Ionomer thermoplastic polyurethane

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

 

This invention relates to a new ionomer thermoplastic polyurethane, which can be obtained and used in solid form and which can be easily transformed in an aqueous dispersion with the ionic nature.

Among thermoplastic polyurethanes are those commonly referred to as the main TPU - known for some time dispersible in water ionomer type is based on the introduction of monomers having able to ionize the group as a cation, for example, can neutralized through or able to become Quaternary tertiary amino, or anionic, for example, a free carboxyl or sulfopropyl capable neutralized through the grounds in the aquatic environment.

In U.S. patent No. 3479310, published in 1969, described the specified type TPU and a wide range of monomers, including capable of ionization components, although specific examples of TPU, including blocks only monomers from groups of cationic character, mainly N-methyldiethanolamine.

In the above-mentioned patent States that the monomer containing an ionic group can be introduced in the precursor polymer, which is then dispersed in the aqueous medium by neutralizing agent in order to conduct his final polymerization. Also state that you can get a lot of polyurethane, and after the floor is merisalo add miscible with water, an organic solvent, for example acetone, and dispersing the dissolved mass in water with a neutralizing agent in order to obtain a ready to use aqueous dispersion TPU after removal of the organic solvent.

Water dispersion of ionomer TPU have numerous applications, among which we can mention the use of them as industrial adhesives, for example, in the Shoe industry, as well as their use as coating materials for flexible foundations, such as fabrics and materials that mimic the skin, and hard bases, for example, in industrial paints and varnishes.

In U.S. patent No. 3412054 described polyurethanes, which can dissolve in water, obtained by reaction of polyisocyanates with gidroksilirovanii carboxylic acids of the formula

where R is hydrogen, hydroxymethyl or alkyl containing carbon atoms to 20, and preferred was mentioned 2,2-di(hydroxymethyl)propionic acid, also known as 2,2-dimethylolpropionic acid, or simply dimethylolpropionic acid or DMPC.

These monomers is introduced into the polyurethane by conventional processes described in the mentioned patent; at the final stage of the process enter the water and a neutralizing agent to obtain aqueous dispersions.

In U.S. patent No. 4956438 described that monomial is R, containing ionic groups is included in the precursor polymer, neutralized in an aqueous medium and then transferred to the elongation of the polymer chain in the specified environment. In other words, the described process leads directly to the receiving water dispersion TPU.

This way, with the various options is what is usually used when obtaining dispersions TPU, for example, the method proposed in U.S. patent No. 5155163 and describes the following process:

1. Preparation of the precursor polymer by reaction of the diisocyanate, the solvent is a polyhydric alcohol - and DMPK.

2. Partial extension of the precursor polymer diatomic alcohol with a low molecular weight (if desired).

3. Neutralization of the carboxyl groups of the base.

4. The dispersion or emulsification of the polymer in water.

5. Final elongation chain of the diamine with a low molecular weight.

6. Regulation of the ratio of the solids and the viscosity of the dispersion.

Thus, this method indicates that the water dispersion of ionomer TPU obtained in the overall process of polymerization or at the end of the stage, or during the transfer of the dispersion in water and neutralization at the stage of the precursor polymer to the final elongation of the polymer chains; the latter option is the most widespread the United way.

This assumes that the user is applying a water dispersion of TPU, and he usually does not coincide with the manufacturer of the polymer, must acquire and store the prepared aqueous dispersion, which typically have large quantities of water, usually more than 50% wt., that makes transportation and storage more expensive and reduces the stability of the polymer.

In U.S. patent 4276044 described the decision to eliminate this drawback, which is to obtain aqueous solutions TPU (no dispersion), which is applicable only in case in contrast to the numerous applications of TPU in the form of an aqueous dispersion, namely in the final finishing of fabrics. In the mentioned patent describes polymers derived from the following monomers:

a) an organic diisocyanate with a molecular mass of 160-300,

b) tri - and/or tetraethyleneglycol,

c) possibly, other glycols with a molecular mass of 62-200 and

d) glycols with molecular weights below 500 containing carboxyl or sulfopropyl,

in the ratio of equivalents of NCO/OH is less than 1:1, with the carboxyl or sulfopropyl at least partially transferred after the reaction in carboxylate or sulphonate group, and differ in that they contain

e) from 25 to 40% wt. groups, urethane,

f) from 0.03 to 1.5% wt. hydroxyl groups,

g) from 10 to 80 milliequivalents 100 g carboxylat the x or sulphonate groups and

h) from 10 to 40% wt. put three blocks and/or tetraethyleneglycol, or between two urethane groups or urethane group and hydrogen.

These polymers contain a very high proportion of polar carboxyl and/or sulfo and can be directly dissolved in water by adding a rationale for their use in the final finishing of fabrics. This patent indicates that its object - polymers - can be obtained in the form of solidified resin, which is easily soluble in water, which can be stored and delivered to the final user so that the user can prepare an aqueous solution.

It is clear that not only the polymers described in U.S. patent No. 4276044, provide an opportunity to eliminate these drawbacks, though only for TPU, are capable of forming aqueous solutions, and not the variance, and using in this particular case among the numerous applications of the TPU. Therefore, there is still the disadvantage of having to look for alternative solutions that can be used in other applications TPU.

Part of the object of the present invention is a new ionomer thermoplastic polyurethanes (TPU), which can be stored and used in solid form for further use when floor the treatment of aqueous dispersions of TPU, having use as industrial adhesives and materials for coatings on flexible and rigid foundations.

Part of the object of the present invention are the following aspects that make up the same concept of the invention:

the method of obtaining ionomer TPU object of the invention

- the use of ionomer TPU according to this invention to obtain aqueous dispersions and

- a method of obtaining a water dispersion of the ionomer resin TPU according to this invention.

The objects of this invention ionomer thermoplastic polyurethanes (TPU) is distinguished by the fact that they can be obtained through the continuous reaction of the following monomers in the mass ratios are given relative to the weight of the total amount of the monomers to the reaction at a temperature in the range from 180 to 300°during the time interval from 30 seconds to 5 minutes and in the absence of solvents:

(i) from 4 to 50% of aliphatic or aromatic diisocyanate or a mixture of aliphatic or aromatic diisocyanates;

(ii) from 35 to 95% of a bifunctional polyhydric alcohol or a mixture of bifunctional polyols selected from the

a) polycaprolactone with an average molecular weight in the range from 500 to 15000 General formula (I)

where n is an integer, avisame from molecular weight, a R1- linear or branched C2-C10Allenova group, possibly substituted by carboxyl and/or sulfopropyl and/or possibly substituted by an oxygen atom and/or a benzene or naphthalene ring,

b) polyetherdiol with an average molecular weight in the range from 500 to 15000 with the General formula (II)

where n is an integer dependent on the molecular weight, and R2and R3independently represent a linear or branched C2-C10alkylenes group, possibly substituted by carboxyl and/or sulfopropyl and/or possibly substituted by an oxygen atom and/or a benzene or naphthalene ring;

c) polyetherdiol selected from polypropylenglycol with an average molecular weight in the range of from 400 to 15,000, polytetramethylene with an average molecular weight in the range from 500 to 1500 and polyethylene glycol with an average molecular weight in the range from 500 to 5000;

d) polycarbonatediol with an average molecular weight in the range from 500 to 15000 General formula (III)

where n is an integer dependent on the molecular weight, a R4represents a linear or branched C2-C10alkylenes group, possibly substituted by carboxyl and/or sulfopropyl and/or possibly substituted by an atom of oxygen is a and/or benzene or naphthalene ring;

(e) copolymers obtained by reaction of at least two

bifunctional polyols from groups a), b), C) or d);

(iii) from 0.2 to 16% lengthening chain glycol of General formula (IV)

where R5represents a linear or branched C2-C10alkylenes group, possibly included in the chain an oxygen atom and/or a benzene or naphthalene ring, and

(iv) from 0.2 to 3% lengthening chain ionomer glycol anionic type General formula (V)

where R6represents a linear or branched C2-C10alkylenes group, possibly substituted benzene or naphthalene ring, And possibly neutralized carboxyl or alphagraph.

For professionals it is obvious that the polymerization reaction can be used are well-known catalysts, such as metal salts or metal complexes, preferably tin or bismuth, with C6-C22aliphatic carboxylic acids, for example tin salt of octanoic acid. For professionals it is also clear that to the reaction mixture, you can add antioxidants, such as IRGANOX, preferably phenolic structure, as well as antioxidants type TINUVIN, preferably sterically difficult amines or benzo Rizoli.

Organic aliphatic and/or aromatic diisocyanates are well known specialist in the field of polyurethane chemistry and are available on the market. Preferred for the purposes of this invention known as colorvision (TDI), 4,4'-diphenylmethanediisocyanate (DHS), naphthalenedisulfonate, delete the entry, xradiation (CBI), tetramethylhexadecane (TMTDI), isophorondiisocyanate (IPDI), 4,4'-dicyclohexylmethane (HMDI) and hexamethylenediisocyanate (GDI).

Preferably the mass fraction of diisocyanate relative to the total weight of the monomers before the reaction is in the range from 4 to 15%, more preferably from 7 to 12%.

Polycaprolactones are known among bifunctional polyols products that get through polymerization ε-caprolactone in the presence of initiator type of diatomic alcohol with the formula HO-R1-OH, where R1represents the aforementioned group. For the purposes of this invention, preferred are those where R1is a linear C2-C6alkylenes group, most preferably butylene, though other mentioned cases.

The preferred polycaprolactones are those in which the average molecular weight is in the range from 3000 to 10000.

Polyetherdiol that is well known in the art and described in many patents, for example, in column 4, lines 9-18 U.S. patent No. 4092286, which is incorporated herein by reference; and preferred are polyetherdiol General formula (II), where R2and R3independently represents a C2-C10alkylenes group, most preferably butylene.

Preferred polyetherdiols are those in which the average molecular weight is in the range from 3000 to 10000.

Also known polycarbonatediol obtained by reaction of alkyl - or dellcorporate, and carbonates of phosgene with diatomic alcohols of the formula HO-R4-OH, where R4represents the aforementioned group. For the purposes of this invention, preferred are those where R4is hexamethylene, though other mentioned cases.

Preferred polycarbonatediol are those in which the average molecular weight is in the range from 1500 to 2500.

Among the copolymers obtained by reaction of at least two of the bifunctional polyols of the types (a)-(d), preferred are copolymers of polycaprolactone with polyesters or polycarbonates. In this regard, we can mention politicalcorrectness block copolymers, described in Spanish patent application ES213499-A1.

For the purposes of the present invention can be used is only one of the previously described types of bifunctional polyols (a) - e) or mixtures thereof, and especially preferred is the use of at least one polycaprolactone.

Preferably the mass ratio of bifunctional polyhydric alcohol or alcohols to the total weight of used monomers is in the range from 80 to 95%, more preferably from 85 to 93%.

Among the lengthening chain glycols are well known in polyurethane chemistry, are preferred for the purposes of the present invention are glycols selected from 1,4-butanediol, 1,3-propane diol, 1,2-ethanediol, 1,6-hexandiol and dipropyleneglycol, and mixtures thereof.

Preferably these lengthening chain glycols are in a mass ratio of from 0.2 to 2.0% relative to the total mass of the monomers used.

Lengthening the chain ionomer glycols anionic type are well known monomers in chemistry can dispergirujutsja polyurethanes in water; their fairly complete descriptions and chemical structure are in the aforementioned U.S. patent No. 3479310, 3412054 and 4276044 included here as a descriptive reference.

Among the glycols, containing carboxyl groups, are preferred for the purposes of this invention are 2,2-dimethylolpropionic acid (DMPC) and 2,2-dimitrovova acid, while among glycols, including sulfonic acids, preferred are 1,4-dihydr the STI-2-butanesulfonic acid and 3,4-dihydroxy-1-butanesulfonic acid. Especially preferred is DMPC.

Carboxyl and sulfopropyl ionomer glycols can be neutralized by protivoiona, for example, tertiary aliphatic amines with1-C6chain, aromatic amines and heterocyclic compounds such as morpholine and piperidine.

The preferred mass ratio of ionomer glycol relative to the total weight of reactive monomer is from 0.5 to 2%.

If one used a bifunctional polyols contains is able to ionize the carboxyl or sulfopropyl, the ratio of lengthening the chain ionomer glycols adjusted so that the total content is able to ionize anionic components in the final polymer does not exceed the quantity that is contained in the if containing only monomer was ionomer glycol, and the glycol would be in a mass ratio of 3% relative to the total mass involved in the reaction of the monomers, preferably not higher than 2%.

The temperature of the polymerization reaction is preferably supported from 190 to 260°C, more preferably between 235 and 250°C. the reaction Time, which is equal to the time continuous stay of mass in the reactor is preferably from 30 seconds to 3 minutes, more preferred is sustained fashion from 1 to 2 minutes.

After completion of the reaction the product is cut or cast from the molten state so that he upon cooling solidifies into the desired shape. Preferably the extrusion hot at a temperature, which allows you to cut the weight in the form of granules, which when cooled harden and become transparent or opaque appearance depending on the nature of the TPU.

The subject of this invention are those ionomer TPU characteristics which substantially match the properties of the TPU obtained under the reaction conditions and of the above-mentioned monomers, therefore TPU, which can be obtained using the processes of another type, for example in a periodic process, also form part of the object of the present invention in that, if the TPU have properties substantially the same as the specified.

The object of this invention is also a method of obtaining the previously described ionomer resin TPU, which is characterized in that it comprises the following stages:

(A) a mixture of different monomers in the reactor continuous action in the absence of solvents, in the presence of a polymerization catalyst and at a temperature in the range from 180 to 300°C

(B) aging the reaction mass in the reactor of continuous operation during the time interval, the amount is from 30 seconds to 5 minutes, and

(C) shaping and cooling the resulting product.

The reaction temperature preferably is maintained between 190 and 260°C, more preferably between 235 and 250°C. the residence Time of the pulp in the reactor continuous operation preferably is in the range from 30 seconds to 3 minutes, more preferably from 1 to 2 minutes.

The polymerization catalyst preferably is a salt of tin or bismuth with6-C22aliphatic carboxylic acid, such as tin salt of octanoic acid.

Preferably also be added to the reaction mixture an antioxidant, for example the type antioxidants IRGANOX, preferably phenolic structure, and antioxidants type TINUVIN, preferably sterically difficult amines or benzotriazole.

The reaction can be carried out in the extruder, having the form of a reactor, twin screw, adjusting the speed of rotation so that the progress of the reaction mass was allowed to receive the previously mentioned time.

The product can be ekstradiroval and cut at a temperature in the range between 180 and 230°depending on its average molecular weight in order after cooling to get the hardened transparent or opaque granules.

Thus obtained the object of the invention ionomer TPU - can without difficulty arr is processed, to store, for example, in bags, drums or boxes and transport, as they have the structure, hardness and stability, which are suitable for this purpose.

Of the above ionomer resin TPU can be easily obtained water dispersion in which free carboxyl and/or sulforaphane at least partially neutralized by a base, having application in various industries, such as adhesives or coatings on flexible and rigid surface.

These dispersions have a look whitish or bluish translucent liquids with solids content in the range from 30 to 60 wt.%, preferably from 35 to 55 wt.%, and with a pH in the range from 6 to 10, preferably from 7 to 9.

The method of obtaining the object of this invention is aqueous dispersions ionomer TPU is characterized in that it comprises the following stages:

(A) dissolving TPU in mixing with water, an organic solvent, if necessary under heating, to achieve dissolution;

(B) adding water and an inorganic or organic base in a quantity sufficient to make final pH of the resulting dispersion was in the range of from 6 to 10;

(C) distillation of the organic solvent and adding an additional amount of water until, until the desired dispersion with a solids content in which Arvale from 30 to 60 wt.%.

Miscible with water, an organic solvent may be any of that while maintaining these conditions can dissolve ionomer TPU, even when heated. Although this guidance is sufficient for specialists, we can mention, among other solvents, acetone, tetrahydrofuran, pyrrolidone and dimethylformamide; however, for the purposes of this invention, the preferred solvent is acetone.

The amount of organic solvent to be used in each case will depend on such factors as the composition of the monomers in the polymer and its molecular weight, but in any case it should be enough to get almost complete dissolution, at least when heated.

The Foundation stage (C) is preferably added dissolved in water and can be organic or inorganic type. From organic bases amongst you, without going into details, to mention a linear aliphatic amines with chain C1-C6such as triethylamine, possibly introduced hydroxyl groups, aromatic amines and heterocyclic compounds such as morpholine and piperidine. Among the inorganic bases include hydroxides of ammonium or alkali and/or alkaline earth metals, such as sodium hydroxide, potassium hydroxide or the Hydra is xed ammonium, and salts with basic properties, among which may be mentioned carbonates and bicarbonates, such as sodium carbonate or potassium.

The amount of base that must be added depends on the pH, which is desirable to obtain a water dispersion, preferably is a number of grounds, providing the pH of the final product from 7 to 9. If you want, you can add a buffer system that allows you to set the pH at the desired interval.

After the neutralization of the organic solvent is removed by distillation, aided by the choice of solvent with a relatively low boiling point such as acetone.

At that time, when the solvent is removed, add a further amount of water to fill the volume, possibly in combination with non-ionic surface-active compound, to obtain a dispersion with the desired solids content, preferably from 35 to 55 wt.%.

The examples below are given to ensure sufficiently clear and complete explanation of the present invention for specialists, but they should not be construed as limiting essential aspects of the object of the invention, as it was explained in previous sections of this description.

EXAMPLES

Examples 1-5. Getting ionomer TPU.

a) Total SP who own synthesis

Various monomers are mixed in the extruder, in the form of a reactor, twin screw, secured by heating at a temperature of from 235 to 250°and when the content of tin salts of octanoic acid from 20 to 200 ppm (parts per million) if used aromatic diisocyanate, and from 300 to 500 ppm, if using aliphatic diisocyanate. If desired, add a small amount of an antioxidant of the type IRGANOX, preferably with the structure of the phenol or type of TINUVIN, preferably sterically obstructed amines or benzotriazoles.

This mass moves through the reactor by means of a rotational movement while maintaining the previously specified temperature, so that the residence time of the reaction mass in the reactor ranged from 1 to 2 minutes.

At the exit of the extruder the product is cut in the form of pellets, cooled and dried; thus, it can be packaged and sent to storage.

C) Obtaining ionomer TPU

Following the above General method for the synthesis of ionomer resin obtained TPU examples 1-5 of the monomers shown in table 1.

Table 1

Examples 1 through 5
The monomerApp.1 (kg)App.1 (kg)PR (kg)PR (kg)PR (kg)
4,4'-diphenylmethanediisocyanate (DHS)454450530350-
Isophorondiisocyanate (IPDI)----407
Polycaprolactone with an average molecular weight of 3800 (formula I, R1=butylene)3800---3800
Polycaprolactone with an average molecular weight of 5000 (formula I, R1=butylene)-500050003070-
The polyethylene glycol with an average molecular weight 600--175--
Polycarbonate with an average molecular weight of 2000 (formula III, R4=hexalen)---500-
1,4-butanediol36,418,923,110,836,4
2,2-dimethylolpropionic acid (DNC)58,58578,264,458,5
Antioxidant TINUVIN4553the 3.8

Examples 6 through 10. Receive their aqueous dispersions.

a General way to obtain

In a suitable reactor equipped with a heating system, a reflux condenser and a distillation system, enter acetone, and then with stirring - TPU granules obtained in examples 1-5. The mixture is heated to the boiling point of acetone and stirring is continued until, until complete dissolution. Then add water in which dissolved sodium hydroxide, and the neutralization reaction proceeds for a further one hour at a temperature of from 50 to 60°C.

After neutralization of the acetone is distilled off in the course of the distillation of acetone, water is added, in which you have previously dissolved non-ionic surface-active compound (preferably polyoxyethylene 80 moles of ethylene oxide), with the same speed with which Argonauts acetone.

Thus obtained water dispersion of ionomer TPU having a pH of from 6 to 10 and bluish-white color.

b) Obtained ionomer dispersion TPU

Using the above General method, under specified quantities of reagents and solvents, the obtained dispersions of examples 6-10 in table 2.

PR (kg)
Table 2

Examples 6-10
Reagents and solventsPR (kg)PR (kg)PR (kg)PR (kg)
Acetone9000115001050090009000
TPU of example 13000----
TPU of example 2-3000---
TPU of example 3--3000--
TPU of example 4---3000-
TPU of example 5----3000
Deionized water (1)680680680680680
Sodium hydroxide11,713,311,513,711,9
Deionized water (2)45004500450045004500
Non-ionic surface-active compound6060606060

1. Ionomer thermoplastic polyurethane, characterized in that it can be obtained through a continuous reaction in temp is the temperature in the range from 180 to 300° Since, during the time interval from 30 s to 5 min in the absence of solvents, the following monomers in the mass ratios shown in relation to the total mass of monomers before the reaction:

(i) from 4 to 50% of aliphatic or aromatic diisocyanate or a mixture of aliphatic or aromatic diisocyanates;

(ii) from 35 to 95% of a bifunctional polyhydric alcohol or a mixture of bifunctional polyols chosen from:

a) polycaprolactone with an average molecular weight of from 500 to 15,000 and the General formula (I)

where n is an integer dependent on the molecular weight, a R1- linear or branched C2-C10Allenova group, possibly substituted by carboxyl and/or sulfopropyl and/or possibly substituted by an oxygen atom and/or a benzene or naphthalene ring;

b) polyetherdiol with an average molecular weight of from 500 to 15,000 and the General formula (II)

where n is an integer dependent on the molecular weight, a R2and R3independently represent a linear or branched C2-C10alkylenes group, possibly substituted by carboxyl and/or sulfopropyl and/or possibly substituted by an oxygen atom and/or benzene or naphtha is inovem ring;

c) polyetherdiol selected from polypropylenglycol with an average molecular weight of from 400 to 15,000, polytetramethylene with an average molecular weight of from 500 to 15,000 and polyethylene glycol with an average molecular weight from 500 to 5000;

d) polycarbonatediol with an average molecular weight of from 500 to 15,000 and the General formula (III)

where n is an integer dependent on the molecular weight, and R4- linear or branched C2-C10Allenova group, possibly substituted by carboxyl and/or sulfopropyl and/or possibly substituted by an oxygen atom and/or a benzene or naphthalene ring, and

(e) copolymers obtained by the reaction of at least two of the bifunctional polyols from groups a), b), C) or d);

(iii) from 0.2 to 16% lengthening chain glycol of General formula

where R5- linear or branched C2-C10Allenova group, possibly substituted by an oxygen atom and/or a benzene or naphthalene ring; and

(iv) from 0.2 to 3% lengthening chain ionomer glycol anionic type General formula (V)

where R6- linear or branched C2-C10Allenova group, possibly substituted intalnim or naphthalene ring, and possibly neutralized carboxyl group or perhaps neutralized alphagraph.

2. Ionomer thermoplastic polyurethane according to claim 1, characterized in that when a continuous reaction add a polymerization catalyst consisting of a metal salt or complex of a metal, preferably tin or bismuth, with C6-C22aliphatic carboxylic acids.

3. Ionomer thermoplastic polyurethane according to claim 1 or 2, characterized in that a continuous reaction type antioxidant type IRGANOX preferably phenolic structure or antioxidant type TINUVIN, preferably sterically difficult amines or benzotriazole.

4. Ionomer thermoplastic polyurethane according to claim 1, characterized in that the diisocyanate selected from colordistance, 4,4'-diphenylmethanediisocyanate, naphthalenedisulfonate, Finlandization, calolziocorte, tetramethylethylenediamine, isophoronediisocyanate, 4,4'-dicyclohexylmethane and hexamethylenediisocyanate.

5. Ionomer thermoplastic polyurethane according to claim 1 or 4, characterized in that the mass ratio of the diisocyanate to the total weight of the monomers to the reaction is in the range from 4 to 15%, preferably from 7 to 12%.

6. Ionomer thermoplastic polyurethane according to claim 1, characterized in that polycaprolactone General formula (I) R1PR is dstanley a linear or branched C 2-C6alkylenes group, preferably butylene.

7. Ionomer thermoplastic polyurethane according to claim 1 or 6, characterized in that polycaprolacton has an average molecular weight of from 3000 to 10000.

8. Ionomer thermoplastic polyurethane according to claim 1, characterized in that polyetherdiol General formula (II) R2and R3independently represent a2-C10alkylenes group, preferably butylene.

9. Ionomer thermoplastic polyurethane according to claim 1 or 8, characterized in that polyetherdiol has an average molecular weight of from 3000 to 10000.

10. Ionomer thermoplastic polyurethane according to claim 1, characterized in that polycarbonatediol General formula (III) R4is hexamethylene.

11. Ionomer thermoplastic polyurethane according to claim 1 or 10, characterized in that polycarbonatediol has an average molecular weight of from 1500 to 2500.

12. Ionomer thermoplastic polyurethane according to claim 1, characterized in that the copolymers obtained by reaction of at least two bifunctional polyols, are copolymers of polycaprolactone with polyesters or polycarbonates.

13. Ionomer thermoplastic polyurethane according to claim 1, characterized in that in relation to the total weight of monomers used, the mass ratio of the bifunctional polyhydric alcohol or the alcohol is in is in the range from 80 to 95%, preferably from 85 to 93%.

14. Ionomer thermoplastic polyurethane according to claim 1, characterized in that the bifunctional polyhydric alcohol is polycaprolacton, alone or in mixture with one of the other bifunctional polyols.

15. Ionomer thermoplastic polyurethane according to claim 1, characterized in that the lengthening chain glycol selected from 1,4-butanediol, 1,2-ethanediol, 1,3-propane diol, 1,6-hexandiol and dipropyleneglycol or mixtures thereof.

16. Ionomer thermoplastic polyurethane according to claim 1, characterized in that the lengthening chain glycol is in a mass ratio being in the range from 0.2 to 2.0% relative to the total weight of the monomers.

17. Ionomer thermoplastic polyurethane according to claim 1, characterized in that the lengthening chain ionomer glycol anionic type selected from 2,2-dimethylolpropionic acid, 2,2-dimethylaminoethanol acid, 1,4-dihydroxy-2-butanesulfonate and 3,4-dihydroxy-1-butanesulfonate.

18. Ionomer thermoplastic polyurethane according to 17, characterized in that the lengthening chain ionomer glycol is a 2,2-dimethylolpropionic acid.

19. Ionomer thermoplastic polyurethane according to claim 1, characterized in that the mass ratio of ionomer glycol to the total mass of the monomers is in the range from 0.5 to 2%.

20. Ionomer thermoplastic polyurethane p is 1, characterized in that the reaction temperature support from 190 to 260°C, preferably from 235 to 250°and the reaction time is in the range from 30 s to 3 min, preferably from 1 to 2 minutes

21. Ionomer thermoplastic polyurethane according to claim 1, characterized in that it has the shape of the hardened granules transparent or opaque type.

22. The method of obtaining ionomer thermoplastic polyurethanes according to claims 1 to 21, characterized in that it comprises the following stages:

(A) a mixture of different monomers in the reactor continuous action in the absence of solvents, in the presence of a polymerization catalyst and at a temperature of from 180 to 300°C;

(B) maintaining the residence time of the reaction mass in the reactor is continuous in the interval of time from 30 s to 5 min and

(C) shaping and cooling the resulting product.

23. The method according to item 22, wherein the reaction temperature support from 190 to 260°C, preferably from 235 to 250°S, and the residence time of the pulp in the reactor continuous action is in the range from 30 s to 3 min, preferably from 1 to 2 minutes

24. The method according to item 22 or 23, characterized in that the polymerization catalyst is a metal salt or complex of a metal, preferably tin or bismuth, with C6-C22aliphatic carboxylic acid

25. The method according to item 22, wherein the reaction mixture are added antioxidant type IRGANOX preferably phenolic structure or antioxidant type TINUVIN, preferably sterically difficult amines or benzotriazole.

26. The method according to item 22, wherein the product is formed by extrusion and slicing at a temperature of from 180 to 230°and cooling it to obtain a solidified granules having a transparent or opaque appearance.

27. The use of ionomer thermoplastic polyurethanes according to claims 1 to 21 to get their aqueous dispersions.

28. The application of item 27, wherein the aqueous dispersions have a solids content from 30% to 60 wt.%, preferably from 35% to 55 wt.%, and pH from 6 to 10, preferably from 7 to 9.

29. A method of obtaining a water dispersion of ionomer thermoplastic polyurethanes according to claims 1 to 21, characterized in that it comprises the following stages:

(A) dissolving TPU in mixing with water, an organic solvent, if necessary under heating, to achieve dissolution;

(B) adding water and an inorganic or organic base in a quantity sufficient to make final pH of the resulting dispersion was in the range of 6 and 10;

(C) distillation of the organic solvent and adding an additional amount of water until will not be obtained dispersion with a solids content of 30 to 60 wt.%

30. The method according to clause 29, wherein miscible with water, an organic solvent chosen from acetone, pyrrolidone, tetrahydrofuran, and dimethylformamide.

31. The method according to clause 29 or 30, characterized in that the organic base is at the stage (C) are selected from aliphatic amines with chain C1-C6such as triethylamine, may gidroksilirovanii, aromatic amines and heterocyclic compounds such as morpholine and piperidine.

32. The method according to clause 29 or 30, characterized in that the organic base is at the stage (C) is selected from ammonium hydroxide or hydroxides of alkali and/or alkaline earth metals, such as ammonium hydroxide, sodium hydroxide or potassium hydroxide, and/or of the salts with basic properties, such as carbonates and bicarbonates of alkali metals.

33. The method according to clause 29, wherein the add a sufficient amount of base and/or a buffering agent for pH of the resulting aqueous dispersion was in the range of from 7 to 9.

34. The method according to clause 29, wherein at the time when the organic solvent is removed, add a further quantity of water to replenish the volume, possibly in combination with non-ionic surface-active compound, to obtain a dispersion with the desired solids content, which preferably is in the interval for the Les from 35 to 55 wt.%.



 

Same patents:
Polymer composition // 2263695

FIELD: polymerizing mixtures for making water-repellent and anticorrosive coats.

SUBSTANCE: proposed polymer composition contains polyester resins, styrene, hardening agent-peroxide compounds and accelerating agent, inert substances, gel-type binder, paraffins and poly-urethanes. Proposed composition increases service life of coat due to reduction of effect of aggressive factors of outside medium on characteristics of coat.

EFFECT: increased rate of polymerization without considerable stresses in coat; facilitated procedure of applying coats on base of this composition.

23 cl, 80 ex

FIELD: polymer production.

SUBSTANCE: invention relates to foamed polyurethane molded products with thickened edge zone with simplified density and clearly expressed more soft cellular core. Soft to semi-rigid polyurethane integral foamed plastics are prepared by interaction of (i) organic and/or modified organic polyisocyanates or their polymeric precursors with (ii) at least one polyol component with hydroxyl number 20 to 200 and functionality 2 to 6, if necessary in combination with (iii) at least one polyol component with hydroxyl number 201 to 899 and functionality 2 to 3, and also (iv) at least one component functioning as chain extension and having hydroxyl number or amine number 600 to 1850 and functionality 2 to 4 in amount 3 to 20% based on the summary weight of (ii) and (iii), and, if necessary, (v) known additives, activators, and/or stabilizers in presence of 0.05-0.6% water (based on summary weight of (ii) and (iii)) and mixtures of pore agents containing 1,1,1,3,3-pentafluorobutane and at least one other fluoroalkane in amount 0.2-10% of the summary weight of components (ii)-(v). Thus obtained foamed plastics with integral structure are characterized by Shore hardness of edge zone 30 to 90, rigidity in compression deformation 30 and 350 kPa, and apparent density 150 to 900 kg/m3.

EFFECT: increased assortment of foamed plastics.

7 cl, 1 tbl, 9 ex

FIELD: corrosion prevention technologies.

SUBSTANCE: method includes serial application of layers of polymer compositions to metallic surface, while serial layers of polymer compositions are made with various thermal expansion coefficients. As said polymer composition polyurethane compound is used with special admixtures and filling agent, influencing thermal expansion coefficient of covering layer, and content of said filling agent in each following layer is set less than content of said filling agent in previous layer.

EFFECT: higher efficiency.

2 cl, 9 ex

FIELD: chemical industry; production of polymeric structural materials from hermosetting compositions based on polyisocyanurates.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to production of polymeric structural materials from thermosetting compositions based on polyisocyanurates. The offered composition for production of the polymeric structural materials contains 100 mass % of a low-molecular quick-tenacious polymer with the terminal hydroxyl groups, 22.5-400 mass % of aromatic diisocyanate, 0.08-20 mass % of dimethylbenzylamine, 0.8-20 mass % of epoxydiane resins, 55-30 mass % of acetone, 2.0-22.5 mass % of a high-porous polymeric filler. At that in the capacity of the indicated polymeric filler they use a flexible polyurethane foam or a synthetic felt material (sintepone - synthetic winterizer). From the indicated composition by an industrial method for a short cycle of hot pressing produce polymeric items with a gradient modulus of elasticity (in any given direction) from 3 up to 2000 MPa. At that the material saves its elastic properties at any value of the modulus in the interval of temperatures from -50 up to 120°C, and may be used in shoe industry and tire industry, instrument-making industry and radio industry.

EFFECT: the invention allows to produce polymeric items with a gradient modulus of elasticity in any given direction within 3 up to 2000 Mpa, the material saves its elastic properties at any value of the modulus at temperatures of -50 °C up to 120°C.

3 cl, 5 ex, 1 tbl

The invention relates to methods for producing polyisocyanates used for various polymeric materials, as well as to compositions based on polyisocyanates

The invention relates to the production of polyurethane elastomers intended for the manufacture of coatings shafts of high-speed paper machines, calender rollers for machines in the production of magnetic tapes, as well as for the manufacture of polyurethane products for various purposes for the aviation and automotive industry

The invention relates to the production of polyurethane elastomers intended for the manufacture of coatings shafts of high-speed paper machines, calender rollers for machines in the production of magnetic tapes, for the coating of other metal surfaces, as well as for the manufacture of polyurethane products for various purposes, for aircraft, automotive and other industries

The invention relates to the production of polyurethane elastomers intended for the manufacture of taps, soles and other parts when repairing bottom shoes

The invention relates to a method for producing foamed thermoplastic polyurethanes using thermally blown microspheres, as well as foamed thermoplastic polyurethanes and reazioni systems used to obtain foamed thermoplastic polyurethanes

The invention relates to method of producing composites based on vinyl chloride polymers, processed by the methods of rolling, extrusion, injection molding and mortar technology for manufacturing a flexible film materials, coatings, adhesives, Shoe soles, hoses, medical products

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

The invention relates to a method for producing foamed polyurethane water materials involving the use of a specific catalyst, and to the thus obtained polyurethane foams
The invention relates to methods for producing polyetherurethanes in solution, namely the solution of ethyl acetate, and can be used in various fields of industry for preparation of adhesives, coatings for fabrics and so on

The invention relates to the field of synthesis of polyurethane curable coatings using catalysts and can be used in paint industry

FIELD: resin industry and organometallic synthesis.

SUBSTANCE: organometallic composition for solidifying polyisocyanate materials, which may be used for binding lignocellulose, contains complex of at least one metal ortho-ether having formula M(ROAcAc)x(OR')y, where M represents titanium, zirconium, or hafnium; ROAcAc represents moiety of acetoacetic acid ester with alcohol ROH wherein R is optionally cyclic, branched, or linear alkyl, alkenyl, aryl, or alkylaryl group having 1 to 30 carbon atoms or mixture thereof; OR' represents alcohol R'OH residue wherein R' is optionally cyclic, branched, or linear alkyl, alkenyl, aryl, or alkylaryl group having 7 to 30 carbon atoms or mixture thereof; each of x and y ranges between 1 and 3 and x+y=4. Mixture to be solidified contains organic isocyanate compound or mixture of organic isocyanate compounds and above-indicated organometallic composition. Lignocellulose product, containing lignocellulose material and polyisocyanate composition including above-indicated organometallic composition, is prepared by bringing lignocellulose material into contact with above polyisocyanate composition to allow lignocellulose material to be bound.

EFFECT: improved process characteristics of organometallic composition.

12 cl, 1 tbl, 7 ex

The invention relates to ORGANOMETALLIC composition based on metals, group IVB, which can be used for binding lignocellulosic material

The invention relates to a method for producing foamed polyurethane water materials involving the use of a specific catalyst, and to the thus obtained polyurethane foams

The invention relates to a light-resistant, elastomeric, polyurethane moulded products

The invention relates to a polymeric film-forming materials, in particular blocked polyisocyanates, and can be used in the manufacture of paint and varnish materials and magnetic media

The invention relates to the production of polymeric materials, in particular the production of polyurethane foams for insulation products purpose in this b - Noy engineering and construction industry, for products with enhanced strength and dielectric characteristics - properties in electronics and communication, as well as for products with variable thickness and a complex profile, medicine and consumer goods
Up!