RU2721424C2 - Fire-retardant and autocatalytic polyesters for polyurethanes - Google Patents

Abstract

FIELD: chemical or physical processes; manufacturing technology.

SUBSTANCE: invention relates to high-molecular polyesters having fire-retardant properties. Disclosed is a fire-resistant polyester polyol, obtained by reacting aromatic or aliphatic dicarboxylic acid and/or anhydride of anhydride with aliphatic high-molecular alcohol or their mixtures and melamine. Also disclosed is a method of producing said polyester, disclosed melamine cyanurate-containing melamine cyanide and melamine polyphosphate-containing polyesters, polyurethane or polyisocyanate fire-resistant foam and method of producing said polyesters.

EFFECT: technical result is disclosed polyol polyester enables to obtain various fire-resistant materials, such as rigid foam plastic foam, mounting foam, cast elastomer, coating, sealant and fiber.

16 cl, 5 dwg, 8 ex

Description

Technical field

The present invention relates to polyester (high molecular weight alcohol) having flame retardant properties, and to its use, in particular for the production of polyurethanes and polyisocyanurate products having equal flame retardant properties.

State of the art

Melamine and melamine cyanurate are known fire retardant compounds commonly used as additives to polymers and polymer blends.

However, melamine cyanurate and melamine are solids, and therefore difficult to use. When using melamine as an additive in polymer blends, due to its solid particles, melamine will precipitate from the system. For example, in spray foam systems, solid melamine particles will clog the spray nozzle.

Some liquid flame retardants, such as halogen-containing or phosphorus-containing chemicals, may be used as additives; however, halogen- or phosphorus-containing chemicals are toxic, aggressive, and generally more expensive than melamine and melamine cyanurate, while melamine does not contain halogen and phosphorus, is non-toxic, non-corrosive, and is generally a less expensive chemical.

JP 1495362 describes a fire retardant polyester made from thermally polymerizable thermoplastic polyester monomers with the addition of melamine and cyanuric acid; the process uses an equal amount of cyanuric acid and melamine, thus forming a complex compound, which is a complex of melamine cyanurate; the resulting mixture is polymerized in the presence of water at 200–300 ° C to obtain a polyester containing melamine cyanurate distributed evenly and finely in polyester. Since melamine is completely neutralized by cyanuric acid, the -NH2 group, which could react with the structure of the polyester, is absent, as a result of which solid melamine cyanurate acts as an additive in the polyester.

EP 376 380 describes an aromatic polymer with a liquid crystal manifestation comprising one or more tri-functional triazine units. The described method involves the interaction of aromatic polyester-forming monomers and the addition of triazine when the polymer reaches the desired degree of polymerization. It was found that the addition of a small amount of triazine (melamine) can improve the mechanical properties and heat resistance of the obtained high molecular weight liquid crystal polymer.

WO 2014/135712 describes a process for the preparation of a high molecular weight polyester, which comprises reacting a dicarboxylic acid and a diol in the presence of a triazine derivative. The concentration of the triazine derivative, which is determined by the concentration of nitrogen atoms, is usually from 1000 to 10,000 ppm. with a preferred concentration of 1000 ppm up to 2500 ppm The addition of a small amount of melamine derivatives is indicated as a suitable method for increasing the crystallization rate of a high molecular weight polymer.

An object of the present invention is to provide a polyester (high molecular weight alcohol) having flame retardant properties, in which melamine is synthesized on a polyester basis.

Another objective of the invention is the creation of a new complex polyester, which is suitable for interaction with isocyanate to form polyurethane or polyisocyanurate, which can also be used for rigid foam, polyurethane foam, soft foam, molded elastomers, TPU (thermoplastic polyurethane), adhesives, coatings, sealants fibers to achieve fire resistance.

SUMMARY OF THE INVENTION

Given the above objectives, the invention allows to obtain a polyester, which is obtained through the polycondensation of a dicarboxylic acid and / or ester or anhydride, with an aliphatic high molecular weight alcohol or a mixture thereof and with melamine, wherein said aliphatic high molecular weight alcohol includes at least glycol and optionally, an aliphatic high molecular weight alcohol having more than two OH groups selected from the group consisting of glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, glucose, sucrose, polyglycerol and mixtures thereof.

In a preferred embodiment, the polyester is prepared according to the reaction equation shown in FIG. 1.

In a preferred embodiment, the resulting polyester is a chemical structure with the general formula (I) as follows:

wherein:

R1 is an aliphatic group, preferably an alkylene group, optionally including one or more oxyalkylene groups, and

R2 is an aromatic or aliphatic group.

Also, the present invention allows to create a complex polyester containing melamine cyanurate, which can be obtained by further neutralizing the complex polyester obtained according to the invention with cyanuric acid; a preferred chemical reaction equation is shown in FIG. 2.

The present invention also allows the creation of a melamine-polyphosphate-containing polyester, which can be obtained from the polyester created according to the invention, preferably from the polyester of formula (I) above, by further neutralizing with polyphosphoric acid. A preferred chemical reaction equation is shown in FIG. 3.

The present invention also provides a method or process for producing polyurethanes and / or polyisocyanurates that use, as the polyester of high molecular weight alcohol, a polyester containing melamine, or a polyester containing melamine polyphosphate, or a melamine cyanurate polyester according to the invention, which were obtained by using any of the chemical equations shown in figures 1-3.

Brief Description of the Drawings

In the attached drawings:

- figure 1 shows a preferred chemical equation for producing a polyester containing melamine according to the invention;

- figure 2 shows the chemical equation for a complex polyester containing melamine polyphosphate according to the invention, and

- figure 3 shows the chemical equation of the complex polyester containing melamine cyanurate according to the invention;

- figure 4 is a diagram showing the rate of foam formation (increase in height relative to time) when producing a sprayable hard polyurethane using the polyester according to the invention in accordance with example 1 (which follows) and using ordinary polyester according to a comparative example;

- figure 5 is a diagram showing the rate of foam formation (reaction rate versus time) when producing a sprayable hard polyurethane using a polyester in accordance with Example 1 and using a conventional polyester in accordance with a comparative example.

According to the invention, additional characteristics and advantages of the polyester and its use are shown using the following examples.

Detailed description

The invention allows to obtain a complex polyester comprising melamine in the polyester chain, preferably in accordance with the above formula (I), and in a preferred embodiment of the invention:

- R ₁ is an alkylene group - (CH ₂ ) _n -, wherein n is an integer from 1 to 20, preferably from 2 to 12, or an oxyalkylene group - [(CH ₂ ) _m O] _p - (CH ₂ ) _r , where m is an integer from 1-10, p is an integer from 1 to 10, and r is an integer from 1 to 10

- R ₂ is an aromatic or aliphatic group, but preferably phenyl; and

- x, y and z, independently of each other, are integers from 1 to 20

The polycondensation reaction is carried out at a temperature of from 120 to 300 ° C, preferably from 150 to 260 ° C, for 5-50 hours using a conventional polycondensation metal catalyst, such as titanates, tin compounds, antimony compounds or without catalyst.

The dicarboxylic acid, its ester or anhydride may be aliphatic or aromatic. Suitable aliphatic dicarboxylic acids and esters thereof include compounds of the formula R-OOC- (CH ₂ ) _n -COOR, wherein n is preferably 2 to 10 and R is H or lower (C ₁ -C ₄ ) alkyl, preferably methyl or ethyl, such as succinic, glutamic, adipic, sebacic, suberic dodecandioic and fumaric acids and their ethyl or methyl esters and mixtures thereof. Also included are the anhydrides of the aforementioned dicarboxylic acids, commonly used in admixture with dicarboxylic acid.

Suitable aromatic dicarboxylic acids and their esters include compounds of the formula ROOC-Ph-COOR, wherein Ph is phenyl and R is H or lower (C ₁ -C ₄ ) alkyl, preferably methyl or ethyl, and the carboxyl groups are in ortho- , meta or para positions, for example terephthalic acid, dimethyl or diethyl terephthalate, isophthalic acid. Other polybasic acids, such as benzene tricarboxylic acids or polycarboxy substituted diphenyls and polyphenyls and the corresponding lower alkyl esters, are also included. Anhydrides of the aforementioned aromatic acids are also included, for example, in particular phthalic anhydride, which is usually used in admixture with a dicarboxylic aromatic acid or ester and recycled polyethylene terephthalate.

Aliphatic high molecular weight alcohol includes, but is not limited to, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol and, as a rule, polyethylene glycols of the formula OH- (CH ₂ -CH ₂ O) _t - _, and t may be from 1 to 20 and as a rule, polypropylene glycols of the formula OH- (CH ₂ —CH (CH 3) O) _t - _, and t may be from 1 to 20.

Particularly preferred is the use of polyethylene glycol having a molecular weight of from 100 to 3000, more preferably together with short-chain glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 3-propanediol, 1,3-butanediol , 4-butanediol, which can be added during the polycondensation reaction to control glycol loss during the reaction and to achieve the desired hydroxyl number.

In order to modify the functionality of the final polyester, some functions of glycols other than 2.0 can be added, such as methoxylated polyethylene glycol, lauryl alcohol, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, glucose, sucrose and polyglycerol.

To modify the properties of the final polyester, some natural oils can be added, for example, soybean oil, rapeseed oil, castor oil, corn oil, and sunflower oil.

The polyester according to the invention can be obtained in accordance with the known chemical structure of the polyester.

During the preparation process, melamine can be added in any quantity suitable to provide flame retardant properties in the resulting polyester.

Melamine can be added so that in the final polyester an amount of melamine from 0.5 to 60 wt.% Based on the final polyester is achieved, preferably from 1 to 50 mass fraction, more preferably from 5 to 50 wt.% And even more preferably from 10 to 40 wt.%.

The resulting polyester contains

a) dicarboxylic acid, its esters or its anhydride derivatives, as described above,

b) derivatives of high molecular weight alcohol, as described above, and

c) melamine derivatives,

in which fragments derived from melamine are present in the polyester chain, preferably in a molar percentage of from 2 to 40% by moles, referred to the sum of a), b) and c), more preferably from 5 to 40% by mole and even more preferably from 10 to 30%.

The polyester according to the invention, preferably a polyester of formula (I), has a number average molecular weight of 200 to 6000 daltons (measured by gel permeation chromatography), a hydroxyl number of 15 to 600 mg KOH / g, preferably 30 to 500, and acid number from 0 to 10, preferably not higher than 1.

In another embodiment of the invention, the polyester obtained by the above method can be further neutralized with polyphosphoric acid to obtain a polyester containing melamine polyphosphate, with additional improved flame retardant properties, preferably in accordance with the chemical equation shown in figure 2.

Polyphosphoric acid is added to the polyester obtained by the reaction of dicarboxylic acid, polyol and melamine, preferably after lowering the reaction temperature in the range from 10 to 200 ^° C. for a period of 5 minutes to 120 minutes.

As a rule, polyphosphoric acid can be added to the polyester in an amount of from 0.5 to 30 wt.% In terms of the final polyester.

In another embodiment, the polyester containing melamine cyanurate is prepared by the first reaction, in accordance with the polycondensation reaction, of a dicarboxylic acid or its ester or anhydride, polyol and melamine to obtain an intermediate polyester followed by the addition of cyanuric acid, preferably even at a temperature polycondensation, and then carrying out neutralization for 1-30 hours.

The amount of added cyanuric acid can be from 0.5 to 30 wt.% In terms of the final polyester.

The polyester of the invention in all of the above embodiments is particularly suitable for preparing polyurethanes or polyisocyanurates in accordance with a conventional reaction with an isocyanate, optionally using a blowing agent.

It was found that the new melamine-containing polyester according to the invention exhibits autocatalytic function due to the N (nitrogen) amino group of melamine.

Therefore, a smaller amount of catalyst can be used to produce polyurethanes or polyisocyanurates in accordance with the PUR (polyurethane) or PIR (polyisocyanurate) technology.

Examples

Example 1

Melamine-containing polyester

Method:

A catalyst, diethylene glycol, PEG200 (polyethylene glycol, molecular weight 200), glycerin, terephthalic acid, phthalic anhydride and melamine were charged into a four-necked glass flask equipped with a nitrogen inlet, stirrer, column and thermometer. The temperature was raised to 240 ° C, and the column temperature was maintained using an electrode. As the reaction progressed, the nitrogen content was increased and stirring was increased to facilitate removal of water, but not too quickly so as not to blow out the glycol.

The amount of hydroxyl and acid number was checked as necessary, and the glycol loss during the reaction was adjusted with diethylene glycol until a theoretical hydroxyl number was reached. The reaction was considered complete when the amount of hydroxyl and acid number reached the expected amount.

Example 2

Melamine-containing polyester

Method:

A catalyst, diethylene glycol, PEG200 (polyethylene glycol, molecular weight 200), glycerin, terephthalic acid and phthalic anhydride were charged into a four-necked glass flask equipped with a nitrogen inlet, stirrer, column and thermometer. The temperature was raised to 240 ° C, and the column temperature was maintained using an electrode. As the reaction progressed, the nitrogen content was increased and stirring was intensified to facilitate removal of water, but not too quickly so as not to blow out the glycol. When the acid number dropped below 2.0, melamine was added.

The amount of hydroxyl and acid number was checked as necessary, and the glycol loss during the reaction was adjusted with diethylene glycol until a theoretical hydroxyl number was reached. The reaction was considered complete when the amount of hydroxyl and acid number reached the expected amount.

Example 3

Melamine-containing polyester

Method:

A catalyst, diethylene glycol, PEGG200 (polyethylene glycol, molecular weight 200), glycerin, ethylene glycol, terephthalic acid, phthalic acid anhydride and melamine were charged into a four-necked glass flask equipped with a nitrogen inlet, stirrer, column and thermometer. The temperature was raised to 240 ° C, and the column temperature was maintained using an electrode. As the reaction progressed, the nitrogen content was increased and stirring was increased to facilitate removal of water, but not too quickly so as not to blow out the glycol.

The amount of hydroxyl and acid number was checked as necessary, and the glycol loss during the reaction was adjusted with diethylene glycol and ethylene glycol to achieve a theoretical hydroxyl number. The reaction was considered complete when the amount of hydroxyl and acid number reached the expected amount.

Example 4

Melamine-containing polyester

Method:

A catalyst, diethylene glycol, adipic acid and melamine were charged into a four-necked glass flask equipped with a nitrogen inlet, stirrer, column and thermometer. The temperature was raised to 240 ° C, and the column temperature was maintained using an electrode. As the reaction progressed, the nitrogen content was increased and stirring was increased to facilitate removal of water, but not too quickly so as not to blow out the glycol.

The amount of hydroxyl and acid number was checked as necessary, and the glycol loss during the reaction was adjusted with diethylene glycol until a theoretical hydroxyl number was reached. The reaction was considered complete when the amount of hydroxyl and acid number reached the expected amount.

Example 5

Melamine-containing polyester

Method:

A catalyst, diethylene glycol, PEG200 (polyethylene glycol, molecular weight 200), soybean oil, sorbitol (70%), terephthalic acid, phthalic anhydride and melamine were charged into a four-necked glass flask equipped with a nitrogen inlet, stirrer, column and thermometer. The temperature was raised to 240 ° C, and the column temperature was maintained using an electrode. As the reaction progressed, the nitrogen content was increased and stirring was increased to facilitate removal of water, but not too quickly so as not to blow out the glycol.

The amount of hydroxyl and acid number was checked as necessary, and the glycol loss during the reaction was adjusted with diethylene glycol until a theoretical hydroxyl number was reached. The reaction was considered complete when the amount of hydroxyl and acid number reached the expected amount.

Example 6

Melamine Polyphosphate Polyester

Method:

A catalyst, diethylene glycol, PEG200 (polyethylene glycol, molecular weight 200), trimethylolpropane, terephthalic acid, phthalic anhydride and melamine were charged into a four-necked glass flask equipped with a nitrogen inlet, stirrer, column and thermometer. The temperature was raised to 240 ° C, and the column temperature was maintained using an electrode. As the reaction progressed, the nitrogen content was increased and stirring was intensified to facilitate removal of water, but not too quickly so as not to blow out the glycol.

The amount of hydroxyl and acid number was checked as necessary, and the glycol loss during the reaction was adjusted with diethylene glycol until a theoretical hydroxyl number was reached. The reaction was considered complete when the amount of hydroxyl and acid number reached the expected amount. The temperature was reduced to 100 ° C; polyphosphoric acid with stirring for 30 minutes.

Example 7

Polyester containing melamine cyanurate

Method:

A catalyst, diethylene glycol, PEG200 (polyethylene glycol, molecular weight 200), terephthalic acid, phthalic anhydride and melamine were charged into a four-necked glass flask equipped with a nitrogen inlet, stirrer, column and thermometer. The temperature was raised to 250 ° C, and the column temperature was maintained using an electrode. As the reaction progressed, the nitrogen content was increased and stirring was increased to facilitate removal of water, but not too quickly so as not to blow out the glycol.

The amount of hydroxyl and acid number was checked as necessary, and the glycol loss during the reaction was adjusted with diethylene glycol until a theoretical hydroxyl number was reached. The reaction was considered complete when the amount of hydroxyl and acid number reached the expected amount. The temperature was maintained at 250 ° C; cyanuric acid was added and the mixture continued to cook for 12 hours. The amount of hydroxyl and acid number was checked as necessary, and the glycol loss during the reaction was adjusted with diethylene glycol until a theoretical hydroxyl number was reached. The reaction was considered complete when the amount of hydroxyl and acid number reached the expected amount.

Comparative example

This example illustrates the preparation of melamine-free polyester.

Method:

A catalyst, diethylene glycol, PEG200 (polyethylene glycol, molecular weight 200), glycerin, terephthalic acid and phthalic anhydride were charged into a four-necked glass flask equipped with a nitrogen inlet, stirrer, column and thermometer. The temperature was raised to 240 ° C, and the column temperature was maintained using an electrode. As the reaction progressed, the nitrogen content was increased and stirring was intensified to facilitate removal of water, but not too quickly so as not to blow out the glycol.

The amount of hydroxyl and acid number was checked as necessary, and the glycol loss during the reaction was adjusted with diethylene glycol until a theoretical hydroxyl number was reached. The reaction was considered complete when the amount of hydroxyl and acid number reached the expected amount.

The polyesters according to the invention are particularly suitable for producing polyurethane and / or polyisocyanurate products having initial flame retardant properties without the need for adding solid or liquid flame retardants, by adding substantially lower amounts of solid or liquid flame retardants than are used.

Accordingly, the present invention also includes the production of polyurethane and polyisocyanurate products, in particular polyurethane foams, from the polyester polyols described above, as well as finished products of polyurethanes and polyisocyanurates.

The preparation of polyurethane or polyisocyanurate products using the polyesters described herein can be carried out by any of the methods known in the art, see Saunders and Frisch, Volumes I and II, Polyurethanes. Chemistry and Technology ”, 1962, John Wiley and Sons, New York, N.Y. or Gum, Reese, Ulrich, “Reaction Polymers,” 1992, Oxford University Press, New York or Klepper and Sendyarevich, “Polymer Foams and Foam Technology,” 2004, Publications by Hanser Gardner, Cincinnati, Ohio.

In many applications, it is convenient to provide components for polyurethane or polyisocyanurate foams in pre-mixed formulations. Typically, the composition of the foam is pre-mixed with two components. Isocyanate and, optionally, other raw materials compatible with isocyanate, including, without limitation, blowing agents and some silicone surfactants, contains the first component, which is usually called component "A". The composition of the mixture of high molecular weight alcohols, including a surfactant, catalysts, blowing agents and optional other ingredients, contains a second component, which is usually called component "B". Polyurethane or polyisocyanurate foams are easily prepared by combining side components A and B either by manual mixing for small doses, or, preferably, by machine mixing to form blocks, plates, laminates, filling panels and other items used in spraying foam, foam and the like. like that. Alternatively, other ingredients, such as a relatively small amount of flame retardants, colorants, auxiliary blowing agents, water and even other high molecular weight alcohols, can be added by stream to the mixing head or reaction area. However, it is most convenient when they are all included in one component B, as described above.

Polyurethanes and polyisocyanurates are prepared by reacting a di- or polyisocyanate with the described polyether polyol, which can be used as a single polyester or in a mixture with ordinary polyether polyols and polyester polyols.

A foamable composition suitable for forming polyurethane foam or polyisocyanurate can be prepared by reacting an organic polyisocyanate and a premix polyol composition described above, including the polyester of the invention. Any organic polyisocyanate, including aliphatic and aromatic polyisocyanates, can be used in the synthesis of polyurethane foam or polyisocyanurate. Suitable organic polyisocyanates include aliphatic, cycloaliphatic, aromatic and heterocyclic isocyanates, which are well known in the field of polyurethane chemistry. They are described, for example, in US patent No. 4868224; 3,401,190; 3,454,606; 3,277,138; 3,492,330; 3001973; 3,394,164; 3,124,605; and 3201372. A preferred class is aromatic polyisocyanates.

Typical organic polyisocyanates correspond to the formula:

R (NCO) z

 where R is a polyvalent organic radical, which is either aliphatic, aralkyl, or aromatic, or mixtures thereof, and z is an integer that corresponds to valency R and is at least two. Representative organic polyisocyanates presumed here includes, for example, aromatic diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, crude toluene diisocyanate, methylene diphenyl diisocyanate, crude methylene diphenyl diisocyanate and the like; aromatic triisocyanates, such as 4,4 ′, 4 ″-triphenylmethanetriocyanate, 2,4,6-toluene triazocyanates; aromatic tetraisocyanates, such as 4,4'-dimethyldiphenylmethane-2,2'5,5'-tetraisocyanate and the like; arylalkyl polyisocyanates such as xylylenediisocyanate; an aliphatic polyisocyanate such as hexamethylene-1,6-diisocyanate, methyl ester of lysinediisocyanate and the like; and mixtures thereof. Other organic polyisocyanates include polymethylene polyphenyl isocyanate, hydrogenated methylene diphenyl isocyanate, m-phenylenediisocyanate, naphthylene-1,5-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-4-dimethoxy-4-dimethoxy-4-dimethoxy-4-dimethoxy biphenyldiisocyanate, 3,3'-dimethyl-4,4'-biphenyldiisocyanate and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate; Typical aliphatic polyisocyanates are alkylenediisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate and hexamethylene diisocyanate, isoporendiisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate) and the like; typical aromatic polyisocyanates include m- and p-phenylenediocyanate, polymethylene polyphenyl isocyanate, 2,4- and 2,6-toluene diisocyanate, dianisidine diisocyanate, bitolinocyanate, naphthylene 1,4-diisocyanate, bis (4-isocyanatophenyl) methane, bis (2 -isocyanatophenyl) methane and the like. Preferred polyisocyanates are polymethylene polyphenyl isocyanates, in particular mixtures containing from about 30 to 85 parts by weight of methylene bis (phenyl isocyanate) with the rest of the mixture containing polymethylene polyphenyl polyisocyanates with a functionality of more than 2. These polyisocyanates are prepared by conventional methods in the art. In the present invention, the polyisocyanate and high molecular weight alcohol are preferably used in amounts that result in a stoichiometric NCO / OH ratio in the range of about 0.9 to 5.0. In the present invention, the equivalent NCO / OH ratio is preferably about 1.0 or more and about 3.0 or less, with an ideal range of about 1.1 to 2.5. A particularly suitable organic polyisocyanate includes polymethylene polyphenyl isocyanate, methylene bis (phenyl isocyanate), toluene diisocyanates, or combinations thereof.

In the preparation of polyisocyanurate foams, trimerization catalysts are used to convert the mixtures, in combination with an excess of component A, into polyisocyanurate-polyurethane foams. The trimerization catalysts used can be any catalyst known to one of skill in the art, including, but not limited to, glycine salts, tertiary amine trimerization catalysts, quaternary ammonium carboxylates and alkali metal carboxylic salts, and mixtures of various types of catalysts. Preferred species within the classes are sodium acetate, potassium octoate, and N- (2-hydroxy-5-nonylphenol sodium) methyl N-methyl glycinate; (2-hydroxypropyl) trimethylammonium-2-ethylhexanoate (sold by TMR® “Aerial Products and Chemicals”); (2-hydroxypropyl) trimethylammonium (sold by TMR® “Aerial Products and Chemicals”); and Toyokat-TRX sold by Tosox Corporation .

Due to the autocatalytic function of the polyester according to the invention, small amounts of catalyst can be used.

In addition to the ingredients previously described, other ingredients, such as colorants, fillers, pigments and the like, may be included in the foam. Dispersing agents and element stabilizers may be included in the mixture. Typical fillers for use here include, for example, aluminum silicate, calcium silicate, magnesium silicate, calcium carbonate, barium sulfate, calcium sulfate, fiberglass, carbon black and silica. The filler, if used, is usually present in an amount by weight of from about 5 to 100 parts per 100 parts of high molecular weight alcohol. The pigment that can be used here can be any conventional pigment, such as titanium dioxide, zinc oxide, iron oxide, antimony oxide, green crown, yellow crown, azure sienna, orange molybdate and organic pigments such as red paranitroaniline, benzidine crowns, toluidine red, ink and phthalocyanines. The resulting polyurethane or polyisocyanurate foams can vary in density from about 0.5 pounds per cubic foot to about 60 pounds per cubic foot, preferably from about 1.0 to 20.0 pounds per cubic foot, and most preferably from about 1.5 to 6 , 0 pounds per cubic foot. The density obtained depends on how much of the mixture of the blowing agent or blowing agent plus the amount of auxiliary blowing agent, such as water or other joint blowing agents, is present in components A and / or B or, in accordance with another embodiment of the invention, is added during preparation foam. The foam may be rigid, flexible or semi-rigid, may also have a closed structure of elements, an open structure of elements, or a mixture of open and closed elements. Such foam has many well-known applications, including, without limitation, thermal insulation, cushioning, flotation, packaging, adhesives, void filling, crafts and decorative products, as well as cushioning.

The polyester according to the invention can also be used for the production of molded elastomers, thermoplastic polyurethanes, adhesives, coatings, sealants, fibers with flame retardant properties.

Example 8: Composition of sprayed rigid polyurethane foam

Polyester: Example of Invention 1 or Comparative Example

Carpol MX-425: Mannich-Polyester from Carpenter

Carpol GSP-355: sucrose / glycerin-initiated polyester from Carpenter

Jeffcat DMEA: Huntsman Amine Catalyst

Dubco K-15: Potassium Octoate Catalyst from Air Products

Polycat 33: Amine Catalyst from Air Products

HFC-245fa: Honeyvel Foaming Agent

Dabco DC193: Airborne Silicone Surfactant

PAPI 27: Dow Polymer Isocyanate

Method:

Foam was prepared by manual mixing using a batch mixer. The materials used were kept at room temperature until they were used. A superconcentrate of mixed polyester, polyester, all catalysts, water, a blowing agent and a surfactant was prepared and mixed very well to form component B. 50 g of component B was added to a paper cup. Then component A (polymer isocyanate) was added to the mixture and stirring was continued for 6 seconds. The rate of foam formation was controlled by measuring the height and speed of foaming using a foaming tool (supplied by Messtekhnik LLC). Physical properties were maintained after 2 weeks at room temperature.

Physical properties of sprayed rigid polyurethane foam

burning in time: Test device for controlling the spread of fire in the mines of the Mining Bureau

Chimney: ASTM D3014

compressive strength: ASTM D1621

fragility: ASTM C421

closed elements: ASTM D2226

Claims (27)

1. The flame retardant polyester polyol obtained by reacting an aromatic or aliphatic dicarboxylic acid and / or its ester or anhydride with an aliphatic high molecular weight alcohol or mixtures thereof and with melamine, wherein said aliphatic high molecular weight alcohol contains at least glycol and optionally , an aliphatic macromolecular alcohol having more than two OH groups selected from the group consisting of glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, glucose, sucrose, polyglycerol and mixtures thereof, said polyester polyol containing compounds of the formula

(I) wherein R ₁ is an alkylene group - (CH ₂ ) _n -, and n is an integer from 1 to 20, or an oxyalkylene group is [(CH ₂ ) _m O] _p - (CH ₂ ) _r , and m is an integer from 1 up to 10, p is an integer from 1 to 10 and r is an integer from 1 to 10; - R ₂ is an aromatic or aliphatic group; and - x, y and z, independently of each other, are integers from 1 to 20. 2. The polyester according to claim 1, wherein R ₂ is phenyl. 3. The polyester according to claim 1, in which R ₁ is an alkylene group - (CH ₂ ) _n -, and n is an integer from 2 to 12. 4. The polyester according to claim 1, having an average molecular weight of not more than 6000 daltons. 5. The polyester according to claim 1, obtained by reacting said aliphatic or aromatic dicarboxylic acid, ester or anhydride with said aliphatic polyol or a mixture of aliphatic polyols in the presence of added melamine at a temperature of from 120 to 300 ° C for 5 to 50 hours. 6. The polyester according to claim 1, where melamine is added in order to achieve in the final polyester the amount of melamine from 10 to 40 wt.% In terms of the weight of the final polyester. 7. The polyester according to claim 1, containing: a) dicarboxylic acid, its ester or its anhydride, derivative fragments, b) derived fragments of high molecular weight alcohol and c) fragments obtained from melamine, and fragments obtained from melamine are present in the structure of the polyester in an amount of from 5 to 40 molar percent, associated with the amount of a), b) and c) mol. 8. The polyester according to claim 1, in which these fragments obtained from melamine are present in the structure of the complex polyester in an amount of from 10 to 30 mol. % 9. Melamine cyanurate-containing polyester obtained by further neutralizing the polyester according to claim 1 with cyanuric acid. 10. The melamine cyanurate-containing polyester according to claim 9, containing fragments obtained from cyanuric acid, in an amount of from 0.5 to 30 wt.% In terms of the final polyester of melamine cyanurate. 11. Melamine polyphosphate-containing polyester obtained by further neutralizing the polyester according to claim 1 with polyphosphoric acid. 12. Melamine polyphosphate-containing polyester according to claim 11, containing polyphosphoric acid in an amount of from 0.5 to 30 wt.% In terms of a polyester containing the final melamine polyphosphate. 13. A method of producing a polyurethane or polyisocyanurate foam having fire retardant properties by reacting a polyester according to any one of paragraphs. 1, 9 or 11 with di- or polyisocyanate. 14. Polyurethane or polyisocyanate foam having fire-retardant properties obtained by the interaction of melamine-containing polyester according to any one of paragraphs. 1, 9 or 11 with di- or polyisocyanate. 15. A method of producing a polyester polyol according to claim 1
by reacting an aromatic or aliphatic dicarboxylic acid and / or its ester or anhydride with an aliphatic high molecular weight alcohol or mixtures thereof and with melamine, said aliphatic high molecular weight alcohol containing at least glycol and, optionally, an aliphatic high molecular weight alcohol having more than two OH groups selected from the group consisting of glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, glucose, sucrose, polyglycerol and mixtures thereof, said polyester polyol containing: a) dicarboxylic acid, its ester or its anhydride, derivative fragments, b) derived fragments of high molecular weight alcohol and c) fragments obtained from melamine, and fragments obtained from melamine are present in the polyester structure in an amount of from 10 to 40 molar percent, calculated on the basis of a), b) and c) mol, wherein said polyester having melamine in the structure polyester and with a number average molecular weight of 200 to 6000 daltons. 16. A method of producing a polyurethane or polyisocyanurate foam having fire retardant properties by reacting a di- or polyisocyanate with a polyester polyol obtained by the method of claim 15.

Images