Polyol composition for polyurethane production

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

 

The present invention relates to the composition of polyol as one composition, suitable for the production of polyurethane cold molded and can be used for the manufacture of industrial goods hardness from 20 to 50 shore A.

Polyurethane elastomers are effectively used in the furniture industry, automotive, construction, insulation and packaging, in the Shoe industry, etc.

Each application imposes compliance requirements for composition of component polyurethane compositions. Polyol as one component, as a rule, is a physical mixture, which includes several types of oligoesters, extension cords, and suturing of the polymer, catalysts, surfactants, modifiers and other excipients known in polyurethane chemistry (Oligoesters. Isocyanates. System. - Directory. - Niitekhim. 1987, p.18, 23).

To reduce primariamente and (or) reduction of polymers, including polyurethanes, they injected fillers.

As fillers are natural (chalk, limestone, marble and synthetic precipitated) calcium carbonate, magnesium silicate (talc), barium sulfate (heavy spar), aluminum hydrosilicate (kaolin), trihydroxide aluminum, mica, sand, fillers vegetable origin (wood flour, ground walnut MSE of the magnifier, sawdust), industrial and household waste (plastics, foams, natural and synthetic fiber, feathers, shredded tyre chips and carpets, lignosulfonates, recovered paper) (Cockroaches OG Shamov IV, Alpern E Filled foams. M.: Chemistry, 1989. P.78-82).

The principal disadvantage of polyol as one of the compositions using the above fillers is that they form a suspension component, to which is added. To prevent sedimentation of the filler feed tank must be equipped with mixers and recirculation systems. You must also use special pumps suitable for pumping slurries. In addition, the filler is always in greater or lesser degree, are incompatible with the polymer phase, changes the parameters of the foaming and, as a consequence, the macrostructure of the final polymer material. It is known that the structure of the filled polyurethane depends on many characteristics of the filler and, above all, on its contents and homogeneous distribution in the polymer matrix. In order homogeneous mix the filler with the polyol, or need to handle it the appropriate sizing, or to improve the content in the polyol as one of the composition of surface-active substances, or take a polyol with a higher content of hydroxyethyl links, or use speciallycreated.

All these measures lead to excessive complexity of the process, the complexity of its hardware design and increase the cost of the final polymer product.

To improve the rigidity of the block and molded foams using stable dispersions of polymers in a simple polyester - polymer-polyols. The preferred polymers are polystyrene and copolymers of styrene with Acrylonitrile. Dispersed particles of the solid phase can be considered as fillers like conventional inorganic fillers type caso3(Gier D.R.O Nell, M.R.Adams et al. Fillers, Hard Phases and Copolymer Polyols-their. Different Mechanism to Reinforce Flexibe Polyurethane Foams/ Polyurethanes Expo 98, September 17-20. 1998, p.227-236).

Known, for example, polyol as one composition to obtain a flexible polyurethane foam, comprising simple polyetherdiol brand Laprol 5003-2B-10, containing more than 75% of primary hydroxyl groups, prestabilization, catalyst, foaming agent, a primary diamine, oxyalkylene the Ethylenediamine (Lupranol) and the variance of the product of the copolymerization of Acrylonitrile and styrene in the environment simple polyetherdiol representing liquid white product viscosity 1800-12400 MPa with a hydroxyl number of 26 to 30 mg KOH /g and a content of the filler 20 wt.% (Awts of the USSR №1495341, publ. 23.07.1989). The variance is obtained by copolymerization ravnomernijeg quantities specified monomial is at 100° With subsequent distillation of the volatile. Offer polyol as one composition when mixed with the isocyanate component allows to reduce density, increase the elastic properties of manufactured parts.

The disadvantage of this composition is its high viscosity. The result is a decrease in the fluidity of the reaction mass, which causes difficulties in obtaining products from polyurethane foam and adversely affects the properties of the foams. Known polyol as one composition to obtain latexotica flexible foams, obtained by the interaction of two different polyols with an isocyanate component in the presence of a catalyst, cross-linking and foaming agents, prestabilization. Used polyols are: the basic amount of the polymer polyol containing primary polyol having a molecular weight in the range from 2500 to 6500, an average nominal functionality of at least 2.0, a primary hydroxyl content of at least 40% and stably dispersed therein a polymer; the minimum number of hydrophilic polyol having a molecular weight of from 2000 to 5500, the content of ethylene oxide is not less than 40 wt.% and a primary hydroxyl content of at least 50% (RF patent No. 2166516, publ. 10.05.2001).

The obtained flexible polyurethane foams have good elasticity, however, used the may recipe is complicated and expensive.

Closest to the technical nature of the proposed formulation polyol as one of the composition is a polyol as one composition for the production of cellular polyurethane molded products with a compact surface, consisting of at least one simple polyetherpolyols with a molecular weight of 2000-10000, and/or at least one compound polyetherpolyols with a molecular weight of 2000-10000, at least one difunctional regarding the polyaddition reaction of the isocyanate compound with a molecular weight 62-199,9, taken in an amount of 2-15% by weight of the polyol as one component, a blowing agent and other excipients known in polyurethane chemistry, in which the polyols are used: simple polyetherdiol having a molecular the weight of 4000 and a content of ethylene oxide 30%; simple polyetherdiol having a molecular weight of 6200 and the content of ethylene oxide 20%; simple polyetherdiol having a molecular weight of 4800 and a content of ethylene oxide 15%; simple polyetherdiol with inoculated in 20% of the total weight of the mixture of styrene and Acrylonitrile (weight ratio 40:60) and a content of ethylene oxide 15%; the molecular weight of the grafted polyester is 6000, and in which as difunctional regarding the polyaddition reaction of the isocyanate compounds used ethylene glycol, 1,4-butanediol or a mixture of such p is ostich diols; as pore-forming substance use carbamates, water (patent RF №2138523, publ. 27.09.1999 - prototype).

Get the foam properties density: 200-700 kg/m3, hardness shore a: 20-70.

Common faults of styrene-Acrylonitrile mixtures as the preferred monomers to obtain a polymer polyols are:

- high viscosity, limiting the concentration limits the use of the polymer-polyol;

- the tendency to form agglomerates, leading to problems during storage and processing;

- discoloration of the foam due to the formation of cyclic polymers;

- smell.

Use in the composition of the polyol as one of the composition of the patent of the Russian Federation No. 2166516 Monomeric mixtures enriched with styrene, gives the dispersion with lower viscosity, color, odor.

During the synthesis of the same concentrated dispersions with solids content 35-43%) is necessary to ensure an acceptable viscosity of the polymer polyol, its high stability, the minimum size of the suspended particles and their agglomeration.

Dispersion polymers mentioned in the above patents, compared to many other fillers, less abrasive, but prone to sticking. But their main drawback is the high cost compared to the cost of polyurethane. It does in most cases not very effective use dis is ersi polymers as fillers.

Disadvantages filled polyol as one of the compositions can be minimized when the filler is combined with the liquid oligomeric composition, i.e. the filler must form a homogeneous system (solution) component, in which he entered. In this case, the amount of filler is limited only by the quality of the structure is filled with polyurethane. It is also desirable that the filler was not singled out in a separate phase when mixed component polyurethane compositions, as well as in the resulting polymer. While the introduction of the filler should not create difficulties in the production of goods or impair their operational properties.

The present invention is to provide a composition filled polyol as one composition, suitable for the production of polyurethane cold molded, eliminating the above disadvantages.

The solution of this problem is achieved by using a polyol as one composition containing simple polyetherdiol or a mixture of simple polyetherdiol with a molecular mass of 4500-6500 and an average hydroxyl functionality of 3, extender chain, a catalyst, a blowing agent, a silicone foam controller, an organic filler. As a last polyol as one composition contains a high-boiling by-product of the production of isoprene based on alkyl - and axial issuesany 1,3-dioxanes with a mass fraction of hydroxyl groups of 1-4% or its mixture with the oil plasticizer.

In accordance with the invention as a simple polyetherdiols use connections trademarks Laprol 5003-2B-10, 5003-2-15, Laprol 6003-2B-18 or a mixture thereof; represent the ethoxylated polyoxypropylene with a molecular mass of 4500-6500 obtained by the method of anionic polymerization of propylene oxide and ethylene using glycerol as the starting compound. Issued by TU 226-006-10488057-94 and THE 2226-020-1-488057-94.

As chain extension using ethylene glycol, 1,4-butanediol or a mixture of such simple diols.

As a catalyst for the reaction of retinoblastoma use triethylenediamine and if necessary in a mixture with ORGANOTIN compound (octoate tin or dibutyltindilaurate).

Foaming at the expense of carbon dioxide emitted in the interaction of MDI with water.

Stabilization of the cellular structure in the foaming process is achieved by using a known silicone blockcopolymer - "Penta" (trademark), produced by THE 2257-008-40243042-99.

As the organic filler used high-boiling by-product of the production of isoprene from formaldehyde and isobutylene (Rakhmankulov DL, Karaganov R.A., Slotsky SSI other Chemistry and technology of 1,3-doxacycline. The results of science and technology. Technology of organic in the substances V.5, M.: VINITI, 1979, 288 C.). High-boiling by-product is a mixture of various alkyl - and oxyalkylene 1,3-dioxanes with a mass fraction of hydroxyl groups of 1-4% (Ogorodnikov S. Kaliev, Idlis G.S. isoprene Production. L.: Chemistry, 1973, 296 C.). The specified product is a clear yellow oily liquid and has the following physicochemical properties:

Density at 20°C, g/cm31,02-1,09

Essential number, mg KOH /g of 1,5-4,0

Mass fraction of hydroxyl groups, %, within 1-4

The flash point in an open crucible, °C, not below 130

Pour point, °s, not higher than minus 40

As the plasticizer oil origin use petroleum oil selected from the group of domestic oils, including starplast-62, stabiloy-18, necaxa, neveplast, vaseline oil AND 8A. Petroleum oils are produced by industry:

starplast-62 on THE 38.101545 - 80

stabiloy-18 on THE other 38. 101367 - 78

naloxol on THE 38. 101999 - 84

neveplast beyond 38 101936 - 83

vaseline oil AND 8A according to GOST 20799 - 88

Offer polyol as one composition to obtain a polyurethane cold molded preferably includes the components in the following ratio in the composition, parts by weight:

simple polyetherdiol or a mixture of simple polyetherdiols - 100;

the glycol - 3,5-6,2;

1,4-butanediol - 3,5-8;

triethylenediamine - 0,53-065;

water-0,25-0,5;

kremniiorganicheskie foam controller - 0,002-0,004;

organic filler, or its mixture with oil

the plasticizer - 2-100.

The composition is prepared in a known manner by mixing the components. Simple polyetherdiol or a mixture of simple polyetherdiols, silicone foam controller, chain extension, catalyst, blowing agent are combined and the resulting mixture is mixed with an organic filler. The obtained polyol as one composition is stable during storage (at least 8 weeks). During this time, the composition does not separate and does not lose its activity in relation to the isocyanate component.

A distinctive feature of the proposed formulation polyol as one composition is used in its composition as the organic filler high-boiling by-product of the production of isoprene based on alkyl - and oxyalkylene 1,3-dioxanes with a mass fraction of hydroxyl groups of 1-4% or its mixture with the oil plasticizer. The amount of filler in the composition is 100 parts by weight per 100 parts by weight of a simple polyetherdiol. As the plasticizer used petroleum oil.

Industrial applicability the proposed polyol as one composition confirmed at pilot saw the e products using industrial machines low pressure and unheated forms.

Conditions for processing:

- mass ratio of the components in the processing depending on the requirements of the rigidity of the resulting foam may vary from 2.5 to 3.2;

the temperature of the reactants (polyol as one component and polyisocyanate component) - 18-23°C;

- stay in shape - 3 min;

the fluidity is good.

The technological characteristics of the foam obtained by the method of free foaming in accordance with THE 6-55-32-89 (polyurethane System. Method of conducting a technology preview):

- start time - (15...2);

the time of rise of the foam (35...45) C.

Properties of foam:

- apparent density, kg/m3350-400

- hardness shore a (unit scale) 20-50

- ultimate tensile strength, n/cm260-90

- relative elongation, % 150-220

To evaluate physical and mechanical readings of finished products were used normative documents: GOST 409-77 (volumetric weight of the foam), GOST 15873-70 (elongation at break).

The compositions of polyol as one of the compositions shown in the table.

The introduction to the recipe polyol as one of the components of the high-boiling by-product of the production of isoprene based on alkyl - and oxyalkylene 1,3-dioxanes with a mass fraction of hydroxyl groups of 1-4% in different proportions with the commonly used simple polyetherdiols provides the following benefits: simplifies the I process of preparing polyol as one of the composition; increases the manufacturability of the processed compositions; the convenience and safety of operation due to its low pour point and high flash point; the possibility of introducing in relatively large quantities thanks to compatibility with simple polyetherdiols, including water; reduced the number of simple polyetherdiols; increases the rigidity of the foam.

In addition, because the cost of a by-product of the production of isoprene and oil plasticizer less than the cost of a simple polyetherdiol, partial replacement of their polyetherdiol leads to cheaper formulations while retaining all the indicators of the quality of molded products.

Thus, the proposed polyol as one composition suitable for the production of polyurethane cold molded, which indicators can be used in various industries, including automotive, as gaskets, seals.

Table
Polyol as one recipe
ComponentsContent
123
Laprol 5003-2B-1087--
Laprol 5003-2-15 -98100
Laprol 6003-2B-18132-
Ethylene glycol3,56,26
1,4-Butanediol53,58
Triethylenediamine0,530,630,65
Water0,250,40,5
Silicone foam controller-0,0020,004
Organic filler, or mixtures thereof with   
oil plasticizer248100

1. Polyol as one composition to obtain a polyurethane cold molded, including simple polyetherdiol or a mixture of simple polyetherdiol with a molecular mass of 4500-6500 and an average hydroxyl functionality of 3, a glycol, 1,4-butanediol, triethylamine, water, silicone foam controller and an organic filler, wherein the organic filler it contains high-boiling by-product of the production of isoprene based on alkyl - and oxyalkylene doxycyclinw with a mass fraction of hydroxyl groups of 1-4% or with whom thou art with oil plasticizer, in the following ratio of components, parts by weight:

simple polyetherdiol or mix

polyetherdiols 100

the glycol 3,5-6,2

1,4-butanediol 3,5-8,0

triethylenediamine 0,53-0,65

water 0,25-0,50

silicone foam controller 0,002-0,004

organic filler or

mix with oil plasticizer 2-100

2. Polyol as one composition according to claim 1, characterized in that as oil plasticizer it contains petroleum oil selected from the group comprising starplast, - 62, stabiloy - 18, necaxa, neveplast, vaseline oil AND 8A.



 

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6 ex, 1 dwg

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6 ex, 1 dwg

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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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2 ex, 1 dwg

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