Method of production of an elastomer

FIELD: chemical industry; methods of production of a thermosetting elastomers.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the methods of production of a thermosetting polyurethane elastomer and also to the elastomer produced according to the given method. The invention presents the method of production of the polyurethane elastomer having a total apparent density exceeding 150 kg/m3 and providing for an interaction of polyisocyanate and a reactive to isocyanate composition not necessarily at presence of water, according to which the reaction conduct at an isocyanate index of 85-120. At that the polyisocyanate component is composed of: al) 80-100 mass % of diphenylmethanediisocyanate containing at least 40 mass % of 4.4'- diphenylmethanediisocyanate and-or a derivative of the indicated diphenylmethanediisocyanate, which (the derivative) is a may be a liquid at the temperature of 25°C and has NCO value of no less than 20 mass % and a2) 20 mass % of the other polyisocyanate; the reactive to isocyanate composition b) consists of b1) 80-100 mass % of a simple polyol polyester having an average nominal functionality - 2-8, average reactive equivalent weight of 750-5000, an average molecular mass of 2000-12000, the share of oxyethylene - 60-90 mass % and the share of the primary hydroxyl groups of 70-100 mass % calculated for the total number of the primary and the secondary hydroxyl groups in polyol; b2) a reactive to isocyanate extender of the chain in such a quantity, that the ratio of the rigid block makes less than 0.45; and b3) - 20-0 mass % of one or more of other reactive to isocyanate composition excluding water. At that the amount of the polyol of 61) and the reactive to isocyanate composition 63) is calculated from the total amount of the indicated polyol 61) and the composition 63). The invention presents also description of the thermosetting elastomer produced according to the indicated method.

EFFECT: the invention ensures production of a thermosetting polyurethane elastomer.

10 cl, 2 ex

 

The present invention relates to a method for thermoautotrophica elastomer and the elastomer obtained in accordance with this method.

More specifically the present invention relates to a method for thermoautotrophica elastomer using polyoxyethylene/polyoxypropyleneglycol having a high content of oxyethylene, and MDI, having a high content of 4,4'-diphenylmethanediisocyanate ((4,4'-MDI(4,4'-MDI)).

It is known from US 5792829 that polyurethane elastomers having a short time demoulded and improved cohesive strength, can be obtained using polyoxypropyleneglycol low unsaturation, having from 1 to about 20% of the mass. internal oxyethylene residues. Thus obtained elastomers show low water absorption. Further improvement in cohesive strength and grooves of the shape is possible through the use of a polyol as one of the mixtures having a multimodal molecular mass distribution, in combination with low unsaturation. These polyols can be used to get free from turbidity polyoxyethylenated polyols containing 1-20% of the mass. statistical internal and 5-25% of the mass. blocked oxyethylene groups.

Using polyoxypropylene/polyoxyethyleneglycol low what unsaturation, containing up to about 30% of the mass. oxyethylene fragments in relation to the weight of the specified polyoxypropylene/polyoxyethyleneglycol at least part of which is statistical internal oxyethylene fragments, prepolymers with isocyanate ends, to obtain a polyurethane elastomer having a short time demoulded and improved cohesive strength, is known from, for example, US 5965778, US 5849944, US 5728745 and US 5670601.

In addition, obtaining elastomers made from polyols having a high content of oxyethylene, polyisocyanates containing not less than 85% by mass. 4,4'-MDI or its variant, and out of the water covered in WO 97/21750 and WO 98/00450.

US 5418260 considers REEF-method (reaction injection molding) using a prepolymer of reconmendations DHS and polyetherdiol having a molecular weight of 400-6000 and content oxyethylene 10-85 wt. -%, and using polyetherpolyols with 65-100% of the mass. oxyethylene links, and an aromatic diamine. Celebrated short time demoulded.

At the same time this application WO 00/55232 describes a method of obtaining a molded polyurethane material such as elastomer, by reacting 4,4'-diphenylmethanediisocyanate or its variant - polyol having a high content of oxyethylene, and water. Re-forming what may be made without the need to handle the form for easy demoulded after how was the first item.

It has been unexpectedly found that when using the polyol, which has a high content of oxyethylene and high primary hydroxyl groups, light extraction from the mold is also provided.

In addition, the elastomers obtained in accordance with the method according to the present invention can have the recipe, made with relatively low amounts of catalyst, and are still relatively quickly retrieved from the form.

Therefore, the present invention relates to a method for producing polyurethane thermoautotrophica elastomer having an apparent overall density of more than 150 kg/m3including interaction of MDI and reactive to isocyanate compositions, optionally, in the presence of water, in which the reaction is carried out at isocyanate index 85-120, the polyisocyanate consists of a) 80-100% of the mass. diphenylmethanediisocyanate containing at least 40 wt. -%, preferably, at least 60 wt. -%, and most preferably at least 85% of the mass. 4,4'-diphenylmethanediisocyanate and/or a derivative thereof specified diphenylmethanediisocyanate, which (derived) is liquid at 25°and has an NCO value of at least 20% of the mass. (polyisocyanate a), and b) 20-0% of the mass. another MDI (polyisocyanate b), and in which reaktionsmotor the traveler to the isocyanate composition consists of a) 80-100% of the mass. simple polyetherpolyols, having an average nominal functionality of 2-8, an average equivalent weight of 750-5000, and the average molecular weight of 2000-12000, the content of oxyethylene ((SW) (MA)) 60-90% of the mass. and the content of primary hydroxyl groups 70-100%, calculated on the total number of primary and secondary hydroxyl groups in the polyol, (b) reactive toward isocyanate chain extension in such a quantity that the ratio of the hard block is less than 0.50, preferably less than 0.45, and (C) 20-0% of the mass. one or more other reactive to isocyanate compounds, excluding water, the amount of polyol a) and reactive to the isocyanate compound (C) is calculated on the total amount of said polyol a) and compound (C).

These elastomers can be easily extracted from the mold even without the use of internal agents for lubricating forms and without reuse of external agents for lubrication of the form after it has been received the first item, as described in the concurrently pending application WO 00/55232.

The elastomers obtained according to the present invention have a glass transition temperature Tgbelow 25°C.

Preferably, the elastomer has a ratio of the dynamic modulus of elasticity (E') at 20°and the dynamic modulus of elasticity (E') at 120°between 0.75 and 1.5, tg δ 100°With men who e 0.1 and the maximum value of tg δ more than 0.8, and tg δ represents the ratio of loss modulus (E") and dynamic modulus (E'). Preferably, the maximum value of tg δ is more than 1.0. The ratio of the dynamic modulus of elasticity (E') at 20°and the dynamic modulus of elasticity (E') at 120°C is preferably between 0.8 and 1.2, and most preferably between 0,85 and 1.00. Preferably have tg δ 100°With less than 0.05. Most preferably tg δ 100°C is less than 0.3. The main peak tg δ preferably takes place at temperatures below 0°S, most preferably below -10°C. Dynamic modulus and loss modulus determined by dynamic mechanical thermal analysis(DMTA)(DMTA) measurements according ISO/DIS 6721-5). In addition, the elastomers have very good properties of wet-aging, good creep, smell, fading, and flame resistance. In addition, these elastomers can be obtained with a relatively low amount of catalyst. Since the elastomers according to the present invention can be extracted from a form with a reduced number of external lubrication form elastomers can be easily painted.

In the context of the present invention, the following terms have the following meanings:

1) Isocyanate index, or NCO-index, or the index:

agains the MCO-groups reactive to isocyanate hydrogen atoms, present in the formulation given in percent:

In other words, the NCO-index expresses the percentage of isocyanate actually used in a formulation with respect to the amount of isocyanate theoretically required for interaction with the number of reactive to isocyanate hydrogen used in the recipe.

It should be noted that the isocyanate index, as used here, is considered from the point of view of the actual polymerization method, which gives an elastomer comprising isocyanate ingredient and reactive to isocyanate ingredients. Any isocyanate groups are consumed at the preliminary stage of obtaining modified polyisocyanates (including such isocyanatophenyl known in the art prepolymers), or any active hydrogens consumed at the preliminary stage (for example, interacting with the isocyanate with obtaining the modified polyols or polyamines), are not taken into account in the calculation of the isocyanate index. Only the free isocyanate groups and free reactive to isocyanate hydrogens (including hydrogens of water)present at the stage of actual polymerization, are taken into account.

2) the Expression "reactive to isocyanate hydrogen atoms"is used here for purposes of calculating the isocyanate index, refers to the total active hydrogen atoms in hydroxyl groups and amino groups present in the reactive compositions; this means that for purposes of calculating the isocyanate index at the way the actual polymerization is considered that one hydroxyl group contains one reactive hydrogen, it is believed that one primary amino group contains one reactive hydrogen, and it is believed that one molecule of water contains two active hydrogen.

3), the Reaction system: a combination of components, where the polyisocyanates are contained in one or more containers separately from reactive to the isocyanate component.

4) the Expression "polyurethane material, or elastomer", as used here, refers to a porous or non-porous products obtained by the reaction of polyisocyanates containing (reactive to isocyanate hydrogen) compounds, optionally, using foaming agents, and, in particular, includes a porous products obtained with water as reactive foaming agent (including the interaction of water with the isocyanate groups to give urea communication and carbon dioxide with getting polyurea-urethane foams), and polyols, aminoalcohols and/or polyamines as reactive to isocyanate compounds.

5) the Term "average nomi is real hydroxyl functionality" is used here to indicate srednetsenovoj functionality (number of hydroxyl groups per molecule) of the polyol or polyol as one song with the assumption it is srednetsenovoj functionality (number of active hydrogen atoms per molecule) of the initiator (s)used in their preparation although in practice it is often somewhat less because of some terminal unsaturation.

6) the Word "average" refers to the middle number, if not specified otherwise.

7) the Term "respect the hard block" refers to the amount (% wt.) MDI + reactive to isocyanate materials having a molecular weight of the largest 1000 (where the polyols having a molecular weight of more than 1000 introduced into the polyisocyanate prepolymers, are not taken into account)divided by the amount (% wt.) all MDI + all used reactive to isocyanate materials.

Preferably, the polyisocyanate a) is selected from 1) diphenylmethanediisocyanate containing at least 40 wt. -%, preferably at least 60% of the mass. and most preferably not less than 85% by mass. 4,4'-diphenylmethanediisocyanate, and the following preferred derivatives such diphenylmethanediisocyanate: 2) carbodiimide and/or reconmendations derived MDI 1), a derivative having an NCO value of 20% of the mass. or more; 3) arithmeticians derived MDI 1), a derivative having an NCO value of 20% of the mass. or more and which are the product of mutual the steps of excess MDI 1) and polyol having an average nominal hydroxyl functionality of 2-4 and an average molecular weight of the largest 1000; 4) prepolymer having an NCO value of 20% of the mass. or more and which is a product of the interaction of an excess of any of the above polyisocyanates 1-3) and a polyol having an average nominal functionality of 2-6, an average molecular weight of 2000-12000 and preferably a hydroxyl number of 15-60 mg KOH/g; and 5) mixtures of any of the abovementioned polyisocyanates.

The polyisocyanate 1) contains at least 40% of the mass. 4,4'-MDI. Such polyisocyanates known in the art and include pure 4,4'-MDI, and isomeric mixtures of 4,4'-MDI, and up to 60% of the mass. 2,4'-MDI and 2,2'-MDI. It should be noted that the amount of 2,2'-MDI in isomeric mixtures is rather at the level of impurities and usually does not exceed 2 wt. -%, and the rest are 2,4'-MDI and 4,4'-MDI. The polyisocyanates, such as are known in the art and commercially available, for example, trademark Suprasec MPR (provider - Huntsman Polyuretanes), which is issued by the company Huntsman International LLC (which owns the trademark of Carbodiimide and/or reconmendations derivatives of the above MDI 1), also known in the art and commercially available, for example, Suprasec 2020 (provider-Huntsman Polyurethanes).

Arithmetician derivatives of the above MDI 1) is also known in the art (smot and, for example, The ICI Polyurethanes Book by G.Woods, 1990, 2nd edition, pages 32-35).

The above prepolymers of MDI 1), having an NCO value of 20% of the mass. or more, also known in the art. Preferably, the polyol used to obtain these prepolymers selected from the complex polyether polyols and simple polyether polyols, and especially of polyoxyethylene/polyoxypropyleneglycol, having an average nominal functionality of 2-4, the average molecular weight of 2500-8000 and preferably a hydroxyl number of 15-60 mg KOH/g and preferably any content of oxyethylene 5-25 wt. -%, which (oksietilenom) is at the end of polymer chains, or the content of oxyethylene 50-90 wt. -%, which (oksietilenom) preferably statistically distributed along the polymer chain.

Can also be used mixtures of the aforementioned polyisocyanates (see, for example, The ICI Polyurethanes Book by G.Woods, 1990, 2nd edition, pages 32-35). For example, one such commercially available polyisocyanate is Suprasec 2021 (supplier Huntsman Polyurethanes).

Another polyisocyanate (b) may be selected from aliphatic, cycloaliphatic, alifaticheskih and preferably aromatic polyisocyanates, such as colorvision in the form of its 2,4 - and 2,6-isomers and mixtures thereof and mixtures of diphenylmethanediisocyanate (MDI) and oligomers having isocyanate functionality of more than 2, known in the art as "cheese is th" or polymeric MDI (polymethylene/polyphenylisocyanate). Can also be used a mixture colordistance and polietilen/polyphenylisocyanate.

If you are using prepolymers having an NCO value of 20% of the mass. or more, derived from polyols having a molecular weight of 2000-12000, the number of these polyols in the prepolymers in comparison with the total amount of these polyols used in obtaining the elastomer is preferably less than 50 wt%. and more preferably less than 30% of the mass.

Polyol 1)with high EO content and a high content of primary hydroxyl acids selected from polyols, having an EO content of 60-90% of the mass. and preferably 65 to 85 wt. -%, designed for a lot of simple polyetherpolyols, and the content of primary hydroxyl 70-100% and preferably 80-100%, calculated on the total number of primary and secondary hydroxyl groups in the polyol. These simple polyether polyols contain other oxyalkylene groups, such oxypropylene and/or oxybutylene groups; preferably these simple polyether polyols are polyoxyethylene/polyoxypropyleneamine. These polyols have an average nominal functionality of 2-8, and more preferably 2-4, an average equivalent weight of 750-5000 and preferably 1000-4000 and the molecular weight of 2000-12000, preferably 2000-10000 and more preferably 2500-8000. As long as there is to the reasonable oxyethylene groups at the end of the polymer chains so that to meet the requirement of the content of primary hydroxyl, distribution oxyethylene and other oxyalkylene groups on the polymer chains may be of the type of statistical distribution, the block copolymer distribution or combinations thereof. Can be used a mixture of polyols. Methods of obtaining such polyols are known, and such polyols are commercially available; examples are Caradol 3602 from the company Shell and Lupranol 9205 from BASF.

Reactive to isocyanate extender chain can be selected from amines, aminoalcohols and polyols; polyols are preferably used. In addition, the chain extenders may be aromatic, cycloaliphatic, analiticheskie and aliphatic; are preferably used aliphatic chain extenders. Extension chains have a molecular weight less than 2000 and preferably 62-1000. Most preferred are aliphatic diols having a molecular weight of 62-1000, such as ethylene glycol, 1,3-propandiol, 2-methyl-1,3-propandiol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-propandiol, 1,3-butanediol, 2,3-butanediol, 1,3-pentanediol, 3-methylpentane-1,5-diol, 2,2-dimethyl-1,3-propandiol, diethylene glycol, dipropyleneglycol and dipropyleneglycol and his propoxycarbonyl and/or ethoxylated products. The amount of extension of the chain is such that the wearing of a hard block is less than 0.50 and preferably less than 0.45.

Other reactive to isocyanate compounds which can be used in an amount up to 20% of the mass. and preferably up to 10 wt. -%, can be selected from a simple politicalarena, complex polyether polyols and simple polyether polyols (different from above)having a molecular weight of 2000 or more, and, in particular, from such other simple polyether polyols which can be selected from polyoxyethyleneglycol, polyoxypropyleneglycol, polyoxyethylene/polyoxypropyleneglycol with the content of oxyethylene less than 60% of the mass. or more than 90 wt. -%, and polyoxyethylene/polyoxypropyleneglycol with the content of primary hydroxyl less than 70%. Preferred polyoxyethylene/polyoxypropyleneamine are such which have a content of oxyethylene 5-30% of the mass. and preferably 10-25 wt. -%, where all oxyethylene group are at the end of polymer chains (the so-called EO-blocked polyols), and those who are content oxyethylene 60-90% of the mass. and have all oxyethylene group and oxypropylene group, statistically distributed, and a hydroxyl content of 20-60%, calculated on the total number of primary and secondary hydroxyl groups in the polyol. Preferably these other simple polyether polyols have an average nominal functionality of 2-6, more prepact the tion of 2-4 and an average molecular weight of 2000-10000, more preferably 2500-8000. In addition, other reactive to isocyanate compounds may be selected from crosslinking agents that are reactive to isocyanate compounds having an average molecular weight below 2000, preferably up to 1000, and the functionality of 3-8. Examples of such crosslinking agents are glycerin, trimethylolpropane, pentaerythritol, sucrose, sorbitol, mono-, di - and triethanolamine, Ethylenediamine, toluidines, diethyltoluenediamine, polyoxyethyleneglycol, having an average nominal functionality of 3 to 8 and an average molecular weight of less than 2000, for example, ethoxylated glycerin, trimethylolpropane, sucrose and sorbitol having a specified molecular weight, and (easy polyester) diamines and triamine having an average molecular weight below 2000, the most preferred cross-linking agents are polyol as one cross-linking agents.

More other reactive to isocyanate compounds may be selected from polyesters, complex polyetherimides, simple policyeview, polycarbonates, Polyacetals, polyolefins or polysiloxanes. Complex polyether polyols which can be used include the reaction products of hydroxyl endings diatomic alcohols, such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butand the ol, neopentylglycol, 1,6-hexanediol or cyclohexanedimethanol, or mixtures of such diatomic alcohols and dicarboxylic acids or their ester derivatives, for example succinic, glutaric and adipic acids or their dimethyl complex esters, sabatinovka acid, phthalic anhydride, tetrachlorophthalic anhydride or dimethyl terephthalate or mixtures thereof. Complex polyetherimide can be obtained by the inclusion of aminoalcohols, such as ethanolamine, polyesterification mixture.

Simple politicality that may be used include products obtained by condensing thiodiglycol either alone or with other glycols, acceleratedly, dicarboxylic acids, formaldehyde, aminoalcohols or aminocarbonyl acids. Polycarbonatediol that may be used include products obtained by the interaction of diols, such as 1,3-propandiol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol or tetraethylene glycol, with dellcorporate, such as diphenylcarbonate, or with phosgene. Politicalpower, which can be used include politicalpower obtained by the interaction of glycols, such as diethylene glycol, triethylene glycol or hexanediol, with formaldehyde. Suitable Polyacetals may also be obtained by polymerization of cyclic acetals. Fit poliolefine polyols include butadiene homopolymers and copolymers with hydroxyacetone, and suitable polysiloxane polyols include polydimethylsiloxanes.

Can also be used mixtures of the above other reactive to isocyanate compounds. Preferably other reactive to isocyanate compounds are polyols selected from the above-mentioned preferred polyols.

The polyols may contain dispersions or solutions of polymers obtained stepwise polymerization, or condensation polymers in polyols described above. Such modified polyols, often referred to as "polymer polyols", fully described in the art and include products obtained by the in situ polymerization of one or more vinyl monomers, for example styrene and/or Acrylonitrile, in the above simple afibrillar or in situ by the interaction between a polyisocyanate and an amino - and/or hydroxyquinoline compound, such as triethanolamine, in the above-mentioned polyol. Especially used are polyoxyalkylene containing from 1 to 50% of the dispersed polymer. The particle size of the dispersed polymer is less than 50 microns are preferred.

In recent years, there are several ways to get simple polyether polyols having a low level of unsaturation. These developments made it possible to use simple polyether polyols in high the m finite interval of molecular weight, as such polyols can now be obtained with an acceptable low level of unsaturation. According to the present invention can also be used polyols with low unsaturation. In particular, can be used such high molecular weight polyols having a low level of unsaturation.

Additionally you can use the following optional ingredients: catalysts, enhancing the formation of urethane linkages, such as tin catalysts, such as octoate tin, dibutyltindilaurate, tertiary amine catalysts, such as triethylenediamine, and imidazoles such as dimethylimidazole, and other catalysts, such as complex maleate esters and complex acetate esters; surfactants; foam stabilizers, such as celexalexaprooa copolymers; flame retardants; smoke suppressors; UV stabilizers; dyes; microbial inhibitors; organic and inorganic fillers; internal lubricating the form of agents (such agents can be used to further improve the release of the obtained materials, but are insignificant) and external lubricating the form of agents, preferably used only before receipt of the items, as explained below.

Class of catalyst that can be used is carbon Ratna salt of an alkali metal or alkaline earth metal. The catalyst may be a salt of any metal of groups IA and IIA of the periodic system of elements, but usually preferred are alkali metal salts, such as potassium and sodium salts, especially potassium salts. If necessary, can be used a mixture of such salts, for example a mixture of potassium and sodium salts.

A catalytically effective amount of salt is usually in the range of 0.1 to 10, preferably 0.2 to 5 mass 100 mass reagents.

The carboxylate may be selected from aliphatic carboxylates having 2-10 carbon atoms, for example, acetate, hexanoate, 2-ethylhexanoate and octanoate.

Especially carboxylate may be selected from carboxylates having the formula R-E-A-COO-, in which

A represents a hydrocarbon diradical having 1-6, preferably 1-3, carbon atoms;

E represents-O - or-O-(C=O)-; and

R is X-R1-(OR2)n-where X represents CH3- or is HE,

R1represents a hydrocarbon diradical having 1-8, preferably 1-4 carbon atoms;

R2represents a hydrocarbon diradical having 2 to 4 and preferably 2 or 3 carbon atoms; and

n is 0-10, preferably 0-5.

And can be selected from diradicals, for example-CH2-, CH2CH2- -CH2CH2CH2-, -CH2=CH2CH2-, -CH 2(CH-)CH3, -CH=CH-, -CH=(-) CH3and CH2=(- ) CH2-. The most preferred diradical is-CH=CH - or CH2=(- ) CH2-.

R1can be selected from diradicals specified for a While, and of radicals obtained by removing two hydrogen atoms from, for example, butane, pentane, hexane and octane. The most preferred radicals for R1are methylene, ethylene, trimethylene, tetramethylene and propylene.

R2may be selected from ethylene, trimethylene, tetramethylene, ethylethylene and propylene. The most preferred groups are ethylene and propylene.

Such catalysts and their getting are known as such (see EP 294161, EP 220697 and EP 751114).

Examples of catalysts are sodium acetate, potassium acetate, hexanoate potassium 2-ethylhexanoate, potassium ethoxyacetic potassium, ethoxyacetic sodium, potassium salt Hemi(complex ether), maleic acid and ethoxyethane, atoxicity, ethylene glycol, diethylene glycol, triethylene glycol, tetraethyleneglycol, propylene glycol, dipropyleneglycol, tripropyleneglycol, methanol, ethanol, propanol or butanol, and potassium salt Hemi(complex ester) such hydroxysteroid connection with malonic, succinic, glutaric, adipic or fumaric acid. Can also be used mixtures of these catalysis is tori.

The elastomer may be a solid, solid or foamed (microgestin) elastomer. Microequities elastomers obtained by carrying out the reaction in the presence of a blowing agent, for example, hydrocarbons, fluorocarbons, chlorofluorocarbons, gases, similar to the N2and CO2, and water. It is most preferable as a blowing agent is water. The amount of blowing agent depends on the desired density. The amount of water should be less than 1.5, preferably less than 0.8 wt. -%, calculated on the amount of all other ingredients.

Reaction with getting the pen is held at NCO-index 85-120, preferably 90-110 and most preferably 90-105.

The density of the elastomers is higher than 150 kg/m3preferably above 250 kg/m3and preferably above 400 kg/m3.

The elastomer preferably are in the form. The method may be implemented in any type of form known in the art. Examples of such forms are the forms used in industries for production of polyurethane Shoe soles, automotive parts such as steering wheels, armrests, covers for dashboard and door panels and headrests. Preferably the reaction is carried out in zamknutoi form. The forms are preferably metal, such as aluminum or article is further, the form or shape of the epoxy resin.

The ingredients used to obtain a foam, served in a form at a temperature of from ambient temperature up to 80°and preferably up to 70°and the form in process support at a temperature from ambient temperature up to 80°and preferably up to 70°C. Time demoulded is relatively small, although preferably used directionspanel to isocyanate compounds containing amino groups; depending on the amount of catalyst and process conditions times demoulded can be less than 10 min, preferably less than 5 minutes, more preferably less than 3 minutes and most preferably less than 1 minutes

Method of molding can be carried out in accordance with the method of the reaction injection molding (RIF) and the injection molding method.

In General reactive to isocyanate ingredients are pre-mixed, optionally together with an optional ingredients before bringing into contact with the polyisocyanate.

The elastomers according to the invention are particularly suitable for use in applications that require good energy absorption and fatigue strength and good elastomeric behavior in a wide temperature range, for example in the car and footwear industry.

Elastomers can be used as soles, spacers and top of the shoes and boots and in steering wheel, soundproofing mats, seals, air filters and casings dashboard.

Since the elastomers according to the present invention can be easily extracted from the mold without the use of external lubrication forms after the first part, the present invention also relates to a method for producing a polyurethane elastomer having a total apparent density of more than 150 kg/m3in the form in which (way), conduct the following steps:

1. external lubrication of the form is applied at least on those surfaces of the forms that are in contact with the ingredients used to obtain an elastomer and/or end of the elastomer;

2. the ingredients used to obtain elastomer, served in the form;

3. the ingredients allow you to react to form a polyurethane material that contains the MDI interaction and reactive to isocyanate composition, optionally in the presence of water, where the reaction is carried out at isocyanate index 40-120, the polyisocyanate consists of

a) 80-100% of the mass. diphenylmethanediisocyanate containing at least 40 wt. -%, preferably at least 60% of the mass. and most preferably at least 85 wt. -%, 4,4'-diphenylmethanediisocyanate and/or PR is izvorovo specified diphenylmethanediisocyanate, which (derived) is liquid at 25°and has an NCO value of at least 20% of the mass. (MDI), and

b) 20-0% of the mass. another MDI (polyisocyanate b), in which reactive to isocyanate composition consists of a) 80-100% of the mass. simple polyetherpolyols, having an average nominal functionality of 2-8, an average equivalent weight of 750-5000, an average molecular weight of 2000-12000, the content of oxyethylene (MA) 60 to 90% of the mass. and the content of primary hydroxyl 70-100%, calculated on the number of primary and secondary hydroxyl groups in the polyol, (b) reactive toward isocyanate chain extension in such a quantity that the ratio of the hard block is less than 0.50 and preferably less than 0.45, and (C) 20-0% of the mass. one or more other reactive to isocyanate compounds, excluding water, the amount of polyol a) and reactive to the isocyanate compound (C) is calculated on the total amount of said polyol a) and compound (C);

4. the so formed polyurethane material is removed from the mold; and

5. stage 2, 3 and 4 is repeated at least 10 times without repeating stage 1.

The obtained materials have comparable physical properties, regardless if the material after stages 2, 3 and 4, conducted once, 10 times, 25 times, 40 times or even more.

Method of molding can be carried out in the open form and closed form; preferably the reaction takes place in a closed form. When the method of forming is carried out in closed form, the form can be closed after stage 2 and is opened after stage 3, or the form can be closed after stage 1 and is open after stage 3; in the latter case, the ingredients for receiving the elastomer serves to form through the respective inlets. Molding can be carried out by methods known in the art, similar to the injection molding and reaction injection moldable (RIF). As indicated, stages 2-4 is repeated at least 10 times without repeating stage 1; preferably it is at least 15 times and most preferably at least 25 times. Although it would be desirable for stage 2-4 can be repeated as many times without repeating stage 1, the practice shows that it may be desirable to repeat stage 1 after stage 2-4 were repeated a significant number of times without repeating stage 1. In General we can say that stage 1 should be repeated when there is a significant increase in the effort required to remove molded parts, compared with the force required to remove the first molded parts, in such an extent that it is expected that the next notch of the form cannot be completed without damage to the parts. Engaged in the notch of the forms on industrial lines receiving STRs is obny easy to identify whether and when stage 1 must be repeated. Although there is still necessary due to the deterioration of the characteristics demoulded, however, it should be desirable to repeat stage 1 after a certain period of time in order to have a proper way to obtain. In this context, it may be desirable to repeat stage 1, for example, every hour or between two shifts (for example, 8 hours), 24 hours or one week depending on the complexity of the shape. It should be noted that the normal cycle is usually between 0.5 and 20 min and often between 1 and 10 minutes

The method may be implemented in any type of form known in the art. Examples of such forms are the forms used in industries for production of polyurethane Shoe soles, automotive parts such as steering wheels, armrests, headrests and covers for the dashboard and door panels.

Material form can be selected from materials known in the art, such as metal, for example steel, aluminum, and epoxy resin.

Stage 1 of the method according to the invention can be carried out in any manner known in the art. The application of external grease forms on the surface of the mold, which (on the surface) are in contact with the ingredients used to produce material and/or material, includes any method of applying tacos the lubricant on the surface, for example, rubbing, brushing, spraying, and combinations thereof, and the application of any agent or agents designed to facilitate last demoulded. Can be used one or more lubricating the form of agents or a mixture of external lubricating the form of agents.

External lubrication in the form of agents can be applied as such or in the form of a solution, emulsion or dispersion in a liquid.

External lubrication in the form of agents, applied in stage 1, can be applied in one or more stages. Can be applied any external lubrication in the form of the agent, known in the art; examples of suitable external lubricating the form of agents are Kluberpur 41-0039 and 41-0061 (both from the company Kluber Chemie), Desmotrol D-10RT from the company Productos Concentrol SA, Acmosil 180 STBH, from the firm of Fuller and Johnson Cire 103 from the company Johnson and Johnson.

The present invention is illustrated by the following examples.

Example 1

Mixing 100 mass parts (MASC) Caradol SA 3602, supplier Shell (polyol having a nominal hydroxyl functionality of 3, HE-the number of 36 mg KOH/g, the content of oxyethylene approximately 77% of the mass. and the content of primary hydroxyl groups of about 90%), 4,34 mass of ethylene glycol, 0,50 mass water 0,75 mass DABCO EG (amine catalyst from the company Air Products). To this add 39,8 mass Suprasec 2020 (reconmendations DHS from MDI containing more than 95% of the mass. 4,4'-MDI, Meuse what about the NCO value of 29.5 wt. -%, supplier - firm Huntsman Polyurethanes; Suprasec is a trademark of the company Huntsman International LLC). After thorough mixing (table mixer of Heidolph, about 4500 rpm for 10-15 s) 105 g of this formulation is poured into aluminum form (20×15×1.5 cm) and allow to react (form left closed). After 8 min the resulting elastomer is easily removed from the form. Mold temperature is 50°and before the formulation is poured into the form, the inner wall of the form is wiped with a sponge containing solid wax LH-1 Chem Trend, and then sprayed soapy aerosol ES-940/M (supplier - firm Muench). After demolding the first elastomer 12 other elastomers are easily extracted from the mold according to the above method, but without treatment of the inner walls of the mold. After 13 forming experiment deliberately stop.

Example 2

90 mass Caradol SA 3602 mixed with 10 mass 1,4-butanediol, 1,5 mass Dabco 25S (amine catalyst, the supplier Air Products) and 0.1 mass Dabco 120 (oleomargarine catalyst, the supplier Air Products). 100 mass this polyol as one recipe (temperature 30°C) and 50 mass MDI having an NCO value 26,2% of the mass. and which is a mixture of 1) MDI obtained by the interaction 42,55 mass DHS, containing more than 95% of the mass. 4,4'-MDI, and of 5.05 mass mixture tripropyleneglycol, propylene glycol and 1,3-butanediol (59:18, 7922, 21 by mass), and 2) Suprasec 2020 (52,4 mass), is formed into the reaction injection molding (RIF) using KM Comet 20/20; the form is flat fixture 60×30×0.4 cm; output is 450 g/C; mold temperature is 65°With; the inner wall of the form process once the wax 36-3534 (supplier-firm Acmos) before the ingredients is injected into the mold. The elastomer has a density of 1230 kg/m3.

Without additional internal walls of the mold 24 other elastomeric parts are made the same way and have similar properties, get easy demoulding with minimal time demoulded 15 C. the Experiment deliberately stop.

Elastomers have the following properties:

The overall apparent density (DIN 53420), kg/m31231
Shore hardness A (DIN 53505)58
Wear, mg loss, 20 m (DIN 53516)196
Tensile strength (DIN 53504), MPa3,3
Elongation (DIN 53504), %161
Tensile strength in hydrater.4

condition (DIN 53504)*, MPA

The elongation in hydrater. condition (DIN 53504)*, %202
Test p is sdir (DIN 53515), N/mm21

* The same test as above, but after humid aging (7 days at 70°C at 100% humidity, followed by 1 day at 70°when humidity environment).

The above experiment is repeated with the following differences. Change the number of MDI and polyol Caradol SA 3602 substituted as indicated below;

also the results:

EXPERIMENT (COMPARATIVE)23
The polyisocyanate, mass5252,7
Polyol 1, mass3060
Polyol 2, mass6030
The minimum time demoulded,6060
The number of undamaged grooves form45

Polyol 1 is: glicerinization polyoxyethylene/polyoxypropylene having a molecular weight of 4000, EA - content of 75% of the mass. (all statistics) and the content of the primary HE is 42%.

Polyol 2 is: (dipropyleneglycol)-initiated polyoxyethylene/polyoxypropylene, containing about 27% massao (all blokirobvannii) and having a molecular weight of about 3750.

1. A method of obtaining a polyurethane thermoautotrophica elastomer having a total apparent density of more than 150 kg/m3including interaction of MDI and reactive to isocyanate composition, optionally in the presence of water, whereby the reaction is carried out at isocyanate index 85-120, and the polyisocyanate consists of

a) MDI comprising isocyanate components:

A1) 80-100 wt.% diphenylmethanediisocyanate containing at least 40 wt.% 4,4'-diphenylmethanediisocyanate and/or a derivative thereof specified diphenylmethanediisocyanate, which (derived) is liquid at 25°and has an NCO value of at least 20 wt.%, and

A2) 20-0% by weight of another MDI, and reactive to isocyanate composition consists of

b) a polyol as one component, consisting of

B1) 80-100 wt.% simple polyetherpolyols, having an average nominal functionality of 2-8, an average equivalent weight of 750-5000, an average molecular weight of 2000-12000, the content of oxyethylene 60-90 wt.% and the content of primary hydroxyl groups 70-100%, calculated on the total number of primary and secondary hydroxyl groups in the polyol,

B2) reactive to isocyanate chain extension in such a quantity that the proportion of the hard block is less than 0.45, and

B3) 20-0% by weight of one or more other reactive to isocyanate compounds, excluding water, the amount of polyol B1) and reactive to isocyanate compound B3) is calculated on the total amount of said polyol B1) B3).

2. The method according to claim 1, in which the content of oxyethylene is 65-85 wt.%, average nominal functionality of 2-4, an average equivalent weight is 1000-4000 and the average molecular weight is 2000-10000, and the polyisocyanate contains 80-100 wt.% diphenylmethanediisocyanate containing at least 85 wt.% 4,4'-diphenylmethanediisocyanate and/or a derivative thereof specified diphenylmethanediisocyanate.

3. The method according to claims 1 and 2, in which the elastomer is obtained in the form and perform the following steps:

1) put the external agent lubricant forms, at least on those surfaces of the forms that are in contact with the ingredients used to obtain elastomer, and/or with the final elastomer;

2) is served in the form of ingredients used to obtain elastomer;

3) carry out the method according to claim 1 with the formation of the elastomer;

4) the so formed elastomer is removed from the mold and

5) stages 2, 3 and 4 is repeated at least 10 times without repeating stage 1.

4. The method according to claim 3, in which the stage 2, 3 and 4 repeat not m is it 25 times without repeating stage 1.

5. The method according to p-4, in which stage 1 is repeated after one week.

6. The method according to p-4, in which stage 1 is repeated in 24 hours

7. The method according to p-4, in which stage 1 is repeated after 8 hours

8. The method according to claims 1 to 7, in which the method is carried out in closed form.

9. The method according to p-8, which uses the form of metal or of epoxy resin.

10. Termotehnica elastomer obtained in accordance with the method according to claims 1-9.



 

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