Composition based polyols

 

The invention relates to compositions based polyols, and also to a method for production of polyurethane foam using such compositions, which can be used for pipe insulation. Describes a single-phase mixture of polyols comprising 20-65 wt.% the polyol of the first type having srednekamennogo molecular weight of more than 800, a hydroxyl number of less than 200 mg KOH/g and a content of ethylene oxide is less than 75 wt.%, and 35-80 wt.% the polyol of the second type having srednekamennogo molecular weight less than 1000, a hydroxyl number greater than 300 mg KOH/g and an amine content, expressed in percentage N content of at least 0.2 wt.%. This mixture, together with catalysts, cross-linking and foaming agents and other auxiliary substances, forms a composition, which when interacting with the polyisocyanate component to form a polyurethane foam. Obtained in this way, the foams have satisfactory heat resistance and melting point is 120oWith or more. 3 S. and 4 C.p. f-crystals, 3 tables.

The invention relates to compositions based on polyols and particularly, although not exclusively, relates to compositions based polyols per se and the method of receiving the s, having actually a structure with closed cells currently use for isolation of semi-flexible pipes that can be used in heating systems or simply for transporting hot liquids.

The production and use of semi-flexible pipe is connected with a number of advantages. For example, in the manufacture of such pipes can be used essentially continuous process, which allows to achieve high performance and to reduce the use of raw materials, because the filling pipe is almost no need for shipping containers. In addition, the flexibility of such pipes allows you to wrap them in the Bay, which facilitates their transport and installation. Further, at the place of use can be installed over long sections of pipe, which reduces the number of joints required for pipe connections.

The foams used in pipes, shall, in addition to compliance flexibility to have other necessary properties and must be able to withstand relatively high temperatures. For operating temperatures up to 95oSince you can use the inner plastic tube containing a foaming system with low heat resistance. However, when the working temperature ol the m-Nickel, that requires adapted systems foam. For manufacturers phenoplasts it is desirable to make a foam, which would meet both the requirements for heat resistance, as mentioned above.

Known to use mixtures of polyols with different properties, to obtain a semi-flexible polyurethane foams. One known compound (described in comparative example C1) may satisfy the requirements for heat resistance; however, the polyols used are incompatible and must be mixed before use, which is a disadvantage. Other systems based on compatible polyols are commercially available. However, on the basis of the known systems are formed of polyurethane foams, which is unsatisfactory from the point of view of the requirements for heat resistance or form foams having a low degree of flexibility.

The purpose of the present invention is to solve the above problems.

U.S. patent 4568702 describes the mixture of polyols consisting of 25-75 wt.% flexible simple polyester polyol and 75-25 wt.% hard simple polyester polyol. It is not disclosed single-phase mixture of compatible polyols.

In accordance with the first aspect of it, "said first polyol"), having srednekamennogo molecular weight greater than 800, a hydroxyl number of less than 200 mg KOH/g and a content of ethylene oxide is less than 75 wt.%, and forming with it a compatible mixture of 35-80 wt. % polyol of the second type (hereinafter referred to as "the specified second polyol"), having srednekamennogo molecular weight less than 1000, a hydroxyl number greater than 300 mg KOH/g and an amine content (expressed in the framework of the percentage of N ) at least 0.2 wt.%.

Said first polyol may have a molecular weight of more than 1500, more acceptable to 2000, preferably more than 2500, more preferably more than 2700 and more particularly 2900. Acceptable, when said first polyol has a molecular weight less than 20,000, preferably less than 15,000, more preferably less than 10,000, particularly less than 8000.

Acceptable, when said first polyol has a hydroxyl number of less than 150, preferably less than 100, more preferably less than 80, especially less than 60 mg KOH/g is Acceptable, when said first polyol has a hydroxyl number of at least 10, preferably at least 15, more preferably at least 20, especially at least 25 mg KOH/g

The functionality of the polyol is defined as the average number of hydroxyl groups nachtfalke at least 2,2, more preferably at least 2,4, especially at least a 2.5. Acceptable, when said first polyol has a functionality of 6 or less, preferably 5 or less, more preferably 4 or less, especially of 3.5 or less.

The content of ethylene oxide by weight in the specified first polyol may comprise at least 5%, preferably at least 8%, more preferably at least 10%, especially at least 12%. The specified content of ethylene oxide in the specified first polyol may be less than 60%, acceptable less than 50%, preferably less than 40%, more preferably less than 30%, especially 20% or less. The rest of the content accelerated specified in the first polyol may be a propylene oxide. Thus, preferably said first polyol is a polyol based on a simple poly(oxyalkylene)ether, in particular adduct of ethylene oxide and/or propylene oxide.

The ethylene oxide may be introduced into the polymer chain of the specified first polyol by any known method, for example in the form of internal blocks, terminal blocks and statistically distributed units.

Said first polyol may include a polymer polyol, which is soderzhanie included in this description by reference. The main polyol may have any of the characteristics specified first polyol described in this application in various aspects. When the text refers to the mass. % first polyol in the composition, this Mac. % refers to the number of primary polyol, when using the polymer polyol.

The polymer dispersed in the main polyol, in principle, can be any such polymer which is traditionally used for these purposes. So, acceptable polymers include polymers based on Ethylenediamine monomers and especially polymers vinylaromatic hydrocarbons, such as styrene, alpha-methylsterol, methylsterol and various other alkyl substituted styrene. Among them, the use of styrene is preferred. Vinylaromatic monomer may be used alone or in combination with other Ethylenediamine monomers such as Acrylonitrile, Methacrylonitrile, vinylidenechloride, various acrylates and related diene, such as 1,3-butadiene and isoprene. However, the preferred polymers are polystyrene and copolymers of styrene and Acrylonitrile (SAN). Another reasonable class of polymers are polymers based on polyureas and polyurethanes. In this oth alcohols and aromatic diisocyanates. Particularly preferred polymer is the condensation product of triethanolamine and colordistance (TDI). Acceptable, when dispersed polymer is present in an amount of 5 to 50 wt.% calculated on the total weight of the polymer polyol. In the case where the polymer is polystyrene or SAN polymer, the preferred amount of the solid residue are in the range from 5 to 35 wt.%, whereas in the case of polyurethane polymers, polyurea preferred amount of polymer is from 5 to 20 wt.%.

Examples of industrial polymeric polyols include polyurethane polyol CARADOL SP50-01 and DESMOPHEN 7652, as well as polystyrene CARADOL polyols MD25-01 and CARADOL MD30-01 (CARADOL and DESMOPHEN are trademarks).

Preferably, when the second polyol has a molecular weight greater than 100, preferably greater than 200. Acceptable when the specified molecular weight of less than 900, preferably less than 750, and particularly preferably 500 or less.

Acceptable, when the specified second polyol has a hydroxyl number of at least 300, preferably at least 400, more preferably at least 450 mg KOH/g Specified hydroxyl number may be less than 750, preferably less than 700,the percentage of nitrogen in the polyol) may comprise at least 0.5 wt.%, acceptable at least 0.7 wt.%, preferably at least 1 wt. %, more preferably at least 2 wt.% and especially at least 3 wt.%. The amine content may be less than 15 wt.%, preferably less than 12 wt.%, more preferably 8 wt.% or less.

Aromaticity (or the content of aromatics) specified the second polyol may be a value lying in the range from 0 to 30%, preferably in the range from 5 to 25%, more preferably in the range from 10 to 20%, particularly from about 16%.

Aromaticity refers to the mass percentage of aromatic carbon atoms, i.e., the carbon atoms contained in the aromatic ring structure present in the compound or formulation with respect to the total mass of this compound or composition. Alkalization specified in the second polyol may be one or EA.

Said first and/or second specified polyols can include a mixture of polyols or solution of polyols, in this case, all distinctive features of the first and second of these polyols (e.g., wt. %, hydroxyl number, molecular weight, functionality and content of ethylene oxide) refer rather to the average values of indicators of mixtures is a mixture of polyols comprises at least 30 wt. % specified the first polyol. Preferably, when the specified composition comprises 60 wt.% or less than the specified first polyol. Preferably, when the specified composition comprises from 40 to 60 wt.% specified the first polyol. Preferably, when the specified composition includes at least 40 wt.% the specified second polyol. Preferably, when the mixture comprises 70 wt. % or less than the specified second polyol. Preferably, when the mixture comprises 60-40 wt.% the specified second polyol.

The mixture of polyols may contain additional components and excipients used in the manufacture of rigid and flexible polyurethane foams. For example, the composition-based polyols may include a catalyst foaming and/or cross-linking agent, for example glycerol and/or agent of the growth of the chain, for example 1,4-butanediol. Can be used as such excipients as fillers, flame retardants, foam stabilizers, foaming agents, and dyes. Conveniently, when the composition based polyols contains ("wt.h." refers to the number of parts by weight to 100 parts by weight of the first and second polyols): (a) 0-8 wt.h. one or more of polyurethane, catalization and include various compounds. Great list of catalysts for the formation of polyurethane, for example, in the description of U.S. patent 5011908. The preferred catalyst is an amine, especially a tertiary amine. The preferred amine catalysts include amine group is substituted by at least two optionally substituted, preferably unsubstituted, lower alkyl groups, which may be the same or different, but preferably the same. The lower alkyl group can contain up to 8, preferably up to 6, more preferably up to 4, carbon atoms, of which particularly preferred are methyl and ethyl groups. The catalyst based on the tertiary amine can choose from a number of compounds such as bis(2,2'-dimethylamino)ethyl simple ether, trimethylamine, triethylamine, triethylenediamine, dimethylethanolamine, N,N',N'-dimethylaminopropionitrile and N,N-dimethylcyclohexylamine. Examples of industrial catalysts based on tertiary amines are substances sold under the trademarks NIAX, TEGOAMIN, JEFFCAT (from Huntsman Chemicals) and DABCO (all names are trademarks).

The specified catalyst foaming is usually used in a quantity lying in the range from 0 using cross-linking agents in the production of polyurethane foams are well known. For these purposes a polyfunctional alkanolamine. Preferred amines that can be included in the composition of polyols to improve or maintain the compatibility of the first and second polyols include diethanolamine, often referred to in abbreviation as DEOA, triethanolamine, often abbreviated to reduce as TEOA. If a crosslinking agent is used, it is injected in amounts up to 10 wt.h., for example from 0.5 to 5 wt.h.

In the composition-based polyols can also be activated foaming agent. Acceptable blowing agents include water, acetone, (liquid) carbon dioxide, halogenated hydrocarbons, aliphatic alkanes and alicyclic alkanes. Due to the depleting ozone action completely chlorinated, fluorinated alkanes (HFA) using a blowing agent of this type is not usually preferred, although they can be used in the scope of claims of the present invention. Halogenated alkanes, in which at least one hydrogen atom is not substituted by a halogen atom (the so-called GHFA and GFA), are far less effect ozone depletion and therefore are the preferred halogenated hydrocarbons, the Ohm type GHFA is 1-chloro-1,1-differetn. It is also well known about the water quality (chemical) a blowing agent. Water interacts with the isocyanate groups on the well-known reaction of NCO/H2Oh, which produces carbon dioxide, which causes the effect of spray. As an alternative blowing agents for GFA were developed, in the end, aliphatic and alicyclic alkanes. Examples of such alkanes are butane and pentane (aliphatic) and cyclopentane (alicyclic). It should be understood that the above foaming agents can be used singularly or as mixtures of two or more agents. It is established that to achieve the objectives of the present invention from all of these foaming agents are particularly acceptable as a blowing agent is water, contributing to the emissions of carbon dioxide. In cases when you want to use a blowing agent, its amount generally corresponds to the traditionally used quantities, namely in the range from 0.1 to 5 wt.h. in the case of the water and in the range from about 0.1 to 20 wt. h in the case of halogenated hydrocarbons, aliphatic alkanes, alicyclic alkanes and liquid carbon dioxide.

This composition based polyols preferred for obtaining a polyurethane foam having a softening temperature of 120oWith or above and which is semi-flexible. Whether the composition based polyols are acceptable, can be evaluated by the next test.

This test includes the interaction, when the 21oWith 100 wt.h. composition based polyols in the presence of 1.8 wt.h. water, amine catalyst and 1.0 wt. including silicone explore only briefly-active substances (for example, TEGOSTAB B8404), with a polymeric MDI having properties CARADATE 30, described below with isocyanate number 110. The content of the catalyst is chosen so that the time fiberizing was 30 s (plus or minus 5 seconds).

This composition is based on what aimogasta with polymeric MDI in terms described in the above-cited test method, formed a semi-flexible polyurethane foam having a softening temperature of 120oC and above.

The present invention extends to a method of obtaining single-phase compositions on the basis of the polyols of the first aspect, which comprises mixing a specified first polyol and the second polyol.

In accordance with a second aspect, a method of obtaining a polyurethane foam, which is semi-flexible and which has a softening temperature of 120oWith, or above, this method involves the interaction of a component based on MDI with composition-based polyols in accordance with the first aspect.

This method is preferably carried out at ambient temperature, acceptable, when this temperature is in the range from 20 to 25oC.

The polyisocyanates that can be used for carrying out the method, are those polyisocyanates, which are traditionally used in the production of flexible, semi-flexible or rigid polyurethane foams. Suitable polyisocyanates must contain at least two isocyanate groups and include both aliphatics Auda in the production of flexible polyurethane foams. You can also use a mixture of two or more of these aliphatic and/or aromatic polyisocyanates. Examples of acceptable polyisocyanates include 2,4-colorvision (2,4-TDI), 2,6-TDI, mixtures of 2,4-TDI and 2,6-TDI, 1,5-attendaient, 2,4-methoxyphenylhydrazine, 4,4'-diphenylmethanediisocyanate (MDI), 4,4'-biphenylenediisocyanate, 3,3'-dimethoxy-4,4'-biphenylenediisocyanate, 3,3'-dimethyl-4,4'-biphenylenediisocyanate and 3,3'-dimethyl-4,4'-diphenylmethanediisocyanate, 4,4',4"-triphenyltetrazolium, 2,4,6-colortransparent, 4,4'-dimethyl-2,2', 5,5'-diphenylmethanediisocyanate, polymethylenepolyphenylisocyanate modified with carbodiimide isocyanates, MDI prepolymers and mixtures of two or more of these compounds. Can also be used polymeric MDI, mixtures of MDI with MDI as a main component.

Isocyanate number used MDI may lie in the range from 100 to 140, preferably in the range from 105 to 130, more preferably in the range from 105 to 120.

The flexibility of the foam can be estimated by the method of DIN 53423. The value of flexibility may amount to not less than 10 mm, it is acceptable not less than 11 mm, preferably not less than 12 mm, more preferably not less than 13 mm, and particularly not less than 14 mm

S, more preferably not less than 135oC.

Bulk foam under conditions of free expression, determined in accordance with method ISO 845, may be at least 20, preferably at least 30, more preferably at least 40, particularly not less than 50 kg/m3. Bulk foam free rise may be 160 or less, preferably 120 or less, more preferably 100 or less, particularly 80 kg/m3or less.

The present invention extends to a method of obtaining a polyurethane foam, which is semi-flexible and has a softening temperature of 120oWith, or above, this method involves the interaction of a component based on MDI with a first polyol, as described above, and the specified second polyol, as described above.

Acceptable when this polyurethane foam has a clear structure with closed pores.

Further, the present invention applies to polyurethane foam, which is semi-flexible and has a softening temperature of 120oWith or above and which is obtained using the composition-based polyols, as described above, and/or the described method.

The present invention is.

Molded product preferably is a tube. It preferably includes the inner tube and the layer on the outside of this inner tube, this layer is preferably tubular and made of the specified polyurethane foam. The specified outer layer acceptable adjacent to the said inner tube. The specified inner tube may include such synthetic material, such as cross-linked polyethylene. However, preferably, when it is made of metal, such as copper, steel or chrome-Nickel.

Any distinctive feature of any aspect of any invention or variant implementation of the invention described in this application may be combined with any distinctive feature of any other aspect of any invention or variants of its implementation described in this application.

Further, the essence of the present invention will be explained using the following examples, in which the polyols with 1 to V are examples of the above first polyols, and polyols a - C are examples of second polyols. In these examples, the following symbols apply to the following compounds.

Polyol I - EA simple polyester polyol based on glycerol containing 14% stake II - IN simple EA polyester polyol based on glycerol containing 18% EA end-links, with a hydroxyl number of 36 mg KOH/g and a molecular weight of 4700.

Polyol III - EA simple polyester polyol based on glycerol containing 15% statistically distributed EO-units having a hydroxyl number of 40 mg KOH/g and a molecular weight of 4000.

Polyol IV - EA simple polyester polyol based on glycerol containing 13% statistically distributed and end links, having a hydroxyl number of 56 mg KOH/g and a molecular weight of 3000.

Polyol V - EA simple polyester polyol based on glycerol containing 15% of the units having a hydroxyl number of 56 mg KOH/g and a molecular weight of 3000.

Polyol VI - EO simple polyester polyol based on glycerol containing 75% statistical EO-units having a hydroxyl number of 36 mg KOH/g and a molecular weight of 4700.

Polyol A - simple polyester polyol based on diethanolamin/aromatic with a hydroxyl number 520 mg KOH/g, a functionality of 3.0 mEq/mol, the content of aromatics 16% and the content of the amine (expressed in nitrogen content) of 3.6%.

The polyol In the polyol based on the Ethylenediamine/aliphatic, having a hydroxyl number of 650 mg KOH/g, funko polyol, having a hydroxyl number of 500 mg KOH/g, a functionality of 3.0 mEq/mol and a content of aromatics of 30%.

Polyol D is a simple polyester polyol based on glycerol/sorbitol, having a hydroxyl number of 510 mg KOH/g and srednekamennogo functionality of 4.5 EQ/mol.

Polyol E is a simple polyester polyol based on glycerol/sorbitol with a hydroxyl number of 500 mg KOH/g and medium-numerical functionality of 4.8 mEq/mol.

Polyol F is a simple mixture of a polyester polyol based on sorbitol and glycerol with an average hydroxyl number of 350 mg KOH/g and an average functionality of 3.5 mEq/mol.

Polyol G is a simple mixture of a polyester polyol based on sorbitol and glycerol with an average hydroxyl number of 450 mg KOH/g and an average functionality of 3.9 mEq/mol.

Wt.h. refer to "mass parts".

V refers to TEGOSTAB B8404 - silicone surfactant (for example, Goldschmidt).

CARADATE 30 - polymeric MDI equivalent weight 133,33 EQ/g, srednekislye functionality of 2.7 mEq/mol and an NCO content of from 30% to 32% (Shell).

DIME 6 - N,N-dimethylcyclohexylamine catalyst (Shell).

D33LV - DABCO 33LV, 33% TED (tetramethylaniline) in di-ethylene glycol, obtained from the company "Air Products".

Example 1.

Polyol 1 (50 wt.h.) and the Polyol is Vav mechanical stirrer rotating at a speed sufficient to obtain a homogeneous mixture). It turned out that they are compatible in all proportions and form a clear single-phase liquid.

Then prepared foams in open Polterovich bags. All of the components described in table 1 was passed at a temperature of 21oWith all, except DHS, mixed in a plastic Cup with a speed of 3000 rpm on a mixer. DHS added within 5 seconds and the mixture was stirred for another 5 seconds before pouring it into a plastic bag. Measured retention time of reactivity, the magnitudes of which are shown in table 1.

From the Central part of the bag has selected a sample of foam and held it tests. Table 1 presents the results of the tests. Flexibility was determined by the method of DIN 53423 in the direction of lifting of the foam, but also in the direction perpendicular to the direction of lifting foam. Shows the value represents the offset of the center of the cross section of the foam sample at break. Results presented are the average results of measurements in two directions. The softening temperature was determined using a thermal analysis TMA 7 firm "Perkin Elmer". All measurements were carried out under the atmosphere gain. The remaining results are presented in table 1, obtained using standard test methods.

Examples 2-7.

The polyols listed in table 1, mixed, and found that they are compatible. Then carried out the reaction in a mixture similar to that described in example 1. The results are presented in table 1.

Comparative examples C1-C6.

The polyols listed in table 2 were mixed, but it turned out that they are incompatible. Then carried out the reaction in a mixture similar to that described in example 1. The results are presented in table 2. It should be appreciate that, although the softening temperature of the foam, referred to in the examples are quite high, but compatibility is an issue. It is believed that the incompatibility may be due to the absence of any amine in the polyols D and E.

Comparative examples C7-C9.

The polyols listed in table 3, were mixed and determined that they are compatible. Then carried out the reaction in a mixture similar to that described in example 1. The results are presented in table 3. It should be appreciate that although compatible polyols formed from them foams have sufficient flexibility at too low a softening temperature (examples C7 Claims

1. Single-phase mixture of polyols consisting essentially of 20-65 wt.% the first polyol having srednekamennogo molecular weight of more than 800, a hydroxyl number of less than 200 mg KOH/g and a content of ethylene oxide is less than 75 wt.%, forming a compatible mixture with 35-80 wt.% second polyol having srednekamennogo molecular weight less than 1000, a hydroxyl number greater than 300 mg KOH/g and an amine content, expressed in percentage N content of at least 0.2 wt.%.

2. Mix on p. 1, wherein said first polyol has a molecular weight of more than 2500 and a hydroxyl number of less than 150 mg KOH/g and a specified second polyol has a molecular weight of less than 450.

3. Mix on PP. 1 and 2, characterized in that said first polyol has a functionality of at least about 2.2.

4. The mixture according to any one of paragraphs.1-3, characterized in that said first polyol has a content of ethylene oxide is less than 40 wt.%.

5. The mixture according to any one of paragraphs.1-4, characterized in that it contains at least 40 wt.% specified the first polyol and at least 40 wt.% the specified second polyol.

6. The composition of polyols containing: (a) 100 wt.h. single-phase mixture of polyols according to any one of paragraphs.1-5; (b) 0-8 wt.h. one or more catalysts formed by the second agent, and (e) optionally, other excipients.

7. A method of obtaining a polyurethane foam, which is semi-flexible and has a softening temperature of 120oWith, or above, the interaction of the polyisocyanate component with the composition of polyols, as stated in paragraph 6.

 

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FIELD: organic chemistry, polymer materials.

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

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

2 ex, 1 dwg

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