JPS6036522A - Air-permeable flexible polyurethane foam and its manufacture - Google Patents

Abstract

PURPOSE:To obtain a flexible polyurethane foam with improved air-permeability and organic solvent resistance, useful as sound attenuation material, etc., by the reaction, in the presence of catalyst, foaming agent and foam stabilizer, between a specific polycaprolactone polyol and polyisocyanate. CONSTITUTION:The objective foam can be obtained by the reaction, in the presence of catalyst (e.g., devalent tin salt of fatty acid), foaming agent (e.g., dichloro difluoromethane) and foam stabilizer, between (A) a polycaprolactone polyol with an average hydroxyl value 30-200 and an epsilon-caprolactone residue 5-95wt% and (B) a polyisocyanate (e.g., tolylenediisocyanate, diphenyl-methanediisocyanate). Said polyol will normally be prepared by the reaction, in the presence of catalyst such as tetrabutyl titanate, between polyhydric alcohol such as ethylene glycol, epsilon-caprolactone and, if required, polybasic acid (anhydride) at 140-230 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing flexible polyurethane foam with improved air permeability and organic solvent resistance. The present invention relates to a method for producing flexible polyurethane foam with excellent properties.

Furthermore, by removing the remaining cell membranes from the soft urethane foam, we can create a highly breathable film for clothing, household materials, air filters, gas-liquid catalyst devices, catalyst transport devices, and furniture. 717 units, door mats, drain pads, wipe pads, sponges, tire liners,
It can be used for manotresses, pillows, special cushioning materials, fillings, and a variety of other uses.

Polyols for producing such flexible polyurethane foams include polyhydric alcohols, ε-tunozololactone, and optionally polybasic acids or their anhydrides, with an average hydroxyl value of 30 to 200 and an ε-caprolactone content of 5. It is preferable to use a polycaprolactone polyester polyol containing ~95% by weight.

- The polyhydric alcohols that are raw materials for the polycaprolactone polyester polyol used in the present invention as described in the following are ethylene glycol, propylene glycol, ], 3
Butylene glycol, 1.4 butylene glycol, 2-
Methyl-1,3-soropanediol, 1,5-pentyl glycol, neopentyl glycol IJ:, -l, ], 6-
Hexanediol, diethyl alcohol, sigropyrene glycol, hydroxypivalate ester of neopentyl glycol, 2,3.5-)rimedylbentanediol, AOGK24 (Product name: Daicel Chemical Industries (1) A mixture of C1□ and CI4 α-olefin glycols λglycerin, trimethylolpropane, jetanolamine, triethanolamine, textulose, sucrose, pentaerythritol, and sigly jusuntoru are used alone or in combination. be able to.

Polybasic acids include maleic acid,
Succinic acid, fumaric acid, adipic acid, sepacic acid, azelaic acid, dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, trino')nob acid or the like fl(+(water, etc.) can be used.

The third raw material, ε-caprolactone, can be industrially produced by oxidizing cyclohexanone with a peracid such as hydrogen peroxide or peracetic acid by Bayer-Villiger reaction. Of course, the ring-opened oxycaproic acid of ε-caprolactone or its Cl-C
It also includes 4-argyl ester. Furthermore, lactones other than ε-caprolactone can be used in combination with ε-caprolactone as long as they do not impair the characteristics of the present invention. The polycaprolactone polyester polyol synthesized from polyhydric alcohol td and ε-caprolactone, and if necessary, polybasic acid or its anhydride, has an average hydroxyl value of 30.~2001.The content of ε-notuprolactone is 5. ~95% by weight, fj5L <40~9
It is 0% by weight. Polycaprolactone polyester polyol is produced by mixing and heating a poly-1'-bent alcohol, ε-caprolactone or oxycaproic acid or its C1-C4 alkyl ester, and if necessary, a polybasic acid or its anhydride, followed by a dehydration esterification reaction and ring opening. It can be synthesized by reaction, transesterification and K.

Alternatively, a polyester polyol synthesized by a dehydration esterification reaction of a polyhydric alcohol and a polybasic acid or its anhydride, and a polycubine synthesized by subjecting the polyhydric alcohol to a ring-opening reaction of ε-caprolactone [after mixing with J sicton polyol] The desired product can also be obtained by transesterifying the two. Alternatively, it can also be synthesized by ring-opening polymerization of ε-caprolactone to a polyester polyol having a small molecular weight.

When a polybasic acid or its anhydride is essential, it can be added to the extent that the properties of the desired polyol can be adjusted.

These reactions are carried out at 130-240″c1 preferably ]/1
It is carried out at 0-230°C. If the temperature exceeds 250°C, not only the resin will be colored, but also a depolymerization reaction of caprolactone will occur, making it impossible to obtain the desired product.

This reaction uses a catalyst of 0.05 to 1000 pp [Il, preferably 01-]. The catalyst and I~ are organic titanium compounds such as tetrabutyl titanate I, tetrapropyl titanate, dibutyltin laure-1, tin octylate, dibutyltin oxide, Jm ([1 tin, stannous bromide, A tin compound such as stannous iodide can be used.It is preferable to carry out the reaction while passing an inert gas such as nitrogen from the viewpoint of preventing the A color of the resin.

As the polyisocyanate component, compounds having at least two incyanate groups, such as teacup family polyisocyanates, are suitable. For example, tolylene diisocyanate isocyanate, polymethylene polyphenylinocyanate, xylylene diincyanate, other aromatic polyisocyanates, hexamethylene diisocyanate, impolone diincyanate, and other non-aromatic polyisocyanates. and so on. These polyisocyanates can be modified (<l 1., even if modified to polyisocyanate-1) by various treatments and compounds. These polyisocyanates are 144% (isomer mixtures and unpurified products can be used as the polyisocyanate 1-component. Use foaming agent 1~
Commercially available commercially available silicon compound-based foams with a temperature range of 2°C and 2°C for soft polyurethane foams with special scales are preferred.Specific commercially available foam stabilizers and examples include the following: ga3i 7. ,). Examples of foam stabilizers that can obtain rigid polyurethane foams that have good moldability and excellent legal stability include varnish, -332 (manufactured by Koniker Corporation) and H-i 90. ” (made of Toshi silicone ■), but these usually have slightly higher thermal conductivity. Of course, foam regulating firmness (':'
The foam stabilizer is not limited to foam stabilizers, and various foam stabilizers for hard polyurethane foam can be used4).・Flexible polyurethane foam, the foaming agent and 1 to 1 are water,
Dichlorofluoromethane, trichlorfluoromethane, methylene chloride, and other compounds.

Examples include hydrocarbons and formic acid.

It is also necessary to use a catalyst and a divalent tin salt of a fatty acid with a small amount (both 1 flφ) and/or a tertiary amine with a small amount (both 14φ).

In addition, in order to remove the cell walls of the polyurethane membrane obtained in the invention, a method of immersing it in the presence of an alkali and removing a part of the cell wall. The acids used (1, sulfuric acid, phosphoric acid, phosphorous acid, etc., and when an alkali is used, sodium hydroxide, potassium hydroxide, 4r, 1':i:l) are preferred.

The present invention will be explained below in detail with reference to Examples"-4],
The present invention is not limited only to these examples.
Synthesis Example 1 4 units equipped with a stirrer, temperature control, nitrogen inlet tube, and condenser for removing Nispul produced water [1 flask contains 40 ml of adipic acid]
66 parts, neopentyl glycol 4. O],, 55
20 parts of tetrabutyl titanate and 1,300 parts of C-caprolactone were charged, and heated at 1,400°C to 220°C for 27°C.
Perform a time dehydration esterification reaction, k i'1llj
O, 54K Q Hyrg, / j; l, hydroxyl value 56
A polyester polyol of 3KOHq/.9 (hereinafter the unit is omitted) was obtained. This polynisder polyol had a melting point of -10 to O''C and a content of 3-0 ε-caprolactone (reactive residue) of 65.

Synthesis Example 2 2277.6 parts of adipic acid, diethylene glycol], 819.
0 parts, 76968 parts of trimethylol broth, 6336 parts of ε-caprolactone, and 20 parts of TBT were charged.
A dehydration esterification reaction was carried out at 140°C to 220°C for 0 hours to obtain a polyester polyol with an acid value of 0 and a hydroxyl value of 85.0 KOH/g. Content (reactive residue) is 65
%Met.

Example Component A> Toluene-2,4-diisocyanate-1 in a sealing vessel equipped with a stirrer and a device for retaining nitrogen gas for scavenging.
・and l.ruen-26-dithcyane 1.s.
o: 60 parts by weight of the 20 different IJ-1 and 2JM compounds and 50 parts by weight of the polyester polymer synthesized in Synthesis Example 1 are added at room temperature.

The mixture was placed IV'I under a nitrogen atmosphere for 1 hour.

Raise the temperature to approximately: 30°C.

Component B> 80 parts by weight of the polynisder polyol obtained in Synthesis Example 2, foam stabilizer], -532 (If this Unicar) 15 parts by weight, 45 parts by weight of water, and 1 part by weight of diethyl ethanol.
Heat the 9-fold h'L part to 35°0 and mix.

Now add 100 parts by weight of component A to 80 parts by weight of component B and mix thoroughly for about 2 seconds at a starting temperature of about 30°C.

The mixture is then immediately poured into a foaming container.

After about 10 minutes, the injection forms a foam and the foam is aged for 16 hours at 70°C. Remove this from the container and cut it into blocks.

The block has a density of 0.0309/CO.

The cell shape of the foam is extremely small, and the average cell diameter is 0.
．． It was 3 meters.

Block (12,5X7) asked by J2 operation
．． Pour 5 x 25 (・1 rL) into a 10 wt% hydroxide Ukawa-Lium water bath solution at 50°C, allow it to completely immerse in the solution, and after 5 minutes take out the block, squeeze it, and add it to a 10 wt% acetic acid water bath solution. Neutralize and finally rinse the foam with water.

The foamed material thus obtained has a good lattice network]
1 to 1, and the cell wall has been removed. Almost no deterioration due to sulfur hydroxide is observed in the lattice network forming body after the treatment. The foamed materials obtained in this way are suitable for the production of building material carriers, as air filters and for sound deadening, and exhibit excellent resistance to organic solvents.

Claims (2)

[Claims] (1) Reacting a polyisocyanate component such as a polycaprolactone polyol component having an average hydroxyl value of 30 to 200 and containing 5 to 95% by weight of ε-caglolactone residue in the presence of a catalyst, a blowing agent, and a foam stabilizer. A method for producing flexible polyurethane foam characterized by: (2) A polycaprolactone polyol component having an average hydroxyl value of 30 to 200 and containing 5 to 95% by weight of ε-caprolactone residue and a polyincyanate component are reacted in the presence of a catalyst, a blowing agent, and a foam stabilizer. Breathable flexible polyurethane foam obtained by removing the cell walls of the obtained flexible polyurethane foam.