A method of obtaining a solid foams containing urethane and optionally urea and which group

 

The invention relates to foamed hydrocarbon polyurethane foams, which can be used in the refrigeration industry. Describes a method of obtaining a solid foams containing urethane and optionally urea and which groups, by reacting aromatic MDI with a polyol as one component comprising initiated aromatic amine polyester-based 70-100 wt.% 1,2-propylene oxide and 0-30 wt.% of ethylene oxide with a molecular weight of 300-800 initiated mainly sucrose polyester on the basis of 70-100 wt.% 1,2-propylene oxide and 0-30 weight. % of ethylene oxide with a molecular weight of 400-1000 and initiated propylene glycol polyester-based 70-100 wt.% 1,2-propylene oxide and 0-30 weight. % of ethylene oxide with a molecular weight of 500-1500, and water, n - and/or isopentane as a pore-forming additives, excipients. Obtained in this way, the foams have a high adhesion, high tensile compressive strength and low thermal conductivity. 3 C.p. f-crystals, 1 table.

The invention relates to a process for the production of foams, and more particularly to a method for producing rigid foams containing urea oblast (polyurethane) - foamed low-boiling alkanes, which are mainly used cyclic alkanes, which, due to their low gas thermal conductivity, contribute enormously to thermal conductivity of the foam. This preferably is cyclopentane.

A useful property of the polyurethane foam used as insulation material for refrigeration equipment confront negative commercial aspects. So, for example, due to the properties of cyclopentane as solvent need a certain quality of the inner surface of polystyrene vessels.

In addition, cyclopentane because of its relatively high boiling point 49oWith has a drawback consisting in the fact that at low temperatures (which is normal when using polyurethane foam as insulation material for refrigeration equipment) it is condensed. Because of the undesirable condensation of the blowing agent in the cell vacuum is created, which, in turn, can be prevented high hardness foam, increased bulk density.

Compared to acyclic homologues of compounds pentane - n - and isopentane - cyclopentane requires higher zetia polyurethane foam known for a long time. Their disadvantage is higher in comparison with cyclopentane thermal conductivity of the gas, which reduces the insulating ability of the respective foams.

In addition, the solubility of n - or isopentane in polyatomic alcohols worse than cyclopentane that has a negative effect on the strength of the material and the adhesion of the foam coated.

The closest analogue of the invention is the application WO 95/18175 published on 6 July 1995, the object of which is a method of obtaining a solid foams containing urethane and optionally urea and which group, by reacting an aromatic isocyanate with a polyol as one component comprising initiated aromatic amine polyester, water, mixtures of alicyclic alkanes with 5 or 6 carbon atoms and a mixture of n - and isopentane as a blowing agent and optionally additives and auxiliary substances.

The present invention is to develop a method of producing rigid foams containing urethane and optionally urea and which group to use as a blowing agent and/or isopentane, which allows to obtain a foam with a high adhesive is anaplastic, containing urethane and optionally urea and which group, by reacting an aromatic isocyanate with a polyol as one component, including inetsirovany aromatic amine polyester-based 70-100 weight. % 1,2-propylene oxide and 0-30 wt.% of ethylene oxide, having a molecular weight 300-800, water, n - and/or isopentane as a blowing agent and optionally additives and auxiliary substances, due to the fact that the use of polyol as one component, including additional initiated mainly sucrose polyester on the basis of 70-100 wt.% 1,2-propylene oxide and 0-30 wt.% of ethylene oxide, having a molecular weight of 400-1000, and initiated propylene glycol polyester-based 70-100 wt.% 1,2-propylene oxide and 0-30 wt.% of ethylene oxide, having a molecular weight of 500-1500, while initiated aromatic amine polyester, initiated mainly sucrose polyester and initiated propylene glycol polyester are used in a weight ratio of(30-80): (10-40):(5-30), and water in the amount of 0.5-3.5% by weight of the above polyester and polyol as one component has on average at least 3 reactive towards isocyanate groups of a hydrogen atom.

Molar weight initiated aromatic amine poly the hat 35-70 wt.%. As the aromatic amine is preferably used on-toluylenediamine.

Molar weight initiated mainly sucrose polyester is preferably 400-1000, in particular 500-600. Its share in the polyol as one component is preferably 15-35 wt.%. As coinitiator you can use diethylene glycol, ethylene glycol or propylene glycol in the amount of 10-30 wt.%.

Molar weight-initiated propylene glycol polyester is preferably 900-1100. Its share in the polyol as one component is preferably 15-25 wt.%.

Serves as sporoblasts water is preferably used in amounts of 1.5 to 2.5% by weight of the above polyester polyol as one of the components.

As aromatic polyisocyanates are preferably used technologically readily available polyisocyanates, for example 2,4 - and 2,6-toluylenediisocyanate, as well as any mixtures of these isomers ("TDI"), polyvinylpolypyrrolidone you get with the help of aniline-formaldehyde condensation and subsequent vosganian ("crude MDI") and polyisocyanates containing carbodiimide groups, urethane groups,-raftiline group, isocyanate group, macavinta, which is derived from 2,4 - and 2,6-toluylene diisocyanate, respectively, from 4,4'- and/or 2,4'-diphenylmethanediisocyanate).

As additives and auxiliary substances include, for example, waxes or solid alcohols, dimethylpolysiloxane, pigments or dyes, stabilizers against aging and weathering, plasticizers, substances acting as policeoffice and as a bacteriostatic, fillers such as barium sulphate, infusoria earth (silica), carbon black or primer chalk, surfactants, prestabilization, regulators then, inhibitors of the reaction.

In the manufacture of foams according to the present invention, the foaming may be carried out in closed form. When this reaction mixture is injected into the mold, made for example from metal, for example aluminum, or a polymer, such as epoxy resin. Foaming in the mold can be carried out in such a way that the molded product has on its surface a porous structure. But it may also be carried out and so that the molded product has a compacted surface film and a porous core. According to the method of the present invention in the first of these cases, the process is conducted in such bradnam of these cases, the technology is in the form contribute more expanded onto the reaction mixture than is necessary to fill the internal volume of the shaped foam.

In the latter case, the process occurs in "overload", similar to the way the process is known, for example, from U.S. patent 3178490 and 3182104.

A preferred manner, the method according to the present invention is used for filling cavities with foam in the refrigeration and freezing device.

Needless to say that the foam can also be obtained by foaming in the block or use a dual tape mount.

The foam obtained according to the present invention finds application, for example, in construction, as well as for pipe heating and containers.

The following examples will illustrate the invention.

Example 1 (comparative) the Composition for polyurethane foam Component: 75 weight. parts (75% by weight of the mixture of the polyether - polyester-based propylene oxide with a molecular weight of 600, initiated by sucrose (80 wt.%) and propylene glycol (20 weight%), 25 weight. parts (25% by weight of the mixture of the polyether - polyester based on 1,2 - propylene oxide with a molecular weight of 1,000-initiated propylene glycol, 2,5 weight.part (2.5% of the weight of the mixture is produced by the company Goldschmidt, Germany, under the trade nameTegostabIn 8423"), 2.0 weight. part (2.0% of the weight of the mixture of polyesters - activator Decorated 726b, representing dimethylcyclohexylamine (trade product by Bayer AG, Germany).

Component B: 128 weight.parts of crude MDI (NCO content of 31.5 wt.%), 100 weight. parts components And mixed with 11 weight.parts of n-pentane and 141 weight. parts components B using a mixer (1000 rpm) at 20oWith and condense in closed form up to 34 kg/m3.

Example 2 (comparative)
Component:
50 weight.parts (50% by weight of the mixture of the polyether - polyester based on 1,2-propylene oxide with a molecular weight of 560, initiated by tolylenediamine,
50 weight.parts (50% by weight of the mixture of the polyether - polyester based on 1,2-propylene oxide with a molecular weight of 600, initiated by sucrose (80 wt.%) and propylene glycol (20 wt.%),
2,5 weight.part (2.5% of the weight of the mixture of polyesters) - water,
2.0 weight.part (2.0% of the weight of the mixture of polyesters - prestabilization In 8423 (a commercial product of the company Goldschmidt, Germany),
2.0 weight.part (2,0 by weight of the mixture of polyesters - activator Decorated 726 b (trade product by Bayer AG, Germany).

Component B:
141 weight.part of crude MDI (NCO-content is OSU mixer (1000 rpm) at 20oWith and condense in closed form up to 34 kg/m3.

Example 3 (comparative)
Component:
75 weight.parts (75% by weight of the mixture of the polyether - polyester based on 1,2-propylene oxide with a molecular weight of 560, initiated by tolylenediamine,
25 weight.parts (25% by weight of the mixture of the polyether - polyester based on 1,2-propylene oxide with a molecular weight of 1,000-initiated propylene glycol,
2,5 weight.part (2.5% of the weight of the mixture of polyesters) - water,
2.0 weight.part (2.0% of the weight of the mixture of polyesters - prestabilization In 8423 (a commercial product of the company Goldschmidt, Germany),
2.0 weight.part (2.0% of the weight of the mixture of polyesters) activator Decorated 726 b (trade product by Bayer AG, Germany).

Component B:
115 weight.parts of crude MDI (NCO content of 31.5 wt.%),
100 weight. parts components And mixed with 11 weight.parts of n-pentane and 115 weight. parts components B using a mixer (1000 rpm) at 20oWith and condense in closed form up to 34 kg/m3.

Example 4 (according to the present invention)
Component:
50 weight.parts (50% by weight of the mixture of the polyether - polyester based on 1,2-propylene oxide with a molecular weight of 560, initiated by tolylenediamine,
30 weight.parts (30% by weight of the mixture of the polyether - polyester based on 1,2-propylene oxide with a molar is IRow) - polyester-based 1,2-propylene oxide with a molecular weight of 1,000-initiated propylene glycol,
2,5 weight.part (2.5% of the weight of the mixture of polyesters) - water,
2.0 weight.part (2.0% of the weight of the mixture of polyesters - prestabilization In 8423 (a commercial product of the company Goldschmidt, Germany),
2.0 weight.part (2.0% of the weight of the mixture of polyesters - activator Decorated 726 b (trade product by Bayer AG, Germany).

Component B:
124 weight.part of crude MDI (NCO content of 31.5%),
100 weight.parts components And mixed with 11 weight. parts of n-pentane and 124 weight. parts components B using a mixer (1000 rpm) at 20oWith and condense in closed form up to 34 kg/m3.

Results
Using plates of the foams produced in examples 1-4 are testing. The results presented in the table.

As shown in the experiments, only the foam of example 4 obtained according to the method of the present invention, showing good to very good properties regarding conductivity, compressive strength, adhesion to the steel sheet and the solubility of pentane in a mixture of polyol as one.

Comparative example 1 gives a foam with high thermal conductivity, however, the solubility of pentane in a polyol as one CME is y; the solubility of pentane lies in the boundary region.

Comparative example 3 gives a foam with high adhesion and good solubility in pentane mixture of polyol as one, but has insufficient tensile strength under compression.


Claims

1. A method of obtaining a solid foams containing urethane and optionally urea and which groups, by reacting aromatic MDI with a polyol as one component comprising initiated aromatic amine polyester-based 70-100 wt.% 1,2-propylene oxide and 0-30 wt.% of ethylene oxide having a molecular weight 300-800, water, n - and/or isopentane as a blowing agent and, if necessary, additives and excipients, characterized in that use polyol as one component, including additional initiated mainly sucrose polyester on the basis of 70-100 wt.% 1,2-propylene oxide and 0-30 wt.% of ethylene oxide having a molecular weight of 400-1000, and initiated propylene glycol polyester-based 70-100 wt.% 1,2-propylene oxide and 0-30 wt.% of ethylene oxide having a molecular weight of 500-1500, while initiated aromatic amine polyester, initiated mainly sucrose polyester and the INIC is t weight of these polyesters, moreover polyol as one component has on average at least 3 reactive towards isocyanate groups of a hydrogen atom.

2. The method according to p. 1, characterized in that use polyol as one component comprising initiated aromatic amine polyester-based on-toluylenediamine.

3. The method according to p. 1, characterized in that use polyol as one component, comprising 50-60 wt.% initiated on-toluylenediamine polyester based on 1,2-propylene oxide having a molecular weight of 450-650.

4. The method according to p. 1, characterized in that use polyol as one component comprising 10-25 weight. % initiated propylene glycol polyester based on 1,2-propylene oxide having a molecular weight of 800-1200.

 

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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

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

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

EFFECT: composition for production of polyurethane with increased hardness.

2 cl, 1 tbl, 3 ex

FIELD: polymer materials.

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

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

41 cl, 2 tbl, 12 ex

FIELD: polymer production.

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

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

3 cl, 3 tbl, 6 ex

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