A method of obtaining a molded polyurethane material

 

(57) Abstract:

The invention relates to the production of molded polyurethane materials, in particular foams, using significant amounts of polyol with a relatively high content of oxyethylene links, which are used as structural elements in different areas of technology and household appliances with good performance properties. A method of obtaining a polyurethane material in the form includes the following stages: 1) the application of an external lubricant to form at least those surfaces of the forms that will be in contact with the ingredients used to obtain a polyurethane material, and/or the resulting polyurethane material; 2) feed ingredients used to obtain the polyurethane material into the form; 3) the ingredients give the opportunity to react with obtaining a polyurethane material; 4) the so formed polyurethane material is removed from the form, and 5) repeat stages 2, 3 and 4 at least 10 times without repeating stage 1, where at least 25 wt.% ingredients used to produce polyurethane material, excluding the and with functionality in the range 2-6, with equivalent weight in the range 500-5000 and content oxyethylene units, at least 50 wt.%. 2 C. and 13 C.p. f-crystals.

The present invention relates to a method for producing a molded polyurethane materials, in particular foams obtained using significant amounts of polyol with a relatively high content of oxyethylene (EO) units.

EP 547765 describes an elastic foams using a number of simple polyetherpolyols containing significant amounts of oxyethylene groups. Obtaining molded articles described in the General plan.

WO 97/21750 describes obtaining molded elastomers using the same type of polyols with high content.

U.S. patent 5700847 and U.S. patent 5668191 also describe obtaining a molded flexible foams.

None of these cited documents are not relevant to the problems faced in obtaining such molded foams on an industrial scale. On an industrial scale such foams obtained using the forms before using processed: surfaces that will be in the Tata polyurethane material, process one or more so-called external lubricants for the form. After receiving 5 or 6 molded surface data will need more time to process external lubricant for the form. In most cases, applying to the surface of the external lubrication for the form is held by hand; or when applied manually or with automatic application of this repeated application of an external lubricant to form increases the cycle time and the number of external lubrication for the form. In addition, as was found from practical experience, external lubricant to form during the molding process concentrates on some parts of the surface form (the so-called “deposits”), which requires regular thorough cleaning of the surface.

EP 547760 describes a method of obtaining a molded elastomers; without applying external lubrication for the form can be made more than 100 molded products. Used the reaction system contain modified allophanate groups of a polyisocyanate and a significant number of simple polyetherpolyols with a relatively high content of oxypropylene links.

In the past ; the consult, for example, EP 119471 and EP 173888 and description of the prior art discussed in these papers.

It would be advantageous to have the possibility of obtaining a molded flexible foams without having so frequent application of external lubrication for the form, as at present. In addition, it would be advantageous to reduce the full quantity of external lubrication for the form used in obtaining molded products, and reduce the amount of sediment.

Unexpectedly, applicants have found that in use when obtaining a molded material of a significant amount of polyol containing significant amounts of oxyethylene groups, there is the possibility of reducing the required number of external application of the lubricant to form a complete number of external lubrication for the form used in the method of molding, and amount of sediment.

Therefore, the present invention relates to a method for producing a polyurethane material in a form that includes the following stages:

1. The application of an external lubricant to form at least those surfaces of the forms that will be in contact with the ingredients used to obtain polyurethane m is utilized to obtain a polyurethane material, in the form;

3. The interaction of the ingredients to obtain a polyurethane material;

4. Removing from the mold thus obtained polyurethane material and

5. Repeat stages 2, 3 and 4 at least 10 times without repeating stage 1, where at least 25 wt.% ingredients used to produce polyurethane material, except water in this calculation, if such is used, composed of simple polyetherpolyols with an average nominal functionality in the range of 2-6, an average equivalent weight in the range 500-5000, and contents of oxyethylene at least equal to 50 wt.%.

In the context of the present invention, the following terms have the following meanings:

1) isocyanate index, or index NCO, or index:

the ratio of NCO groups to the number of reactive towards isocyanate hydrogen atoms present in the composition, expressed in percent:

In other words, the NCO index expresses the percentage of isocyanate groups, which are really used in composition, in comparison with the number of isocyanate groups that theoretically required to undergo reaction with the amount of reaktsionnosposobnykh, what isocyanate index as it is used herein, is considered from the point of view of the actual foaming process or other process conducted in the form of using isocyanate ingredients and reactive towards isocyanate ingredients. Any number of isocyanate groups used in the preliminary stage for the production of modified polyisocyanates (including such derivatives of isocyanates, which are state of the art referred to as prepolymers), or any number of active hydrogens spent at the preliminary stage (for example, as a result of reaction with isocyanate to obtain a modified polyols or polyamines), when calculating the isocyanate index is not taken into account. Shall be taken into consideration only the free isocyanate groups and free reactive towards isocyanate hydrogens (including hydrogens of water) present in the actual reaction mixture in the form.

2) the Expression “reactive towards isocyanate hydrogen atoms” as it is used herein for the purpose of calculating the isocyanate index, oboznachayuschih compositions; this means that for the purpose of calculating the isocyanate index in the actual process of foaming is considered that one hydroxyl group contains one reactive hydrogen, one primary amino group is considered as containing one reactive hydrogen and it is believed that one molecule of water contains two active hydrogen.

3), the Reaction system: a combination of components, where the polyisocyanates are stored in one or more containers separately from components that are reactive towards isocyanate.

4) the Expression “polyurethane foam” as it is used herein refers to cellular products obtained from the reaction between polyisocyanates and compounds containing reactive towards isocyanate hydrogens, using foaming agents, and in particular includes cellular products obtained when using as reactive foaming agent water (using a reaction between water and isocyanate groups with obtaining mochevinoi relations and carbon dioxide formed as a result polimochevinnykh pins) and when used as reaktsionnosposobnykh hydroxyl functionality” is used herein to indicate the functionality (number of hydroxyl groups per molecule) of the polyol or polyol as one composition by the assumption, this value represents the functionality (number of active hydrogen atoms per molecule) of the initiator(s) used in their preparation although in practice this value is often somewhat smaller due to the presence of some terminal unsaturation.

6) the Term “average” means srednekamennogo value, unless another.

Polyurethane material obtained by the method of the present invention may be an elastomer, microecosystem elastomer, thermoplastic polyurethane, semi-rigid foam with an integral shell, elastic hydrophilic foam or foam-like materials of the type described in EP 707607 and EP 793681. These materials can be used, for example, as structural components in automobiles, such as steering wheels, armrests and headrests, as soles for shoes, as a foam in car seats or the furnishing, medical or hygienic applications, such as dressings on wounds, tampons and diapers, and leisure products such as dolls. The resulting materials have comparable physical properties of atogo, 40-fold or even more.

The molding process can be carried out in the form of an open type and a closed type; preferably the reaction is carried out in the form of a closed type. If the molding process is carried out in the form of a closed type, the form can be closed after stage 2 and to open after stage 3, or the form can be closed after stage 1 and to open after stage 3; in the latter case the ingredients to obtain a polyurethane material serves to form through the respective inlet. Molding can be carried out by methods known state of the art, such as casting without the pressure and reaction injection molding (RIM, including the so-called RIM for foaming thermoplastics).

As already mentioned, stage 2-4 repeat at least 10 times without repeating stage 1; stage preferably repeated at least 15 times, and most preferably at least 25 times. Although it would be desirable to repeat stage 2-4 without repeating stage 1 so many times, as soon as possible, the practice shows that after stage 2-4 are repeated a significant number of times without repeating stage 1, the repetition of stage 1 can be relatime molded parts require a bit more effort compared to the effort necessary to extract the first molded parts, and much more to such an extent that it will seem that the next notch from the mold without damage to the parts produced can not be. Those who produce the notch form in industrial production lines, will easily be able to determine whether to repeat stage 1 and when it needs to be repeated. Despite the fact that the repetition of the stage 1 due to deterioration mode demoulded needs another may not occur, however, after a certain period of time, the repetition of stage 1 may be desirable in order to ensure consistency of the production process. In this context, it may be desirable to repeat stage 1 between two shifts (for example, after 8 hours after 24 hours or by the end of the week depending on the complexity of the design form. It should be noted that in General the normal cycle time is in the range between 0.5 and 20 minutes, and often between 1 and 10 minutes. Practice shows that for elastic foams such repetition of stage 1 is not required to be made 50 molded products.

The ingredients used to obtain polyurethane mattow, except for the amount of water, if such is used, composed of simple polyetherpolyols with srednekamennogo nominal functionality in the range of 2-6, with content oxyethylene groups, at least 50 wt.%, and preferably 60-90 wt.% (calculated on the weight of simple polyetherpolyols) and srednegalechny equivalent weight in the range of 500-5000. Simple polyetherpolyols may contain together with oxyethylene groups and other oxyalkylene groups, such as oxypropylene and oxybutylene group.

If a simple polyetherpolyols will contain other oxyalkylene group, then a simple polyetherpolyols may be a block copolymer, a statistical copolymer, or a combination of a block copolymer and a statistical copolymer. Most preferably the use of statistical copolymers. Can also be used polyoxyethyleneglycol, such as polyoxyethyleneglycol, with a molecular weight in the range of 1000-2000.

Most preferably, when a simple polyetherpolyols is polyoxyethylene polyoxypropyleneglycol with srednekamennogo nominal functionality in the range of 2-4, with srednegalechny equivalent weight in PR is etilen polyoxypropyleneglycol is statistical polyol such polyols can be purchased commercially, examples are Daltocel 442 from Huntsman Polyurethanes (Daltocel is a trademark of Huntsman ICI Chemicals LLC), Arcol 2580 from Lyondell and SR from DOW. Can also be used and mixtures of these polyols with a high content of oxyethylene.

The amount of the above-mentioned polyol in the calculation of the quantity of all the ingredients used, except the amount of water, if such is used, is preferably in the range of 50-90 wt.%, and more preferably in the range of 60-85 wt.%.

As such known and other ingredients used in the preparation of polyurethane materials, and they are the polyisocyanates and if you receive a foamed polyurethane materials, foaming agents. In addition, as optional ingredients can be used the following ingredients: additional reactive towards isocyanate compounds such as simple polyether polyols related to the type other than the types described above, for example, polyoxypropyleneamine may contain less than 50%, and preferably less than 25 wt.% oxyethylene groups at the end of polymer chains (the so-called polyols with limit SW), complex pkey functionality in the range 2-6, preferably 2-3 and srednegalechny equivalent weight in the range 50-5000, preferably 1000-3000, such as extension cords, chains and cross-linking agents, which will be reactive towards isocyanate compounds with an equivalent weight of less than 500 and functionality equal to 2 and 3-8, respectively.

Examples of such extenders chains and crosslinking agents are ethylene glycol, propandiol, 2-methylpropane-1,3-diol, butanediol, pentanediol, hexanediol, diethylene glycol, propylene glycol, dipropyleneglycol, diols and trioli of polyoxyethylene with an equivalent weight of less than 500, glycerin, trimethylolpropane, pentaerythritol, sucrose, sorbitol, mono-, di - and triethanolamine, Ethylenediamine, toluidines, diethyltoluenediamine and diamines and triamine polyether with an equivalent weight of less than 500.

In addition, there may be used the following optional ingredients: catalysts that promote the formation of urethane linkages, such as metal-containing catalysts, such octanoate tin and dilaurate dibutylamine, catalysts based on tertiary amines, such triethylenediamine, and imidazoles, such dimethylimidazole, and other catalysts, such maleate complex EF the division; stabilizers that inhibit the action of ultraviolet radiation; dyes; additives that inhibit the growth of microorganisms; fillers; internal lubrication for the form (such additives can be used to further facilitate extraction of the obtained materials from the form, but they do not play a big role, as demonstrated in the examples).

The polyols used in the preparation of polyurethane materials and, in particular, elastic foams can contain dispersions or solutions of the additive polymers, or polymers obtained by polycondensation.

Such modified polyols, often referred to as “polymer polyols”, were fully described in the prior art and include products obtained by the in situ polymerization of one or more vinyl monomers, such as styrene and/or Acrylonitrile, in the above-mentioned simple polyether polyols or by carrying out the reaction in situ between a polyisocyanate and an amino and/or hydroxyquinoline compound, such as triethanolamine, in the above-mentioned polyol.

The amount of dispersed polymer may be in the range from 0.1 to 10 wt.% in relation to the number of all ingr the wifi years was described a few ways to get simple polyether polyols with low unsaturation content. These developments have made possible the use of simple polyether polyols relating to the upper end of the range of molecular masses, as currently such polyols can be obtained with acceptable low content of unsaturation. In accordance with the present invention can also be used and polyols with low unsaturation content. In particular, such high molecular weight polyols with low unsaturation can be used to produce flexible foams with high elasticity to bounce and elasticity.

In that case, if you receive a foamed polyurethane, use a foaming agent. Can be used foaming agents known state of the art, such as hydrocarbons, so-called CFC and HCFC, N2, CO2and the water. Most preferably used as the foaming water, possibly in conjunction with CO2. The amount of blowing agent will depend on the desired density. Specialists in the relevant field will be able to determine the number depending on the desired density and foaming agent used. If water is used, its amount is isoimage in car seats and the elements of the situation, the amount of water will be in the range of 0.8 to 5 wt.%; if microactuator elastomer and semi-rigid foam with integral membrane in the General case, use the amount up to 0.8 wt.%, and for hydrophilic foams use more than 5 wt.%, preferably 20-300 wt.% all quantities are defined in relation to the number of all other ingredients.

The polyisocyanates used to obtain polyurethane materials may be selected from aliphatic, cycloaliphatic and alifaticheskih polyisocyanates, in particular diisocyanates, such hexamethylenediisocyanate, isophoronediisocyanate, cyclohexane-1,4-diisocyanate, 4,4-dicyclohexylmethane and m - and p-tetramethylethylenediamine, and in particular from aromatic polyisocyanates, such colordistance (TDI), Finlandization, naphthalenedisulfonate, and most preferably from etilendiamindisuktsinatov (MDI) and their homologues with isocyanate functionality greater than two, such crude MDI and polymeric MDI.

The preferred polyisocyanates are methylene-diphenyldiisocyanate selected from pure 4,4’-MDI isomer mixtures, 4,4’-MDI, 2,4’-MDI and less than 10 wt.% 2,2’-MDI and the e group, such modified uretonimine and/or carbodiimide groups MDI, NCO content which is at least 20 wt.%, and modified urethane groups MDI obtained by the reaction between an excess of MDI and a low-molecular polyol (molecular weight up to 1000), the NCO content of which is at least 20 wt.%.

If necessary, can be used and mixtures of the aforementioned isocyanates.

If necessary, the polyisocyanate may contain dispersed mcevenue particles and/or urethane particles obtained in the usual way, for example, by adding the polyisocyanate small number of isophorondiamine.

The most preferred polyisocyanate is a polyisocyanate containing at least 65, preferably at least 80, and most preferably at least 95 wt.% 4,4’-diphenylmethanediisocyanate or its variants. He may consist essentially of pure 4,4’-diphenylmethanediisocyanate or from mixtures of this diisocyanate with one or more other organic polyisocyanates, especially with other isomers diphenylmethanediisocyanate, for example, 2,4’-isomer, vosmoy of the polyisocyanate composition, containing at least 65 wt.% 4,4’-diphenylmethanediisocyanate. State of the art MDI variants are well known, and for use in accordance with this invention and, in particular, include liquid (at 25 ° C) products obtained by introducing the above-mentioned polyisocyanates uretonimine and/or carbodiimide groups, and such modified carbodiimide and/or uretonimine groups of the polyisocyanate is preferably index NCO, is at least equal to 20 wt.%, and/or as a result of the reaction of such a MDI with one or more polyols with hydroxyl functionality in the range of 2 to 6 and a molecular weight within 62-1000 obtaining a modified MDI, preferably with the value of the index NCO, is at least equal to 20 wt.%. With this most preferred polyisocyanate can be used up to 25 wt.% another MDI; other preferred polyisocyanates are polymeric MDI, colorvision.

The reaction of obtaining polyurethane materials, except hydrophilic foams can be performed when the value of the NCO index in the range of 40-150, and predpochtite is isawanya a large amount of water.

Polyurethane materials can be obtained by one-step method and the method of obtaining the prepolymer. In accordance with the one-stage method in the form serves a polyisocyanate, a simple polyetherpolyols containing at least 50 wt.% oxyethylene groups, and other, optional ingredients, and conducting the reaction in the form; if necessary, a simple polyetherpolyols and other optional ingredients are pre-mixed.

In accordance with the method of obtaining prepolymer conduct preliminary reaction between part or all of a number of reactive towards isocyanate compounds, with the exception of water, if used, and excessive amounts of MDI with obtaining prepolymer containing urethane and isocyanate end groups; for thus obtained prepolymer carry out the reaction with the remainder of the reactive towards isocyanate compounds and/or water. In a particularly preferred embodiment of the present invention is used in the method of the present invention the prepolymer containing urethane and isocyanate end groups, with the value of the NCO index in the range of 3-30, and ucaut elastic polyurethane foam. The prepolymer is a containing urethane and isocyanate end groups of the prepolymer obtained by the reaction of excess MDI containing at least 65 wt.% 4,4’-diphenylmethanediisocyanate or its variant, polyoxyethylene polyoxypropyleneglycol with srednekamennogo nominal functionality in the range of 2-4, with srednegalechny equivalent weight within 750-2500 and content oxyethylene in the range of 60-90 wt.%.

The receipt of such prepolymers and prepolymers state of the art known; see, for example, EP 547765.

For the avoidance of doubt when calculating the number of simple polyetherpolyols content oxyethylene at least equal to 50 wt.%, in the polyurethane material into account also must be taken and the number of such polyol in the prepolymer.

When using such a prepolymer elastic foam produced by the reaction of the prepolymer with water and possibly with an additional simple polyetherpolyols content oxyethylene groups, at least 50 wt.%, and possibly with an additional reaction capable towards isocyanate ingredients and Vela 0.8 to 5 wt.% in relation to the number of all other ingredients. To obtain an elastic foams can be used a small amount, up to 25 wt.% based on the weight of prepolymer, of another MDI; preferably such other polyisocyanates are polymeric MDI and/or colorvision.

Flexible foams may be apparent overall density in the range from 20 to 150 kg/m3(ISO 845).

The method can be implemented in any type of forms known state of the art. Examples of such forms are forms that are used commercially for the manufacture of polyurethane furnishing items, car seats and automotive parts such as steering wheels, armrests and headrests.

Material form can be selected from materials known state of the art, such as metal, for example aluminum, and epoxy resin.

Stage 1 of the method of the invention can be performed in any way known state of the art. The application of an external lubricant to form on the surface of the mold, which will be in contact with the ingredients used to produce material and/or material, includes any method of applying takoi additive or additives, intended to facilitate the subsequent extraction from the mold. Can be used one or more external lubricants for a form or a mixture of external lubricants for the form.

External lubrication for the form can be applied either as such or in the form of a solution, emulsion or dispersion in a liquid.

External lubrication for the form, applied in stage 1, can be applied in one or in several stages. Can be used any external lubrication for the form known state of the art; examples of suitable external lubricant forms are Kluberpur 41-0039 and 41-0061 (both from the company Kluber Chemie), Desmotrol D-10RT from the company Productos Concentrol S. A., Acmosil 180 STBH from Fuller and Johnson Cire 103 from the company Johnson and Johnson.

In addition, surprisingly, it was found that the flexible polyurethane foams obtained as described earlier in this document, and characterized by a relatively high density, detect and extraordinary combination of properties. Therefore, the present invention additionally relates to a molded flexible polyurethane foam with an apparent overall density in the range of 55-150, and preferably 55-100 kg/m3with the coefficient of the oscillations at the resonant frequency in the range of 1.5 to 3.2, when the result of the efforts of the indentation (ILD) 25%, in the range of 15-25 kg, and containing oxyethylene and oxypropylene group with their mass ratio in the range from 1:1 to 8:1 and oxyethylene group of 25-80 wt.%, in the calculation of the mass of foam.

Preferably, such foams resonant frequency would be in the range from 2.6 to 3.4 Hz coefficient of the oscillation at 6 Hz would be less than 1, preferably would be in the range of 0.3 to 0.9, the elasticity would be at least equal to 50%, and preferably 55-80%, and the content oxyethylene groups would be in the range of 35-75 wt.%.

Measurement of the density, the coefficient of the variation in resonance frequency and at 6 Hz, the resonance frequency, firmness and elasticity was carried out as follows:

density, kg/m3: ISO 845,

the coefficient of the oscillations at the resonant frequency: JASO B407-82

the coefficient of the oscillation at 6 Hz: JASO B407-82

resonance frequency: JASO B407-82

hardness, when the ILD 25% kg: ISO 2439: 1977 (E)

elasticity, %: ISO 8307:1990 (E).

This test JASO In 407-82 conducted at 23 ° C and 50% relative humidity, using a sample 4504501000 mm and the indenter related to the type of Tekken, the indenter has a lot of what solanto and polyols, mentioned above in this document.

Foams with a resonant frequency below 3.5 Hz have been described in EP 394487; however, such foams contain a large number oxypropylene groups.

The present invention is further illustrated by the following examples.

Example 1

Molded flexible polyurethane foam was obtained in the metallic form (internal dimensions 30307 cm). On the part of the form, which will be in contact with the ingredients used to obtain a foam and/or foam, first rubbing inflicted drug Johnson Cire 103 (wax, acquired by Johnson and Johnson), and then they sprayed the drug Kluberpur 41-0039 (external lubricant to form acquired company Kluber Chemie).

To obtain the foam used the following ingredients:

- polyol 1: statistical polyoxyethylene polyoxypropyleneglycol with a nominal functionality equal to 3, the content of oxyethylene approximately equal to 77 wt.%, and with a molecular mass of approximately 4000;

- Suprasec MPR from Huntsman Polyurethanes, Suprasec is a trademark of Huntsman ICI Chemicals LLC;

- Niax A1, amine catalyst from OSi; and

is water.

With whom.D. the thionyl chloride was obtained prepolymer. The prepolymer had an index value of NCO, equal to 7.8 wt.%.

86,7 mass parts of this prepolymer and a mixture of 11.8 mass parts of polyol 1, and 0.15 mass parts Niax A1 and 1.38 mass parts of water, manually mixed in a Cup (3000 rpm for 7 seconds) and this mixture was poured into a form; the full amount of the mixture was 495 grams. The form was closed, giving the ingredients a chance to react (mold temperature 45C). 6 minutes later after closing the form was opened and removed the foam.

Immediately after removing the Styrofoam and without carrying out any processing in the form poured the same amount of ingredients (a prepolymer, polyol 1, Niax A1 and water), as mentioned above, the form was closed, giving the ingredients a chance to react, and after the same time of molding the foam from the mold removed; this operation was repeated 50 times. After this experiment was deliberately interrupted. In aggregate, was received 52 sample molded flexible foams; all foams can be removed from the mold without difficulty and without any damage to the foam. The resulting foams had Caius the use of the following ingredients with the difference, that used the form has not been treated with drugs Johnson Cire 103 and Kluberpur 41-0039; the form used the way it was after you have made 52 molded product in example 1.

Ingredients:

- Suprasec 2010 from Huntsman Polyurethanes,

- polyol 1,

2-methylpropan-1,3-diol (Mr),

- Dabco DC-2 (catalyst from Air Products).

Mixed mass of 62.4 parts of polyol 1, 6,9 mass parts of Mr and 0.14 mass parts DC2. This mixture was mixed as in example 1, from 30.5 mass parts Suprasec 2010. The molded material was obtained as in example 1 with the difference that the form is not closed. Received 16 molded without the use of external lubrication for the form. All molded product can be removed easily and without damage to them.

Example 3

The foams obtained in a manner similar to what was used in example 1 had the following physical properties:

apparent total weight: 71 kg/m3(ISO 845),

the coefficient of the oscillations at the resonant frequency: 1,99 (JASO B407-82),

resonance frequency: is 3.08 Hz (JASO B407-82),

hardness (ILD 25%): 20 kg (ISO 2439: 1977 (E)),

elasticity: 64% (ISO 8307: 1990 (E)),

residual Dostoyanie: -1,7% (TSM 7100),

the coefficient of the oscillation at 6 Hz: 0,73 (JASO B407-82).

1. A method of obtaining a polyurethane material in a form that includes the following stages: 1) the application of an external lubricant to form at least those surfaces of the forms that will be in contact with the ingredients used to obtain a polyurethane material, and/or the resulting polyurethane material; 2) feed ingredients used to obtain the polyurethane material into the form; 3) the interaction of the ingredients to obtain a polyurethane material; 4) removing the thus obtained polyurethane material from the mold, and 5) repeat stages 2, 3 and 4 at least 10 times without repeating stage 1, where at least 25 wt.% ingredients used to produce polyurethane material, except water in this calculation, if such is used, composed of simple polyetherpolyols with an average nominal functionality in the range of 2-6, an average equivalent weight in the range 500-5000, and contents of oxyethylene at least 50 wt.%.

2. The method according to p. 1, where stage 2, 3 and 4 repeat at least 15 times without repeating stage 1.

3. The method according to p. 1, where stage 2, 3 and 4 shall poliuretan get by reacting MDI, simple polyetherpolyols and water.

5. The method according to one of paragraphs.1-3, where the ingredients include 1) containing urethane and isocyanate end groups of the prepolymer obtained from excess MDI containing at least 65 wt.% 4,4'-diphenylmethanediisocyanate or its variant with polyoxyethylene/polyoxypropyleneglycol with srednekamennogo nominal functionality in the range of 2-4, with srednegalechny equivalent weight within 750-2500 and content oxyethylene in the range of 60-90 wt.%, moreover, the value of the index NCO of the prepolymer is in the range of 3-15 wt.%, and 2) is water.

6. The method according to one of paragraphs.4 and 5, where the amount of water is in the range of 0.8-5% (based on the quantity of all the ingredients used.

7. The method according to one of paragraphs.4-6, where the number of simple polyetherpolyols containing at least 50% oxyethylene groups, at least 50% (based on the quantity of all the ingredients used.

8. The method according to one of paragraphs.4-7, where the reaction is carried out at the NCO index in the range of 40-150.

9. The method according to p. 8, where the index is in the range of 70-110.

10. The method according to one of paragraphs.1-9, where stage 1 is repeated after one week.

11. Socotora after 8 o'clock

13. Molded flexible polyurethane foam with an apparent overall density in the range of 55-150 kg/m3with the coefficient of the oscillations at the resonant frequency in the range of 1.5 to 3.2, with the resonant frequency at most equal to 3.5 Hz, and hardness (ILD 25%) in the range of 15-25 kg, and containing oxyethylene and oxypropylene group at a mass ratio of from 1:1 to 8:1 and oxyethylene group of 25-80%, based on the weight of the foam.

14. Polyurethane foam under item 13, where the density is in the range of 55-100 kg/m3resonance frequency is in the range from 2.6 mm to 3,4 Hz, the coefficient of the oscillation at 6 Hz is less than 1, the elasticity at least equal to 50% and the content of oxyethylene groups is in the range of 35-75 wt.%.

15. Polyurethane foam according to one of paragraphs.13 and 14, where the coefficient of the oscillation at 6 Hz is in the range of 0.3 to 0.9, and the elasticity is in the range 55-80%.

 

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The invention relates to the rubber industry, in particular to the unvulcanized rubber grease

FIELD: chemical industry; methods of production of a thermosetting elastomers.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the methods of production of a thermosetting polyurethane elastomer and also to the elastomer produced according to the given method. The invention presents the method of production of the polyurethane elastomer having a total apparent density exceeding 150 kg/m3 and providing for an interaction of polyisocyanate and a reactive to isocyanate composition not necessarily at presence of water, according to which the reaction conduct at an isocyanate index of 85-120. At that the polyisocyanate component is composed of: al) 80-100 mass % of diphenylmethanediisocyanate containing at least 40 mass % of 4.4'- diphenylmethanediisocyanate and-or a derivative of the indicated diphenylmethanediisocyanate, which (the derivative) is a may be a liquid at the temperature of 25°C and has NCO value of no less than 20 mass % and a2) 20 mass % of the other polyisocyanate; the reactive to isocyanate composition b) consists of b1) 80-100 mass % of a simple polyol polyester having an average nominal functionality - 2-8, average reactive equivalent weight of 750-5000, an average molecular mass of 2000-12000, the share of oxyethylene - 60-90 mass % and the share of the primary hydroxyl groups of 70-100 mass % calculated for the total number of the primary and the secondary hydroxyl groups in polyol; b2) a reactive to isocyanate extender of the chain in such a quantity, that the ratio of the rigid block makes less than 0.45; and b3) - 20-0 mass % of one or more of other reactive to isocyanate composition excluding water. At that the amount of the polyol of 61) and the reactive to isocyanate composition 63) is calculated from the total amount of the indicated polyol 61) and the composition 63). The invention presents also description of the thermosetting elastomer produced according to the indicated method.

EFFECT: the invention ensures production of a thermosetting polyurethane elastomer.

10 cl, 2 ex

FIELD: chemical industry; other industries; lubricants and the methods for production of the molded plastic articles.

SUBSTANCE: the invention is pertaining to the lubricants used for production of the molded articles out of the plastic material, which reduce the concentration of the undesirable potentially harmful for the people health substances along the edges and on the surface of the molded article, and also to the method of production of the plastic molded articles with the small amount of the harmful substances at usage of such a lubricant. The technical result of the invention is development of the lubricant for the molds, which ensures reduction of the harmful substances concentration in the surface layer of the finished article and at that does not render the negative effect on the mechanical properties of the finished article. The technical result is attained due to the fact, that the lubricant contains, at least, one compound active in respect to the aromatic amines selected from the group, which includes the derivatives of the inorganic and organic acids, metacarbonic acid, sulfur-containing compounds and the organic cyclic compounds with the molecular weight from 200 up to 3000 g/mole.

EFFECT: the invention ensures, that the lubricant for the molds reduces the harmful substances concentration in the finished article surface layer without the negative effect on the mechanical properties of the articles.

2 cl, 16 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: composition contains ceresin, oxidised polyethylene wax, diaminedioleate in the solution of a solvent. The polyethylene wax used has molten viscosity at 140 C° of 25-80 P.s 10-3 and the dispersion stabiliser is selected from non-ionic surfactants. The composition also contains petroleum naphtha, acetone and anthraquinone dye 2g.

EFFECT: combination of components in a defined ratio prevents inflammability, increases homogeneity of the coating, improves anti-adhesion properties, intensifies the drying process and increases scaling resistance.

4 cl, 2 dwg, 4 tbl, 6 ex

FIELD: organic chemistry, polymer materials.

SUBSTANCE: polyester-polyols are obtained by double metalcyanide catalyzed polyaddition of alkylenoxide to starting material containing active hydrogen atoms. Alkylenoxide is continuously fed into reactor during induction period while maintaining constant pressure in reactor.

EFFECT: method for polyester-polyol production with decreased induction time.

2 ex, 1 dwg

FIELD: organic chemistry, in particular polyol composition for cold-cured polyurethane production.

SUBSTANCE: claimed composition contains (pts mass): polyethertriol or mixture of polyethertriol with molecular weight of 4500-6500 and average hydroxyl functionality of 3 - 100; ethylene glycol - 3.5-6.2; 1-4-butandiol - 3,5-8,0; triethylene diamine - 0.53-0.65; water - 0.25-0.50; organosilicate foam regulator - 0.002-0.004; and high boiling by-product from isoprene production based on alkyl- and oxyalkyl-substituted dioxacyclanes (e.g., 1,3-dioxane containing 1-4 mass % of hydroxyl groups) as organic filler - 2-100. Said filler may be used in mixture with oil plasticizer. Polyurethane obtained according to present method has Shore A hardness of 20-50, and is useful in automobile industry, and as material for gasket and sealing.

EFFECT: composition for production of polyurethane with increased hardness.

2 cl, 1 tbl, 3 ex

FIELD: polymer materials.

SUBSTANCE: polyurethane resin is a product of reaction of at least one diisocyanate component and isocyanate-reactive components having first group of at least one polyol, second group of at least one polyol, and third group of at least one polyol, at least one amine, and, additionally, reaction-stopping agent, all polyols of the first group having average molecular mass between 1000 and 10000 g/mole, those of second group having average molecular mass between above 10000 and 20000 g/mole, and those of third group having average molecular mass equal to or higher than 800 g/mole. Ratio of diisocyanate component to isocyanate-reactive components is selected such that all isocyanate groups are present as products of reaction with isocyanate-reactive functional groups. Resin is used as film-forming binder in coating compositions, in particular in printing inks for printing on polyolefin substrates. Printing ink is preferably used for manufacturing printed layered articles.

EFFECT: increased gluing ability and heat resistance of ink laid on plastic substrate.

41 cl, 2 tbl, 12 ex

FIELD: polymer production.

SUBSTANCE: polyol polyethers are prepared by cycle-cleaving polymerization of ethylene oxide and at least one alkylene oxide having at least three carbon atoms in molecule and attachable to H-functional initiator in presence of catalyst. H-functional initiator binds up to 40% (based on the weight of final polyol polyether) of ethylene oxide or mixture thereof with aforesaid alkylene oxide with at least 98 wt % ethylene oxide in presence of catalyst, which is at least one basic compound. To thus obtained polyol polyether, at least one alkylene oxide as defined above or mixture of ethylene oxide with the latter containing up to 20 wt % ethylene oxide is chemically added using as catalyst at least one metal cyanide-based compound.

EFFECT: enabled preparation of polyol polyethers with high level of ethylene oxide and low hydroxyl number.

3 cl, 3 tbl, 6 ex

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