 6 were mixed and used. The foaming agents shown in Tables 4 to 6 were used. The following foaming agent, catalyst, foam stabilizer and flame retardant were added to and mixed with the polyol mixture and the foaming agent to obtain a polyol composition. As a catalyst, N, N ′, N ″ -tris (dimethylaminopropyl) hexahydro-S-triazine (trade name: Polycat 41, manufactured by Air Products) and diethylene glycol solution of potassium 2-ethylhexanoate (potassium concentration) 15%, trade name: PACCAT 15G, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was used at a ratio of 2 parts by mass to 3 parts by mass, and the amount used was such that the gel time was 25 seconds. As a foaming agent, 1.5 parts by mass of SH-193 was used, as a flame retardant, 20 parts by mass of TMCPP, and as a polyisocyanate compound, polymethylene polyphenyl polyisocyanate (trade name: MR-200, Nippon Polyurethane Industry Co., Ltd.) The amount of polyisocyanate compound used was set to 200 in terms of isocyanate index. .

The polyol composition and the polyisocyanate compound were mixed at a liquid temperature of 20 ° C. and placed in a wooden box having a length of 200 mm × width of 200 mm × height of 200 mm, and a rigid urethane-modified polyisocyanurate foam was foamed and produced.

(Evaluation)
The obtained rigid foam was evaluated for core density (unit: kg / m ³ ), low temperature shrinkage (unit:%), high temperature shrinkage (unit:%), adhesiveness and cell appearance. The low temperature shrinkage is -30 ° C, the dimensional change rate in the direction perpendicular to the foaming direction after 24 hours, and the high temperature shrinkage is 70 ° C, the dimensional change rate in the direction perpendicular to the foaming direction after 48 hours. Indicates. Regarding adhesiveness, the laminated paper was spread in a box before foaming, foamed, the foam was removed after 30 minutes of stirring, and the initial adhesiveness when the laminated paper was peeled off was evaluated as good ○ and bad ×. As for the cell appearance, the produced foam was cut, and the internal cell state and the rough state of the bottom surface of the foam were evaluated as ○: good, ×: poor.

As shown in Tables 1 to 6, each of the rigid foams produced by the method for producing a rigid foam of the present invention had a low density, and exhibited good initial adhesion, cell appearance, and dimensional stability.

(Evaluation 2)
Next, to the polyol compositions used in Examples 1-8, 22-27, 32-39 and 53-58, a mineral spirit solution of lead 2-ethylhexanoate (lead concentration: 20%, trade name: Nikka Octix Lead) 1.0 part by mass of 20%, manufactured by Nippon Chemical Industry Co., Ltd. was further added and mixed. This liquid and polymethylene polyphenyl polyisocyanate (trade name: C-1155, manufactured by Nippon Polyurethane Industry Co., Ltd.) as a polyisocyanate compound are sprayed at a liquid temperature of 35 ° C. and a room temperature of 10 ° C. using a gasmer foaming machine. The foaming was applied to the wall surface by foaming.

The resulting foam showed a good foaming process even though it was manufactured at a room temperature of 10 ° C. and a low temperature assuming winter, and the density of the resulting rigid foam was a core density of 31 kg / m ³ or less. It was sufficiently low and showed good cell appearance, initial adhesion, and self-extinguishing properties.

For the rigid foams of Examples 32-39 and Examples 53-58, which are production examples of rigid urethane-modified polyisocyanurate foams, the core portion is cut out to a thickness of 15 mm, and the cone calorimeter (manufactured by Toyo Seiki Seisakusho) is used. The combustion test according to ISO5600Part1 was conducted. As a result, it was found that the prescribed flame retardancy was satisfied.

The manufacturing method of the rigid foam which is lightweight and excellent in adhesiveness based on this invention is suitable for construction of the rigid foam by spray foaming constructed | assembled at a construction site.

Claims (5)

In the method for producing a rigid foam synthetic resin by reacting a polyol compound and a polyisocyanate compound in the presence of a fluorine-containing compound represented by formula 1, a foaming agent, a foam stabilizer and a catalyst,
The manufacturing method of the hard foam synthetic resin characterized by using the polyol mixture which contains the following polyol (A) as a polyol compound and whose hydroxyl value is 100-700 mgKOH / g, and using water as a foaming agent.
Polyol (A): produced by ring-opening addition polymerization of only ethylene oxide using at least one selected from the group consisting of aliphatic amines and alicyclic amines as an initiator, and having a hydroxyl value of 150 to 800 mgKOH / g A certain polyoxyethylene polyol.

(In Formula 1, R ^f is a fluorine-containing organic group having 2 to 27 carbon atoms, n is an integer of 1 to 100, and A is an alkylene group having 2 to 4 carbon atoms in the straight chain part of the bond, A in the formula when R is 2 to 100 may be the same or different, and R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an acyl having 1 to 18 carbon atoms. Group.) The method for producing a rigid foam synthetic resin according to claim 1, wherein piperazines are used as an initiator of the polyol (A). The method for producing a rigid foam synthetic resin according to claim 1 or 2, wherein the polyol mixture contains the following polyol (BA) and / or polyol (BB).
Polyol (BA): A polyoxyalkylene polyol having a hydroxyl value of 100 to 700 mgKOH / g, produced by ring-opening addition polymerization of alkylene oxide using an aromatic compound as an initiator.
Polyol (BB): A polyester polyol having a hydroxyl value of 100 to 700 mgKOH / g, produced by polycondensation of a monomer containing an aromatic compound. The method for producing a rigid foam synthetic resin according to claim 3, wherein at least one selected from the group consisting of a Mannich condensation product, diaminotoluene, and bisphenol A is used as an initiator of the polyol (BA). The manufacturing method of the hard foam synthetic resin of Claim 1, 2, 3 or 4 with which a fluorine-containing compound is represented by Formula 1a.

However, in Formula 1a, ^Rf is a C2-27 fluorine-containing organic group, k and m are the integers of 1-99 each independently, and k + m is 2-100.