DE2110278A1 - Polyetherpoly esterpolyols - used in mfe of polyurethanes for laminating - Google Patents

Abstract

Polyetherpolyester polyol of formula (I): (where n is 5-30; m is 1.2-5.0; Y is a residue formed by removal of reactive H-atoms from NH3 or an amino cpd.; R and R11 are H or (substd.) alkyl or aryl; R1 is a residue formed by removal of the COOH gps. from a dicarboxylic acid), are prepd. by reacting a polyether polyol of formula: a dibasic carboxylic acid anhydride of formula: and an oxirane cpd. of formula: The anhydride may be phthalic anhydride. The oxirane cpd. may be propylene oxide.

Description

Process for the production of polyether cushion polyols The invention relates to a process for the production of polyols, which are used for the production of Polyurethanes are united, It is known to split off thin layers of polyurethane foam on substrates made of fiber materials, metals, wood, plastics or other solid materials Materials according to the so-called flame lamination process or according to the dielectric lamination process to apply without using an adhesive. Those previously produced by this process However, composites are not satisfactory when polyurethane foams are used from known polyether polyols or. Polyester polyols have been produced, be used. When thin them from polyurethane foams made from known Polyether polyols have been produced by the flame lamination process or after the dielectric process is laminated, it is impossible to obtain a good one To achieve adhesive strength. The adhesive strength obtained using thin films is obtained from polyurethane foams that from known polyeater polyols are produced, however, is not as low as the adhesive strength, which in the from polyether polyols produced polyurethane foams will.

Polyurethane foams made from the well-known polyester polyols are, however, very easily subject to hydrolysis.

It has also been proposed that the Xether foams can be laminated to be improved by the flame lamination process or by the dielectric process, but this improvement is at the expense of mechanical properties such as hardness, Tensile strength, elongation, compression set and resistance to scorching achieved.

Attempts have also been made to use polyester polyols and polyether polyols to be used in a mixture for the production of polyurethane foams, however these polyols are practically immiscible, and the foaming process with polyester polyols is very different from the foaming process for polyether polyols0 In this way therefore, no satisfactory results can be achieved.

The invention relates to polyols with which polyurethane foams can be produced, the excellent laminatability after the flame lamination process and the dielectric process and have good mechanical properties. The invention also includes a process for making these polyols.

According to the invention, polyester polyols of the general formula prepared by a process in which a polyether polyol of the general formula a dibasic carboxylic acid anhydride of the general formula and an oxirane compound represented by the general formula reacted, where in the above formulas n is 5 to 30, m is 1.2 to 5.0, Y is a radical which has been obtained by removing active hydrogen atoms from an ammonia or amino compound, x is the number of active hydrogen atoms in the ammonia or amino compound, R and R 'each stand for a hydrogen atom or an optionally substituted alkyl or aryl radical and R ″ - a residue obtained by removing COOH groups from a dibasic carboxylic acid, for the process according to the invention Polyether polyols (1I) with a hydroxyl number of 45 to 200 mg KOH / g, in particular 45 to 110 mg KOH / g, are preferably used.

The polyether polyols can be prepared in a customary manner by reacting an initiator of the general formula Y (H) with an oxirane compound of the general formula getting produced. In the formulas given above, Y, R, n and x have the meanings given above, while x is an integer of 2 or more, preferably from 2 to 8.

The initiators of the general formula Y (H) x are ammonia or Amino compounds used.

Suitable amino compounds are, for example, amines with 2 to 8 active hydrogen atoms. Typical examples of such amines are amino alcohols such as ethanolamine, diethanolamine and triethanolamine, amino-1,3,5-triazines, e.g.

Meramine, benzoguanamine, acetoguanamine and phthaloguanamine, and others primary or secondary amines, e.g. ethylenediamine, diethylenetriamine, o-, m- or p-phenylenediamine, 2,4- or 2,6-diaminotoluene and 4,4'-netbylenedianiline are suitable Oxirane compounds that are reacted with the initiators mentioned above, are for example ethylene oxide, propylene oxide, butylene oxide, styrene oxide, phenylglycidyl ether and allyl glycidyl ether. n is an integer from 5 to 30, preferably from 7 to 25. The polyether polyols of the above general formula are those with a hydroxyl number of about 45 to 200 mg KOH / g, preferably about 45 to 110 mg KOH / g used.

As oxirane compounds (IV) can be used for the process according to the invention Similar compounds to the oxirane compounds that make up the polyether polyol can be used.

In the dibasic carboxylic acid anhydrides of the general formula (III), R 'is a radical which has been formed by removing two COOH groups from a dibasic carboxylic acid and which contains 1 to 8 carbon atoms. R 'is preferably an alkylene radical or alkenylene radical with 1 to 4 carbon atoms, e.g. -OH2-, -CH2CH2-, -CH = CH-, -CH2CH2CH2-, -CH = CH-CH2-, -CH2CH2CH2CH2-, Phenylene, a halogen-substituted phenylene radical, e.g.

Tetrachlorophenylene and tetrabromophenylene, tetrahydrophenylene, endomethylene tetrahydropbenylene and endodichloromethylene tetrahydrophenylene O Suitable dibasic carboxylic acid anhydrides are for example maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, Phthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, 3,6-endodichloromethylene tetrachlorophthalic anhydride, Tetrachlorophthalic anhydride and tetrabromophthalic anhydride, the method according to of the invention can be carried out at a temperature of about 70 to 2000C, preferably about 100 to 150ob and at a pressure of 0 to 3.0 atmospheres Carrying out the method according to the invention are preferably certain amounts the dibasic acid anhydride (III) added to the polyether polyol (II), whereupon the mixture is heated and the oxirane compound (IV) is slowly added. It is also possible, the dibasic acid anhydride (III) and the oxirane compound (IV) to add to the polyether polyol (II) during the course of the reaction, or the reaction can be triggered by the compounds (II), (III) and (IV) at the same time be mixed.

In the process according to the invention, the initiator can be the general Formula Y (H) x together with other common initiators that do not have a nitrogen atom included. Examples of these common initiators are: Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerine, hexanetriol, Trimethylol propane, pentaerythritol, sorbitol and sucrose.

Since the object of the invention is the production of polyether polyester polyols is of the structure represented by the formula (I), the kind and amount of the starting compounds determined by the polyester polyol to be produced in each case.

The dibasic carboxylic acid anhydride (III is theoretically used in an amount of about m mol, ie about 1.2 to 5.0 mol, preferably in an amount of about 2.0 to 3.5 mol per group of the formula in de R has the meaning given above, is used.

The oxirane compound (IV) is obtained in an approximately equimolar amount to the dibasic acid anhydride.

After the reaction has ended, the acid number of the product can be reduced to zero are, however, you may not be able to convert some of the materials leave, i.e. the reaction is terminated when the acid number of the product rises a value of no more than about 1 mg KOH / °, preferably no more than about 0.5 mg KOH / g has been lowered.

In this way, there becomes a polyether polyester polyol of the above formula (I) obtained with a hydroxyl number of about 30 to 80 mg KOH / g.

Until now it was impossible to produce polyether polyester polyols from Polgäthern, dibasic carboxylic anhydrides and oxirane compounds at normal pressure without Use of polymerization catalysts such as alkali catalysts and acid catalysts to manufacture. When a catalyst for the manufacture of polyether polyester polyols is used, the catalyst remains in the polyols and often has an adverse effect Influence on the reaction of the polyol with an isocyanate compound. The catalyst must therefore be removed from the polyol, for example by filtration, distillation or stripping removed. However, there are catalysts such as zinc oxide, which after conventional separation processes cannot be removed.

When polyether polyols of the formula (II) with a dibasic carboxylic acid anhydride and an oxirane compound are reacted, the reaction proceeds very smoothly without Catalysts such as alkaline or acidic catalysts. In other words, according to According to the invention, it is readily possible to use catalyst-free polyether polyester polyols to manufacture.

The polyether polyester polyols prepared by the process according to the invention kt. Used for the production of polyurethanes, which are used for the production from Foams, adhesives, coating compounds, paints, plastomers, etc. are suitable. In particular, polyurethane foams can advantageously be used with the polyether polyester polyols which are excellent for lamination using the flame lamination process or dielectric processes are suitable and have good physical and mechanical properties to have.

The polyurethanes can be prepared in a customary manner by reacting the polyether polyester polyol be prepared according to the invention with an isocyanate compound.

Suitable isocyanate compounds for the production of the polyurethanes are for example hexamethylene diisocyanate, phenylene diisocyanate (m-isomer, p-isomer etc.), ethylene diisocyanate, propylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, Tolylene diisocyanate (m-isomer, p-isomer, o-isomer), (o, W '-diisocyanate dimethylba Jol (o-, m- and p-isomers), o, w '-diisocyanatdimethylcyclohexane (o-, m- and p-isomers), 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 4,4'-diphenylene diisocyanate, 3,3'-diphenyl-4,4'-biphenylene diisocyanate, 3, D'-dichloro-4,4'-biphenylene diisocyanate, triphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, p, p'-diphenylmethane diisocyanate, p, p'-dicyclohexylmethane diisocyanate and trichlorotolylene diisocyanate.

In the reaction of the polyols according to the invention and the isocyanate compound Catalysts are not always necessary because the polyether polyester polyols of the invention have the same properties as amines. However, it is often advisable to use catalysts e.g. tertiary amines such as N-methylmorpholine and triethylenediamine, organotin bonds such as tin (II) -2-ethylhexoate and tin (II) octyldilaurate to be used.

For the production of polyurethane foams, a blowing agent, e.g. water and halogenated hydrocarbons (e.g. trichlorofluoromethane) and foam stabilizers (e.g.

Silicone oils).

Preferably used for the production of polyurethane foams together a known polyether polyol with the polyether polyester polyol of the present invention used. For example, known polyether polyols which have a hydroxyl number are suitable from about 30 to 160 mg KOH / g and by addition polymerization of an initiator (e.g. Xt-ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerine, Hexanetriol, trimethylolpropane, pentaerythritol, sorbitol and sucrose) with an oxirane compound (e.g.

Ethylene oxide, propylene oxide and styrene oxide) are produced. That known polyether polyol is in an amount of about 1 to 85 wt, -, preferably about 30 to 80% by weight, based on total polyol, is used.

By using a phosphorus-containing polyol with one according to the invention Polyether polyester polyol and optionally the usual polyether polyol in the Production of polyurethane foams can reduce the laminatability of the obtained Polyurethane foams using the flame lamination process and the dielectric Process to be further improved. Phosphorus-containing polyols are suitable, which by Addition polymerization of oxirane compounds (z * BO ethylene oxide and propylene oxide) with an active hydrogen containing phosphorus compound (e.g. phosphorous Acid, phosphoric acid, phosphoric acid monoester, phosphonic acid, pyrophosphoric acid, Pyrophosphoric acid monoester, diphosphonic acid and diphosphonic acid monoester) will.

It is usually advantageous to use phosphorus-containing polyols with a hydroxyl number of about 100 to 250 mg KOH / g, the phosphorus-containing polyol can be used in an amount of about 0.1 to 0.5%, calculated as P (ß) and based on the Total polyol content.

In the following examples, the parts are parts by weight, unless otherwise stated. Parts by weight relate to parts of space like grief to cubic centimeters.

Example 1 In a 2 l four-necked flask fitted with a thermometer, feed tube is provided for propylene oxide, stirrer, condenser and nitrogen supply pipe 1410 parts of benzoguanamine-initiated polyoxypropylenetetraol (hydroxyl number 56.9 mg KOH / g) and 420 parts of phthalic anhydride. After the temperature this Mixture has been brought to 140 ° C, propylene oxide with a metering pump fed. Some of the unreacted propylene oxide is outside the reaction vessel condensed and circulated. The rest is circulated through the system, to remove the sublimed phthalic acid. Awake for a reaction time of 4 hours an acid number of 0 is determined. The vaporized component (unreacted Propylene oxide) is expelled with nitrogen, with 2105 parts of a reaction product lag behind.

This polyether polyester polyol has a hydroxyl number of 42.8 mg KOH / g and a pH of 9.1.

Example 2 447 parts of phthalic anhydride and 1380 parts of polyoxypropylene polyol (Hydroxyl number 61.3 mg KOH / g), prepared using triethanolamine and 4,4'-methylenedianiline in a hydroxyl equivalent ratio of 1: 1 as a coinitiator, are mixed in the vessel described in Example 1. After the temperature of the mixture has been brought to 14,000, propylene oxide is set to that in Example 1 introduced into the mixture as described. The reaction is 2 hours and Carried out for 20 minutes. The reaction mixture has an acid number of 0.025 mg KOH / g. Unreacted propylene oxide is driven off with nitrogen, whereby 2006 Parts of a reaction product are obtained. The polyether polyester polyol thus obtained has a hydroxyl number of 45.0 mg KOH / g and a pH value of 8.9.

Example 3 1400 parts of polyoxypropylene tetraol (hydroxyl number 57.0 mg KOH / g), prepared using 4,4'-methylenedianiline as initiator, and 420 parts of phthalic anhydride are mixed in the vessel described in Example 1.

The temperature of the mixture is raised to 140 ° C., whereupon propylene oxide is fed. The acid number falls during the course of the reaction. After 5 hours it is 0.05 mg KOH / °, whereupon the reaction is stopped. After removal of unreacted propylene oxide, 2037 parts of a reaction product are obtained. The polyether polyester polyol thus prepared has a hydroxyl number of 43.0 mg KOH / °.

Example 4 470 parts of the polyoxypropylene polyol used in Example 2 (Hydroxyl number 61.3 mg KOH / °), 950 parts of polyoxypropylenetriol (hydroxyl number 56.0 mg KOH / °), made using glycerine as initiator, and 420 parts Phthalic anhydride are mixed in the vessel described in Example 1. the The temperature of the mixture is increased to 1400C, whereupon propylene oxide is added to the mixture is introduced. The acid number falls during the course of the reaction. After 4 hours if it has fallen to zero, whereupon the reaction is aborted. After removal of unreacted propylene oxide with nitrogen are 2030 parts of a reaction product obtain. The polyether polyester polyol thus prepared has a hydroxyl number of 40.3 mg KOH / g.

Production of polyurethane visual foam Example 5 At room temperature the following compounds are mixed well: 54.0 parts polyoxypropylenetriol (Hydroxyl number 56.0 mg KOHIg), 1.0 part phosphorus-containing polyol (manufactured by Addition polymerization of propylene oxide and dibutyl pyrophosphate, hydroxyl number 210 mg KOH / g, viscosity 2500 cP (250C), water content 0.1Clo or less, P content 12.0 g), 45 parts of the polyether polyester polyol prepared according to Example 1, 4.0 parts of water, 0.05 parts of triethylenediamine and 1.5 parts of silicone oil (F-220, manufacturer Shin-etsu Chemical Industry Comp., Sud.). 0.20 parts of tin (II) -2-ethylhexoate are added to the mixture and 49.0 parts of tolylene diisocyanate (ratio of 2,4-isomer to 2,6-isomer = 80:20), whereupon the mixture is stirred for about 7 seconds. Within 2 minutes the result is an open-cell polyurethane foam with a density of 24 kg / m3. The adhesive properties of this foam are shown in Table 2 along with the values for further foams produced according to the invention and a comparison foam called.

Examples 6 to 8 In the manner described in Example 5 are used open-cell polyurethane foams made from the components listed in Table 1 manufactured. The foams have a volume weight of 24 kg / m30. The adhesive properties of the foams are given in Table 2.

For comparison, an open-cell foam (a) was chosen from those in Table 1 of the components mentioned. This foam had a density of 24 kg / m3. The adhesive properties of the foam are in the table below called.

Table 1 Example 5 6 7 8 (a) Polyoxypropylenetriol (OH number 56 mg KOH / °) 54 54 54 54 97 Polyether polyester polyol (prepared according to Example 45 - - - -Polyether polyester polyol (prepared according to Example 2) - 45 45 - -Polyether polyester polyol (manufactured according to Example 4) - - - 45 -Phosphorus-containing polyol 1 1 1 1 triethylenediamine 0.05 0.1 0.1 0.1 water 4 4 4 4 silicone oil (F 230) 1.5 1.5 1.5 1.5 1.5 tin (II) -2-ethylhexoate 0.2 0.18 0.16 0.18 0.3 TDI * 49 49 49 49 5.0 * toluylene diisocyanate (ratio of 2,4-isomers to 2,6-isomers = 80:20) Table 2 Example 5 6 7 8 (a) Can be laminated by flame lamination (g / 2 cm) 460 480 480 490 230 Can be laminated by dielectric Laminated 210 210 210 230 130 (E / 3 cm) The concealability through Flame lamination and dielectric method were tested as follows: 1) Can be laminated with the flame liner process The polyurethane foam is Partially melted on a hot plate by heating to 320 ° C for 5 seconds will. A plain weave nylon fabric is placed on top of the melted foam and pressed for 15 seconds at 3 kg / cm2. The material produced in this way is after Tested for adhesive strength for 24 hours with an Instron »-ZuC testing machine (speed of the clamping clamps 10.16 cm / minute).

2) Adhesion strength according to dielectric lamination of polyurethane foam is applied to a synthetic leather made of polyvinyl chloride under pressure for 3 seconds using laminated with a dielectric laminating machine (power 2 kW, f = 40, 18 MHz, Electrode size 3 mm x 5 mm, manufacturer Fuji Denkikoki Co., Sud.). The one made in this way Laminate is tested for adhesive strength after 1 hour on the Instron tensile tester checked (speed of the clamps 5.08 cm / minute).

Claims (5)

Claims for the process for the preparation of polyether polyester polyols of the general formula where n is a number from 5 to 30, m is a number from 1.2 to 5.0, Y is a radical formed by removing active hydrogen atoms from ammonia or an amino compound, x is the number of active hydrogen atoms im Ammonia or in the amino compound, R and R "represent hydrogen atoms or optionally substituted alkyl radicals or acrylic radicals and R 'is a radical which has been formed by removing two COGK groups from a dibasic carboxylic acid, characterized in that a polyether polyol is used general formula in which the individual members have the meanings given above, a dibasic carboxylic acid anhydride of the general formula wherein R 'has the meaning given above, and a Cxiranverbindungen of the general formula in which A "has the meaning given above, are reacted with one another. 2) Method according to claim 1, characterized in that m one Has value from 2 to 3.5. 3) Method according to claim 1, characterized in that Y is a through Removal of active hydrogen atoms from ammonia or an amino compound is a residue obtained with 2 to 8 active hydrogen atoms. 4) Method according to claim 1 to 3, characterized in that R and R "represents a hydrogen atom or a methyl radical. 5) Method according to claim 1, characterized in that R is -CH2-CH2-, -CH = CH- or stands.