Very soft polyurethane elastomer

FIELD: polymer production.

SUBSTANCE: invention relates to process of producing elastomeric polyurethane material having Shore hardness up to 5 (DIN 53505), density 500 kg/m3 or higher (DIN 53420), compressive load (40%) deflection 600 kPa or less (DIN 53577), and elasticity 25% or less (ISO 8307). Process is accomplished by interaction of (i) polymethylene-polyphenylene-polyisocyanate with average isocyanate functionality 2.4 or more; (ii) polyol with average equivalent mass at least 500 and average nominal hydroxyl functionality 2-4; (iii) polyoxyalkylenemonool with nominal hydroxyl functionality 1 and average equivalent mass at least 500; and (iv) optional additives and auxiliary substances known per se in amount less than 5%. Reaction is carried out at index 90-110 and equivalent amount of polymer (iii) lies within a range of 25-80% based on accessible NCO equivalents. Elastomeric polyurethane material accordingly obtained is a soft gel-like material showing some degree of tackiness. Advantageously, this material is obtained using as little additives and auxiliary substances as possible, which results in reduced content of washed out products and residual reactive group in elastomeric polyurethane material. The latter can be employed in vehicle interior objects such as elbow-rests and instrumentation panels, in bicycle sittings, and in mouse tappets.

EFFECT: improved consumer's quality of elastomers.

1 tbl, 12 ex

 

The present invention relates to elastomeric polyurethane material and to a method for producing such materials. More specifically the present invention relates to very soft elastomeric polyurethane material and to a method for producing such material using monooly.

JP-07-324161 describes the use of polyoxyalkylene as a plasticizer in obtaining newspring polymer with improved vibration isolation characteristics in a certain temperature range.

US 3875086 describes the preparation of solid elastomers as a result of the reaction between polyisocyanate, a polyol and an agent of an open circuit on the basis of simple monohydroxylated that allows you to achieve softening of the elastomer. The resulting elastomers contain a large amount of filler.

WO 01/57104 describes how to obtain viscoelastic polyurethane foam using the low molecular weight polyols and monooly.

US 4863994 describes obtaining elastomers using a small number of polyoxyalkylene. Manual is used to obtain single-phase low-viscosity mixture of polyols used.

The present invention relates to a method for producing an elastomeric polyurethane material as a result of the reaction between 1) polymethylenepolyphenylisocyanate with the medium is nd isocyanate functionality, 2.4 or higher, and preferably of 2.5-3.2; 2) a polymeric polyol with an average equivalent weight of at least 500 and preferably 700-2000, and an average nominal hydroxyl functionality equal to 2-4, preferably 2; 3) polymer, which is polyoxyalkylene with a nominal hydroxyl functionality equal to 1, and an average equivalent weight of at least 500 and preferably 500-3000; 4) possibly with the use of additives and auxiliary substances, known in themselves, where the reaction is carried out at an index of 90-110, and preferably 98-102 and an equivalent amount of polymer 3) is in the range of 25-80%, preferably 35-70% of the available NCO equivalents.

In addition, described elastomeric polyurethane material obtained as described above.

Another in addition is described elastomeric polyurethane material with a density equal to 500 kg/m3or more deflection under the action of the compressive load at 40% of 600 kPa or less, elasticity, equal to 25% or less, and the material preferably does not contain a plasticizer, non-polymer 3). The materials are very soft material that can be used in the interior of the transport/vehicles, such as armrests and instrument panel; seat bike accelerates then the Dov and mopeds and mouse pads and supports for arms for computers. In addition, the materials exhibit adhesive properties.

In the context of the present invention, the following terms shall have

the following value:

1) isocyanate index or NCO-index or the index:

the ratio of NCO groups to the number of reactive towards isocyanates of hydrogen atoms present in the composition, expressed as a percentage:

[NCO] x 100< / br>
[active hydrogen]
(%)

In other words, the NCO-index expresses the percentage of isocyanate actually used in the composition relative to the amount of isocyanate theoretically required for the reaction used in the composition of a number of reactive towards isocyanates hydrogen atoms.

It should be noted that the isocyanate index in accordance with its use, adopted in this document is considered from the point of view of the actual polymerization process, leading to the elastomer, with the inclusion of the isocyanate ingredient or ingredients, reactive towards isocyanates;

2) the expression "reactive towards isocyanates hydrogen atoms" in accordance with its use, adopted in this paper for the calculation of the isocyanate index, the relative is raised to the full amount of the active hydrogen atoms in hydroxyl and amine groups, present in the reaction compositions; this means that for the calculation of the isocyanate index in the actual polymerization process one hydroxyl group is considered as a group, containing one reactive hydrogen atom, one primary amino group is considered as containing one reactive hydrogen atom and one water molecule is considered as containing two active hydrogen atom;

3), the reaction system: a combination of components, where the polyisocyanates contain one or more containers separately from reactive towards isocyanate components;

4) the expression "polyurethane material" in accordance with its use, adopted herein, refers to a porous or non-porous materials obtained by the reaction between polyisocyanates and compounds containing reactive towards isocyanates hydrogen atoms, optionally with the use of foaming agents, and may include a porous products obtained with water as reactive foaming agent (with the inclusion of the reaction between water and isocyanate groups, leading to the urea linkages and carbon dioxide and the formation of polyurethane foams);

5) the term "average nominal hydroxyl is Naya functionality in accordance with its use, adopted herein, indicates srednekamennogo functionality (number of hydroxyl groups per one molecule) of the polyol or polyol as one of the songs on the assumption that this value represents srednekamennogo functionality (number of active hydrogen atoms per molecule) of the initiator (s)used in their preparation although in practice it will often be somewhat less because of the presence of some terminal unsaturation;

6) the term "average" means srednesemennyh unless stated other;

7) the term "proportion of the hard blocks" refers to the amount (mass parts) materials polyisocyanate + reactive towards isocyanate compound with a molecular weight of 500 or less (where introduced in the polyisocyanates polyols with a molecular weight greater than 500, are not taken into account)divided by the amount (mass parts) of all the materials used in the polyisocyanate + reactive towards isocyanate compound.

The polyisocyanate used in the invention, is widely known at the present level of technology as diphenylmethanediisocyanate (MDI) including homologues of diphenylmethanediisocyanate with isocyanate functionality equal to 3 or more (Polimeri unpretentiously); such polyisocyanates known state of the art as polymeric or crude MDI.

It is a result of vosganian mixture of polyamines obtained by acid condensation of aniline and formaldehyde.

Getting as poliamidowych mixtures and polyisocyanate mixtures is well known. The condensation of aniline with formaldehyde in the presence of strong acids, such as hydrochloric acid, yields a reaction product containing diaminodiphenylmethane together with polymethylenepolyphenylisocyanate with higher functionality, the specific composition will be known to depend, inter alia, on the ratio aniline/formaldehyde. The polyisocyanates obtained vosganian poliamidowych mixtures, and different proportions of diamines, triamines and polyamines of higher functionality will result in a corresponding proportions of diisocyanate, triisocyanate and polyisocyanates of higher functionality. Corresponding proportions of diisocyanate, triisocyanate and polyisocyanates of higher functionality in the compositions of the crude or polymeric MDI determine the average functionality of the compositions, i.e. the average number of isocyanate groups per one molecule. In warer is of the original proportions of the reactants can be varied, the average functionality of the polyisocyanate compositions. Isocyanate functionality can be improved with the removal of MDI. Average isocyanate functionality preferably is in the range of 2.5-3.2. NCO-value data for polymeric or crude MDI, at least, equal to 29% of the mass. Polymeric or crude MDI containing diphenylmethanediisocyanate, and the rest of the songs are polymethylenepolyphenylisocyanate with functionality greater than two, together with by-products formed during the receipt of such polyisocyanates in the result of vosganian.

Polymer polyol 2)used in the invention can be any representative polyols or mixtures thereof, used in the preparation of polyurethanes having an average hydroxyl equivalent weight of at least 500 and preferably 700-2000, and an average nominal hydroxyl functionality equal to 2-4, and preferably 2. These polyols can be polyether polyols based on ethers, polyether polyols based on esters, polyethylenepolyamine based esters, policyethiopian on the basis of simple thioethers, polycarbonatediol, politicalmilitary, poliolefinujemy and the like.

The polyether polyols based on ethers that can be used include products obtained by p is liberizatsii cyclic oxide, for example, ethylene oxide, propylene oxide, butilenica or tetrahydrofuran, in the presence of polyfunctional initiators. Suitable connections initiators contain several active hydrogen atoms and include water, butanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropyleneglycol, ethanolamine, diethanolamine, triethanolamine, toluidines, diethyltoluenediamine, phenyldiamine, diphenylmethylene, Ethylenediamine, cyclohexanediamine, cyclohexanedimethanol, resorcinol, bisphenol a, glycerol, trimethylolpropane, 1,2,6-hexanetriol and pentaerythritol. You can use a mixture of initiators and/or cyclic oxides.

Particularly suitable polyether polyols based on ethers include polyoxypropylene and-trioli and poly(oxyethylenenitrilo)diols and-trioli obtained as a result of simultaneous or successive addition to the two - or trifunctional initiators ethylene and propylenoxide that is fully described in the prior art. Preferred copolymers containing oxyethylene 5-90% of the mass. based on the weight of polyol, where these polyols can be block copolymers, statistical/block-copolymers or statistical copolymers. Mixtures of the above-mentioned diols and triolo may be particularly suitable. Other especially in the tee suitable polyether polyols based on ethers include polytetramethylene, obtained by polymerization of tetrahydrofuran.

The polyether polyols based on esters that can be used off having a terminal hydroxyl group of the products of reaction between polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentylglycol, 1,6-hexanediol, cyclohexanedimethanol, glycerin, trimethylolpropane, pentaerythritol or polyether polyols on the basis of simple esters or mixtures of such polyhydric alcohols, and polybasic carboxylic acids, in particular dibasic carboxylic acids or their derivatives, forming an ester, for example succinic, glutaric and adipic acids or their dimethyl esters, sabatinovka acid, phthalic anhydride, tetrachlorophthalic anhydride or terephthalate or mixtures thereof. It is also possible to use polyesters obtained by polymerization of lactones, such as caprolactone, in cooperation with the polyol, or hydroxycarbonic acids, such as gidroksicarbonata acid.

Poliefirimidnoy based esters can be obtained by introducing into the mixture to obtain polyesters aminoalcohols, such as ethanolamine.

Politicality on the basis of simple thioethers, which can be used include products obtained by condensing thiodiglycol, either one or with other glycols, acceleratedly, dibasic carboxylic acids, formaldehyde, aminoalcohols or aminocarbonyl acids.

Polycarbonatediol that can be used include products obtained by the reaction between dialami, such as 1,3-propandiol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol or tetraethylene glycol, and dellcorporate, such as diphenylcarbonate, or phosgene.

Politicalpower that can be used include those that are a result of the reaction between glycols, such as diethylene glycol, triethylene glycol or hexanediol, and formaldehyde. Suitable Polyacetals can also be obtained by the polymerization of cyclic acetals.

Suitable paleoseismology include having a terminal hydroxyl group of Homo - and copolymers of butadiene and appropriate polisiloksanovoy include polydimethylsiloxanes and-trioli. You can also use a mixture of polyols.

The most preferred polyols are polyether polyols on the basis of simple esters with a nominal hydroxyl functionality of 2, in particular polyoxyethylenesorbitan content oxyethylene 5-90% of the mass. based on the weight diol and an average equivalent weight of 700-2000.

Polymer 3, called the th later in this document as the "monorom", you can choose from Manolov with an equivalent weight of at least 500.

The preferred Manorama are polyoxyalkylene with an equivalent weight of 500-3000, such as polyoxypropylene, polyoxyethylene and polyoxyethylenesorbitan. Such monooly obtained alkoxysilane monohydroxy alcohol. Monohydroxy alcohols can be selected from branched and unbranched aliphatic, cycloaliphatic and aromatic alcohols, preferably containing 1-20 carbon atoms and more preferably containing 1 to 8 carbon atoms. Examples of aliphatic alcohols are methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, tert-butanol and various isomers pentalofos alcohol, hexyl alcohol, oktilovom alcohol (for example, 2-ethylhexanol), danilovogo alcohol, delovogo alcohol, lauric alcohol, miristinovoi alcohol, cetyl alcohol and stearyl alcohol, and fatty alcohols and alcohols, waxes, which are found in nature, or which can be obtained by hydrogenation of naturally occurring carboxylic acids. The cyclohexanol and its homologues are examples of cycloaliphatic alcohols. You can also use and aromatic hydroxyl compounds such as phenol, cresol, thymol, Charvak the ol, benzyl alcohol and phenylethanol. The most preferred of the above-mentioned aliphatic alcohols containing 1-4 carbon atoms. If the polymer polyol 2) will polyetherpolyols on the basis of simple esters, the polymer polyol (2) and the polymer 3) can be obtained together, for example, as a result of oxyalkylene mixtures of one or more polyhydric alcohols and one or more monohydroxy alcohols. In the most convenient case of polymer polyol (2) and the polymer 3) receive separately and mixed when used.

In addition, you can use additives and excipients known in themselves and are usually used in the preparation of polyurethanes. Examples of such additives and auxiliary substances are foaming agents, extension cords, chains, staplers, catalysts, promoting the formation of urethane and/or urea groups, mould release preparations, plasticizers, pigments, fillers, like (hollow) microspheres, calcium carbonate, barium sulfate, carbon black, colloidal silicon dioxide and nanoglide; dyes, flame retardants, additives, reduces smoke, antimicrobial agents, antioxidants and polymer superabsorbents. Additives and auxiliary substances are defined as any ingredient used in a manner different from MDI, polymeric polyol and m is moola.

In the General case of total used amount of additives and auxiliary substances less than 20% of the mass. based on the weight of MDI, polymeric polyol 2 and polymer 3), and preferably less than 10 wt. -%, and more preferably less than 5% of the mass. and most preferably less than 2% of the mass. If you use the foaming agent can be selected from those known at the present level of technology. It is preferable to use water. In order to obtain elastomeric material with a density equal to 500 kg/m3or more, the amount of water is less than 1% of the mass. in calculating the masses polyisocyanate, polymer polyol (2) and polymer 3), next in this document called "the 3 essential ingredients". Preferably the foaming agent is not used.

Extension cords chains are reactive towards isocyanate compounds containing 2 reactive hydrogen atoms and characterized by a molecular weight of less 1000 such as ethylene glycol, butanediol and polyethylene glycol with a molecular weight of less 1000. If they use the number of extension circuits will not exceed 5% of the mass. in the calculation of the mass of the 3 essential ingredients. It is preferable not to use them.

The staplers are reactive towards isocyanate compounds containing 3 or the more reactive hydrogen atoms and characterized by the equivalent mass, least 500, similar to glycerol, trimethylolpropane, pentaerythritol, sucrose and sorbitol. If they use the number of staplers will not exceed 5% of the mass. in the calculation of the mass of the 3 essential ingredients. It is preferable not to use them.

Examples of the above-mentioned catalysts are tertiary amines and ORGANOMETALLIC compounds known state of the art, such as those described in the ICI Polyurethanes Book, 2ndedition, 1990, by G. Woods, pages 41-45. If they use their number will not exceed 2% of the mass. in the calculation of the mass of the 3 essential ingredients. Their number is preferably in the range of 0.01-1% wt. in the calculation of the mass of the 3 essential ingredients.

Plasticizers can be selected from those known at the present level of technology, such esters obtained from polybasic (preferably dibasic) carboxylic acids and monohydroxy alcohols. Examples of polybasic carboxylic acids are: succinic acid, isophthalic acid, trimellitate acid, phthalic anhydride, the anhydride tetrahydrophthalic acid anhydride hexahydrophthalic acid anhydride andmathematical acid, glutaric acid anhydride, maleic acid anhydride, fumaric acid and dimeric and trimeric fatty acids such as ainova acid), which can be mixed with Monomeric fatty acids. Suitable monohydroxy alcohols are branched and unbranched aliphatic alcohols containing 1-20 carbon atoms, such as methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, tert-butanol and various isomers pentalofos alcohol, hexyl alcohol, oktilovom alcohol (for example, 2-ethylhexanol), danilovogo alcohol, delovogo alcohol, lauric alcohol, miristinovoi alcohol, cetyl alcohol and stearyl alcohol, and fatty alcohols and alcohols, waxes, which are found in nature, or which can be obtained by hydrogenation of naturally occurring carboxylic acids. The cyclohexanol and its homologues are examples of cycloaliphatic alcohols. You can also use and aromatic hydroxyl compounds such as phenol, cresol, thymol, carvacrol, benzyl alcohol and phenylethanol. An example of a widely used plasticizer is dioctylphthalate.

As also suitable plasticizers and esters of phosphoric acid, obtained using the above-mentioned branched and unbranched aliphatic, cycloaliphatic and aromatic alcohols. If appropriate, you can also use and phosphates, halogenated alcohols, such as trichlorethylene is. Such phosphates, halogenated alcohols particularly advantageous in that they also give the final flame retardant properties. Of course, you can also use a mixture of esters obtained from the above-mentioned alcohols and carboxylic acids.

You can also use the so-called polymeric plasticizers. Examples of such commercial polymeric plasticizers are polyesters derived from adipic acid, sabatinovka acid or phthalic acid. As plasticizers can also be used phenylsulfonyl, for example phenylpropanolamine.

If they use their number is less than 5 wt. -%, and preferably less than 2% of the mass. in the calculation of the mass of the 3 essential ingredients. One of the surprising discoveries of the present invention was that of very soft elastomeric materials of good quality can be obtained without the use of plasticizers, non-polymer 3). The advantage of this is that no leaching of material such other plasticizers may not take place; as stated, this washout is the cause of certain health problems. To prevent leaching further reduces the degree of tarnishing the Windows of the car, if the elastomeric material BU what should be used in the interior of the car. In addition, the prevention of such leaching allows to achieve a better quality (softness) of the material over time. Therefore, it is most preferable not to use any other plasticizer, non-polymer 3).

Materials produced by mixing the ingredients, after which they leave for the passage of reaction between them. It may be advantageous to pre-mix only the amount of polyol 2), polymer 3) and, in the case of their use, additives and auxiliary substances, followed by stirring the mixture with a polyisocyanate, and then the mixture is left for the passage of reaction.

The materials can be obtained in accordance with the method of obtaining prepolymer or one-step method. The preferred single-stage method. The materials can be obtained in an open container at the conveyor belt and in an open or closed form. Upon receipt in the form of a material can be obtained in accordance with the method of the reaction injection molding and method of injection molding without pressure.

The resulting materials are characterized by 1) a density equal to 500 kg/m3or more (DIN 53420); preferably, they do not churn, 2) the deflection under the action of the compressive load at 40% (DIN 53577) 600 kPa or less, and preferably 10-300 kPa, 3) elasticity (ISO 8307)is 25% or less, and preferably 0-15%, and 4) the proportion of the hard blocks in them preferably less than 0,30, and more preferably is in the range from 0.05 to 0.20; preferably these materials do not contain plasticizer, non-polymer 3), and most preferably these materials contain only the catalyst in an amount of 0.01-1% wt. in the calculation of the mass of material.

Elastomeric materials, consistent with the present invention, are soft, gel-like materials having a certain degree of stickiness. Their hardness shore a, preferably at most equal to 5 when measured in accordance with DIN 53505, and more preferably at most equal to 3, and most preferably at most equal to 1. Since the material is most preferable to get as close as possible to the index = 100, and since the material is most preferable to obtain when using a possibly smaller quantities of additives and auxiliary substances, the materials contain a reduced amount of discharge products and reduced the amount of residual reactive groups. At higher index, for example 120, the materials become harder, while a lower index, for example 85, the result is a liquid paste.

The invention is further illustrated by the following examples:

Used ingredients:

1) is olil 1: polyoxyethylenesorbitan with molecular weight of 2000, content oxyethylene approximately 73% of the mass. (all oksietilenom statistically distributed) and the content of the primary hydroxyl of approximately 51%;

2) polyol 2: polyoxyethylenesorbitan with molecular weight of 2300, content oxyethylene equal to 15% of the mass. (all oksietilenom is in the limit position);

3) manual 1: monoethoxylate polypropylenglycol with a molecular weight of 1000;

4) manual 2: monoethoxylate polyoxyethylenesorbitan with a molecular mass of approximately 985, and content oxyethylene approximately 64% of the mass. (all oksietilenom statistically distributed);

5) manual 3: monoethoxylate polyoxyethylenesorbitan with a molecular mass of approximately 1475, and content oxyethylene approximately 66% of the mass. (all oksietilenom statistically distributed);

6) a polyisocyanate 1: polymeric MDI c NCO value of 30.7% of the mass. and isocyanate functionality of 2.7;

7) a polyisocyanate 2: polymeric MDI c NCO-value 30,35% of the mass. and isocyanate functionality of 2.9;

8) diaminobenzoate as a catalyst in the amount of 0.25% of the mass. in calculating the used amount of diol.

Polyol and manual pre-mixed and then mixed with the polyisocyanate and leave the mixture in an open Rea the traditional Cup for the passage of reaction. Measured/identified the following physical properties:

- contents Mineola, %: equivalent number of Mineola in the form of a percentage of the available number of equivalents of NCO;

- index: calculated;

- the proportion of the hard blocks is calculated;

- stickiness: on the basis of sensory perception;

0 - complete absence of stickiness;

10 is an extremely high stickiness;

the deflection under the action of the compressive load at 40% (CLD), kPa: DIN 53577;

- elasticity, %: ISO 8307.

The results are shown in the following table (machine hours = mass parts):

-
Example123456789101112
Polyol 1, M.Ch.----33,029,7-----39,9
Polyol 2, M.Ch.36,543,339,635,6--36,132,741,336,132,7-
Manual 1, M.Ch.51,9----------
Manual 2, M.Ch.-45,148,752,4--------
Manual 3, M.Ch.----57,1of 60.554,558,049,154,558,050,0
The polyisocyanate 1, M.Ch.-----------the 10.1
The polyisocyanate 2, M.Ch.the 11.6the 11.6the 11.611,79,99,89,59,49,69,59,4-
Contents Mineola,%625458625458545848545846
Index100100100100 100100100100100100100100
The proportion of the hard blocksthe 11.6the 11.6the 11.611,79,99,89,59,49,69,59,4the 10.1
Stickiness256109106626610
CLD568043173817311593311526
ElasticityThe CONCENTRATION isThe CONCENTRATION isThe CONCENTRATION isThe CONCENTRATION is74737735

N.O. = not determined.

1. The method of obtaining elastomeric polyurethane material having a shore hardness And, at most, 5 (DIN 53505)density 500 kg/m3or more (DIN 53420)deflection under the action of the compressive load at 40% (CLD) of 600 kPa or less (DIN 53577) and the elasticity of 25% or less (ISO 8307), by interaction

1) polymethylenepolyphenylisocyanate with an average isocyanate functionality of 2.4 or more,

2) a polymeric polyol with an average equivalent weight of at least 500 and an average nominal hydroxyl functionality equal to 2-4,

3) polyoxyalkylene with a nominal hydroxyl functionality equal to 1, and an average equivalent weight of at least 500 and

4) optionally using additives and auxiliary substances, known in themselves, in the amount of less than 5 wt.% [based on the weight of MDI, polymeric polyol 2 and polymer 3)], where the reaction is carried out at an index of 90-110, and an equivalent amount of polymer 3) is in the range 25-80% of the available NCO equivalents.

2. The method according to claim 1, where the average isocyanate functionality in the range of 2.5-3.2, polymer polyol 2) is characterized by an average equivalent weight of 700-2000, and an average nominal hydroxyl functionality of 2, polymer 3) is characterized by an average equivalent weight of 500-3000, the quantity of additives and auxiliary substances is less than 5 wt.% based on the weight of MDI, polymeric polyol 2 and polymer 3), and where the index is equal 90-110, and an equivalent amount of polymer 3) is in the range 35-70% of the available NCO equivalents.

3. The method according to claim 1 is 2, where as plasticizer use only the polymer 3).

4. The method according to claims 1 and 2, where the catalyst is used in an amount of 0.01-1 wt.% based on the weight of MDI, polymeric polyol 2 and polymer 3).

5. The method according to claims 1 and 2, where the polymer polyol 2) represents a simple polyetherdiol, and polymer 3) represents polyoxyalkylene.

6. The method according to claims 1 and 2, where the index is within 98-102.

7. The method according to claims 1 and 2, which use less than 2 wt.% additives and auxiliary substances [based on the weight of MDI, polymeric polyol 2 and polymer 3)].

8. The method according to claims 1 and 2, where the material is not foamed, the deflection under the action of compressive load equal 10-300 kPa and elasticity equal 0-15%.

9. The method according to claims 1 and 2, where the proportion of the hard blocks is in the range from 0.05 to 0.20, and the shore hardness And at most equal to 3 (DIN 53505).

10. The method according to claims 1 and 2, where the plasticizer is used only polymer 3), the catalyst is used in an amount of 0.01-1 wt.% based on the weight of MDI, polymeric polyol 2 and polymer 3), polymer polyol 2) represents a simple polyetherdiol, and polymer 3) represents polyoxyalkylene, the index is within 98-102 and use less than 2 wt.% additives and auxiliary substances [based on the weight of MDI, polymeric polyol 2 and polymer 3)].



 

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FIELD: polymer production.

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EFFECT: increased strength of foamed material and reduced content of diisocyanate monomer therein.

2 cl, 2 tbl, 4 ex

FIELD: polymer materials.

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FIELD: chemistry of polymers, chemical technology.

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11 cl, 7 tbl, 8 ex

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5 cl, 3 tbl

FIELD: polymers, covering compositions.

SUBSTANCE: invention relates to photoactivating aqueous-base covering composition. The proposed composition comprises the following components: a)(meth)acryloyl-functional polyurethane dispersion wherein this (meth)acryloyl-functional polyurethane comprises from 5 to 18 weight % of alkylene-oxide groups and (meth)acryloyl functionality represents a value in the range from 2 to 40, and b) UV-initiating agent. The presence of reactive diluting agent in the covering composition is preferable. (Meth)acryloyl-functional polyurethane can be prepared by carrying out the following interactions: a) at least one organic polyisocyanate; b) optionally, at least one organic compound comprising at least two isocyanate-reactive groups and having an average molecular mass in the range from 400 to 6000 Da; c) at least one isocyanate-reactive and/or isocyanate-functional compound comprising non-ionogenic dispersing groups; d) at least one isocyanate-reactive (meth)acryloyl-functional compound; e) optionally, at least one chain elongating agent comprising active hydrogen, and f) optionally, at least one compound comprising active hydrogen and ionic groups. Aqueous-base covering composition is useful especially for applying as a clear cover. Covers based on the proposed composition show resistance to water, solvents and scratches and flexibility and high adhesion also.

EFFECT: improved and valuable properties of composition.

15 cl, 12 tbl, 17 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to ionomer thermoplastic polyurethane, method for preparation thereof, use of indicated ionomer thermoplastic polyurethane to prepare aqueous dispersions thereof, as well as to a method for preparing aqueous dispersions of ionomer thermoplastic polyurethanes. Ionomer thermoplastic polyurethane is prepared via continuous reaction of (i) 4-50% if diisocyanate; (ii) 35-95% of bifunctional polyatomic alcohol selected from group comprising (a) polycaprolactone with mean molecular mass between 500 and 15000 and general formula I: (I), (b) polyesterdiol with mean molecular mass between 500 and 15000 and general formula II: (II), (c) polyesterdiol selected from polypropylene glycol, polytetramethylene glycol, and polyethylene glycol, (d) polycarbonatediol with mean molecular mass between 500 and 15000 and general formula III: (III), and (e) copolymers obtained from two bifunctional polyatomic alcohol from groups (a), (b), (c), or (d); (iii) 0.2-16% of chain-elongation glycol of general formula IV: (IV); and (iv) 0.2-3% of chain-elongation anionic-type ionomer glycol of general formula V: (V).

EFFECT: enabled preparation of ionomer polyurethane suitable for being stored in solid form for subsequent preparation of aqueous dispersions of thermoplastic polyurethanes appropriate as industrial adhesives and coating materials for flexible and rigid substrates.

34 cl, 2 tbl, 10 ex

The invention relates to rigid polyurethane foams and methods for their preparation using a mixture of polyols

FIELD: polymer materials.

SUBSTANCE: invention relates to ionomer thermoplastic polyurethane, method for preparation thereof, use of indicated ionomer thermoplastic polyurethane to prepare aqueous dispersions thereof, as well as to a method for preparing aqueous dispersions of ionomer thermoplastic polyurethanes. Ionomer thermoplastic polyurethane is prepared via continuous reaction of (i) 4-50% if diisocyanate; (ii) 35-95% of bifunctional polyatomic alcohol selected from group comprising (a) polycaprolactone with mean molecular mass between 500 and 15000 and general formula I: (I), (b) polyesterdiol with mean molecular mass between 500 and 15000 and general formula II: (II), (c) polyesterdiol selected from polypropylene glycol, polytetramethylene glycol, and polyethylene glycol, (d) polycarbonatediol with mean molecular mass between 500 and 15000 and general formula III: (III), and (e) copolymers obtained from two bifunctional polyatomic alcohol from groups (a), (b), (c), or (d); (iii) 0.2-16% of chain-elongation glycol of general formula IV: (IV); and (iv) 0.2-3% of chain-elongation anionic-type ionomer glycol of general formula V: (V).

EFFECT: enabled preparation of ionomer polyurethane suitable for being stored in solid form for subsequent preparation of aqueous dispersions of thermoplastic polyurethanes appropriate as industrial adhesives and coating materials for flexible and rigid substrates.

34 cl, 2 tbl, 10 ex

FIELD: polymers, covering compositions.

SUBSTANCE: invention relates to photoactivating aqueous-base covering composition. The proposed composition comprises the following components: a)(meth)acryloyl-functional polyurethane dispersion wherein this (meth)acryloyl-functional polyurethane comprises from 5 to 18 weight % of alkylene-oxide groups and (meth)acryloyl functionality represents a value in the range from 2 to 40, and b) UV-initiating agent. The presence of reactive diluting agent in the covering composition is preferable. (Meth)acryloyl-functional polyurethane can be prepared by carrying out the following interactions: a) at least one organic polyisocyanate; b) optionally, at least one organic compound comprising at least two isocyanate-reactive groups and having an average molecular mass in the range from 400 to 6000 Da; c) at least one isocyanate-reactive and/or isocyanate-functional compound comprising non-ionogenic dispersing groups; d) at least one isocyanate-reactive (meth)acryloyl-functional compound; e) optionally, at least one chain elongating agent comprising active hydrogen, and f) optionally, at least one compound comprising active hydrogen and ionic groups. Aqueous-base covering composition is useful especially for applying as a clear cover. Covers based on the proposed composition show resistance to water, solvents and scratches and flexibility and high adhesion also.

EFFECT: improved and valuable properties of composition.

15 cl, 12 tbl, 17 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to polyurethane-polyol compositions comprising product of reaction of a polyol and Herbert alcohol, the two containing In average 12 carbon atoms. Preferred polyols are α,β-diols and α,β-diols. Polyurethane-polyol compositions exhibit very low viscosity and are particularly suitable in coating compositions with very low content of volatile organics. Hardened coating obtained from claimed compositions ensure high resistance to cracking and can be applied on various substrates such as metal, plastic, wood, glass, ceramics.

EFFECT: increased strength of coatings on a variety of substrates.

5 cl, 3 tbl

FIELD: composite materials.

SUBSTANCE: in particular, invention relates to employment of polyisocyanates compositions as binders for composites containing lignocellulose fibers such as oriented wood chipboard.

EFFECT: improved performance characteristics regarding detachment of product as compared to conventional polyisocyanates employed for binding lignocellulose material.

11 cl, 7 tbl, 8 ex

FIELD: polymer production.

SUBSTANCE: invention relates to process of producing elastomeric polyurethane material having Shore hardness up to 5 (DIN 53505), density 500 kg/m3 or higher (DIN 53420), compressive load (40%) deflection 600 kPa or less (DIN 53577), and elasticity 25% or less (ISO 8307). Process is accomplished by interaction of (i) polymethylene-polyphenylene-polyisocyanate with average isocyanate functionality 2.4 or more; (ii) polyol with average equivalent mass at least 500 and average nominal hydroxyl functionality 2-4; (iii) polyoxyalkylenemonool with nominal hydroxyl functionality 1 and average equivalent mass at least 500; and (iv) optional additives and auxiliary substances known per se in amount less than 5%. Reaction is carried out at index 90-110 and equivalent amount of polymer (iii) lies within a range of 25-80% based on accessible NCO equivalents. Elastomeric polyurethane material accordingly obtained is a soft gel-like material showing some degree of tackiness. Advantageously, this material is obtained using as little additives and auxiliary substances as possible, which results in reduced content of washed out products and residual reactive group in elastomeric polyurethane material. The latter can be employed in vehicle interior objects such as elbow-rests and instrumentation panels, in bicycle sittings, and in mouse tappets.

EFFECT: improved consumer's quality of elastomers.

1 tbl, 12 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing stable aqueous dispersions of polycarbodiimide for using as a cross-linking agent and no containing organic solvents. Method is realized by carrying out interaction of polyisocyanate in the presence of 0.5-3% of catalyst in reaction for formation of carbodiimide to form polycarbodiimide intermediate substance at 120-1800C for aliphatic polyisocyanate and at 80-1200C for aromatic polyisocyanate up to preparing 5-10% of NCO wherein polyisocyanate is represented by toluene-2,4-diisocyanate, toluene-2,6-diisocyanate or their mixture, diphenyl-4,4'-diisocyanate, 1,4-phenylenediisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, 1,6-hexyldiisocyanate, 1,4-cyclohexyldiisocyanate, norbornyldiisocyanate or their mixture. Then method involves carrying out break and/or elongation of polycarbodiimide chain of intermediate substance by addition of equivalent compound comprising hydrophilic group and one or more amino- and/or hydroxyl functional groups during formation of polycarbodiimide intermediate substance or after formation of polycarbodiimide at temperature 70-1000C for aliphatic polycarbodiimide intermediate substance and at temperature 40-700C for aromatic polycarbodiimide intermediate substance. Then reaction in mixture is carried out up to disappearance of isocyanate functional group wherein a hydrophilic group-containing compound is represented by polyethoxymono- or diol, polyethoxy/polypropoxymono- or diol, polyethoxymono- or diamine, polyethoxy/polypropoxymono- or diamine, diol or diamine with polyalkoxy-containing by-side chain, hydroxy- or aminoalkylsulfonate, or dialkylaminoalkyl alcohol or -amine, or their mixture. Prepared compound is dispersed in water at temperature 40-1000C at pH 11-14 by addition of a base and/or buffer to water used for dispersing, and/or to prepared aqueous dispersion wherein a base is represented by alkaline metal hydroxide, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, or trialkylamine, or trialkylamine containing hydroxy-groups, and wherein buffer is represented by usually used buffer with effective pH value 11-14. Polycarbodiimide dispersions prepared by above described method are stable for at least some weeks at temperature 500C. Also, invention describes a covering mixture comprising polycarbodiimide dispersions and solidified material prepared by applying abovementioned covering mixture on substrate and evaporation of water.

EFFECT: improved preparing method of dispersions.

3 cl, 2 tbl, 15 ex

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