JPS5883020A - Condensation type resin-dispersed polyol composition - Google Patents

Abstract

PURPOSE:A composition containing stably dispersed particulate condensation type resin and being useful in the production of polyurethanes excellent in compressive strength and flame retardancy, prepared by reacting a polyamine with a polycarboxylic acid and a polysulfonic acid in polyether-polyol. CONSTITUTION:A condensation type resin-dispersed polyol composition in which condensation type resin fine particles are disperesed and which is used as a polyurethane material, prepared by reacting a polyamine (e.g., ethylenediamine) with a polycarboxylic acid (derivative) (e.g., bi- to tetravalent aliphatic or aromatic polycarboxylic acid) or aromatic polycarboxylic acid) or a polysulfonic acid (derivative) (e.g., aliphatic or aromatic disulfonic acid) in polyether-polyol (e.g., adduct between ethylene glycol and propylene oxide). This composition contains stably dispersed fine particles of a condensation type resin such as polyamide and, therefore, can form a polyurethane excellent in compressive strength and flame retardancy.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a condensed resin-dispersed polyol composition used as a raw material for polyurethane such as polyurethane foam, and particularly to a condensed resin-dispersed polyol composition that is prepared by carrying out a condensation reaction in a polyether polyol. It is about things.

Vinyl polymer fraction polyether polyols obtained by polymerizing vinyl monomers in polyether polyols are
It is widely known as a polymer polyol. on the other hand,
It is also known to carry out condensation reactions in polyether polyols to produce polyether polyols partitioned with conjugated resins. For example, JP-A-50-15832 describes an aminoblast condensate-dispersed polyether polyol obtained by reacting an organic substance such as urea or melamine with an aldehyde in a polyether polyol. Japanese Patent Publication No. 52-16747 describes a polyurea or polyhydrazocicabonamide-dispersed polyether polyol obtained by reacting a starting material such as a polyamine or hydrazine with a polyiso7anate in a polyether polyol. ing. Condensation resin-dispersed polyether polyol is used for polyurethane foam, similar to vinyl polymer-dispersed polyether polyol.
+yyt It is not only effective for improving properties, but also effective for reducing flammability and bath agent resistance.

The present inventor further conducted various research studies to find a new condensation resin-dispersed polyether polyol, and found that
A novel condensation resin-dispersed polyol composition obtained by reacting polyamines, polybasic acids, and all-polyether polyols? ! I ended up finding 7. This new condensation resin-dispersed polyol composition is not only effective in improving the mechanical strength and flame retardance of polyurethane such as polyurethane foam, but also in imparting new properties such as improved heat resistance. be. Even when a polyamine and a polybasic acid are reacted in a polyether polyol, the polybasic acid preferentially reacts with the polyamine and rarely reacts with the hydroxyl groups of the polyether polyol. It is thought that polyether polyesters, which are produced by the reaction of polyamines such as polyamides and polybasic acids in the condensation resins used, and polyether polyesters produced by the reaction of polyether polyols and polybasic acids, are considered to be rare. The polybasic acid may also be a derivative thereof such as anhydrous chloride or acid chloride. The present invention relates to a polyether polyol in which this condensation resin is dispersed, that is, a fine particulate condensation system prepared by completely reacting a polyamine with a polycarboxylic acid, a polysulfonic acid, or an acid derivative thereof in a polyether polyol. This is a polyol composition for polyurethane raw materials in which resin is dispersed.

The fl'ii thread resin-dispersed polyol composition of the present invention is
It is a polyether polyol in which fine particles of condensation resin such as polyamide are dispersed in a tri-layer. Rida, which has good dispersion stability, not only has a small average particle size of the condensed synthetic resin, but also has some polyether polyols and condensed resins that are polybasic acids (hereinafter referred to as polycarboxylic acids, polysulfones, etc.). It is speculated that this is due to the grafting of residual funds (indicating acid derivatives). Many of the polyether polyols react with polybasic acids, which is undesirable because it increases the total viscosity of the condensed resin-dispersed polyol composition and lowers the hydroxyl value.

For this reason, it is preferable that the amount of polybasic acid used is approximately equivalent or less to the polyamine. As long as a polyamine is present, the polybasic acid reacts preferentially with the polyamine and rarely reacts with the polyether polyol. Since the dispersion stability of the condensed resin-dispersed polyol composition of the present invention is high, the condensed synthetic resin particles do not separate from the 5-riether polyol by standing still or the like. Conveniently, it can be used in the same manner as known vinyl polymer dispersed polyether polyols. That is, it can be used as a polyether polyol as a raw material for polyurethane without requiring any other special method of use due to its somewhat high viscosity.

The condensation resin in the present invention is produced by reacting a polyamine with a polycarboxylic acid, a polysulfone, or an acid derivative thereof. Acid derivatives are derivatives capable of reacting as acids with polyamines such as acid anhydrides, halides, and esters, and are preferably substantially anhydrides and chlorides. In the following description, the term -C1 polycarbonate and polysulfonic acid is intended to include VSS and di-these acid derivatives, which are not specifically mentioned.

Polyamine u (R'-)-+NHR2)n C'm'
:' n 1 organic residue, R2: hydrogen atom or H
J Lukyl group.

n: an integer of 2 or more], and especially R
Diamines represented by 2NH-R1-, NHR2 [sometimes R2 is hydrogen, or a lower alkyl group] are preferred. R1
is a divalent or higher aliphatic, aromatic, or other hydrocarbon residue,
Alternatively, it may be a derivative thereof, such as a derivative containing an imino group, an ether group, an ester group, a halogen, or the like. Preferred R1 alkylene groups and arylene groups, particularly preferred are alkylene groups having 2 to 12 carbon atoms. Preferred polyamines are polymethylenediamines represented by R2NH (CH2-NHR2 [m = an integer of 4 to 12]) or derivatives thereof. Specific examples of polyamines include ethylenediamine, hexamethylenediamine, and hexamethylenediamine.

Examples include tetramethylene diamine, octamethylene diamine, nonamethylene diamine, diaminodiphenylmethane, xylylene diamine, and piperazine.

The polycarboxylic acid is a compound represented by (R3HC00H)k [R3: divalent organic residue, ni: an integer of 2 or more], and polycarboxylic acids with k of 2 to 4 are sometimes preferred. R
3 may be a d-conductor containing divalent or higher aliphatic, aromatic, or other hydrocarbon residues, or derivatives thereof, such as ether groups, ester groups, and halokenes. Preferred R is di- to tetravalent aliphatic or aromatic carbon. All specific examples of polyamines include the following: Succinic acid, adipic acid, azelain, sebacic acid, dimer acid, maleic acid, phthalic acid, phenylene diacetate, trimellitic acid, pyromellitic acid, butanetetracarboxylic acid.

Polysulfonic acid is an organic compound having two or more -8o, H fundamental sounds, (R3++, 503)■), k[R
3 and k have the same meanings as above. In the case of polysulfonic acids, preferred are disulfonic acids, and particularly preferred are alkylene disulfonic acid/sulfonic acid having 4 to 12 carbon atoms.

As mentioned above, the polybasic acid may be an acid derivative.

As acid derivatives, acid anhydrides and acid chlorides are particularly preferred. In addition, 2 each of the above polyamines and polysalts 4wrts
A condensation resin can also be produced by using two or more species in combination.

For example, polycarbonate or polysulfone
Of course, polycarbonate and polysulfonic acid can be used together. The reaction between the polyamine and the polybasic acid is preferably carried out in substantially equivalent amounts as described above. Further, when forming an imide bond, 1/2 equivalent of carboxylic acid or the like is reacted with the amine group. The use of excess polyamines or polybasic acids may cause disadvantages. In particular, polyether polyols with residual carboxyl, acid groups, or sulfonic acid groups often have an adverse effect on the polyurethane production reaction. Therefore, it is preferable to taste away the excess raw material. The resulting condensation resin is thought to have the following structural units, but is of course not limited to these.

℃ stop-R'-NHCO-R"-Co)-, -(Ll(
'-NHCO-R'-'s '-NHCO-R' - 'Koukei 1 Condensation-based resin The polyether polyol that is used as the raw material can be used in any way, but polyether polyols suitable as raw materials for producing polyurethane are preferred.The reason is that This is because the properties such as the hydroxyl value and number of hydroxyl groups of the resulting condensed resin-dispersed polyol composition mainly depend on the properties of the polyether polyol as the medium used.The properties of the polyether polyol are not particularly limited. No, but the hydroxyl value is about 2
Polyether polyols having an average number of hydroxyl groups of about 2 to 8 are suitable. Particularly preferred polyether polyols are polyether polyols that have been conventionally used or known as raw materials for flexible or semi-rigid polyurethane foams, and have a hydroxyl value of about 30 to
150, a polyether polyol having an average number of hydroxyl groups of about 2 to 4.

The polyether polyol is preferably one obtained by adding an epoxide to an initiator having two or more active hydrogens. The initiator may be a mixture of two or more types. As an initiator, for example, an active flat hydrogen atom that can react with an epoxide such as a hydrogen atom of a polyhydric alcohol, a sugar alcohol, an alkanolamine, an amine, a polyhydric phenol, or a hydrogen atom of an amine group is used. This is a compound having the above. As the initiator, it is also possible to use the target polyether polyol obtained by adding epoxide to these two or more active hydrogen-blind initiators, or a hydroxyl group-containing compound such as a polyether polyol with a small amount of epoxide added. . Examples of typical initiations include the following: Ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, hexanetriol.

diglycerin, pentaerythritol, sorbitol,
Mannitol, sucrose, ethanolamine, ethanolamine, triethanolamine, diglobanol famine, ethylenediamine, quetilintriamine, tolylenediamine, diaminodiphenylmethane, polymethylenepolyphenylamine, bisphenol A.

Novolac.

The epoxide added to the above initiator is %
Although alkylene oxide is preferred, the present invention is not limited to this. For example, epoxides such as styrene oxide and various glycidyl ethers can be used. As the alkylene oxide, epoxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, epichlorohydrin, and butylene oxide are preferred, and propylene oxide alone or a combination of propylene oxide and ethylene oxide is particularly preferred. When propylene oxide and ethylene oxide are combined, a method can be used in which both are thoroughly mixed and added to the initiator, or a method in which both are added separately and sequentially. Although the addition ratio of both is not particularly limited, the ratio of ethylene oxide in the polyether polyol is preferably 60% by weight or less.

Furthermore, since ethylene oxide generates primary hydroxyl groups, by forming the terminal blocks of polyether polyol into oxyethylene blocks, polyether polyols having highly active primary hydroxyl groups can be obtained.

As polyether polyols, in addition to those obtained by adding epoxide to the above-mentioned initiator, polyether polyols obtained by ring-opening of cyclic ethers having four or more members, such as poly( All phases, such as oxytetramethylene) glycol, can also be present.

By reacting a polyamine and a polybasic acid in a polyether polyol, the above-mentioned stable condensed resin-dispersed polyether polyonyl can be obtained. The ratio of condensation resin to polyether polyol is 60% or less, especially 40%
m [quantity coefficient or less is preferable. If the proportion of the condensation resin increases further, the viscosity of the polyether polyol increases and the dispersion stability tends to decrease. The lower limit of the ratio of the condensed resin to the polyether polyol is not particularly limited. However, in order to exhibit various desired properties, the lower limit is often about 5 folds. The condensation resin is dispersed as fine particles in the polyether polyol. The average particle size is usually 40μ or less, especially 0.1~
Approximately 10μ is appropriate. The average particle size of the condensation resin can be adjusted by adjusting the temperature and other reaction conditions, and is preferably adjusted to a relatively small particle size. One of the reasons for the high dispersion stability of the combination resin-dispersed polyol composition of the present invention is that the average particle size of the condensation resin is small.

As mentioned above, one of the reasons why the dispersion stability of the condensed resin in the polyether polyol is high is thought to be that a part of the polyether polyol is grafted with the condensed resin. All combination resins are manufactured in advance,
In this method of dispersing in polyether polyol, even if the average particle diameter of the condensed resin is about the same, the dispersion stability is lower than that of the condensed resin-dispersed polyol composition of the present invention. The fact that the polyether polyol and the polybasic acid have reacted is confirmed by the fact that the hydroxyl value is different from that expected if the polyether polyol does not react with the polybasic acid at all. Usually, the reaction between the polyether polyol and the polybasic acid calculated from this is small, but its contribution to dispersion stability cannot be ignored.

The reaction between the polyamine and the polybasic acid in the polyether polyol can also be carried out in the presence of other compounds. Examples of these additives include catalysts that promote the reaction between polyamines and polybasic acids, polyols other than polyether polyols, chain terminators for W1 resins, and inert additives such as colorants and fillers. There is.

As a catalyst, a glazing base can be used, for example when a combination acid chloride such as a carbodiimide is used. As polyols other than polynigel polyol, low molecular weight polyols such as polyhydric alcohols, polyester polyols, etc. can be used.

The condensed resin-dispersed polyol composition of the present invention can be used as it is as a polyol for polyurethane raw materials. Moreover, this polyol composition wJ can also be diluted with a -chill polyol and used. The polyether polyol to be diluted may be the polyether polyol used as a raw material for this polyol set Km, or may be another polyether polyol.

Furthermore, other polyols, such as polynisder polyols and polyhydric alcohols, can also be added.

The condensed resin-dispersed polyol composition of the present invention can be used as a raw material for various polyurethanes, like conventional polymer polyols and condensed resin-dispersed polyols. Although polyurethanes can be divided into foam and non-foam, the polyol composition of the present invention is particularly suitable as a raw material for polyurethane foam. Of course, it can also be used as a raw material for non-foam polyurethanes such as paints and paints. Polyurethane foams include flexible, semi-rigid,
The polyol paulownia composition of the present invention is particularly used as a raw material for soft and semi-rigid polyurethane foams. Polyurethane foams are produced from reactive mixtures comprising the polyol compositions of the present invention and polyisocyanates. As the polyisocyanate, aromatic, alicyclic, aliphatic and other polyisocyanates can be used, but aromatic polyisocyanates are particularly preferred. Furthermore, as the polyisocyanates, so-called modified polyisocyanates can also be used.

Specifically, the polyisocyanate includes tolylene diisocyanate, diphenylmethane diisocyanate,
Polymethylene polyphenylisocyanate, naphthalene/incyanate.

Examples include isophorone diisonanate, methylene bis(cyclohexyl isocyanate), hexamethylene diisocyanate, and xylylene diisocyanate. In addition to the above two main components, various additives are added to the reactive mixture VC. Usually essential additives are catalysts and blowing agents.
Furthermore, foam stabilizers are often added. As a catalyst,
Typical examples include a tertiary amine catalyst and an organometallic compound such as an organotin compound or an organolead compound, and these are often used in combination. Typical blowing agents include trichlorofluoromethane, dichlorodifluoromethane, metele chloride/other halogenated hydrocarbon blowing agents, water, and inert gases such as air. A hydrogen blowing agent alone or a combination of a hydrogen blowing agent and water is often used. As foam stabilizers, various organic silicon compounds are mainly used.
Examples include 1M filler, 1M refueling agent, 1M stabilizer, 9M reinforcing agent, and 9M colorant.

EXAMPLES The present invention will be specifically explained below using Examples and Reference Examples, but the present invention is not limited to these Examples.

Example 1 Propylene oxide was added to glycerin, and then ethylene oxide (i715 wt%) was added to create a polyether triol with a molecular weight of 15000 and 160 f.
'ft: Pour into the third flask and stir while stirring.
Thoroughly dehydrate under reduced pressure at ℃.

After introducing nitrogen into the system, diaminodiphenylmethane 24f is obtained by completely removing water while flowing nitrogen,
Add anhydride and 16f'i of phthalic acid, and stir and mix at 80°C. The system once becomes transparent and homogeneous, and then gradually becomes cloudy. After reacting at 80° C. for 4 hours, the temperature was raised to 160° C. and the reaction was further continued for 2 hours. After the reaction, complete vacuum degassing is performed to recover trace amounts of low-boiling components. The resulting polyol was yellowish-white and opaque with a viscosity of 4.500 CP (at 25°C). As a result of all the filtration tests carried out using an 800 mesh stainless wire mesh, there were no residual resin particles that had been separated on the wire mesh, and all of them passed through.

Example 2 Polyether polyol 140r'i3 with a molecular weight of 3,000, which was obtained by adding propylene oxide to glycerin and further adding ethylene oxide to give a concentration of 113 wt%.
Pour into a second flask and thoroughly dehydrate under reduced pressure while stirring. After introducing nitrogen into the system, 18.9 f of ethylenediamine and 100 f of ethylamine were added while flowing nitrogen roughly, and the temperature was raised to 30°C while stirring.

64.1f of 7-taloyl chloride was added dropwise from the dropping funnel over 2 hours. After the dropwise addition was completed, the reaction was continued at 30°C for an additional hour, and then the temperature was raised to 90°C and the reaction was continued for 7.2 hours. After the reaction, excess triethylamine was removed by degassing under reduced pressure to obtain a yellowish-white opaque polyol. Viscosity ij 5,200 CP
(at 25°C), passed through an 800-mesh stainless steel wire mesh without any f markings.

Example 3 Polyether polyol 1 used in Example 1
The mixture was placed in three 80 ft flasks and thoroughly dehydrated under reduced pressure while stirring. After introducing nitrogen into the system, 2,5-dimethylpiperazine7.
2f,) Add ethylamine 32,000 ml and heat to 30° C. while continuing to stir.

From the dropping funnel m-benzenedisulfonyl chloride 1
7. Drop for 2 hours or more. 30 minutes after completion of dripping
After reacting for an additional 1 hour at °C, the temperature was raised to 90 °C and the reaction was continued for 2 hours. After the reaction, excess triethylamine was removed by degassing under reduced pressure to obtain a yellow, opaque polyol. The viscosity is 2,
It passed through an 800-mesh stainless steel wire mesh at 500CP (at 25°C) without any special markings.

Example 4 Polyether polyol 160 f used in Example 2
Place 3 pieces in a flask and thoroughly dehydrate under reduced pressure while stirring. After introducing nitrogen into the system, 26.29 ml of pyromellitic anhydride and 301 ml of dehydrated methanol were added and heated at 60° C. for 1 hour without passing nitrogen. Hexamethylene diamine 13.8 f'ft: added, 60
After continuing stirring at ℃ for 30 minutes, the temperature was raised to 140℃ and methanol was added.

Remove water under reduced pressure for 5 hours. The obtained polyol was yellowish white and opaque with a viscosity of 4,250 CP (at 25
℃) and passed the 800 mesh wire mesh passage test without any residue.

Example 5 Polyether polyol 80 f' used in Example 1
Next, pour into the third flask and thoroughly dehydrate under reduced pressure while stirring. After introducing nitrogen into the system, flow 3 more nitrogen]m
While stirring, add 16.8t of maleic anhydride,
Stir at °C. m-xylylenediamine 23.2S” (
i7 A solution of polyol 802 dissolved in M is added dropwise for about 2 hours using a dropping rotor. 160 minutes after completion of dripping
Degassed under reduced pressure at °C for 2 hours to obtain a yellowish-white opaque polio-#'i.
Profit*. The test fitting passed through an 800 mesh wire mesh at a viscosity iU of 3.800 CP (at 25°C) without any residue.

The results of foaming the retan foam are shown in Figure 1.

Claims (1)

[Scope of Claims] 1. A polyol composition for polyurethane raw materials in which imitative granular condensation resins obtained by reacting polyamines with polycarboxylic acids, polysulfonic acids, or their acid derivatives in polyether polyol are dispersed. thing. 2. The composition according to item 1 of the specified scope, characterized in that the polyamine is an aliphatic or aromatic diamine. 3. The composition according to claim 1, wherein the polycarboxylic acid is a di- to tetravalent aliphatic or aromatic polycarboxylic acid. 4. The composition according to claim 1, wherein the polysulfonic acid is an aliphatic or aromatic disulfonic acid. 5. The composition according to claim 1, wherein the acid derivative is an acid anhydride or a chloride. 6 The ratio of condensation resin in the polyol composition is 5 to 60
A composition according to claim 1, characterized in that it is by weight. 7. The composition according to claim 1, wherein the average particle diameter of the fine particulate condensed raspberry is 40 μm or less.