PL100366B1 - METHOD OF MANUFACTURING A POL-PRODUCT INTENDED FOR THE PREPARATION OF POLYURETHANE ELASTOMER - Google Patents

Description

The invention relates to a manufacturing process stable intermediate based on polyethers i polyesters, intended for compounding polyurethane, used for covering surfaces and sports facilities.

It produces according to hitherto known methods polyurethane mass for coating large na¬ surface directly on site nia.

For this, all raw materials such as polyethers or polyesters, diisocyanates, inorganic fillers small, flexible fillers, stabilizing additives jace and dyes are transported to the place where a flexible surface is to be produced nia.

All ingredients are introduced under the condition technological components required during sintering nanny polyethers or polyesters, for tanks with with high-speed stirrers or for machines continuous action and produces liquid ma se polyurethane, which is applied directly a hard surface on which the mass continues cross-linking and solidifying to form an elastic na¬ outer.

Such behavior is not always the same my technological assumptions lead to a product with the same physical and physical properties chanicals. A large number of different agents are used grooves, changing weather conditions, size tanks or equipment for continuous production lo of polyurethane mass as well as humidity and temperature the nature of the environment influences the diversity of properties you physical-mechanical product. In some unfavorable cases, especially if The pouring of the mass is carried out with high humidity In the air, you get clippings of the lined air elastomer surfaces with physical properties co-mechanical deviates from the established norms for the material to such an extent that it is sometimes necessary cutting out certain parts of the superimposed surface.

According to the patent description No. 75,918 it produces a mass of polyurethane elastomer, alloy Suitable for covering surfaces with water-free linear and branched polyether polyols of prepolymers obtained from diisocyanate monates, polyethers and polyhydric alcohols as well as flexible and inelastic fillers agents, pigments, light stabilizers, stabilizer anti-aging compounds, anti-fume compounds decay and rot-inhibiting compounds.

Reactions between polyols and prepolymers, e.g. containing isocyanate or toluene groups The diisocyanate is converted to the cat organometallic lysers, being additives is introduced accordingly to the process in progress, the course of the reaction.

According to this description, slurries are produced polyurethane elastomer in the gun flowing continuously, consisting of three screw feeders, connected in series 100 366toisei supply tanks mixed with each other loose ingredients for mixing heads where to mix mixed liquids are possible. Such a device is big, has a complicated foud, there is a problem-- possible to transport, assemble and disassemble on site 5 scu work.

Also a solution according to the patent description U.S. Pat. No. 3,272,098 relates to the production of plastics flexible to cover the treadmill and station diones, from polyether linear poly- 10 isocyanates, fillers, pigments and additives cows. In this process, it extrudes itself directly polyurethane mass and forms it into carpets or discs, which are then transported to place markings and sticks to a concrete base. 15 The essence of the invention is the preparation of a semi-pro a product intended for the preparation of elastomer polyurethane from a mixture of crude polyethers Made in the process of hydro-alkoxylation alkali catalysts and 20 polyesters. In this process, raw polyethers Fr. the alkaline reaction acts with mineral acids compounds or decomposing compounds with an acid evolution of water, and then stirring Shanine is dehydrated by draining the water to a content of 25 of less than 0.1 * 71 water, while the rest of the water is removed by bonding it chemically applying to this for the purpose of diisocyanates or anhydrous prepolymer obtained from diisocyanates and polyethers. Na¬ stepwise precipitated salts are separated also into a hydrousine 30 polyether mixtures are incorporated into the polyesters fillers and additives. Everything is dehydrating again giving an anhydrous stable homogeneous semi-pro product that is transported in sealed barrels to the place of destination and make up a mass of poly- 33 urethane by foaming with diisocyanates.

By the method according to the invention, the intermediate was intended for used for the production of polyurethane elastomer prepared by treating the mixture with raw materials of polyethers prepared in the presence of catalysts alkaline dough, containing 2-10 parts by weight polyethers with a particle weight of 180-500 obtained in the process of oltsyalkylation of phenols, cresols, xylenols and condensation with formaldehyde or up to 10 parts by weight of polyethers with a 200-500 fine grains obtained on the road by oxyalkylation of hydroquinone, resorcinol, a pyrocatechin or a pyrocatechin fraction and 0-80 parts by weight of yeast weight polyethers bin 2000-4000, obtained by the oxy-50 process alkyleneation of glycol and / or glycerin and / or resor tin and / or hydroquinone and / or pyrocatechia fractions new. The alkali catalysts contained in the polyethers many are lost in the form of salt by action with mineral or organic acids, or 55 not decomposing compounds water to acids. Everything warms up while stirring under reduced pressure to a temperature of 80- -120 ° C and kept at this temperature up to lowering the water content by weight to 0.1%. in Then 0.1-1.0 parts by weight are added to ilylene diisocyanate or 4,4'-diphenylmethane- of the diisocyanate of a relatively anhydrous prepoly mer obtained from polyethers and toluene diiso- cyanate. c5 These compounds introduced in small amounts of wind for chemically residual water contained in the mixture not polyethers. Salts in the form of a precipitate derived from inorganic catalysts from it divides by mechanical means, for example by centrifugation or drainage.

The dehydrated polyethers are mixed with 20-90 parts by weight of the polyesters, preferably 50-75 parts by weight using polyesters with a weight 2000-4000 obtained from acid acid pinic, glycol or diglycols. To the mixture 5-50 parts of polyether-polyester are introduced those by weight fillers, 8-15 parts by weight flame-inhibiting compounds, 0.2-5.0 cleans . main pigments, 0.1 to 0.5 parts by weight solid a stabilizer against aging and € .2-Q, 5 parts of weight rot-inhibiting compounds. The mixture of ho can be carried out on rubbing devices, horse preferably three-rollers until the seed diameter is obtained rhenium of solids in a mixture of the size grains less than 50 microns.

Preferably, mixtures are used for neutralization nines of polyethers - up to pH = 6.8-5.5 - POCI, PC13, PCl5, phosphorus bromo, thionyl chloride, chlorine sulfur dioxide, sulfuryl chloride, chlorosulfonic acid or acetic acid anhydride.

These compounds are introduced into the raw mixture of polyethers in stoichiometric amounts based on the content of alkaline catalysis tora in a mixture. Neutralization is carried out in temperature 50-70 ° C, the cations coming from decomposition of the catalyst with acid residues of introduced neutralizing factors creates salts that easily lose out. Then have The shannin is heated to a temperature of 80-120 ° C under low pressure in the order of 10-200 mm Hg. IN under these conditions, it is passed through the mixture by bubbling nitrogen gas or carbon dioxide i dehydrates the polyol mixture like this as long as the water content has not dropped to 0.1% by weight. Trace amounts of polyether water removed, then treating the mixture with a compound with decomposing stones to amines.

Gypsum is preferably used as fillers, kaolin clay, chalks, talcum, diatomaceous earth or ground minerals.

As anti-smoking compounds Compositions of antimony trioxide are used with a connection to halogenated compounds such as polyvinyl chloride nyl, chloroparaffin, hexo-chlorocyclohexane relatively tribromotoluene, using for 1 gram mole of antimony, 3 grams of halogen, or com positions obtained from 1-5, preferably 1-2 parts by weight of red phosphorus and 7-12 parts of the shaft of the main halogenated compounds mentioned previously.

They are used as decay inhibitors preferably pentachlorophenol, mercury phenylacetate, oxygen mercury nek or copper oxide, and as dyes i pigments are used for non-reactive compounds isocyanate memories, preferably inorbent pigments powerful hiding power like red-green copper or copper oxide.

It is preferable to introduce solids100 366 only for combing polyethers, so that averaging on rolling mill to grain sizes below 50 microns solids, lead in a dense mass. After homogeneous mass with the rest of the polyethers and poly of the esters are mixed in the reactor and then passed through the mass is again dewatered into a table conditions previously used, that is, heating jac the mixture under the reduced pressure of the row —200 mm Hg up to a temperature of 80—120 ° C and bar- running through a mixture of nitrogen or gaseous two Carbon monoxide. After draining the water to the content less than 0.1% of total weight, introductory the mixture is taken to a mixture of 0.2-2.0 parts by weight toluene diisocyanates or 4,4'-diphenylmethane no-diisocyanate or prepolymer is obtained made of anhydrous polyethers and toluene dibasic isocyanate. . ! Such a number of introduced isocyanate groups for polyethers is sufficient for stoichiometric complete water binding of polyethers and composition solids and at the same time increases the viscosity of the product, giving an anhydrous intermediate, not sedating mentoring in storage.

The obtained intermediate is homogeneous and has the same concentration by weight shows a conc varnish systems of the order of 300cC = Pw 25 ° C and not hives % sedimentation in less than 6 weeks. Za¬ small body particles suspended in a thick liquid steels with a size of less than 50 microns are half badly immobile.

The intermediate product obtained according to the invention was introduced They are loaded into barrels or cisterns and transported to the place where the pavement is to be produced flexible, for example a stadium.

EXAMPLE 1 A heated reactor capacity 20 liters equipped with a stirrer, thermo meter, manometer, feed of substrates and devices bubbling and evacuation of vapors to vacuum ni, 2000 g of linear polyether o with a hydroxyl number of 50 mg KOH / g obtained from glycol, propylene oxide and ethylene oxide If the chains are terminated, 2000 g are split fused polyether obtained from glycerol, oxygen towards propylene and ethylene oxide with the number hydroxyl chloride 58 mg KOH / g, 800 g linear volume a polyether obtained from the pyrocatechin fraction and ethylene oxide with a hydroxyl number of 100 mg KOH / g, 200 g of low molecular weight polyether cairn with a hydroxyl number of 220 mg / KOH / g a obtained by condensation with formaldehyde alkoxylated phenol and alkoxylated pi- rocatechins. The polyethers used contain alkaline catalysts, mainly KOH in average amounts 0.2 wt.% based on polyol and KOH. Change The chained polyethers are heated to 60 ° -70 ° C and neutralized it takes 6 g of 100% phosphoric acid or a compound that, under the influence of the water contained in in polyols decomposes into mineral acid, e.g.

6 g of SO2C12 in an amount sufficient to obtain the pH mixtures of 6.2-6.8. Neutralized mixture heated to a vacuum of 10-50 mm Hg at temperature 110-120 ° C until the water content is obtained dy less than 0.1%. To speed up dehydration a mixture of CO2 or N2 is bubbling up. Dehydrated the mixture is cooled to 40 ° C — 70 ° C and stirred adds 25 g of toluene diisocyanate very slowly nu TDI-80 to bind residual water and accelerate the release of mineral SOU. Everything is sucked Aug 9 from the suspension, preferably with the addition of carbon afcr- ! active; The mixture of polyethers prepared in this way with an bones less than 1.5 thousand cP at 25 ° C is introduced up to 5000 g of linear polyesters with a hydro number l xylate 50 mg KOH / g and a viscosity of approx. 20 thousand. cP at 25 ° C and obtained from glycols, diglycols and acid adipine supplement with the addition of glycerin for Czech cross-linking of the product, - After mixing polyester and polyethers it will tighten make a mixture with a viscosity below 4 thousand. cP ^ f'35 ° C, to which are introduced 3000 g of talcum powder, 700 g 1a # j- antimony oxide, 200 g of polyvinyl chloride suspension, 20 g of pentachlorophenol and ca- The love mixes well and then grinds into a trivalent carce to obtain fragmentation of the solid phase below 50 | x. The whole mass with the consistency of varnish introduced into the device "described above and heated under a vacuum of 10-25 mm Hg and temperature 100-120 ° C, bubbling gas mass QQ * or N2 until the water content is poftitatj 0.1% by weight. Then the mass cools to 60-70 ° C and slowly add 100 g while stirring 4,4'-diphenylmethane diisocyanate, to which -1 the donation causes additional dehydration of the mass a; mainly polyol stabilization and sediment inhibition the tation of solids.

The resulting mass gives with the prepolymer or 4,4'- -diphenylmethane diisocyanate elasto | er o hardness 45 ^ 55 ° Sh A. Component stability fK> lio- for sedimentation is approx. 2 months, the chemical stability is 1 year.

Example II to XII. Basic operations run as in example I, while change 40 grades and weight ratios of polyethers are grown (P), neutralizing agent (C), solids reagent balancing the mass and dehydrating (Z), filling or (W), flame retardant additives (A), pig¬ (B) and anti-rot agents (H).

The resulting basic intermediate for elasto of a polyurethane polymer is stable in transit and the elastomer obtained therefrom had gives great flexibility and its hardness varies from within 30 ^ 65 ° Sh A depending on the ones used 45 50 55 polyol ingredients.

Claims (6)

Patent claims 1. • 1. A method of producing a semi-product for the preparation of polyurethane elastomer from polyethers obtained in the presence of alkali catalysts and polyesters, characterized in that the mixture of polyethers containing 2-10 parts by weight of polyether with a particle weight of 180 500 obtained by the alkoxylation of phenols, cresols, xylenols and subsequently condensed with formaldehyde, or up to 10 parts by weight of polyethers with a molecular weight of 800-2000 obtained by the alkoxylation of hydroquinone, re-100 366 7 s Table Name of the substrates polyester LOH 30— L —ie polyether linear with LOH 40-100 ps ^ branched ether with LOH 40-100 linear polyether from pyrocatechin or pyrocatechin fraction with LOH 100—550 mg KJ & H / g linear path from re - aoreins e LQH 100-550 mg KOH / g linear polyether from hydroquinone with LOH 100-550 mg KOH / g polyether condensed from oxyalkylene hydroxybenzenes and formalin with LOH 200-500 PCI, PBr , PC15 PBr5 POCI, POBr, 1 (O4 -T ^^ AND SO2Cl2 SO2 / OH / Cl 1 S2Cl2 / CHaCO / sO H2SO4 H3PO4 HOOOH talc kaolin kieselguhr ground chalk gypsum ground minerals toluene disocyanate-1 nanate 4,4-diphenylmethane diisocyanate prepolymer with free groups NCO (30-70% TDI) antimony trioxide red phosphorus polyvinyl chloride chloroparaffin hexachlorocyclohexane tribromotoluene. Symbol of substrate. Pi P2 P * P4 P5 P6 P7 Q ct c8 c4 c6 c6 c7 c8 c9 C10 Clt C12 c13 C14 W, w2 w, w4 w5 w6 Z2 z2 z3 Aa A2 A3 A, A5 A6 No examples ar 5000 4500 500 5g or 10g 4000 50 600 800 III 7500 4000 600 400 5.5g or Hg 4000 75 400 900 IV 10000 2000 2000 800 200 5.5g 10 g 2000 4000 1000 150 60 650 V | 5000 4000 1000 7g 2500 500 1800 120 60 300 VI 5000 4000 500 500 6g 200 2000 100 100 60 360 VII | 8000 4000 1000 7g 2000 1000 300 1000 150 150 30 360 vni 8000 4000 800 200 8g 3000 500 2000 150 30 330 IX 10000 2500 1500 1000 9g 4000 2000 200 50 120 330 X 7500 2000 1800 1000 200 9g 2000 500 1000 150 60 180 300 XI 7500 2500 2700 200 9g 2500 2000 250 100 150 60 600 Xli 100G0 4000 800 200 10g 3000 3000 200 150 30 200 330 1100 366 10 Table cd Name of the substrates light stabilizer iron red chrome green pentachlorophenol phenylacetate mercury mercury oxide | copper oxide Symbol substr. St B, B * Hi H2 H8 H4 No No examples II 10 300 20 III 20 400 30 W 25 600 50 V 15 400 20 W 20 400 40 VII 25 500 50 VIII 25 500 50 EX 30 600 30 XL 20 500 30 XJ 20 500 50 1 ^ 30 700 50 1 zorcin, pyrocatechin or pyrocatechin fraction and 0-80 parts by weight, preferably 20-40 parts by weight of polyethers with a particle weight of 2000-4000 and obtained by the alkoxylation of glycol and / or glycerin and / or resorcinol and / or pyrocatechin and / or hydroquinone and / or pyrocatechin fractions containing alkaline catalysts are treated to pH = 6.8-5.6 with mineral or organic acids, or compounds that decompose into acids by water The whole is heated with stirring under reduced pressure to a temperature of 80-120 ° C and kept at this temperature until the water content has fallen to 0.1%, then 0.1-1.0 parts by weight of toluene diisocyanate are added. , 4,4'-diphenylmethane diisocyanate or prepolymer obtained from anhydrous polyethers and toluyls No diisocyanate, as a chemical binding agent for the water, then the precipitate of the precipitated salts is separated, and the water-free polyethers are mixed with 20-90 parts by weight of polyester, preferably with 50-75 parts by weight of polyester with a particle weight of 2000-4000 obtained from adipic acid and glycol or diglycols and add 5-50 parts by weight of fillers, 8-15 parts by weight of flame retardants, 0.2-5.0 parts by weight of pigments, 0.1-0.5 parts by weight to the mixture. by weight of aging stabilizer and 0.2 to 0.5 parts by weight of anti-rotting compounds, the mixture is homogenized on grinding machines, preferably three-rollers, until the grain diameter of the solids in the mixture is below 50 microns, and the mass is then dehydrated in the previous conditions, adding 0.2-2 parts by weight of diisocyanate or a prepolymer containing free isocyanate groups after the water content is below 0.1%. 2. The method according to claim A method according to claim 1, characterized in that sulfuric acid, phosphoric acid, formic acid or compounds which under the influence of water emit mostly mineral acids, such as phosphorus oxychloride and phosphorus pentachloride, phosphorus trichloride, phosphorus tribromide, phosphorus pentobromide, are used as neutralizing compounds, thionyl chloride, surfuryl chloride, chlorosulfonic acid, acetic anhydride, sulfur chloride. 3. The method according to p. A method according to claim 1, characterized in that 10-15 parts by weight of antimony trioxide compositions with halogen derivatives such as polyvinyl chloride, chloroparaffin, hexachlorocyclohexane, tribromotoluene are used as the flame retardants, using 3 grams of a part of halogen or 8-15 parts by weight of antimony. by weight of a composition consisting of 1-5 parts by weight, preferably 1-2 parts by weight, of red phosphorus or an appropriate amount of its compounds with 7-12 parts by weight of the halogenated derivatives mentioned above. 4. The method according to p. The method of claim 1, wherein the fillers are preferably gypsum, rhodium clay, chalk, talc, diatomaceous earth or ground minerals. 5. The method according to p. The process as claimed in claim 1, wherein pentachlorophenol, mercury phenylacetate, mercury oxide or copper oxide are used as the rot-inhibiting compounds. 6. The method according to p. The method of claim 1, wherein the isocyanate-non-reactive dyes are preferably inorganic pigments with high hiding power, such as iron red, chrome green.