JPS5825691B2 - Polyurethane foam polyurethane foam - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyurethane foams, and more particularly to air-blown flexible polyurethane foams, methods of making them, and substrate and foam compositions.

Flexible polyurethane foams with densities below 151 bs/ft3 (240 I/A!) and good physical properties may be used with volatile blowing agents or reactive blowing agents and silicone oil surface agents or cell control agents. It has been found that it can be produced without using

According to the invention, a polyether polyol having terminal camps of at least 2 moles of ethylene oxide per active hydrogen atom or containing internal blocks of at least 3 moles of ethylene oxide per active hydrogen atom or a combination thereof The foam is prepared by foaming a mixture of , and the appropriate polyisocyanate with an inert gas.

The flexible polyurethane foam of the present invention is made of a mixture of the following (1) to (3) foamed with an inert gas.

having a hydroxyl functionality of 2 to 3 and a hydroxyl equivalent weight of 1000 to 2500 and an internal block of at least 3 moles of ethylene oxide per active hydrogen and/or a terminal camp of at least 2 moles of ethylene oxide per active hydrogen. An active hydrogen component (1) consisting of a polyether polyol A, an aromatic amine or glycol B replacing 50% by weight or less of the polyether polyol, if desired, an organic diisocyanate, and 2 to 4 hydroxyl groups per molecule. 53-1
Isocyanate component (2) consisting of a prepolymer A1 having an incyanate end obtained by reaction with a compound having a hydroxyl equivalent of 000, a polymeric polyincyanate B1 a crude aromatic diincyanate C, or a mixture thereof.
and urethane forming catalyst 3, and component (1)
and (2) at an NGO:OH ratio of 0.85:1 to 2.0:1
A mixture that is used in amounts such that it falls within the range of .

The polyurethane foams of the invention are produced by mechanically introducing air or other gaseous substances into the subsequent mixture.

The mixture consists of (1) a polyol component, (2) an isocyanate-containing prepolymer, and (3) a catalyst for urethane formation.

Suitable gaseous substances for use in the present invention are gaseous elements, compounds or mixtures thereof which are in gaseous form at standard conditions of temperature and pressure, i.e. 25°C and 1 atm, such as xenon, helium, carbon dioxide, nitrogen, etc. , oxygen, propane, methane, ethane or mixtures thereof e.g. air,
However, it is a component that does not react with any of the urethane forming components.

Unlike conventionally produced polyurethane foams, the foams of the present invention do not require the use of conventional blowing agents or silicone oil cell control agents; is applied or can be applied to a suitable mold or onto a suitable substrate.

The foamed mixture then becomes a porous polyurethane product.

The foam resulting from the mechanical introduction of an inert gas into the urethane production mixture does not undergo any significant expansion other than due to thermal expansion of the inert gas used.

This expansion is as small as an elbow, less than 1% by volume.

Foaming is obtained by mechanically introducing an inert gas into the foam composition.

This is done by using a mixer, such as a kitchen mixer with blades, to mechanically incorporate or mix air or other inert ingredients into the mixture of urethane-forming ingredients, such as making melange from egg whites or whipped cream. This is easily done with a blade shaped like the one used to make the blade.

Alternatively, and more suitable for large-scale production, the nutreme consisting of a mixture of urethane-forming components, or the nutreme of urethane-forming components and air or other inert gas, may be separately mixed in a suitable foaming mixer, such as an Okenufor. Introduced during the market.

The foamed component emerging from the foam-generating mixer is then passed into a suitable mold or onto a suitable substrate, where the foamed component is processed into a flexible polyurethane foam.

In yet another method, all urethane-forming components except the inert gas and catalyst are introduced into a foam-generating mixer and the resulting foam and catalyst are mixed in a suitable mixer, such as a static mixer.

The resulting catalyst-containing foam is then placed in a suitable mold or onto a suitable substrate.

Polyols advantageously used as component (1) in the flexible foam component of the present invention are those represented by the following general formula.

Z-CX-(R-0)x-(R1-0)xl-(CH2
-CH2-0), -H3n where 2 has 2 or 3 active hydrogen atoms.

It is the residue of a divalent or trivalent initiator compound.

X is nitrogen or oxygen, each R is independently -CH2
-CH2-.

Each R1 is independently the same as R except for the groups -CH, -C12-, each X and Xl are positive integers, and y has a valence of at least 2, typically 2 6.

n has a valence of 2 or 3, and the sum of X, Xl and y is such that it provides a polyol with a hydroxyl equivalent weight of 1000-2500, typically 1000-2000.

Glycols advantageously used as component (1)-b of the present invention are, for example, diethylene glycol, dipropylene glycol, triethylene glycol, butylene glycol, dibutylene glycol, polyoxyalkylene glycol having 2 to 4 carbon atoms in the alkylene group. Aromatic amines which are advantageously used in component (1)-b of the present invention are, for example, 4,4'-methylene chloride (2-''loroaniline), P-phenylenediamine, methylene-binu (2-'' -methoxyaniline), toluidine, dianisidine, 3,3'-dichlorobenzidine and mixtures thereof.

The prepolymers advantageously used as component (2) of the present invention are incyanate-terminated reaction products with organic diisocyanates having an average hydroxyl functionality of from 2 to 4.5 and an OH equivalent weight of from 53 to 1000, typically from 53 to 1000. 100 polyether polyol.

Organic diisocyanates which are advantageously used in the production of the prepolymer are, for example, toluene diisocyanate, hexamethylene diisocyanate) P, P'-diphenylmethane diisocyanate, P-phenylene diisocyanate, naphthalene diisocyanate, dianisidine diisocyanate. and mixtures thereof.

The polyether polyethers which are advantageously reacted with organic diisocyanates for the production of incyanate-terminated prepolymers in the present invention include, for example, vicinal alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and mixtures thereof, e.g. glycerin , trimethylolpropane, pentaerynurritol, ethylene glycol, propylene glycol, ■
.

4-butanediol, 1,5-bentanediol, 1.
condensed with 6-hexanediol or a mixture thereof,
Mixtures of the above compounds with polyether polyols having a hydroxyl equivalent weight of 53 to 1000 and compounds with 5 to 8 hydroxyl groups per molecule such that the average OH functionality of the mixture does not exceed 4.5.

As used herein, crude aromatic diisocyanate refers to diisocyanates containing polymeric derivatives.

Such incyanates are usually made commercially by mixing pure or distilled incyanate with residues or polymers resulting from refining to produce so-called pure or distilled incyanate.

Such crude isocyanates also include commercially available ones.

Suitable polymeric isocyanates include, for example, commercially available polymethylene polyphenylisocyanate.

Mixtures of organic diisocyanates and polymeric isocyanates may also be used.

Suitable catalysts to promote urethane formation used in foam formation include tertiary amines, lead naphthinate, zinc naphthinate, aluminum distearate, aluminum tristearate, lead stearate, lead nutearate (basic), tin octoate, tin Oleate, dibutyltin laurate, aluminum monostearate, zinc stearate, cadmium stearate, silver acetate, lead veragonate, phenylmercury acetate and mixtures thereof.

In addition to the active hydrogen-containing component (1), the incyanate-containing prepolymer (2), and the catalyst, component (3), additives such as fillers and flame retardants may be added to the polyurethane foam production of the present invention.

Although the use of blowing agents is not essential to the production of the polyurethane foams of the present invention, the blowing agent components, which are volatile organic liquids with boiling points below 100° C., such as halohydrocarbons such as methylene chloride and monofluorotrichloromethane, are combined with active hydrogen. It is preferred to use 1-20 parts by weight per 100 parts of water, or 0.1-5 parts by weight per 100 parts of active hydrogen-containing component. Substrates on which the foaming compositions of the invention are advantageously used include, for example: Carpets, especially fluffy carpets, paper, or synthetic and natural fibers such as nylon, polyester, acrylic, cotton, and wool.

The foamed compositions of the present invention can be cured at normal room temperatures, or the curing can be carried out at elevated temperatures.

The following example is illustrative of the invention.

Examples 1-8 and Comparative Experiments 1-111 In the following examples and experiments, a mixture of polyether polyol or polyhydroxyl-containing material and incyanate prepolymer is placed in a Hobart mixer.

This mixer is equipped with blades for kneading air into the mixture, and after kneading the mixture at high speed for a sufficient period of time, usually about 2 minutes, to create foam, the mixture is mixed with triethylene glycol in dipropylene glycol, which is a catalyst. A 33% solution of the amine is added and the resulting foam is stirred for an additional 45 seconds and transferred to an open container for processing.

The amounts and forms of polyols and polyisocyanates used are given in the following table.

Comparative experiment (■) was conducted as described below, in which the polyether polyol used did not contain ethylene oxide, and Example 1
Contrasted with ~4.

Comparative experiment (2) is compared with Example 6, and as described later, pure toluene diisocyanate was used as the incyanate component, and the density of the product was outside the scope of the present invention.

Comparative experiment (2) is compared with Example 7 and uses a silicone cell control agent.

In addition, when glycol B is not used and in place of glycol B, 4,4"-methylene-bis-(2-chloroaniline) is used.
The method of the present invention also gave an excellent foam when using .

Purchased from Dow Corning.

A silicone coat copolymer where the silicone part is dimethylsiloxane and the glycol is a mixture of ethylene and propylene glycol.

Table Note 1 Polyether polyol A is a reaction product of glycerin and propylene oxide, end-capped with 2 moles of ethylene oxide per OH group, and has an OH group equivalent weight of about 1000.

2 Glycol B is diethylene glycol.

3 Prepolymer C is made by adding excess toluene diisocyanate, glycerin and propylene oxide to glycerin 1
A prepolymer with 3% by weight of free NCO groups, which is the reaction product of a reaction product of propylene oxide in a ratio of 3 moles per mole.Polyether polyol D is a reaction product of glycerin and propylene oxide. End-capped with 2 moles of ethylene oxide per OH group, with an OH equivalent weight of approximately 2150°5 Polyether polyol E is a reaction product of glycerin and propylene oxide, with an OH equivalent weight of approximately 1
000゜6 Polyether polyol F is 8 in weight with glycerin
Reaction product of a mixture of 4% propylene oxide and 16% ethylene oxide by weight, end-capped with an additional 4 moles of ethylene oxide per OH group, and O
The H group equivalent weight is about 1540.

7 Polyether polyol G is a reaction mixture of glycerin and propylene oxide, endcapped with 5.5 moles of ethylene oxide per OH, and has an OH group equivalent weight of about 1825.

8 Polyether polyol H is a reaction product of glycerin and propylene oxide, end-camped with 4.5 moles of ethylene oxide per OH group, and has an OH group equivalent weight of 1600.

9 Prepolymer (1) is a reaction mixture of polyoxypropylene glycol having an average molecular weight of about 1000 and a-(7) toluene diisocyanate and has about 26.5% by weight of free NCO.

10 Prepolymer J is the product of reacting excess toluene diisocyanate with a reaction mixture of glycerin and propylene oxide to an equivalent weight of about 230 and has about 32.5 weight percent free NCO.

11 Incyanate is an 80/20 mixture of 2.4/2.6-isomers in toluene diisocyanate.

12 Prepolymer L is a reaction product of excess toluene diisocyanate and a reaction product of a mixture of sacrose and chrycerin in a molar ratio of 1:3 and propylene oxide such that the OH equivalent weight is 114, The prepolymer obtained has 30% free NCO groups.

13 Polyol P is about 1 per glycerin and hydroxyl group
It is the reaction product of 1.6 moles of propylene oxide, followed by about 4.38 moles of ethylene oxide per hydroxyl group, and then 5.5 moles of propylene oxide per OH group.

The resulting polyol has an average molecular weight of about 3,699.

14 Polyol Q is about 2 per glycerin and hydroxyl group
moles of propylene oxide, then 4.0 moles per hydroxyl group.
9 moles of ethylene oxide, finally 15 per hydroxyl group
It is the reaction product with moles of propylene oxide.

The resulting product has an average molecular weight of approximately 3669.

15 Isocyaner) R is 50% by weight polymethylene polyphenylisocyanate with an average functionality of about 2.6 and an equivalent weight of about 134 and 50% by weight of 2.4-/2
．． A mixture with an 80/20 mixture of 6-toluine diisocyanate.

The resulting mixture has an NCO equivalent weight of about 105 and an average functionality of about 2.35.

Claims (1)

[Claims] Polyether polyol A having a hydroxyl functionality of 12 to 3 and a hydroxyl equivalent weight of 1000 to 2500 and internal blocks of at least 3 moles of ethylene oxide per active hydrogen and/or terminal camps of at least 2 moles of ethylene oxide per active hydrogen. and, optionally, an aromatic amine or glycol B replacing 50% by weight or less of the polyether polyol, an organic diisocyanate, 2 to 4 hydroxyl groups per molecule, and 53 to 1000 hydroxyl groups per molecule. an incyanate component (2) consisting of an incyanate-terminated prepolymer A1 obtained by reaction with a compound having a hydroxyl equivalent of forming catalyst (3), and components (1) and (2) in an NCO:OH ratio of 0.
．． 85:1 to 2.0:1 by foaming a mixture used in amounts ranging from 85:1 to 2.0:1 to produce 151 bs//l" (2
40,! The production of flexible polyurethane foams having a density of less than or equal to i+/7 is carried out when the foamable mixture does not contain a silicone cell control agent and by mechanically mixing the foamable mixture with an inert gas. A method for producing polyurethane foam characterized by: