JPH02194015A - Production of flexible high-elasticity foam - Google Patents

Abstract

PURPOSE:To obtain the title foam excellent in heat resistance and mechanical strengths by using a specified aromatic polyether polyamine as the polyalkylene polyether or polyalkylene polyester active hydrogen compound. CONSTITUTION:A mixture comprising a polyalkylene polyether or polyalkylene polyester active hydrogen compound, a catalyst, a foam stabilizer, a blowing agent and other adjuvants is reacted with an organic isocyanate compound in such a way that an aromatic polyether polyamine of formula I (wherein R is an n-valent polyalkylene polyol or polyalkylene polyester residue obtained by removing the OH groups from an n-valent polyalkylene polyether polyol or polyalkylene polyester polyol of an average MW>=400, and n is 1-8), e.g. a compound of formula II or III (wherein a and b are integers equivalent to the molecular weights of the respective groups of about 400 or higher) is used as said active hydrogen compound. In this way, a flexible high-elasticity foam excellent in heat resistance, etc., can be produced.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for manufacturing a soft, highly elastic foam that has excellent physical properties such as heat resistance.

(Prior Art) Conventionally, flexible and highly elastic polyurethane foams have been produced by addition polymerization of organic polyisocyanates with polyalkylene polyether polyols or polyalkylene polyester polyols and water as the main active hydrogen sources, but urethane bonds based on the hydroxyl groups of the polyols have been produced. Because it contains a considerable proportion of , it has limitations in terms of heat resistance and mechanical strength.

The reaction of a polyalkylene polyether polyamine or polyalkylene polyester polyamine active hydrogen compound having an amino group at the terminal with an organic polyisocyanate yields a polyurea polymer containing a urea group, and a polyurethane obtained from the corresponding polyol and polyisocyanate. They are known to have a number of significant advantages compared to polymers.

The use of aliphatic polyalkylene polyether polyamines or aliphatic polyalkylene polyester polyamines as such polyamine-based active hydrogen compounds has been proposed, but they react too quickly with aromatic polyisocyanates and are not active in soft foam formulations. It is difficult to balance the reaction with water, which accounts for the majority of the hydrogen source, and it is difficult to obtain a good soft foam.In other words, the viscosity increases extremely quickly immediately after mixing with aromatic polyisocyanate, resulting in poor filling properties in the mold. This causes product molding defects. This rapid thickening also tends to cause poor mixing of raw materials.

Furthermore, since unreacted groups tend to remain after the reaction, the curing properties are inferior to those using ordinary polyalkylene polyether polyols or polyalkylene polyester polyols, and physical properties are inferior in terms of compressive strain. Ta.

(Problems to be Solved by the Invention) Examples of polyamine-based active hydrogen compounds having appropriate reactivity include aromatic polyalkylene polyether polyamines and aromatic polyalkylene polyester polyamines. Many reports regarding merging have also been submitted. However, the previous reports were in the field of so-called elastomers, in which active hydrogen compounds do not contain water, and no specific reports have been submitted in the field of foams in which water is used as a blowing agent in active hydrogen compounds.

This is different from elastomers, which do not contain water as an active hydrogen source in the reaction system and are produced only through a resin-forming reaction, but since the majority of the active hydrogen source in foam is water, foams undergo a foaming reaction in addition to the resin-forming reaction. It is manufactured through a more complex process in which the two processes occur at the same time. Therefore, in order to obtain a good foam, it is necessary to properly control the reaction balance between both the resinization reaction and the foaming reaction, which is significantly different from that of elastomers in terms of raw material type, properties, and formulation, and is more difficult. This is because a high level of response is required.

Therefore, the present invention overcomes the drawbacks of the conventional manufacturing methods described above, and provides a soft, highly elastic foam with excellent heat resistance and mechanical strength that does not cause poor mixing of reaction materials, poor molding of products, or deterioration of curing properties of products. The purpose is to provide a manufacturing method for.

(Means for Solving the Problems) The object of the present invention is to react a mixture consisting of a polyether or polyester-based active hydrogen compound, a catalyst, a foam stabilizer, a foaming agent, and other appropriate auxiliary agents with an organic isocyanate compound to create a soft, high-quality foam. In producing the elastic foam, an aromatic polyalkylene polyether polyamine or an aromatic polyalkylene polyester polyamine having an aminobenzoate skeleton at the end, which is represented by the following formula (I), is used as a polyether or polyester active hydrogen compound. This was achieved by a method for manufacturing a soft, highly elastic foam.

Formula (I) (In the formula, R represents an n-valent polyalkylene polyether or polyalkylene polyester residue obtained by removing a hydroxyl group from a polyalkylene polyether polyol or polyalkylene polyester polyol having an average molecular weight of 400 or more. , n is 1 to 8.) In the aromatic polyalkylene polyether polyamine or aromatic polyalkylene polyester polyamine represented by the above formula (I) used in the present invention, R is
Preferably, it has a polyether or polyester skeleton having an average molecular weight of 1,000 to 10,000, and is obtained, for example, by addition polymerization of one or more of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, and the like.

Further, the substitution position of the amino group is preferably p-position, but may be ○-position or m-position.

Specific examples of the compound represented by the above formula (1) used in the present invention are listed below, but the present invention is limited thereto.) The aromatic polyether polyamine or polyester polyamine used in the present invention has a monovalent to octavalent content. It is produced by reacting a polyalkylene polyether polyol or polyalkylene polyester polyol with a molecular weight of 400 or more with p-nitrobenzoyl chloride in the presence of pyridine to esterify it to form a polyalkylene nitrobenzoate, and then hydrogenating the nitro group.

The aromatic polyether polyamine or aromatic polyester polyamine used in the present invention is produced by reacting n moles of p-nitrobenzoyl chloride with 1 mole of n-valent polyether polyol or polyester polyol in the presence of pyridine, followed by hydrogenation. It can be obtained by

Examples of the above polyoxyalkylene polyols include:
A monovalent to octavalent molecular weight 40 polymerized by addition polymerization of one or more alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and styrene oxide in any order in the presence of an initiator such as water or a low molecular weight amine.
0 to 10,000 polyoxyalkylene polyols, which can be obtained by known methods.

Polyols used as raw materials for polyetheramine include water, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, trimethylene glycol, 1,3-
and 1,4-butanediol, 1,5-bentanediol, 1,2-hexylene glycol, l,10-decanediol, 1,2-cyclohexanediol, 2-butene-1,4-diol, 3-cyclohexane -1,1-
Dimethatol, 4-methyl-3-cyclohexane-1,
1-Dimetatool, 3-methylene-1,5-bentanediol, (2-hydroxyethoxy)-1-propano-
4-(2-hydroxyethoxy)-1-butanol, 5-(2-hydroxypropoxy)-1-pentanol, 1-(2-hydroxypropoxy)-2-octanol, 3-allyloxy-1,5-bentane diol,
2-Acryloxymethyl-2-methyl-1,3-bentanediol, ((4,4-bentroxy)-methyl)-
1,3-propanediol, 3-(0-propenylphenoxy)-1,2-propanediol, 2,2'-diisopropylidenebis(p-phenyleneoxy)jetanol, glycerin, 1,2,6-hexanetriol ,
1,1.1-trimethylolethane, 1゜1.1-trimethylolpropane, 3-(2-hydroxyethoxy)
-1,2-propanediol, 3-(2-hydroxypropyl)-1,2-propanediol, pentaerythritol, sorbitol, sucrose, lactose, α-methyl glycoside, α-hydroxyalkyl glucoside, novolak resin , polyhydric hydroxy compounds such as phosphoric acid, benzene phosphoric acid, polyphosphoric acid (e.g. tripolyphosphoric acid and tetrapolyphosphoric acid), phenol-aniline-formaldehyde ternary condensation product, aniline-formaldehyde condensation product, ethylenediamine, diethylenetriamine, Polyamines such as triethylenetetramine, methylenebisorthochloroaniline, 4°4'- and 2,4'-diphenylmethanediamine, 2.4-)-lylenediamine, 2.6-)-lylenediamine, triethanolamine, jetanol Alkanolamines such as amines, ethylene oxide, propylene oxide, butylene oxide,
One or two of tetrahydrofuran, styrene oxide, etc.
These are polyether polyols or polytetramethylene ether glycols obtained by adding more than one species.

Also, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, l, 3-
and one or more compounds having at least two hydroxyl groups, such as 1,4-butanediol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, decamethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, etc. 2 or more types, malonic acid, maleic acid, succinic acid, adipic acid, tartaric acid, pimelic acid, sebacic acid, oxalic acid,
Ring-opening of polyester polyols obtained from one or more compounds having a small amount of phthalic acid, terephthalic acid, tolumellitic acid, hemimellitic acid, etc. (both of which have two carboxyl groups), or cyclic esters such as polycaprolactone. Polymers are also used.
No. 7, Special Publication No. 41-3473, Special Publication No. 43-2210
No. 8, Special Publication No. 1974-8230, Special Publication No. 47-4759
No. 7, Special Publication No. 47-47999, Japanese Patent Publication No. 48-349
No. 91, JP-A-51-50398, JP-A-51-70
No. 286, JP-A-52-11249, JP-A-53-4
No. 092, JP-A-53-13700, JP-A-54-6
No. 4264, JP-A-53-78297, JP-A-54-
A so-called polymer polyol composition obtained by graft polymerizing an ethylenically unsaturated compound in a polyether polyol and/or polyester polyol described in No. 133599, JP-A-55-5988, etc. is used. Suitable ethylenically unsaturated compounds for preparing such compositions include acrylonitrile, styrene, and the like. Furthermore, 1.2-polybutane diene polyol,
1.4-Polybutadiene polyols are also used.

The preferable range of the hydroxyl value of the various polyols mentioned above is 20 to 150 mgKOH/g, and these polyols can be used alone or in combination.

As the polyisocyanate compound used in the present invention, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, diphenyl diisocyanate, etc. are preferably used.

As tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2.6-)lylene diisocyanate is preferable, and as diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate,
Preferred are various known modified diphenylmethane diisocyanates modified with carbondiimide groups, etc., and mixtures thereof. As polymethylene polyphenylisocyanate, what is known as crude MDI is preferred.

Further, as the diphenyl diisocyanate derivative, a compound having an incyanate group at the terminal, which is obtained by reacting diphenyl diisocyanate and/or polymethylene polyphenylisocyanate with a polyol having an average functional number of 2 to 4 and a molecular weight of 50 to 5000, is preferable. .

Catalysts that can be used in the present invention are conventionally known catalysts, and are not particularly limited. For example, amine catalysts include triethylenediamine, triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexane-based catalysts, etc. Decyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, monoethanolamine, jetanolamine, triethanolamine, N-methyljetanolamine, N,N-dimethylethanolamine, diethylene triaminochloride, N , N, N"N"-tetramethylethylenediamine, N, N.

N”,N”-tetramethylpropylenediamine, N,N
, N', N''-tetramethylbutanediamine, N, N,
N”,N”-tetramethyl-1,3-butanediamine,
N,N,N",N"-tetramethylhexamethylenediamine, bis[2-(N,N-dimethylamino)ethyl]
Ether, N, N-dimethylbenzyldiamine, N, N
-dimethylcyclohexylamine, N, N, N"N",
N″-pentamethyldiethylenetriamine, formate and other salts of triethylenediamine, oxyalkylene adducts of amino groups of primary and secondary amines, azacyclic compounds such as N,N-dialkylpiperazines, various N, N'
, N''-trialkylaminoalkylhexahydrotriazines, β-aminocarbonyl catalysts described in Japanese Patent Publication No. 52-43517, β-aminonitrile catalysts described in Japanese Patent Publication No. 14279-1980, and the like.

Examples of organometallic urethanation catalysts include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octoate, tin naphthenate, nickel naphthenate, and naphthene. cobalt acid, etc.).

The amount of these catalysts to be used is not particularly limited, but the amount of the amine catalyst is usually 0.05 to 1.0% by weight and the amount of the organometallic catalyst is 0.01 to 0.1% by weight based on the total amount of polyol.

The blowing agent in the present invention is a mixture of one or more of water, trichloromonofluoromethane, dichlorodifluoromethane, methylene chloride, trichlorofluoroethane, dibromotetrafluoroethane, trichloroethane, pentane, n-hexane, and the like.

The foam stabilizer in the present invention is a conventionally known silicon surfactant, such as L-520 manufactured by Nippon Unicar Co., Ltd.
L-532, L-540, L-544, L-550, L
-3550, L-5740S, L-5140M%L-6
202, etc., and 5H manufactured by Tou Silicone Co., Ltd.
-190,5H-192,5H-194,5RX-29
4A, F-114 manufactured by Shin-Etsu Silicone,
F-121, F-122, F-220, F-230%F
-258, F-260B% F-317, F-341, F
-601, F-606, X-20-200, X-20-
201, etc., and the one manufactured by Toshiba Silicone Company is TFA-
4200, TFA-4202, etc.

The amount of these foam stabilizers used is 0.1 to 20 parts per 100 parts of the compound with active hydrogen and the organic polyisocyanate.
Department.

In the present invention, dyes, coloring agents, etc. can be contained as necessary.

To describe an embodiment of the molding method of the present invention, a polyamine, a crosslinking agent, a catalyst, a foaming agent, a foam stabilizer, and other auxiliary agents are mixed to form a resin liquid. A resin liquid and a polyisocyanate are mixed at a predetermined ratio, and the mixture is injected into a mold and foamed. The mixing ratio is such that the equivalent ratio (NGO/H) between NGO groups in the polyisocyanate and active hydrogen in the resin liquid is usually 0.7 to 1.3.
, preferably 0.85 to 1.15.

After foaming is completed, the product is cured for 6 to 10 minutes in a heated oven at 80° C. to 120° C., and removed from the mold to obtain a soft foam molded product.

(Effects of the Invention) According to the present invention, a soft, highly elastic foam with excellent heat resistance and mechanical strength can be obtained without causing poor mixing of reaction materials, poor molding of the product, or deterioration of the curing properties of the product.

(Example) Next, the present invention will be described in more detail based on Reference Examples and Examples. Hereinafter, unless otherwise specified, parts are by weight.

The raw material compounds used in the following are as follows.

AR-201: Aromatic polyether polyamine with aminobenzoate skeleton at the end, manufactured by Mitsui Toatsu Chemical Co., Ltd. Active hydrogen value 33゜OmgKOH/g total amine value
29.9 Base polyol polypropylene triol (molecular weight 5000) PAn-40; Aliphatic secondary amine polyether polyamine, manufactured by Mitsui Toatsu Chemical Co., Ltd. Active hydrogen value 27, 4 mgKOH/g total amine value
25.32 (Secondaryization rate 83.7%) Base polyol polyoxypropylene polyoxyethylene triol (molecular weight 4700) Polymer polyol A; Polyether polyol EP-
3033 and polymer polyol POP31-28 (60:40), polyether polyol EP-3033 manufactured by Mitsui Toatsu Chemical Co., Ltd. Active hydrogen number (
OH value) 34 + OmgKOH/g polymer polyol POP31-28 Active hydrogen value (OH value) 28.
0mgKOH/gJeffamine T-5000;
Aliphatic primary amine polyether polyamine, manufactured by Texaco Active hydrogen value 29.8 mgKOH/g total amine value 25.4 (Primary conversion rate 55.4%) Reference example polypropylene triol (MW 5000) 500
66 g of p-nitrobenzoyl chloride to 100 g of pyridine
The mixture is reacted and esterified by heating to 100° C. in the presence of g. Subsequently, pyridine was discharged by washing with water and centrifugation, and then the system was depressurized and dehydrated to obtain 420 g of polypropylene triol nitrobenzoate.

Polypropylene triol nitrobenzoate 500g
The hydrogenation reaction of ethanol 2 in a high pressure autoclave
50-, polypropylene triol nitrobenzoate and 60 kg of hydrogen in the presence of 2.5 g of palladium catalyst/
After reacting and dehydrating crtrG at high pressure and high temperature, the catalyst was separated by filtration to obtain 415 g of polypropylene triolaminobenzoate.

Example 1 100 parts of aromatic polyether polyamine AR-201, 1.0 parts of foam stabilizer L-5309, 3.0 parts of water, catalyst L
-10200, 6 parts, catalyst A-10, 2 parts, crosslinking agent KL
-2103.0 parts were mixed to prepare a resin liquid. This resin solution was mixed with 38.1 parts of TDI-80/20 incyanate, and the inner size was adjusted to 50°C in advance.
The mixture was poured into a 0x50 mm mold, the lid was closed, and the mixture was foamed. This foam was cured by heating in a hot air oven at 70° C. for 5 minutes, and then taken out from the mold.

Table 1 shows the physical properties of the obtained foam. Also 140℃
The physical properties after being held for 6.5 hours are also shown in the same table. Note that the equivalent ratio of incyanate group to active hydrogen in this example is 1.00.

Example 2 A foam was produced using the same formulation as in Example 1 and the same operation as in Example 1 except that the crosslinking agent was omitted. The results are shown in Table 1.

Comparative Examples 1 to 3 Foams were produced in the same manner as in Example 1, except that the same amount of the following compound was used instead of the aromatic polyether polyamine as the active hydrogen compound, and the amount of catalyst was slightly changed.

PAII-40 Comparative Example I J, T-5000 Comparative Example 2 POP-5340 Comparative Example 3 Table 1 shows the physical properties of the obtained foam.

Furthermore, the heat resistance of the urethane foams obtained in these Examples and Comparative Examples was tested.

The heat resistance test was performed by measuring the mechanical strength (tensile strength and elongation) of a product that was left suspended in a hot air oven at 140°C for 6.5 hours, and expressed as a ratio (rate of change) to the non-heat-treated product as shown by the following formula. Ta.

Mechanical strength value before heat resistance test

Claims (1)

[Claims] 1. A flexible, highly elastic foam produced by reacting a mixture of a polyalkylene polyether or polyalkylene polyester-based active hydrogen compound, a catalyst, a foam stabilizer, a blowing agent, and other appropriate auxiliary agents with an organic isocyanate compound. 1. A method for producing a flexible, highly elastic foam, characterized in that an aromatic polyether polyamine represented by the following formula is used as a polyalkylene polyether or polyalkylene polyester active hydrogen compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is an n-valent polyalkylene polyether obtained by removing the hydroxyl group from a polyalkylene polyether polyol or polyalkylene polyester polyol with an n-valent average molecular weight of 400 or more. or a polyalkylene polyester residue, where n is 1 to 8.)