Transparent tpp (thermoplastic polyurethanes) and pmma (polymethyl(meth)acrylate) with improved frost and impact resistance

FIELD: chemistry.

SUBSTANCE: polymer mixture consists of thermoplastic polyurethane (TPP) and a modified impact resistant methylmethacrylate polymer. Said impact-resistant methylmethacrylate polymer is modified with an impact resistant modifier with a "nucleus/shell/shell" structure. The first shell contains 80-98 wt % repeating (meth)acrylate monomers and 2-20 wt % styrene monomers of a defined formula (1). The second shell contains 50-100 wt % repeating alkylmethacrylate units, having 1-20 carbon atoms, 0-40 wt % repeating alkylacrylate units, 0-10 wt % styrene monomers of formula (1). The nucleus contains 50-99 wt % alkylmethacrylate repeating units having 1-20 carbon atoms, 0-40 wt % alkylacrylate repeating units having 1-20 carbon atoms, 0.1-2.0 wt % cross-linking repeating units and 0-8.0 wt % styrene monomers of formula (1).

EFFECT: polymer mixture is used to obtain moulded articles with high light transmission and high impact resistance at above-zero and subzero temperatures.

9 cl, 1 tbl, 2 ex

 

The present invention relates to transparent mixtures consisting of thermoplastic polyurethanes (TPU) and polymethyl(meth)acrylate (PMMA), and it made of a molded polymeric products with improved maratoualipranti.

With impact strength of the molding material (UE-FM) on the basis of PMMA produced on a large scale. Impact strength of the moulding mass increase, applying the so-called impact strength modifiers. These modifiers compounding in the relevant standard molding material of PMMA.

As impact strength modifiers molding masses of PMMA is often used particle size of 100-1000 nm) type core/shell/shell ("I/O1,/O2"), which is usually produced by the emulsion polymerization. The core of such particles of type I/O1,/O2 consists of a cross-linkable polymer, which is almost fully formed from the same monomers as the matrix (excluding the cross-linking agent). The first shell (O1)forming the elastomeric phase consists of a butyl acrylate rubber, which usually regulate the refractive indices of the matrix by copolymerization with styrene or its derivatives. The second shell binds the particles to the matrix and consists of unstitched polymers, the monomers are very similar to components of the matrix.

Due to the structure of a typical modifier UD the nuclear biological chemical (NBC strength, which are based on butyl acrylate, they do not allow to achieve high impact strength at low temperatures (-40°C). At these temperatures the rubber phase modifier hardens.

With impact strength of the molding material of PMMA can be divided into transparent and opaque molding material of PMMA. Transparent molding material with impact resistance, usually produced by using modifiers on the basis of butyl acrylate. Here you can name the products PLEXIGLAS®zk50 manufactured by Röhm GmbH & Co. KG, ACRYLITE PLUS®zk6 manufactured by Cyro and ALTUGLAS®DR manufactured by Altuglas.

In the German patent DE 4136993 (BASF AG) "Transparent molding material of PMMA modified with impact resistance, superior low temperature and a high resistance to the effects of weather described structure, similar to that in U.S. patent US - PS 3,793,402. In this case, however, necessary to build a solid phase (O1) phenylalkylamine acrylic acid with 1-4 carbon atoms in the alkyl chain. In the examples described molding material of PMMA with good impact strength in the cold. The best on this topic molding composition (example 6) has the following composition:

Modifier:

Kernel: MMA - alismataceae-methyl acrylate = 98,6-0,5-0,9

Shell 1: butyl acrylate-phenylethylamine-allele kilat-1,4-potentialtarget= 72,3-25,8-1,4-0,5

Shell 2: MMA - MMA = 96,0-4,0

The ratio I/O1,/O2"=20/50/30

Forming mass of PMMA: approximate molecular weight of 100,000 g/mol,

MMA - MMA = 99-1

The ratio of mixing the molding material and modifier = 45/55 (by weight).

At room temperature this molding composition has impact strength according to Izod 85, and at -20°C, the strength of 52 kJ/m2.

The impact resistance of conventional impact-resistant molding masses markedly reduced, starting from -10°C. the Modulus of elasticity of such molding masses with high impact strength as PLEXIGLAS®zk50, thus is 950 MPa. Although the impact-resistant molding masses, for example, Acrylite Plus®zk6 the modulus of elasticity is high enough to 1800 MPa, but the magnitude of impact strength are only 80 kJ/m2.

If produce is resistant to weather influences, impact resistant at low temperatures of the molding material, PMMA, they are usually opaque. As the current level of technology in this case, you should specify the following patent applications or patents.

International application WO 2003/066695: good impact strength in the cold here achieved through the use of the modifier of silicone rubber.

German application DE 10260065 A1: reducing the amount of styrene to butyl acrylate rubber modifier, due to the use of this modifier floor is given a good magnitude of impact resistance in cold temperatures down to -20°C. However, due to the reduction of styrene transparency of the molding material is greatly diminished (refractive indices butyl acrylate rubber and PMMA different).

Had to find a mixture based on PMMA with impact strength also at low temperatures. In addition, the molded product produced by injection molding or extrusion of this part, must have acceptable transparency, and it would be possible to print conventional paints. In addition, the molded product must be resistant to weather influences, and still have a high modulus of elongation. By "low temperature" in the sense of the invention involve a temperature in the range from, for example, -10°C to -40°C. Under an acceptable transparency" implies, for example, the value of transmittance of about 80% (d=3 mm).

The problem can be solved by the mixing of the last modification of the impact strength of the moulding mass of PMMA and thermoplastic polyurethanes (TPU) (Mass ratio of shockproof PMMA and TPU=50/90-80/10). Preferably the mass ratio of PMMA to TPU, comprising 70 parts of PMMA to 30 parts TPU, particularly preferably the mass ratio of PMMA to TPU, comprising 60 parts of PMMA to 40 parts of TPU.

So, the values of impact strength of these mixtures according to Charpy at 23°C are more than 100 kJ/ m2and at -40°C they still SOS is ablaut 23 kJ/m 2(and, respectively, significantly greater than those of transparent PMMA, modified for impact resistance). In addition, the transmittance of the samples from this material of 3 mm thickness exceeds 80%. Films of these blends much easier printing than usually applied in such cases, the films made of polyamide or blends of TPU/MABS (methyl methacrylate-Acrylonitrile-butadiene-styrene) and is resistant to weather influences.

In the framework of the present invention, the expression "(meth)acrylate" encompasses the methacrylates and acrylates, and mixtures thereof.

As the molding material of PMMA using a mixture of the two (meth)acrylate polymer component a) and component (b).

Component (a)

Polymetylmetacrylate in the General case is obtained by polymerization of mixtures containing methyl methacrylate. In General, these mixtures contain at least 40 wt.%, preferably at least 60 wt.% and particularly preferably at least 80 wt.% of methyl methacrylate by weight of the total monomers.

In addition, the formula to obtain polymetylmetacrylate can contain other (meth)acrylates that can be shared to polimerizuet with methyl methacrylate. The expression "(meth)acrylate" encompasses the methacrylates and acrylates, and mixtures thereof.

These monomers are well known. To them, among other things, include (meth)acrylates, derived from saturated alcohols, such as, n is the sample, the methyl acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, n-butyl(meth)acrylate, tert-butyl(meth)acrylate, pentyl(meth)acrylate and 2-ethylhexyl(meth)acrylate; (meth)acrylates, derived from unsaturated alcohols, such as, for example, oleyl(meth)acrylate, 2-PROPYNYL(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate; aryl(meth)acrylates such as benzyl(meth)acrylate or phenyl(meth)acrylate, and in each case the aryl residues can be unsubstituted or have up to four substituents; cycloalkyl(meth)acrylates, such as 3-vinylcyclohexane(meth)acrylate, bornyl(meth)acrylate; hydroxyalkyl(meth)acrylates, such as 3-hydroxypropyl(meth)acrylate, 3,4-dihydroxybutyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate; glycolide(meth)acrylates, for example, 1,4-butanediol(meth)acrylate, (meth)acrylates of atherosperma, for example, tetrahydrofurfuryl(meth)acrylate, vinyloxyethoxy(meth)acrylate; amides and NITRILES of (meth)acrylic acid, for example, N-(3-dimethylaminopropyl)(meth)acrylamide, N-(diethylphosphino)(meth)acrylamide, 1-methacryloylamido-2-methyl-2-propanol; methacrylates containing sulfur, such as: ethylsulfinyl(meth)acrylate, 4-thiocyanomethyl(meth)acrylate, ethylsulfonyl(meth)acrylate, thiocyanomethyl(meth)acrylate, methylsulfonylmethyl(meth)acrylate, bis((meth)acryloyloxy)sulfide; polyhydric (meth)acrylates, such as: trimethylolpropane(meth)acrylate.

In addition to the previously mentioned (meth)acrylate compounds, subject to polymerization, can include other unsaturated monomers that can be copolymerizable with methyl methacrylate and the aforementioned (meth)acrylates.

These include including 1-alkenes, for example, hexene-1, hepten-1; branched alkenes, such as vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-Diisobutylene, 4-methylpentene-1; Acrylonitrile; vinylether, for example, vinyl acetate; styrene, substituted styrene with an alkyl substituent in the side chain, such as α-methylsterols and α-atillery, substituted styrene with an alkyl substituent in the ring, as vinyltoluene and p-methylsterol, halogenated styrene, as, for example, monoliteral, dichlorostyrene, dibromostyrene and cerebrosterol; heterocyclic vinyl compounds, such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyridine, vinylpyridine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinyl pyrrolidone, 2-vinyl pyrrolidone, N-vinylpyrrolidone, 3-vinylpyrrolidone, N-vinylcaprolactam, N-vinylboronates vinyloxy, viniferin, Venitian, vinylsilane, vinylthiazole and hydrogenated vinylthiazole, vinylacetal and hydrogenated vinylacetal; vinyl and izoprenil e the Ira; derivatives of maleic acid, such as maleic acid anhydride, the anhydride methylmaleimide acid, maleinimide, methylmaleimide; and dieny, as, for example, divinylbenzene.

In General, these comonomers are used in quantities of from 0 to 60 wt.%, preferably from 0 to 40 wt.% and particularly preferably from 0 to 20 wt.%, based on the weight of monomers, the compounds can be used alone or as a mixture.

The polymerization is usually run using a known radical initiators. To the preferred initiators include, among other well-known specialists azoinitiator, as, for example, azobisisobutyronitrile (AIBN) and 1,1-azabicycloalkanes, and peroxide compounds, such as methylethylketone, acetylacetonate, delauriers, tert-Builder-2-ethylhexanoate, setoperone, methylisobutylketone, cyclohexanedione, Dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy isopropyl carbonate, 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane, tert-butyl peroxy-2-ethylhexanoate, tert-BUTYLPEROXY-3,5,5-trimethylhexanoate, dicumylperoxide, 1,1-bis(tert-BUTYLPEROXY)cyclohexane, 1,1-bis(tert-BUTYLPEROXY)3,3,5-trimethylcyclohexane, cumylhydroperoxide, tert-butylhydroperoxide, bis(4-tert-butylcyclohexyl)PEROXYDICARBONATE, a mixture of two or b is more of the abovementioned compounds with one another, as well as mixtures of the above compounds with other compounds that can form radicals.

These compounds are often used in quantities of from 0.01 to 10 wt.%, preferably from 0.5 to 3 wt.% based on the weight of monomers.

You can use various poly(meth)acrylates, which are different from each other, for example, the molecular weight or composition of the monomers.

In addition, the matrix may contain other polymers, which aim to modify properties. These polymers are, including polyacrylonitrile, polystyrenes, simple and complex polyesters, polycarbonates, and PVC. These polymers can be used individually or as mixtures and copolymers that may occur from the above-mentioned polymers.

The average molecular weight of the homopolymers and/or copolymers used as the polymer matrix, may be varied within wide limits, usually the molecular weight of the set according to the purpose of the application and the method of processing of the molding composition. In General, however, it is between 20000 and 1,000,000 g/mol, preferably from 50,000 to 500,000 g/mol and particularly preferably from 80,000 to 300000 g/mol, but these data do not impose restrictions.

Component (b)

Component b) is a means for modification of the shock strength on the basis of the school is mentioned poly(meth)acrylates. Preferably, component b) have the structure type core/shell/shell.

The preferred means of modification of the shock strength is particles polymerizate characterized by structure type core/shell/shell, which can be obtained by the emulsion polymerization (see, for example, European application EP-A 0113924, EP-A 0522351, EP-A 0465049 and EP-A 0683028). The typical size (diameter) of the particles of these emulsion polymerization is in the range of 100 to 600 nm, preferably 200-500 nm.

Three-layer or three-phase structure comprising a core and two shells can be achieved as follows. The inner (solid), the shell may, for example, consist mainly of methyl methacrylate, small amounts of comonomers such as ethyl acrylate and a crosslinking agent, such as illimitability. Medium (soft) shell may be formed, for example, butyl acrylate and styrene, and external (hard) shell mainly corresponds to matrix polymerizate that provides compatibility and good communication with the matrix.

Preferably, the core includes, in each case, calculated on the total weight,

A) to 50.0 wt.% to 99.9 wt.%, preferably 60,0 wt.% to 99.9 wt.%, preferably from 75,0 wt.% to 99.9 wt.%, particularly preferably from 80,0 wt.% up to 99.0 wt.%, especially from 85.0 wt.% up to 99.0 wt.%, duplicate edit the IC alkylmethacrylamide, having from 1 to 20, preferably from 1 to 12, especially from 1 to 8 carbon atoms in the alkyl residue,

B) from 0.0 wt.% to 40.0 wt.%, preferably from 0.0 wt.% to 24.9 wt.%, preferably from 1.0 wt.% to 29.9 wt.%, in particular from 1.0 wt.% to 14.9 wt.%, repeating units of alkylacrylate having from 1 to 20, preferably from 1 to 12, particularly preferably 1 to 8, especially from 1 to 4, carbon atoms in the alkyl residue,

C) from 0.1 wt.% up to 2.0 wt.% crosslinking repeating units and

D) from 0.0 wt.%. to 8.0 wt.% styrene monomer (repeating units) with the General formula (I)

moreover, it is preferable that the above weight percents amounted to 100.0 wt.%.

This compounds A), B), C) and D), of course, differ from each other, in particular, the compounds (a) and (B) does not include crosslinking monomers C).

The remains of R1to R5in each case, independently of one another denote hydrogen, halogen, in particular fluorine, chlorine or bromine, or alkyl group with 1-6 carbon atoms, preferably hydrogen. The remainder R6means hydrogen or alkyl group with 1-6 carbon atoms, preferably hydrogen. Particularly suitable for use alkyl groups with 1-6 carbon atoms is methyl, ethyl, n-propyl, ISO-propyl, n-butyl, sec-butyl, tert-butyl, n-pen is silt, n-hexyl group, and cyclopentyloxy and cyclohexyloxy group.

Thus, the repeating styrene monomers with the General formula (I) include periodic structural unit obtained by polymerization of monomers with the General formula (Ia).

In particular, the appropriate monomers with the General formula (Ia) include styrene, substituted styrene with one alkyl substituent in the side chain, such as α-methylsterols and α-atillery, substituted styrene with one alkyl substituent in the ring, as, for example, vinyltoluene and p-methylsterol, halogenated styrene, such as, for example, monoliteral, dichlorostyrene, dibromostyrene and cerebrosterol. Under the above-mentioned alkylmethacrylamide recurring units (A) periodic structure, which is produced by polymerization of esters of methacrylic acid. Suitable esters of methacrylic acid are, in particular, methyl methacrylate, ethyl methacrylate, propylbetaine, isopropylacetate, n-butylmethacrylate, second-butylmethacrylate, tert-butylmethacrylate, intermetallic, vexillarius, gettimeformat, octylacrylate, 2-octylacrylate, ethylhexylacrylate, nonillicit, 2-meteoclimatic, 2-tert-BUTYLCARBAMATE, 3-ISO-profileprofile, decylmethacrylate, undecyl acrylat, 5-methylumbelliferyl, dodecylmercaptan, 2-metallodielectric, tridecylamine, 5-methyltrichlorosilane, tetradecylammonium, pentadecylcatechol, hexadecimalscalar, 2-methylhexadecanoic, heptadecologies, 5-ISO-profileproperties, 5-etilachetoachetate, octadecylammonium, nondecimated, acetilsalicilic, cycloalkylation, such as cyclopentylmethyl, cyclohexylmethyl, 3-vinyl-2-butyl-cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, bornilacetate and isobornylacrylat.

According to a particularly preferred variant implementation of the present invention, the core, based on its total weight, contains at least 50 wt.%, preferably at least 60 wt.%, preferably at least 75 wt.%, in particular at least 85 wt.% methyl methacrylate repeating units. Under the above-mentioned alkylacrylate recurring units (B) periodic structure, which is produced by polymerization of esters of acrylic acid. Suitable esters of acrylic acid are, in particular, methyl acrylate, acrylate, propylacetate, isopropylacetate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentylaniline, hexidecimal, heptylamine, octylacrylate, 2-octylacrylate, ating xylakant, nasolacrimal, 2-methyl-octylacrylate, 2-tert-butylcatechol, 3-ISO-propylheptanol, dellaquila, undecidability, 5-methylundecanal, dodecylamine, 2-metallodielectric, tridecylamine, 5-methyltricyclo, tetradecanamide, pentadecylic, hexadecylamine, 2-methylhexadecanoic, heptadecanoyl, 5-ISO-profileproperties, 5-atractylenolide, octadecylamine, nondetergent, ensilability, cycloalkylcarbonyl, as, for example, cyclopentylacetic, cyclohexylacetate, 3-vinyl-2-butyl-cyclohexylacetate, cycloheptylamine, cyclooctylamine, brylcreem and isobutylacetate. Under the above-mentioned repetitive cross-linking units (C) periodic structural unit, which is obtained by crosslinking polymerization of the monomers. Suitable crosslinking monomers include, in particular, those compounds that are able to cause cross linking under the conditions of polymerization. These include, in particular, are

(a) difunctional (meth)acrylates, preferably compounds with the General formula

where R is hydrogen or methyl, a n is a positive integer greater than or equal to 2, preferably between 3 and 20, in particular di(meth)acrylates of propane diol, butanediol, hexanediol, octanediol, nonanediol, decant the Ola and eicosanol;

Compounds with the General formula

where R is hydrogen or methyl, a n is a positive integer between 1 and 14, in particular di(meth)acrylates of telephotos, diethylene glycol, triethylene glycol, tetraethyleneglycol, dodecaurelia, tetradecapeptide, propylene glycol, Dobropillya and tetradecapeptide, glycerine(meth)acrylate, 2,2'-bis[p-(γ-methacrylate-β-hydroxypropoxy)-phenylpropane] or bis-GMA, biphenol-A-dimethacrylate, neopentylglycol(meth)acrylate, 2,2'-di(4-methacryloxypropyl)propane having from 2 to 10 taksigrup molecule and 1,2-bis(3-methacrylate-2-hydroxypropoxy)butane.

(b) three - or polyfunctional (meth)acrylates, in particular, trimethylolpropane(meth)acrylates and pentaerythritol(meth)acrylate.

Grafted cross-linking agents with at least two double bonds With different reactivity, especially alismataceae and allylacetate; aromatic crosslinking agents, in particular, 1,2-divinylbenzene, 1,3-divinylbenzene and 1,4-divinylbenzene.

The choice of the mass fraction of the core components from A) to D) is preferably implemented in such a way that the glass transition temperature of the core Tg was at least 10°C., and preferably at least 30°C. When the glass transition temperature of polymerizate Tg can be determined by known obrazopissetsa differential scanning calorimetry (DSC). In addition, pre-glass transition temperature Tg can also be calculated approximately using equation Fox. According To Fox, T. G., Bull. Am. Physics Soc. 1, 3, page 123 (1956)

,

moreover, xnmean mass fraction (wt.%/100) of the monomer n, a Tgnthe glass transition temperature of the homopolymers of the monomer n in Kelvin. Other useful recommendations for specialist contained in the Polymer Handbook, 2ndEdition, J. Wiley & Sons, New York (1975), where the values of Tg for the most common homopolymerization.

The first shell particles such as "core-shell-shell is characterized by a glass transition temperature below 30°C, preferably below 10°C, in particular in the range from 0 to -75°C. When the glass transition temperature Tg of polymerizate, as already mentioned above, can be determined by differential scanning calorimetry (DSC) or pre-roughly be calculated using equation Fox.

The first shell includes, calculated on the total weight, the following components:

From 80,0% wt. to 98,0% wt. recurring monomers of the (meth)acrylate and

From 2.0 wt.% to 20.0 wt.% styrene monomers with the General formula (I),

moreover, the percentage weights sum up to 100 wt.%.

In particularly preferred form of execution of the present invention in the first shell includes

E-1) from 80,0 wt.% do,9 wt.% repeating units of alkylacrylate, having 3 to 8 carbon atoms in the alkyl residue and/or recurring units of alkylmethacrylamide having from 7 to 14 carbon atoms in the alkyl residue, in particular butyl acrylate and/or dodecylmercaptan monomers, and

E-2) from 0.1 wt.% up to 2.5 wt.% the repeating units of the cross-linkage,

F) from 2.0 wt.% to 20.0 wt.% styrene monomer (repeating units) with the General formula (I),

but it is desirable that these mass percentage amounted to 100.0 wt.%.

In this connection, E-1, E-2) and (F) of course, differ from each other, in particular, the compounds E-1) does not include crosslinking monomers E-2).

The second shell contains, in percent by weight, at least 75 wt.% recurring monomers of the (meth)acrylate.

Preferably it contains

to 50.0 wt.% to 100.0 wt.%, preferably 60,0 wt.% to 100.0 wt.%, especially preferably of 75.0 wt.% to 100.0 wt.%, in particular, 85,0 to 99.5 wt.%, repeating units of alkylmethacrylamide having from 1 to 20, preferably from 1 to 12, especially from 1 to 8 carbon atoms in the alkyl residue,

from 0.0 wt.% to 40.0 wt.%, preferably from 0.0 wt.% to 25.0 wt.%, in particular, from 0.1 wt.% to 15.0 wt.%, repeating units of alkylacrylate having from 1 to 20, preferably from 1 to 12, especially from 1 to 8 carbon atoms in the alkyl residue,

from 0.0 wt.% to 10.0 the AC.%, preferably from 0.0 wt.% to 8.0 wt.% styrene monomers with the General formula (I), but it is desirable that these mass percentage amounted to 100.0 wt.%.

According to a particularly preferred variant implementation of the present invention, the second, relying on its total weight, contains at least 50 wt.%, it is advisable - at least 60 wt.%, preferably at least 75 wt.%, in particular at least 85 wt.% methyl methacrylate monomers.

In addition, the mass fractions of the components of the second shell reasonably be implemented in such a way that the glass transition temperature Tg was at least 10°C., and preferably at least 30°C. When the glass transition temperature Tg of polymerizate, as already mentioned above, can be determined by differential scanning calorimetry (DSC) and/or pre-roughly be calculated using equation Fox.

The total radius of the particle morphology "core-shell", including available if necessary, the second shell is in the range from more than 160 to 260 nm, preferably in the range from 170 to 255 nm, in particular in the range from 175 to 250 nm. The total radius determined by the method of Kultura. This is known in the literature as a way of determining the size of the particles based on the measurement of electrical resistance is, a characteristic way of changing with the passage of the particles through a small hole to measure. Details are set out, for example, in Nachr. Chem. Tech. Lab. 43, 553-566 (1995).

Further, for the purposes of the present invention proved to be particularly favorable to the mass of the cores ranged from 5.0 wt.% to 50.0 wt.%, preferably from 15.0 wt.% to 50.0 wt.%, preferably from 25.0 wt.% to 45,0 wt.%, in particular 30.0 wt.% to 40.0 wt.%,

the weight of the first shell from 20.0 wt.% to 75,0 wt.%, preferably from 30.0 wt.% to 60.0 wt.%, preferably from 35.0 wt.% to 55.0 wt.%, especially from 40.0 wt.% up to 50 wt.%, and

the weight of the second shell from 0.0 wt.% to 50.0 wt.%, preferably from 5.0 wt.% to 40.0 wt.%, preferably 10.0 wt.% to 30.0 wt.%, especially from 15.0 wt.% to 25.0 wt.%.

Moreover, it is preferable that the mass fraction amounted to 100.0 wt.%.

Receiving particles according to the invention of type "core-shell" can be performed by a method known per se, for example by multi-stage emulsion polymerization. It is advisable to conduct it in such a way that in the reaction vessel is placed the water and emulsifier. When this reaction mixture initially contains preferably from 90,00 to 99.99 mass parts of water and from 0.01 to 10.00 parts by weight of emulsifier, and these weights in a reasonable manner in the total 100,00 weight fractions.

In this costatum gradually add in the following sequence of monomers of the core in the desired ratio and polimerizuet them before entry into the reaction of at least 85,0 wt.%, preferably at least a 90.0 wt.%, it is advisable at least 95,0 wt.%, especially at least 99 wt.%, in each case on the total weight of the monomers,

then add the monomers for the first shell in the desired ratio and polimerizuet them before entry into the reaction of at least 85,0 wt.%, preferably at least a 90.0 wt.%, it is advisable - at least 95,0 wt.%, especially at least 99 wt.%, each case on the total weight of the monomers.

If necessary, add the monomers for the second shell in the desired ratio and polimerizuet them before entry into the reaction of at least 85,0 wt.%, preferably at least a 90.0 wt.%, it is advisable - at least 95,0 wt.%, especially at least 99 wt.%, each case on the total weight of the monomers.

In this case, the polymers in the sense of the present invention involve compounds that have at least ten times the molecular weight compared to the particular starting compound from A) to I), the so-called monomer.

Track the polymerization reaction at each stage can in a known manner, for example, gravimetrically or by using gas chromatography.

According to the present invention the polymerization of the steps from b) to d) it is advisable to carry out at a temperature in the range of up to 120°C, preferably in the range from 30 to 100°C.

It is particularly favorable was the temperature of polymerization in the range from 60 to 90°C., preferably in the range from 70 to 85°C., preferably in the range from 75 to 85°C.

The polymerization run using the usual emulsion polymerization initiators. Proper organic initiators are, for example, hydroperoxides such as tert-butyl hydroperoxide or cumene-hydroperoxide. Appropriate inorganic initiators are hydrogen peroxide, and salt peroxidizing acid with alkali metals and ammonium salts, in particular peroxodisulfate sodium and potassium. As the redox initiator systems can be used, for example, combinations of tertiary amines with peroxides or disulfit sodium and salt peroxidizing acid with alkali metals and ammonium salts, in particular peroxodisulfate sodium and potassium, or particularly preferably peroxides. Further details are set out in the literature, in particular, in .Rauch-Puntigam, Th. An active part, "Acryl - and Methacrylverbindungen", Springer, Heidelberg, 1967 or Kirk-Othmer, Encyclopedia of Chemical Technology, Vol.1, Seiten 386ff, J. Wiley, New York, 1978. In the framework of the present invention the use of organic and/or inorganic particularly preferable.

These initiators can be used either separately or in the MCA is I. It is advisable to apply them in a quantity of from 0.05 to 3.0 wt.% from the total mass of the monomers of this particular stage. It is also preferred to conduct the polymerization with a mixture of different polymerization initiators having different time polyreactive to maintain a constant flow of radicals during polymerization, and at various polymerization temperatures.

The stabilization of the mixture is performed preferably by using emulsifiers and/or protective colloids. To maintain low strength dispersion preferred stabilizing emulsifiers. Preferably, the total amount of emulsifiers ranged from 0.1 to 5 wt.%, in particular from 0.5 to 3 wt.% of the total weight of monomers a) to I). A particularly convenient to use the emulsifier is anionic or nonionic emulsifiers or mixtures thereof, in particular:

the alkyl sulphates, mainly those having from 8 to 18 carbon atoms in the alkyl residue, alkylarylsulfonate and alkylarylsulfonates having from 8 to 18 carbon atoms in the alkyl residue and 1 to 50 ethyleneoxide units.

The sulfonates, especially alkyl sulphonates having from 8 to 18 carbon atoms in the alkyl residue, alkylarylsulfonates having from 8 to 18 carbon atoms in the alkyl residue, esters and palefire sulfonterol acid with a monohydroxy alcohols or alkylphenol the AMI, having from 4 to 15 carbon atoms in the alkyl residue; if necessary, these alcohols or ALKYLPHENOLS can be ethoxycarbonyl with 1-40 ethyleneoxide units;

Partial esters of phosphoric acid and their salts with alkali metals and ammonium salts, preferably alkylphosphate and alkylaromatic containing from 8 to 20 carbon atoms in the alkyl (alcylaryl) residue and 1 to 5 ethyleneoxide units;

alkylpolyglycoside, preferably containing from 8 to 20 carbon atoms in the alkyl residue and 8 to 40 ethyleneoxide units;

alkylarylsulphonates, preferably containing from 8 to 20 carbon atoms in the alkyl (alcylaryl) residue and 8 to 40 ethyleneoxide units;

copolymers of ethylene oxide and propylene oxide, preferably block copolymers, preferably having from 8 to 40 ethylenoxide or propyleneoxide units.

According to the invention is preferably used a mixture of anionic and nonionic emulsifiers. Particularly useful was a mixture of ether or Palmyra sulfonterol acid with a monohydroxy alcohols or ALKYLPHENOLS having 4 to 15 carbon atoms in the alkyl residue as anionic emulsifier and alkylpolyglycoside, preferably having from 8 to 20 carbon atoms in the alkyl residue and 8 to 40 ethyleneoxide units, as neion the second emulsifier in a weight ratio of from 8:1 to 1:8.

If necessary, you can use the emulsifiers also in a mixture with protective colloids. Appropriate protective colloids are including partially the saponified polyvinyl acetate, polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, starch, proteins, poly(meth)acrylic acid, poly(meth)acrylamide, polyphenylsulfone acid, melamineformaldehyde, naphthalenedisulfonate, copolymers of styrene-maleic acid and vinilpyrrolidonol acid. If you use protective colloids, then do it, preferably in quantities of from 0.01 to 1.0 wt.%, from the total amount of monomers a) to I). Protective colloids can be placed in the reaction mixture prior to the polymerization or added later.

The initiator is placed in the reaction mixture initially or added later. In addition, you can also place the part of the initiator in the reaction mixture at the outset, and the remainder is added later.

The polymerization is advisable to start by heating the initial mixture to the polymerization temperature and the introduction of the initiator, preferably in aqueous solution. Adding emulsifier and monomer can be conducted individually or in a mixture. Adding mixtures of emulsifier and monomer them are mixed in a mixer, connected to the polymerization reactor. Celje is obratno add the rest of the emulsifier and the remainder of the monomer, which were not introduced into the reaction mixture to begin the reaction, after the start of polymerization separately from each other. It is preferable to start adding after 15-35 minutes after the start of polymerization.

For the purposes of the present invention is also particularly beneficial to the reaction mixture contained the so-called "embryonic latex", which is advisable to obtain polymerization of alkyl(meth)acrylates, and it is also advisable that the particles had a radius in the range from 3.0 to 20.0 nm. These small values can be calculated after carrying out a strictly defined additional polymerization embryonic latex, which formed around him the shell, and the radius is made thus particles measured by the method of Kultura. This is known in the literature as a way of determining the size of the particles based on the measurement of electrical resistance, a characteristic way of changing with the passage of the particles through a small hole to measure. Details are set out, for example, in Nachr. Chem. Tech. Lab. 43, 553-566 (1995).

To embryonic latex add Monomeric components itself, i.e. kernel, the first composition, preferably under such conditions, which would allow to avoid the formation of new particles. Thanks to this polymerizate formed in the first step of the method, deposited in the form of a shell around the embryo is on latex. Similarly add the Monomeric components of the material of the first shell (second team), under such conditions, which would allow to avoid the formation of new particles. Thanks to this polymerizate formed on the second step of the method, deposited in the form of a shell around the existing kernel. These steps should be repeated for each further shell.

According to another preferred variant implementation of the present invention, the particle morphology of core-shell according to the invention is produced by emulsion polymerization method, in which instead of embryonic latex in the reaction vessel pre-placed long-chain aliphatic alcohol, mostly having from 12 to 20 carbon atoms, in emulsified form. In a preferred embodiment of this method as a long chain aliphatic alcohol use stearyl alcohol. A structure of type "core-shell", I get the same as the above method of action through the gradual addition and polymerization of the corresponding monomers, avoiding the formation of new particles. Further details on the method of polymerization, the specialist can take the texts of the German patents DE 3343766, DE 3210891, DE 2850105, DE 2742178 and DE 3701579. Regardless of a particular course of action is in the framework of the present invention proved to be particularly advantageous to dispense with the second and third mixture of monomers in proportion to consumption.

To control the length of the chain, in particular that of polymerizaton second shell, by polymerization of the monomers or mixture of monomers in the presence of a molecular weight regulator, such as, in particular, in presence known in this respect mercaptans, such as n-butylmercaptan, n-dodecylmercaptan, 2-mercaptoethanol or 2-ethylhexylacrylate, pentaerythritol-teratologist; and the molecular weight regulators in General used in amounts comprising from 0.05 to 5 wt.% from a mixture of monomers, preferably in quantities of from 0.1 to 2 wt.%, and particularly preferably in quantities of from 0.2 to 1 wt.% from a mixture of monomers (see, for example, .Rauch-Puntigam, Th. An active part, "Acryl - and Methacrylverbindungen", Springer, Heidelberg, 1967; Houben-Weyl, Methods der organischen Chemie, Bd. XIV/1. Seite 66, Georg Thieme, Heidelberg, 1961, or Kirk-Othmer, Encyclopedia of Chemical Technology, Vol.1, Seiten 296ff, J. Wiley, New York, 1978). It is preferable to use as molecular weight regulator n-dodecylmercaptan.

Upon completion of the polymerization in order to remove residual monomers can spend their additional polymerization using known methods, for example, initiated by additional polymerization.

Since the method according to the invention is particularly convenient for the manufacture of aqueous dispersions with a high solids content greater than 50 wt.% from the total mass is one of dispersion, the relative share of all substances it is advisable to choose so that the total mass of the monomers relative to the total mass of the aqueous dispersion was more to 50.0 wt.%, preferably more of 51.0 wt.%, and more preferably is 52.0 wt.%. Substances that need to be considered in this regard include, in addition to the monomers, and also all other used substances, such as water, emulsifier, initiator and, if necessary, the regulator and protective colloids, etc.

Obtained by this method aqueous dispersions have a low content of coagulate, which, counting from the total mass of the aqueous dispersion is preferably less than 5.0 wt.%, preferably less than 3.0 wt.%, in particular, less than 1.5 wt.%. According to a very preferred embodiment of the present invention, aqueous dispersion, relying on its total weight, contains less than 1.0 wt.%, preferably less than 0.5 wt.%, expediently less than 0.25 wt.%, in particular, 0.10 wt.% or less, coagulate.

Under the term "coagulate" in this regard, see water-insoluble components which should be removed by filtering the dispersion, preferably through the filter cuff with attached filter cloth No. 0.90 according to DIN 4188.

Particle morphology "core-shell" according to the invention can be obtained from the dispersion, for example,spray drying, coagulation by freezing and deposition by adding electrolyte or by mechanical or thermal loads, as you can spend according to the German patent DE 2750682 A1 or U.S. patent US 4,110,843 using a degassing extruder. The method of spray drying is the most common, although other these methods have the advantage that when used from polymerizate at least partially separate the water-soluble excipients polymerization.

If necessary, you can additionally mix the molding of PMMA with diffuser granules, to obtain the scattering. The manufacture of the diffuser granules described, for example, in German patent DE 4231995 in examples 1 to 7. The number of granules diffusers relatively merseyway molding material may be between 0.1 wt.% and 60 wt.%, preferably between 0.2 wt.% and 50 wt.%, and very preferably between 0.5 wt.% and 45 wt.%.

As thermoplastic polyurethane used product related aliphatic units.

Polyurethanes (PUR) are polymers, macromolecules which the monomers (structural units) are connected by urethane groups-NH-CO-O-. In General, polyurethanes are polyprionidae of diatomic or polyatomic alcohols and isocyanates according to

R1and R2this may mean a low molecular weight or is a polymeric aliphatic or aromatic group. Technically important polyurethanes are synthesized from complex polyetherdiols and/or simple polyetherdiols and, for example, 2,4 - or 2,6-colordistance (TDI, R2=C6H3-CH3), 4,4-methylenedi(phenylisocyanate) (DHS, R2=C6H4-CH2-C6H4), 4,4'-methylenedicyclohexyl (HMDI, R2=C6H10-CH2-C6H10) or hexamethylenediisocyanate [GDI, R2=(CH2)6].

Synthesis of PUR can be carried out without solvents or in an inert organic solvents. As catalysts for polyaddition used repeatedly described amines or organic tin compounds. When using bifunctional alcohols and isocyanates in equimolar ratios get linear PUR. Branched and crosslinked products obtained using the original components with a large number of functional groups, and with an excess of diisocyanates, when the isocyanate groups react with urethane groups or urea groups with the formation of allophanate or biuret structures, such as

Accordingly, depending on the selected source component and their stoichiometric ratios get PUR with very different mechanical properties, which find diverse applications as components of adhesives and coatings (polyurethane resin), ionomers, thermoplastic materials for parts of bearings, rollers, tires, rollers, and in a more or less solid elastomers in the form of fibers (elastic fibers, reducing PUE, fibre "lycra or Spandex) or in the form of polifemo-urethane rubber (Reduction in EU or AU according to DIN ISO 1629: 1981-10), in the form of molded resin-example (including reinforcement fibers), and primarily as a foamed plastic; see also polyurethane rubbers, polyurethane varnishes, polyurethane resin. In addition, PUR described in Kunststoffe 85, 1616 (1995), Batzer 3, 158-170 Batzer 3, 158-170; Domininghaus (5.), S.1140 ff.; Encycl. Polym. Sci. Eng. 13, 243-303; Houben-Weyl E 20/2, 1561-1721.

Examples

Mixing molding masses

Example: using an extruder formed compound TPU (Desmopan®W DP85786A, Bayer) with PLEXIGLAS®zk5HC manufactured by Röhm GmbH & Co. KG (ratio of TPU / PLEXIGLAS®zk5HC: 1/2,75). The temperature of extrusion was between 200°C and 260°C.

In addition to this mixture as the comparison used the following molding material:

PLEXIGLAS®zk50, the company Röhm

Comparative example 1: a mixture of silicone modifier, manufactured as described in example 2, in the international application WO 2003/066695, with PLEXIGLAS®7H manufactured by Röhm GmbH & Co. KG (content of silicone modificat the RA: 25 wt.%).

Comparative example 2: a mixture of the modifier "core/shell/shell and PLEXIGLAS®7N, made as described in example in the German patent application DE 10260065 A1.

Comparative example 3: using an extruder formed compound TPU (Desmopan®W DP85786A, Bayer AG) and PLEXIGLAS® 7M manufactured by Röhm GmbH & Co. KG (Ratio of TPU / 7M: 1 / 2,75).

Test molding masses

From the obtained by mixing the molding mass produced samples for testing. The molding material or the corresponding samples were tested by the following methods:

Viscosity ηS (220°C/5 MPa)Determination of the strength of the melt, the ratio test: DIN 54811:1984
MVR (230°C/3.8 kg)Determination of the volume flow index, standard test ISO 1133:1997
Mini-Vicat (16 h/80°C)Determination of the softening point by Vika using device Mini-Vicat, standard test DIN ISO 306: Aug. 1994
The blow. strength (Charpy)Determination of impact strength of the sample with the cut on the Sharpie, the standard of test: ISO 179
The modulus of elasticityDetermination of modulus of elasticity, the ratio test is tions: ISO 527-2
Transmission (D65/10°)Measurement of transmittance at D65 and 10° for the sample with thickness of 3 mm, the ratio test: DIN 5033/5036

The results of the test mixtures are presented in table 1.

Clearly visible are the advantages of the mixture according to the invention compared with conventional molding masses, modified for impact strength (controls 1, 2, 3 and PLEXIGLAS®zk50):

Impact strength, component 124 kJ/m2at 23°C and 50 kJ/m2at -10°C, very high. At -40°C the value of 23 kJ/m2also indicates the presence of some impact strength.

The light transmission plate 3 mm thick, constituting more than 80% at room temperature, sufficient for the intended use as a film for skiing.

The modulus of elasticity of greater than 1200 MPa, shows good mechanical characteristics of the molded product be protected from the mixture.

The stability of shape when heated enough to use as a film for skis with a softening point by Vika is above 85°C.

Due to the low melt viscosity (compare also MVR) material is easily processed.

Tapes of these mixtures is much easier to print than normally used in these cases, polyamide film or films and the mixtures TPU/MABS, these films are also more resistant to weather influences.

Table 1
MixtureUnitsCompare. 1Compare. 2Compare. 3PLEXIGLAS®zk50And
Property
Viscosity ηSPA·s69403400171n/a500
(220°C/5 MPa)
MVR (230°Cml/0,31,4420,19,15
3.8 kg)10 min
Mini-°C9998,589,77587
Vika(16 h/80°C)
transmission%n/a64,680,18983
The blow. stre. (
Sharpie)kJ/m23912224,3break no124
23°C
-10°CkJ/m2-50
-20°CkJ/m2359222,9110,426
-40°CkJ/m2355321,422,923
The modulus of elasticityMPa21201620n/a9501520

1. Transparent moresomeone polymer mixture for the manufacture of molded parts of thermoplastic polyurethane and from high impact modified polymer of methyl methacrylate obtained from a mixture of monomers comprising at least 40 wt.% of methyl methacrylate and 0 to 60 wt.% together polymerized with methyl methacrylate monomer, with specified polymer-modified impact modifier with the structure "kernel/about the shell/shell", in which the first shell includes from 80,0 up to 98 wt.% the repeating units of (meth)acrylate and from 2.0 to 20.0 wt.% styrene units with the General formula (I)

where the remains of R1to R5in each case, independently of one another denote hydrogen, halogen, in particular fluorine, chlorine or bromine, or alkyl group with 1-6 carbon atoms and the remainder R6means hydrogen or alkyl group with 1-6 carbon atoms,
the second shell contains from to 50.0 to 100.0 wt.% repeating units of alkylmethacrylamide having 1 to 20 carbon atoms, from 0 to 40.0 wt.% repeating units of alkylacrylate, from 0 to 10.0 wt.% styrene units of formula (I),
the core includes a 50.0 to 99.9 wt.% repeating units of alkylmethacrylamide having from 1 to 20 carbon atoms, from 0 to 40.0 wt.%, repeating units of alkylacrylate having 1 to 20 carbon atoms, from 0.1 to 2.0 wt.% crosslinking repeating units and 0 to 8.0 wt.% styrene units of formula (I).

2. The polymer mixture according to claim 1, characterized in that the mass ratio of polyurethane and high impact modified polymer of methyl methacrylate is 10-50÷90-50 parts.

3. The polymer mixture according to claim 1, characterized in that the mass ratio of polyurethane and high impact modified polymer of methyl methacrylate is 20-40÷80-60 parts.

4. The polymer mixture according to claim 1, the call is connected with the fact, what high impact modified polymer of methyl methacrylate contains 10-50 wt.% impact modifier in recalculation on weight of the polymer.

5. The polymer mixture according to claim 1, characterized in that the polyurethane is obtained by using aliphatic isocyanates.

6. The polymer mixture according to claim 1, characterized in that as droprate modified polymer of methyl methacrylate contains high impact modified polymer of methyl methacrylate containing additionally from 1 to 50% of the scattering particles with a mean diameter of from 1 to 300 μm, calculated on the total polymer mixture.

7. The application of the polymer mixture according to one of claims 1 to 6 to obtain a polymer molded products with transmission >80% (d=3 mm), impact strength according to Charpy at 23°C>100 kJ/m2at -10°C>30 kJ/m2at -20°C>20 kJ/m2and with a softening point in Vic, determined according to DIN ISO 306 (B) >80°C, and the elastic modulus >1400 MPa.

8. The use according to claim 7, characterized in that the polymer molded product is a film or molded product, or cross detail in the automotive industry or molded polymer products with diffuser granules.

9. The use of claim 8, wherein the film is used to cover sports equipment or body parts in the automotive industry.



 

Same patents:

FIELD: physics; optics.

SUBSTANCE: proposed invention relates to a rear projection screen. The proposed rear projection screen has a scattering layer which contains scattering particles, and a support layer. The scattering layer has half the value of the scattering intensity angle greater than or equal to 15° and has scattering particles with average diametre ranging from 0.1 to 150 mcm. The first fraction of spherical scattering particles has average diametre from 0.1 to 40 mcm, and the second fraction of spherical scattering particles has average diametre from 10 to 150 mcm. The support layer has half the value of scattering intensity angle less than or equal to 6.5° and gloss number R60° less than or equal to 70 and average surface roughness Rz from 3 to 40 mcm. The support layer does not contain scattering particles or contains them in an insignificant quantity.

EFFECT: suppression of spurious reflection from the screen, high image quality.

19 cl

FIELD: physics, optics.

SUBSTANCE: rear projection screen contains one light-diffusing polymethyl methacrylate layer, which includes polymethyl methacrylate matrix, and also spherical diffusing particles (A) and speherical particles (B). At that particles (A) have size from 0.1 to 40 micrometer with index of refraction, which differs from refraction index of polymethyl methacrylate matrix by value from 0.02 to 0.2. Particles (B) have size from 10 to 150 micrometer and refraction index, which differs from refraction index of polymethyl methacrylate matrix by value from 0 to 0.2. Total concentration of particles (A) and particles (B) makes from 1 to 60 wt % in equivalent to mass of light-diffusing polymethyl methacrylate layer. Concentration cPA of particles (A), thickness dS of light-diffusing polymethyl methacrylate layer, and also size DPA of spherical diffusing particles (A) are selected so that ratio cPA·dS/DPA3 makes from 0.001 to 0.015% wt·mm/mcm3, concentration cPB of particles (B), thickness ds of light-diffusing polymethyl methacrylate layer, and also size DPB of spherical particles (B) are selected so that ratio CPB·dS/DPB3 makes from 0.000005 to 0.002% wt·mm/mcm3 and ratio of average roughness RZ of polymethyl methacrylate layer surface squared to size of spherical particles (B) cubed, Rz2/DPB3, makes from 0.0002 to 0.1300 mcm-1.

EFFECT: cocreation of scratch-safe rear rejection screen.

29 cl

FIELD: rear-projection screens.

SUBSTANCE: screen has, at least, one light-diffusing polymethylmethacrylate layer, 0.05 to 4 mm-thick, containing spherical polymer particles with the size of 5 to 35 mcm in concentration of 2 to 60 % by weight on the basis of total weight of light-diffusing polymethylmethacrylate layer. The difference in refractive indices of spherical polymer particles and those of polymethylmethacrylate matrix makes from 0.02 to 0.2. The concentration cp of spherical polymer particles, thickness ds of light-diffusing polymethylmethacrylate layer, as well as the size Dp of spherical polymer particles are selected so that the ration cp•ds/Dp3 varies from 0.001,5 to 0.015% by weight•mm/mcm3. The ration of mean roughness Ra of the polymethylmethacrylate layer surface to size Dp of spherical polymer particles varies from 0.05 to 0.4.

EFFECT: higher-quality image.

20 cl, 1 dwg

FIELD: projection equipment.

SUBSTANCE: method of forming projection screen 3 or projection space is based on supply and/or formation of dissipating (reflecting) of light dissipation centers 2 mainly in laminar transporting flux 2, which centers are supposed to be transferred by transportation flux. According to the invention, dissipating centers 4 are supplied and/or formed in transporting flux 2 in its central (internal) part. Flux stays laminar at some distance from direct vicinity of borders of transition between transporting flux 2 and surrounding area to keep shape of projection screen. Solid, liquid or gaseous matter can be used as centers of dissipation 4 for resilient or non-resilient light dissipation.

EFFECT: improved efficiency of operation.

22 cl, 6 dwg

FIELD: machine-building industry.

SUBSTANCE: invention relates to the method of encapsulating o-rings manufacture for installing them between parts and units of internal combustion engines, between flange connections in chemical industry, for finishing, noise-insulating and thermal insulating panels. The method provides for grinding cork wastes to 0.5-5.0 mm. The cork wastes are mixed up with binding material based on a mixture of urethane and butadiene-acrylo-nitric rubber taken in a weight ratio 10-90:10-90. After rubber mixing with binding material, the mixture is moulded at 143-151°C and 3-10 MPa during 20-60 min. Then it is exposed at room temperature during one day. The sheets of the material are then slit and needed items are cut out. Wastes from cork, shoe and prosthetic and orthopedic production, wastes from finishing, noise and thermal insulating production, proper substandard wastes, flash chipping wastes are used as grinded cork wastes which are taken separately or in any ratios between each other.

EFFECT: invention allows for increasing reliability of o-rings and obtaining multifunctional material.

5 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a curable composition consisting of two parts, which is stable during storage in form separate parts and solidifies when merged to obtain an essentially homogeneous polyurethane-polysiloxane mixture. Said composition contains (a) a first dry part containing a moisture-curable silylated polyurethane resin obtained (i) by reacting a polyurethane prepolymer with terminal isocyanate groups with at least one silane selected from a group consisting of mercaptosilaine and aminosilane, and a cross-linking agent for diorganopolysiloxane with terminal silanol groups; (b) a second part containing diorganopolysiloxane with terminal silanol groups; (c) a catalyst for condensation in the first and/or second part; and possibly (d) at least one additional component selected from a group consisting of diorganopolysiloxane with terminal alkyl groups, filler, a UV stabiliser, an antioxidant, an adhesion promoter, a curing accelerator, a thickener, a plasticiser, a moisture absorber, a pigment, a dye, a surfactant, a solvent and a biocide; where the additional component is present in the first and/or second parts of the composition depending on the part with which it is compatible. The invention also describes an essentially homogeneous polyurethane-polysiloxane mixture used as a sealant, adhesive or coating, obtained during solidification as a result of merging the first and second parts of said composition.

EFFECT: obtaining a composition consisting of two parts, which is stable during indefinite storage but undergoes fast solidification upon merging the two parts to obtain a polyurethane-polysiloxane mixture with good weather resistance and high heat resistance.

13 cl, 5 ex, 2 tbl

Thin condom // 2434896

FIELD: chemistry.

SUBSTANCE: condom contains natural rubber and polyurethane in form of a mixture. Preferably, the condom has single wall thickness of less than 55 mcm and burst pressure of 1.0 kPa or higher. The method of making the condom involves mixing polyurethane latex and natural rubber latex and forming a condom from said mixture.

EFFECT: invention enables to reduce wall thickness of the condom while satisfying burst pressure requirements.

26 cl, 5 dwg, 1 tbl

FIELD: medicine.

SUBSTANCE: present invention refers to cosmetology, more specifically concerns a polymeric ingredient consisting of one polymer or of a number of various polymers, and containing at least one polyurethane; said polymer or at least one of said polymers contain acid groups which are neutralised at least by 40 % at least with one inorganic base and at least by 1 % with triethanolamine. Besides, the invention refers to a cosmetic agent which contains such polymeric ingredients, and also to a method of modification of mechanical properties of the polymeric ingredient by acid group neutralisation at least by 40 % at least with one inorganic base and at least by 1 % with triethanolamine.

EFFECT: invention provides the polymeric ingredients appropriate for making cosmetic agents exhibiting good film-forming properties, and also enables adjusting their mechanical properties, particularly elasticity, and especially a hardness to elasticity relation, to the intended application.

10 cl, 25 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: composition contains the following in pts.wt: 100 - copolymer of butadiene and piperylene with molecular weight 1200-3200 and content of hydroxyl groups 0.8-1.1%, 20-polymethylene polyphenyl isocyanate with content of isocyanate groups 29-31%, 70-100 - rubber crumbs, and 25-20 - high-molecular polyethylene with molecular weight 30000-800000.

EFFECT: high dynamic and physical-mechanical properties of the composition based on the filled foamed polyurethane.

1 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention can be used as structural material for heat insulation slabs for multiple purposes, as well as heat insulation material for sealing window or doorway openings and for heat insulating pipelines. The invention discloses a heat insulation composition which contains hard foamed polyurethane and filler - sol microspheres. The filler used in the composition is in form of sol microspheres which are modified with copolymers of (meth)acrylic acid derivatives - sodium salt, amide, methyl ether with different molecular weight - or γ-aminopropyl triethoxysilane, which provides affinity to the polymer matrix of the hard foamed polyurethane in amount of 5-40 wt %.

EFFECT: high flexural and compression strength, low moisture absorption while keeping the heat conduction coefficient at a low level, broader functionalities and high cost-effectiveness of the heat insulation composition.

2 dwg, 2 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to compositions for impregnating porous surfaces, for example concrete, asbestos cement, wood etc, as well as wet surfaces, at temperature ranging from -5°C to +30°C. The composition contains the following, wt %: 30-36 urethane prepolymer, 6-18 filler, 3-6 plasticiser, 41-55 coal-tar solvent and 0.3-0.4 structuring additive TI as a drying agent.

EFFECT: preparation of a composition based on a single-component urethane film forming agent, capable of moisture curing, having better absorbability into a porous substrate, more dense waterproofing, low rate of increase of viscosity and higher elasticity, which simplifies the technology of depositing the composition.

8 cl, 3 tbl, 1 dwg

FIELD: construction.

SUBSTANCE: composition contains the following components, wt parts: 100 - rubber base, 26-44 - isocyanate hardener, 0.01-0.1 - catalyst of urethane formation and 1-2 - 3,3'-dichloro-4,4'-diaminodiphenylmethane. Rubber base consists of the following components, wt parts: 100 - low-molecular hydroxyl-containing rubber, 60-190 - plasticiser, 100-480 - filler, 1-2 - anti-ageing agent and 1-10 - pigment. Isocyanate hardener represents prepolymer with content of isocyanate groups of 4.0-5.0%. Prepolymer is produced by interaction of 4,4'-diphenylmethanediisocyanate and oligodiendiol with molecular weight of 2000-2200, with 1.2-1.9% content of hydroxyl groups, at the ratio of 2:1 of isocyanate and hydroxyl groups.

EFFECT: increased strength, elasticity and hardness.

6 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: polyurethane composition contains the following in pts. wt: 100 - polyether having molecular weight of 1000-2000; 150-350 2,3-toluene diisocyanate, 1-95 amine hardener, 10-35 plasticiser, 1-20 fluorooligomeric alcohol with molecular weight of 1000-5000 and 5-100 polyol with molecular weight of 1200-3500. Content of NCO- groups in the composition equals 4.09-6.5%.

EFFECT: elastomers obtained from said composition have high durability, good strength properties and high frost resistance, which enables use of articles made from the said composition under heavy loads, in conditions with large differential temperature and in aggressive media.

8 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a composition which contains a specific non-crosslinked medium and at least one microgel, methods of preparing said composition, use of said composition, microgel-containing polymers, rubber, lubricant materials, coatings etc, obtained from said composition. The composition is obtained by mixing at least one non-crosslinked organic medium which does not contain groups which can be crosslinked through functional groups containing heteroatoms or through C=C groups, selected from a group of polyethers or polyether oils, naphthene oils, mineral oils and oils based on renewable raw materials and which has viscosity less than 30000 mP at temperature 120°C an at least one microgel (B) based on butadiene-styrene rubber, wherein microgel (B) is obtained through emulsion polymerisation and the composition contains from 2 to less than 40 wt % microgel (B) of the total amount of the composition, wherein at least one microgel is not crosslinked using high-energy radiation.

EFFECT: improved physical and chemical properties of the composition, control of rheological properties, positive effect on coefficient of friction.

34 cl, 3 dwg, 13 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: polymer powder compositions are obtained via radical polymerisation of one or more ethylenically unsaturated monomers carried out in an aqueous medium in the presence of a nonionic protective colloidal and/or nonionic emulsifying agent, followed by drying. Aqueous dispersions of polymers undergo drying in the presence of an additional 0.1-20 wt % cation-active protective colloid, in terms of the amount of polymer components of the polymer dispersion. The protective colloid is selected from a group comprising homopolymers or copolymers of one or more cation-active monomers as a drying-promoting agent. The invention also describes cation-stabilised and water-redispersible polymer powder compositions for use in construction chemistry and use of the polymer powder composition in construction chemistry products, in production of adhesives and in production of coating materials.

EFFECT: polymer powder compositions have caking resistance and high redispersibility in water.

9 cl, 3 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: polymer material contains acrylic polymer, chlorine-containing polymer and inorganic hydroxide. The acrylic polymer is selected from a homopolymer of alkyl(alc)acrylate or copolymer of alkylmethacrylate and alkylacrylate. The chlorine-containing polymer contains 5-70 wt % halogen. The inorganic hydroxide is selected from magnesium hydroxide, zinc hydroxide or mixtures thereof, except a mixture of magnesium hydroxide and zinc oxide or magnesium hydroxide and zinc stannate. Weight ratio between the chlorine-containing polymer and the acrylic polymer is at least 0.3. Polymer material is obtained by mixing the chlorine-containing polymer and inorganic hydroxide in molten acrylic polymer. The polymer material is used to make articles and structural elements in construction.

EFFECT: inorganic hydroxide gives the material high resistance to atmospheric effects.

45 cl, 3 tbl, 6 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: declared invention concerns hydrogel compositions useful as a dressing material or protective agent, and for application of a wide range of active substances in relation to the skin and tissues of mucosas, such as mouth, including tooth bleaches. The faza-parted, film-forming composition containing an admixture is offered: (a) the first polymer bulking up in water, and the specified polymer is not dissolved in water at pH less than approximately 5.5, or water-soluble polymer; (b) an admixture of hydrophylic polymer and additional low-molecular polymer, capable to formation of hydrogen communications with hydrophylic polymer; (c) the second polymer bulking up in water, and the specified polymer we will not dissolve in water at all value pH; and (d) unessential active substance, in a dissolvent or in an admixture of dissolvents where the composition is exposed to separation of phases at hydration.

EFFECT: treatment of a disease state of various surfaces of a body (teeth, fingernails, skin, mucosas etc).

44 cl, 7 ex

FIELD: medicine.

SUBSTANCE: composition contains water-swelling, water-insoluble polymer, mixed hydrophilic polymer and complementary oligomer able to form hydrogen bond with hydrophilic polymer, and a bleaching agent, preferentially peroxide. The composition is applied a dental bleaching composition and applied on teeth to be bleached, and then removed as the required bleaching is reached. In best versions the composition is unstable and translucent. There are also methods of preparation and application of the compositions.

EFFECT: reduced dental sensitivity and damage or irritation of gums and oral mucous membranes, improved clinical effectiveness.

54 cl, 10 ex

FIELD: chemistry.

SUBSTANCE: there is offered wheel impregnation composition containing aqueous solution of binding agent, oxyethylated lanolin and liquid glass, where a binding agent is a mixed aqueous copolymer emulsion prepared by emulsion polymerisation of methylolmethacrylamide, vinylacetate, butykacrylate, methylmethacrylate and methacrylic acid in mass ratio 1.0:9.0-9.5:2.5-3.0:3.5-4.0:0.04-0.06 respectively with the composition formulation as follows (wt fractions): copolymer emulsion (on dry basis) - 100, oxyethylated lanolin - 3-8, liquid sodium glass - 1-6, water 360-440.

EFFECT: development of wheel impregnation composition improving resistance of sisal-fabric and sisal-cord wheels with operating cost reduction.

1 cl, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: there is disclosed application of inorganic IR-reflecting pigments for dark-coloured moulding compounds containing mixed polymethyl(meth)acrylate and adjugated matrix to 45 wt % containing (wt %): styrene (70-92), acrylonitrile (8-30), additional comonomers (0-22) and inorganic pigments. A moulded piece made of these moulding compounds is characterised with heating rate 50°C/20 min and less. In addition, there is disclosed application of the declared moulded piece over the other moulded piece with using conventional methods.

EFFECT: development of well processed, stable opaque-coloured IR-reflecting moulding compounds.

7 cl, 3 dwg, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to compositions, with low coefficient of friction for use in friction units of living organisms. Proposal is given of an antifriction composition, containing, as polymer binding mixture (with ratio of components in the binder): methyl methacrylate monomer (27-36 mass units), polymethyl methacrylate polymer powder (72-64 mass units), initiator - benzoyl peroxide 1 mass units (polymer binder A); or a mixture (with ratio of components in the binder): methyl methacrylate (27-36 mass units), copolymer powder (72-64 mass units) with the following content of components: methyl methacrylate - 89 mass units, ethyl methacrylate - 8 mass units, methyl methacrylate - 2 mass units, as well as initiator-benzoyl peroxide - 0.6-1.5 mass units (polymer, binder B) and ultrahigh-molecular polyethylene with 1·106 - 12·106 dalton molecular weight, in powder form (2-15 mass units per 85-98 mass units of polymer binder). Compared to the prototype, the value of coefficient of friction decreases by 2-4 times.

EFFECT: design of a composition, which reduces friction in the maxillotemporal joint of a polymer implant.

3 cl, 4 tbl

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