JP2003096152A - Process for producing hard foamed synthetic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a closed-cell hard polyurethane foam having excellent dimension stability, particularly excellent dimension stability even under high temperature high humidity conditions. SOLUTION: A process for producing a hard foamed synthetic resin comprises reacting a polyol with a polyisocyanate compound in the presence of water, a catalyst, and a fluorine-containing compound to be represented by formula 1: R<f> -O-(A-O)n -R (wherein R<f> is a 2-27C polyfluoroalkyl group; n is an integer of 1-100; A is a connecting linear moiety of a 2-4C alkylene group, and when n is 2-100, A may be the same as or different from each other; and R is a hydrogen atom, a 1-18C alkyl group or a 1-18C acyl group).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a rigid foam synthetic resin such as a rigid polyurethane foam, and more particularly to the production of a closed cell rigid foam synthetic resin using water as a main foaming agent.

[0002]

2. Description of the Related Art It is widely practiced to react a polyhydroxyl compound and a polyisocyanate compound in the presence of a foaming agent, a catalyst or the like to produce a hard foam synthetic resin. Examples of the obtained rigid foam synthetic resin include rigid polyurethane foam and rigid polyisocyanurate foam.
The closed-cell foam of rigid foamed synthetic resin has closed cells, and it is possible to enclose a foaming agent with low thermal conductivity such as halogenated hydrocarbons, and it has excellent heat insulation performance. . Although various compounds are known as a foaming agent for producing a foamed synthetic resin, HCFC-141b, which is one of chlorinated fluorinated hydrocarbons, is mainly used.

Chlorinated fluorinated hydrocarbons used as a foaming agent are considered to cause a part of them to leak into the atmosphere and cause ozone layer depletion. Therefore, a large amount of water is used as a foaming agent as an alternative. Is proposed. Water has conventionally been used as an important sub-foaming agent in rigid polyurethane foams, but HCFC-141b is used as the main blowing agent in rigid polyurethane foams.
Was difficult to use in a high ratio that could replace The reason for this is that the closed-cell hard foam synthetic resin that uses a large amount of water has a high rate of carbon dioxide gas permeation through the bubble membrane, so if it is left for a long time, the inside of the cell becomes a negative pressure relative to atmospheric pressure, and gradually There is a problem of contraction and deformation. This phenomenon remarkably appears especially under high temperature and high humidity conditions. As a countermeasure against this, there is a so-called communication type hard foam synthetic resin that breaks the cell membrane, but its heat insulating property is poor and it is not suitable as a heat insulating material.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing a rigid foamed synthetic resin which uses water as a main foaming agent and has a small dimensional change, especially under high temperature and high humidity conditions. The purpose is to

[0005]

The present invention has been made to solve the above-mentioned problems, and it has been found that the above-mentioned problems can be solved by using a specific fluorine-containing compound, and the present invention is completed. Came to. That is, the present invention is a method for producing a rigid foam synthetic resin, which comprises reacting a polyol and a polyisocyanate compound in the presence of water, a catalyst, and a fluorine-containing compound represented by the formula 1. Manufacturing method. I will provide a.

[0006]

Embedded image R ^f —O— (A—O) _n —R Formula 1 (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. A is an alkylene group having 2 to 4 carbon atoms in the straight chain portion between bonds, and A in the formula when n is 2 to 100 may be the same or different. R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an acyl group having 1 to 18 carbon atoms. )

The present invention also provides a method for producing a rigid foam synthetic resin, wherein only water is used as a foaming agent in the method for producing a rigid foam synthetic resin. Further, the present invention provides the method for producing a rigid foam synthetic resin, wherein the fluorine-containing compound is represented by Formula 1a in the method for producing a rigid foam synthetic resin.

[0008]

Embedded image R ^f —O— (CH ₂ CH ₂ O) _k · [CH ₂ CH (CH ₃ ) O] _m —H Formula 1a (In Formula 1a, R ^f is a fluorine-containing organic compound having 2 to 27 carbon atoms. Base,
k and m are each independently an integer of 1 to 99, and k +
m is 2 to 100. )

The present invention also provides a method for producing a rigid foam synthetic resin, wherein the amount of the fluorine-containing compound used is 0.01 to 1 part by mass based on 100 parts by mass of the total amount of the polyol and the polyisocyanate compound. A method for producing a foamed synthetic resin is provided. Further, in the present invention, in the above method for producing a rigid foam synthetic resin, the amount of water used is the amount of polyol 1
Provided is a method for producing a hard foam synthetic resin, which is 4 to 16 parts by mass with respect to 00 parts by mass.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The polyol used in the present invention is not particularly limited, and those normally used as raw materials for rigid polyurethane foam synthetic resins can be used. Water, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, ethylenediamine, toluenediamine, divalent to octavalent active hydrogen-containing compounds such as sucrose are used as an initiator, and alkylene oxides such as ethylene oxide and propylene oxide are added. Polyether polyols obtained by reacting one or more kinds are particularly preferable. Polyester polyol and the like can be optionally used. One type of polyol may be used, or a mixture of two or more types may be used. The hydroxyl value of the polyol is preferably 200 to 500 mgKOH / g, particularly 2
50 to 500 mg KOH / g is preferable.

As the polyisocyanate compound, there are aromatic, alicyclic or aliphatic polyisocyanates having two or more isocyanate groups and modified polyisocyanates obtained by modifying them. Aromatic polyisocyanates and modified products thereof are preferred. Specific examples of the polyisocyanate compound include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate (common name: polymeric MDI) and xylylene diisocyanate, and alicyclic polyisocyanates such as isophorone diisocyanate. , Aliphatic polyisocyanates such as hexamethylene diisocyanate and their urethane modified products, nurate modified products, urea modified products,
There are carbodiimide modified products and the like. As the polyisocyanate compound, one type may be used, or a mixture of two or more types may be used. When the amount of the polyisocyanate compound used relative to the polyol is represented by the number of isocyanate groups (isocyanate index) with respect to the total number of active hydrogen groups of the polyol and water and the like, the isocyanate index is preferably 50 to 300, more preferably 80 to 200, particularly preferably 90 to 1
50.

The fluorine-containing compound is represented by the formula 1. R ^f is a fluorine-containing organic group having 2 to 27 carbon atoms. As the fluorine-containing organic group, a polyfluoroalkyl group having 2 to 27 carbon atoms or a group containing an oxygen atom or a nitrogen atom between carbon-carbon bonds of the polyfluoroalkyl group (hereinafter, these groups are referred to as R ^f0 ) Is preferred. R ^f0 group has 2 carbon atoms
Especially preferred are ~ 27 polyfluoroalkyl groups.

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

R^fBThe group is a perfluoroalkyl group or
The group contains an oxygen atom or a nitrogen atom between the carbon-carbon bonds.
Mu group (hereinafter, these are R^FBGroup) is preferred. R
^fBThe group is preferably a perfluoroalkyl group. Also, direct
A chain structure is preferable. R ^FBThe group is essentially a hydrogen atom
Are all groups substituted with fluorine atoms. R^FBbase
1-16 are preferable and, as for carbon number, 6-14 are especially preferable.
Yes. R^FBThe group is F (CF_Two)_m-(M is an integer from 1 to 16
A group having a linear structure represented by (number) is preferable. m is 4-16
Are preferred, and 6-14 are particularly preferred. Linear structure R
^FBThe base is C_TwoF₅Tetrafluoroethylene of I
Obtained by Romanization. In addition, the branched structure R^FBThe group is tetra
Fluoroethylene, hexafluoropropylene, etc.
Oligomer containing fluorine-containing monomer with catalyst such as KF and CsF
It can be obtained by converting. R containing oxygen atom^FBGroup is hex
Obtained by ring-opening polymerization of safluoropropylene oxide
To be The fluorine-containing compound is R^fBThe carbon number of the group is different
It may be a mixture of two or more compounds. In particular, R
^fBThe main component is a fluorine-containing compound having a carbon number of 6 to 14
And R^fBA mixture in which the average carbon number of the group is 8 to 10 is preferable.
Good

R^f0The C portion in the group has 1 to 5 carbon atoms.
Is a linear or branched alkylene group. Carbon number of C part
Is preferably 2, 3 or 4, particularly preferably 3 or 4.
Good The C portion is an alkylene group having 3 carbon atoms.
Both are preferable. C part is an alkylene group having 3 carbon atoms
If the fluorine-containing compound, the chemical stability and heat resistance
It is an excellent compound. As the C portion, for example, ethi
Ren group, trimethylene group, tetramethylene group, propylene
Group [-CH_TwoCH (CH_Three)-], Butylene group [-C
H (CH_Three) CH_TwoCH_Two-, -CH_TwoCH (CH_Three)
CH_Two-, -CH (CH_Three) CH (CH _Three)-]
You can

In the fluorine-containing compound, n 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 in that case, the average value of n is preferably in the range of 1 to 50,
Further, it is preferably in the range of 2 to 30, particularly 2 to 15.

A in the fluorine-containing compound (formula 1) is
It is an alkylene group having 2 to 4 carbon atoms in the straight chain portion between the joints,
The hydrogen atom of the alkylene group is an aromatic hydrocarbon group or
It may be substituted with an alkoxy group or the like. Straight chain
The number of carbon atoms in a part means that carbon atoms having a bond are at both ends.
The number of carbon atoms in the linear structure containing the two carbon atoms
Say. As A, ethylene group, propylene group, 1,
2-butylene group, 2,3-butylene group, tetramethylene
Group, -CH (C₆H₅) CH_Two-, -CH (CH_TwoOR
¹) CH_Two-And the like. Alkyre with 2 to 4 carbon atoms
Group, preferably an ethylene group, a propylene group, or a
A tramethylene group is particularly preferred. However, R¹Has 1 carbon
10 represents a hydrocarbon group, and R¹As a methyl group,
A tyl group or a 2-ethylhexyl group is preferable. n is
When it is 2 to 100, each A in the formula 1 is the same.
It may or may not be. If they are different,
A is preferably two or three, and particularly two.
Is preferred. A in the fluorine-containing compound is 1 or 2
Seeds are preferably present, especially ethylene and propylene
Preferably two of the groups are present.

(A-O) in Formula 1_nThe part is the ring
Formed by ring-opening addition reaction of a linear ether
The structure is preferably oxyethylene, oxyp
Ropylene, oxy (1,2-butylene), oxy (2,2
3-butylene), oxy (isobutylene), oxy (to
Rimethylene), oxy (1 or 2-methyltrimethylene
), Oxy (phenoxymethylethylene), oxy
(Tetramethylene), oxy (phenylethylene), o
Xy (alkoxyethylene), etc., and selected from these
Examples of the structure include two or more of one or more of the above. This
Among these, (A-O) in Formula 1_nThe part is oxyal
A xylene group or a polyoxyalkylene group is preferred,
Is preferably a polyoxyalkylene group, especially
Oxyethylene or polyoxypropylene groups are preferred
Good Further, (A-O) in Formula 1 _n1 or more parts
An oxyethylene group and one or more oxypropylene groups
Is a block or random structure.
Is preferred.

The (A-O) _n moiety is preferably formed by subjecting a cyclic ether to a ring-opening addition reaction.
The cyclic ether is preferably a compound containing a 3- to 5-membered cyclic ether group having one oxygen atom in the ring,
Particularly preferred is a compound having one 3-membered cyclic ether group (monoepoxide). Furthermore, as a cyclic ether,
Alkylene oxides having 2, 3 or 4 carbon atoms are preferred. 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, alkyl glycidyl ether and the like 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 ring-opening of tetrahydrofuran is a tetramethylene group. One or more cyclic ethers can be used, and it is preferable to use two or more cyclic ethers. When two or more cyclic ethers are used, a mixture of two or more cyclic ethers may be simultaneously used in the reaction, or two or more cyclic ethers may be sequentially used in the reaction.

R in the fluorine-containing compound is a hydrogen atom,
An alkyl group having 1 to 18 carbon atoms or an acyl group having 1 to 18 carbon atoms is shown. As the alkyl group, an alkyl group having 1 to 5 carbon atoms is preferable, and particularly, a methyl group, an ethyl group, n-
A propyl group, an n-butyl group and an n-pentyl group are preferred. 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. As R, a hydrogen atom or a methyl group is preferable, and a hydrogen atom is particularly preferable.

As the fluorine-containing compound represented by the formula 1,
It is preferable that R is a hydrogen atom, n is 2 to 100, and A is an alkylene group having 2 to 4 carbon atoms. Further, the fluorine-containing compound represented by the formula 1 is represented by the formula 1a
Compounds represented by are preferred.

[0022]

[Chemical 5]   R^f-O- (CH_TwoCH_TwoO)_k・ [CH_TwoCH (CH_Three) O]_m-H formula 1a However, the symbols in Formula 1a have the following meanings: (CH
_TwoCH_TwoO) and [CH _TwoCH (CH_Three) O]
Can be in random order, even in blocks
Good. It is preferably a block. R^f: Has the same meaning as in Formula 1. k and m: each independently an integer of 1 to 99, k +
m is 2 to 100.

Independently of k and m, 1 to 30 are preferable, and 2 to 10 are particularly preferable. 2-60 are preferable and, as for k + m, 4-20 are especially preferable. Further, k ≧ m is preferable.

Specific examples of the fluorinated compound (formula 1) include, but are not limited to, the following compounds.
However, in the following compound, the portion corresponding to the R ^fB group may have a linear structure or a branched structure, and the linear structure is preferable. Further, when there is a polyoxyalkylene chain containing two or more kinds of oxyalkylene groups, the chain of them may be block or random. The (C ₃ H ₆ O) moiety represents an oxypropylene group, and is [CH (CH ₃ ) CH ₂ O] or [CH ₂ CH
(CH ₃ ) O]. Also (C ₄ H ₈ O)
The part is a ring-opened product of tetrahydrofuran (CH ₂ C
H ₂ CH ₂ CH ₂ O).

The fluorine-containing compound in the present invention may be used either alone or in combination of two or more kinds.

[Chemical 6] C₈F₁₇C_TwoH_FourO (C_ThreeH₆O)₁₀H,
C₈F₁₇C_TwoH_FourO (C_ThreeH₆O)_Four・ (C_TwoH
_FourO)₈H, C₈F₁₇C_TwoH_FourO (C_TwoH_FourO)_Thirteen
H, C₈F₁₇C_TwoH_FourO (C_FourH₈O)_Three・ (C_TwoH
_FourO)₁₀H, C₈F₁₇C_ThreeH₆O (C_ThreeH₆O)
₁₀H, C₈F₁₇C_ThreeH₆O (C_ThreeH₆O)_Four・ (C
_TwoH_FourO)₈H, C₈F₁₇C_ThreeH₆O (C_TwoH_FourO)
_ThirteenH, C₈F₁₇C_ThreeH₆O (C_FourH₈O)_Three・ (C
_TwoH_FourO)₁₀H, C₈F₁₇C_FourH₈O (C_ThreeH
₆O)₁₀H, C₈F₁₇C_FourH₈O (C_ThreeH₆O)_Four
・ (C_TwoH_FourO)₈H, C₈F₁₇C_FourH₈O (C_TwoH
_FourO)_ThirteenH, C₈F₁₇C_FourH₈O (C_FourH₈O)_Three
・ (C_TwoH_FourO)₁₀H, C₈F₁₇C_FourH₈O [CH
(C₆H₅) CH_TwoO]_Two・ [CH (CH_TwoOCH _Three)
CH_TwoO]_FourH, C₈F₁₇C_FourH₈O (C_ThreeH₆O)
_Four・ (C_TwoH_FourO)₈CH_Three, C₈F₁₇C_FourH₈O
(C_ThreeH₆O)_Four・ (C_TwoH_FourO)₈COC
₁₈H₃₇.

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

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

For example, the R ^fB group in R ^{f of} formula 2 is R
^{In the case of a FB} group and the C moiety has 1 carbon atom, a fluorine-containing hydroxy compound (R ^FB CH ₂ OH) can be synthesized by adding perfluoroalkyl iodine (R ^FB I) obtained by the telomerization to ethylene. Is added and treated with an alkali to give perfluoroalkylethylene (R ^FB CH = CH ₂ )
Then, the perfluoroalkylethylene is oxidized to a perfluoroalkanecarboxylic acid (R ^FB COOH), and the perfluoroalkanecarboxylic acid is further converted to NaBH.
_{4 and the} like.

R in equation 2^fR in^fBGroup is R^FBAt the base
And a fluorine-containing hydroxy group in which the C moiety has 2 carbon atoms
Si compound [R^FB(CH_Two)_TwoOH] synthesis method
Is the above R^FBInsert ethylene in I and R^FB(C
H_Two)_TwoSubstitute I for a terminal iodine atom with a hydroxyl group
Method. R in formula 2^fR in^fBGroup is R^FB
A fluorine-containing group in which the C moiety has 3 carbon atoms
Droxy compound [R^FB(CH_Two)_ThreeOH] synthesis method
As above^FBAdd allyl alcohol to I
R^FBCH_TwoCHICH_TwoOH, then iodine atom
There may be mentioned a method of substituting hydrogen atom with a reducing agent. Formula 2
R^fR in^fBGroup is R^FBThe number of carbons in the C part
Fluorine-containing hydroxy compound [R^FB(C
H_Two)_FourOH] can be synthesized by the above R^FB3 to I
-Add butene-1-ol [R^FBCH_TwoCHI
(CH_Two) _TwoOH] and then replace the iodine atom with a reducing agent.
A method of substituting with a hydrogen atom can be used.

Further, R ^fB CH ₂ CH ₂ CH ₂ (OH) CH, which is an isomer of a fluorine-containing hydroxy compound [R ^FB (CH ₂ ) ₄ OH] when the C moiety has 4 carbon atoms.
Examples of the method for synthesizing ₃ include a method in which R ^FB CH = CH ₂ is obtained by adding a predetermined radical initiator in a large amount of ethanol solvent, stirring the mixture with heating, and adding ethanol in a radical addition reaction. Can be mentioned. The _{^{R F B (CH 2) 5}} OH synthesis methods when the number of carbon atoms of the C moiety is ^5, then adding 4-penten-1-ol _{^{R FB I [R FB CH 2}} CHI (CH 2 ) ₃ OH] and then replacing the iodine atom with hydrogen with a reducing agent.

Next, the fluorine-containing 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 are subjected to a ring-opening addition reaction, they may be mixed and reacted, or may be sequentially reacted. When only one cyclic ether is used, 2
When using more than one species, they may be added all at once or gradually added to the reaction system. Although the amount of the fluorine-containing hydroxy compound (formula 2) charged varies depending on the amount of the cyclic ether compound added, it is preferable to charge 1/10 or more of the internal volume of the reactor in consideration of stirring conditions of the reactor. Considering the volume efficiency in particular, it is desirable that the volume ratio after addition of the cyclic ether is 80 to 95%.

The ring-opening addition reaction is preferably carried out in the presence of a catalyst. As the catalyst, alkali metal catalysts, acid catalysts and metal complex catalysts are preferable, and acid catalysts and metal complex catalysts are particularly preferable. As an alkali metal catalyst, KOH,
Examples include a three-way catalyst consisting of NaOH, CsOH, and NaBH ₄ / NaI / I ₂ , the acid catalyst includes BF ₃ , and the metal complex catalyst includes zinc hexacyanocobaltate ether and / or alcohol complex catalyst. The complex metal cyanide complex of is mentioned.

When the ring-opening addition reaction is carried out under strong alkaline conditions, a side reaction in which HF is eliminated at the R ^f part may occur, so that when an alkali metal catalyst is used, it is a mild alkaline catalyst. It is preferable to use a three-way catalyst consisting of NaBH ₄ / NaI / I ₂ . Further, when an acid catalyst is used, if the acidity of the catalyst is too strong, HF is generated in the R ^f portion.
This may cause a side reaction of elimination of HF.
In order to suppress the reaction, it is preferable to use a diluting solvent if necessary. Examples of the diluting solvent include ether solvents such as glyme, diglyme, triglyme, and methyl-tert-butyl ether. The reaction temperature of the ring-opening addition reaction of the cyclic ether is preferably -20 to 180 ° C, particularly preferably 0 to 130 ° C. When a diluting solvent is used and the diluting solvent is a low boiling point diluting solvent, in consideration of the increase in internal pressure, (boiling point of solvent +20
It is preferable to react at a temperature lower than (.degree. C.).

The compound obtained by subjecting the fluorine-containing hydroxy compound (formula 2) to the ring-opening addition reaction of a cyclic ether is a fluorine-containing compound (formula 1) when the terminal is a hydroxyl group (R is a hydrogen atom), Various properties can be adjusted by modifying (for example, esterifying or alkylating) the terminal hydroxyl group. The esterification is preferably carried out by reacting an organic carboxylic acid, an organic carboxylic acid ester or an organic carboxylic acid anhydride. 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, or stearic acid. Examples of the organic carboxylic acid ester include esters of the monovalent carboxylic acid and a low boiling point alcohol, and examples of the organic carboxylic acid anhydride include acetic anhydride, propionic anhydride, butanoic anhydride, and n-anhydride. Examples include monovalent carboxylic acid anhydrides such as butyric acid.

The esterification is carried out by using the above-mentioned organic carboxylic acid, organic carboxylic acid ester or organic carboxylic acid anhydride,
In addition to the fluorine-containing compound (formula 1) when the terminal is a hydroxyl group (R is a hydrogen atom), after stirring with heating without catalyst or in the presence of a catalyst, dehydration, dealcoholization, or removal of unreacted acid It is preferable to carry out.
As the catalyst, a trace acid catalyst such as paratoluenesulfonic acid or sulfuric acid, or an alkali catalyst such as potassium hydroxide or sodium hydroxide is preferable. Alkylation includes a method of reacting with a monohaloalkyl under strong alkaline conditions, a method of using dialkyl sulfuric acid, and the like. However, a reaction using an alkylating agent such as alkyl sulfuric acid is preferable because the elimination reaction of HF can be suppressed.

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

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

In the present invention, water is the main blowing agent. The amount of water used is 4 with respect to 100 parts by mass of the polyol.
-16 parts by mass is preferable, and 6-12 parts by mass is particularly preferable. Further, in the present invention, it is more preferable to use water as the sole foaming agent. However, a conventional low-boiling halogenated hydrocarbon can be used together as an auxiliary blowing agent depending on the purpose.

The low-boiling halogenated hydrocarbon is not particularly limited, but it is 1,1-dichloro-1-fluoroethane (HCFC-141b), chlorodifluoromethane (HCFC-22), 1,1,1,2. -Tetrafluoroethane (HFC-134a), 1-chloro-1,1-difluoroethane (HCFC-142b), 1,1-dichloro-2,2,3,3,3-pentafluoropropane (HCFC-225ca), 1,3-dichloro-1,
1,2,2,3-pentafluoropropane (HCFC-
225cb), pentafluoroethane (HFC-12
5), 1,1,2-trifluoroethane (HFC-14
3), 1,1,1-trifluoroethane (HFC-14
3a), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea) and its isomers, 1,
1,2,2,3-pentafluoropropane (HFC-2
45ca) and its isomers, 1,1,1,4,4,4
-Hexafluorobutane (HFC-356mff),
1,1,1,3,3-pentafluoropropane (HFC
-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc) and other halogenated hydrocarbons containing a fluorine atom. In addition, a low-boiling halogenated hydrocarbon containing no fluorine such as methylene chloride can be used together as a foaming agent. Although it is not preferable to use a halogenated hydrocarbon as a foaming agent in view of the above-mentioned environmental problems, the technique of the present invention increases the number of parts of water to be used for halogenation without reducing the performance of the foamed synthetic resin. The amount of hydrocarbon used can be significantly reduced.

When a low-boiling halogenated hydrocarbon is also used as a foaming agent, the proportion of the low-boiling halogenated hydrocarbon used is preferably 0.1 to 500 parts by mass with respect to 100 parts by mass of water. In addition, hydrocarbons such as butane, pentane, cyclopentane and hexane, and inert gases such as air and nitrogen can be used together as a foaming agent. When an inert gas is also used as the foaming agent, the use ratio of the inert gas is preferably 0.1 to 500 parts by mass with respect to 100 parts by mass of water.

As the catalyst in the present invention, a commonly used urethane reaction promoting catalyst can be used. As the urethane reaction accelerating catalyst usually used, metal compound catalysts such as organotin compounds, triethylenediamine, N, N, N ′,
Examples thereof include tertiary amine catalysts such as N'-tetramethylhexamethylenediamine. Further, a polymerization catalyst for reacting isocyanate groups with each other such as carboxylic acid metal salt can be used according to the purpose. The amount of the catalyst used may be appropriately selected, but is 0.1 per 100 parts by mass of the polyol.
-10 mass parts is preferable.

Further, in the present invention, it is preferable to use a foam stabilizer for forming good bubbles. As the foam stabilizer, a silicone-based foam stabilizer is preferable. The amount of the foam stabilizer used may be appropriately selected, but is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyol. Other,
Compounding agents that can be used optionally include, for example, fillers, stabilizers, colorants, flame retardants and the like. The flame retardant may be a commonly used flame retardant for urethane, and the compounding amount thereof is preferably 5 to 30 parts by mass with respect to 100 parts by mass of the polyol.
The reaction temperature condition of the present invention is not particularly limited, but the temperature of the raw material is usually preferably in the range of 0 to 50 ° C.
The range of ° C is particularly preferred.

According to the present invention, in the method for producing a rigid foamed synthetic resin by using water as a foaming agent, it is possible to obtain a closed cell having excellent dimensional stability for a long period of time and particularly dimensional stability even at high temperature and high humidity. A rigid foam synthetic resin such as a rigid polyurethane foam can be easily obtained.

[0043]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In addition, in an Example and a comparative example, a part means a mass part.

(Examples 1 to 5) A combination of the polyisocyanate compound and the polyol in the number of parts shown in Table 1 was used.
Fluorine compound, water, general-purpose silicone foam stabilizer, flame retardant, and amine catalyst in the number of parts shown in are mixed at a liquid temperature of 20 ° C.,
To a 400 x 400 x 50 mm aluminum mold heated to 40 ° C, an overall density of 36 to 39 kg /
The reaction was carried out so as to obtain m ³ . Isocyanate group: active hydrogen group = 1.1: 1 (isocyanate index 110). Density of the obtained polyurethane foam (kg /
Table 1 shows m ³ ), compressive strength (MPa), dimensional stability result and closed cell ratio.

The physical properties were measured by the following methods. (1) Method of measuring compressive strength It was performed according to JIS K7220. (2) Dimensional stability measurement method It was performed according to JIS A9511. In the compressive strength and dimensional stability, X and Y mean the lateral direction, and T means the thickness direction. (3) Measuring Method of Closed Cell Ratio The resin volume and the closed cell volume were measured by using a high precision automatic volume meter (VM-100, STEC Co., Ltd.) which measures the resin volume and the closed cell volume by a gas phase substitution method.

[0046]

[Table 1]

Note) The polyisocyanate compounds and other abbreviations in Table 1 are as follows. Polymeric MDI: MR manufactured by Nippon Polyurethane Industry Co., Ltd.
-200, isocyanate group content ratio 31% by mass Polyol A: Propylene oxide was added using a sucrose / glycerin mixture as an initiator to give a hydroxyl value of 450 mg KO.
H / g. Polyol B: Propylene oxide added with sorbitol as an initiator to give a hydroxyl value of 400 mgKOH / g. Polyol C: A compound having a hydroxyl value of 350 mgKOH / g by adding propylene oxide and ethylene oxide using toluenediamine (TDA) as an initiator.

The fluorine-containing compound F1: propylene using a fluorine-containing compound of 12 carbon atoms _{C 8 F 17 CH 2 CH 2} CH (CH 3) OH to the composite metal cyanide complex catalyst (a zinc hexacyanocobaltate / glyme complex catalyst) A mixture of oxide and ethylene oxide in a mass ratio of 30:70 was subjected to ring-opening addition polymerization to give an average molecular weight of 800 (corresponding to a compound of n = about 6.5 in the formula 1) Fluorine-containing compound F2: containing 12 carbon atoms Fluorine compound C ₈
F ₁₇ CH ₂ CH ₂ CH (CH ₃ ) OH was subjected to ring-opening addition polymerization of a mixture of propylene oxide and ethylene oxide in a mass ratio of 30:70 using a complex metal cyanide complex catalyst (zinc hexacyanocobaltate / glyme complex catalyst). The average molecular weight was set to 1000 (in the formula 1, n =
Corresponds to about 11 compounds) Fluorine-containing compound F3: Fluorine-containing compound C ₈ having 12 carbon atoms
F ₁₇ CH ₂ CH ₂ CH (CH ₃ ) OH was subjected to ring-opening addition polymerization of a mixture of propylene oxide and ethylene oxide in a mass ratio of 50:50 using a complex metal cyanide complex catalyst (zinc hexacyanocobaltate / glyme complex catalyst). The average molecular weight was set to 1000 (in the formula 1, n =
Flame retardant: tris (β-chloropropyl) phosphate foam stabilizer: silicone foam stabilizer, Nippon Unicar Co., SZ-
1646 Catalyst: N, N, N ', N'-tetramethylhexamethylenediamine, manufactured by Tosoh Corporation, TOYOCAT-MR

(Comparative Examples 1 to 3) Water, silicone foam stabilizer, flame retardant and amine catalyst were added to the combination of polyisocyanate compound and polyol in the number of parts shown in Table 2 at a liquid temperature of 20 ° C. without adding a fluorine-containing compound. The mixture was mixed in, and charged into an aluminum mold of 400 × 400 × 50 mm heated at 40 ° C. so as to have an overall density of 36 to 39 kg / m ³ and foamed. Isocyanate group: Active hydrogen group =
It was 1.1: 1 (isocyanate index 110). Table 2 shows the density (kg / m ³ ), compressive strength (MPa), dimensional stability result and closed cell ratio of the obtained polyurethane foam.

[0050]

[Table 2]

[0051]

INDUSTRIAL APPLICABILITY According to the present invention, in a method for producing a rigid foamed synthetic resin using water as a foaming agent, a closed cell having excellent dimensional stability, particularly dimensional stability even at high temperature and high humidity, can be obtained. A rigid foam synthetic resin such as a rigid polyurethane foam can be easily obtained.

Continued front page    (72) Inventor Tadanobu Kuroki             25 Asahi, Towada, Kazasu-machi, Kashima-gun, Ibaraki             Glass Urethane Co., Ltd. (72) Inventor Ichiro Shioji             25 Asahi, Towada, Kazasu-machi, Kashima-gun, Ibaraki             Glass Urethane Co., Ltd. F-term (reference) 4J034 CA02 CC08 CD12 CE01 DA01                       DB01 DB04 DB05 DB07 DD07                       DG03 DG04 HA01 HA07 HC03                       HC12 HC17 HC22 HC35 HC46                       HC52 HC61 HC64 HC65 HC67                       HC71 HC73 KA01 KB02 KC17                       KD02 KD12 MA12 MA24 NA03                       QB16 QC01 RA15

Claims (5)

[Claims] 1. A method for producing a rigid foam synthetic resin, which comprises reacting a polyol and a polyisocyanate compound in the presence of water, a catalyst, and a fluorine-containing compound represented by the formula 1. Production method. Embedded image R ^f —O— (A—O) _n —R Formula 1 (In Formula 1, R ^f represents a fluorine-containing organic group having 2 to 27 carbon atoms, n
Is an integer of 1 to 100. A is an alkylene group having 2 to 4 carbon atoms in the straight chain portion between bonds, and A in the formula when n is 2 to 100 may be the same or different. R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an acyl group having 1 to 18 carbon atoms. ) 2. A water-only foaming agent is used.
The method for producing a rigid foam synthetic resin according to 1. 3. The method for producing a rigid foam synthetic resin according to claim 1, wherein the fluorine-containing compound is represented by formula 1a. Embedded image R ^f —O— (CH ₂ CH ₂ O) _k · [CH ₂ C
H (CH ₃ ) O] _m —H Formula 1a (In Formula 1a, R ^f is a fluorine-containing organic group having 2 to 27 carbon atoms,
k and m are each independently an integer of 1 to 99, and k +
m is 2 to 100. ) 4. The rigid foam synthetic resin according to claim 1, wherein the amount of the fluorine-containing compound used is 0.01 to 1 part by mass based on 100 parts by mass of the total amount of the polyol and the polyisocyanate compound. Manufacturing method. 5. The method for producing a rigid foam synthetic resin according to claim 1, wherein the amount of water used is 4 to 16 parts by mass with respect to 100 parts by mass of the polyol.