The method of processing mineral filler phosphate, thus treated mineral filler, polyurethane foams and composite polyurethanes using this filler containing them shaped and unshaped products

 

(57) Abstract:

The invention relates to mineral fillers used for the manufacture of polyurethane foams, in particular to the fillers of the type of carbonate, hydroxides, silicates, sulfates and similar mineral fillers. The method of processing mineral fillers particular particle size distribution using a processing agent type organic phosphate includes a step of desagglomeration and, if necessary, stage of breeding. For the manufacture of polyurethanes, especially polyurethane foam, a mixture of processed organic phosphate mineral filler with a polyhydric alcohol. The polyurethane foams are produced either by foaming without auxiliary blowing agent or with an auxiliary blowing agent. Composite polyurethanes may also contain processed organic phosphate filler. The technical result of the invention is to improve the dispersive ability of the pigment mineral filler in the polyhydric alcohol. 7 C. and 26 C.p. f-crystals, 9 PL.

The present invention relates to the technical field of the manufacture of polyurethane foams, in particular mineral fillers used in this sector is to it.

It is known that polyurethanes or PUR) get in the interaction of a polyhydric alcohol and an isocyanate, such as colorvision or TDI with competing reaction of isocyanate with water.

In the production of foam in the form of the block with the head mixture is injected either, on the one hand, uterine mixture of a polyhydric alcohol and mineral supplements, and on the other hand, the complement polyhydric alcohol and a catalytic system such as an amine catalyst, a tin catalyst or a different catalyst, one or more surfactants, usually a type of silicone, water, colorvision, if necessary, an auxiliary blowing agent, which may be methylene chloride, acetone, and various additives, such as stabilizers, either, on the one hand, a polyhydric alcohol, in which uterine mixture was pre-diluted to the desired concentration, and on the other hand, other previously mentioned additives (catalyst, surfactant and so on).

The reaction of water and isocyanate catalyzed by amine, leads to the production of CO2that forms the foam.

In order to reduce the cost per litre or kilogram molded or unmolded products of g is of filler, present in rigid, semi-rigid or flexible polyurethane foams, while maintaining or improving their physical and chemical properties, such as, for example, compression or rupture, or aesthetic or other properties such as fire resistance required in various industries, such as transport, such as a car, furniture manufacturing, construction or other.

Today, there are several ways of introduction of mineral fillers in these polyurethane compounds.

In the first type of methods (FR 2651236) calcium carbonate is introduced into the plasticizing agent for polyurethane. This method of obtaining a suspension of the filler in the plasticizer, which allows to increase the content of the filler in the polyurethane compound is expensive and too complicated in the implementation plan for possible use in the production of flexible, semi-rigid and rigid polyurethane foams and leads to deterioration of the physico-chemical properties of the foams obtained from the suspension of the filler.

After this, an attempt was made to introduce mineral fillers in flexible, semi-rigid or rigid polyurethane foams with low-cost, simple and not calling znachitelnoy alcohol, one of the components of the polyurethane, known to specialists.

The first technology type provides the graft-copolymerization of methacrylic acid (DE 2654746, DE 2714291, DE 2739620) or other vinyl compounds such as styrene, a polyhydric alcohol. But this type does not provide usability suspension of calcium carbonate in the polyhydric alcohol, because it is difficult to work due to too high viscosity and a poor distribution of the filler in the environment, and problems associated with sedimentation of the suspension.

Another technological type is surface-treated filler before its introduction in the polyhydric alcohol through some substances, such as alcohol with 8-14 carbon atoms (FR 2531971), or phosphate hydroxycarboxylic acid (EP 0202394).

However, these methods cause the same type of deficiencies as described above, since the user is faced with problems of low dispersive ability of the pigment in the polyhydric alcohol thus treated mineral nepantla.

Was also developed (EP 0726298) method of processing mineral filler by at least one processing agent type organic postmagmatic alcohols with high filler contents and low viscosity, i.e., a homogeneous suspension is not affected fatal sedimentation, decantation, or thickening, for the manufacture of rigid, semi-rigid or flexible foams.

According to this document spend processing of mineral fillers for their suspension in polyhydric alcohols with at least one processing agent type organic phosphate of the General formula (1)

in which

- R1represents H, C8-C40alkyl, aryl, alkylaryl or arylalkyl with6-C40,

- R2is8-C40is alkyl, aryl, alkylaryl or arylalkyl with C6-C40,

X is-CH2-CH2-,

- Y is-CH(CH3)-CH2-or-CH2-CH(CH3)-,

- (m+n) varies from 0 to 30 with m30, a n30,

- (p+q) varies from 0 to 30 with R30, a q30.

This last method is satisfactory, there was a new problem associated with special and more recent method of manufacture of PUR foams.

According to the conventional method in the "head of the mixture serves, on the one hand, a mixture of a polyhydric alcohol and a mineral filler, and on the other hand, the complement of Megali tin and surfactant, usually the type of silicone. The reaction leads to the production of CO2as described above, which forms the foam. The foam goes through two main phases, the first is the beginning of foaming, and the second stabilization of the foam block, as a result get foamy mass PUR, which is cut into blocks of the required size for the production of mattresses, seat cover and so on

In recent years there has been developed a new method, described in particular in patents EP 0645226 and WO 96/00644, according to which the CO2pump directly or through a stream of a polyhydric alcohol in the liquid state in the head of the mixture. Thus, the CO2used as an auxiliary blowing agent.

This method has several advantages, especially in terms of significant reduction in the use and formation of toxic or flammable materials, and may need in the future to occupy an increasingly important place.

This new method has, however, a number of additional technical problems in the manufacture of PUR foam.

Probably, also, for the correct implementation of the method of this type, called "polyurethane foam with CO2or a way to CO2", the mouth, and improve the quality of mixing.

According to the invention found that it is possible to solve the problem of duration of mixing and to eliminate the difficulties of the new method with CO2by processing mineral filler method, comparable to the one described in EP 0726298 methods, but more advanced.

It was also revealed in a remarkable way as a result of research carried out by the method with CO2that way the processing of mineral fillers according to the invention also improves the conventional methods used for the manufacture of polyurethane foams.

The invention, however, is not limited ways with CO2that was the first to solve a technical problem, but has, on the contrary, a more General value.

It was also noted that the method of processing of mineral fillers according to the invention is applicable to methods for producing composite materials with mesh and pacaisti the basis of PUR, and regardless of the type of filler used: caso3, only, kaolin, aluminum hydroxide, magnesium hydroxide, etc. that have numerous applications in the automobile components industry, for transport od "composite materials" or "composite PUR" in this case mean polyurethanes, reinforced vegetable, glass or quartz fibers or synthetic fibers, usually cut, or similar. Under "cellular PUR" mean expanding or pressurewise polyurethanes.

The invention relates to a method of processing mineral fillers special particle size distribution using the processing agents of the type of organic phosphate, including the state of desagglomeration and, if necessary, stage of breeding in order to improve methods of manufacture of polyurethane foams or by foaming without auxiliary blowing agent, either by aeration with an auxiliary blowing agent such as methylene chloride, acetone or CO2or other, and composite PUR, which lowers the duration of mixing the thus treated filler, a polyhydric alcohol, and other reagents and eliminates the difficulties arising from agglomerates fillers that clog established for CO2static dispersers and weakens the mechanical properties of foams and cellular and nechastyh composite materials, such as, for example, the resistance of rasdi is characterized in that that called filler:

a) is treated with at least one compound of General formula (1)

where

- R1represents H, C8-C40alkyl, aryl, alkylaryl or arylalkyl with C6-C40,

- R2represents C8-C40alkyl, aryl, alkylaryl or arylalkyl with C6-C40,

X is-CH2-CH2-, or-CH(CH3)-CH2- or-CH2-CH(CH3)-, or -(CH2)5-CO-,

- Y is-CH2-CH2,or-CH(CH3)-CH2- or-CH2-CH(CH3)-, or -(CH2)5WITH,

thus X and Y are the same or different,

- (m+n) is changed from 0 to 60 (inclusive), as (p+q)

0m+n60 and 0p+q60, when X=Y=CH2-CH2-

1m10 and R) and (0n59 and 0q59), when X is different from Y,

b) subjecting the stage of desagglomeration and

C) if necessary, subjected to a stage of selection.

These filler has a special bead size distribution, as described below.

Under the "desagglomeration" means the stage at which reduce the number of agglomerates in the appropriate installation type mill, cha is swetnam way method with standardized caliber North (ISO 1524).

Under the breeding denote the operation aimed to highlight some interval in the grain composition by passing through the "separators" (known screens, centrifugal separators, and so on). This operation does not affect the quality of the product, but may resolve itself to make it or not in order to optimize the product depending on the intended end use.

Under "special granulometric composition according to the invention mean particle size directly obtained by grinding or mixing fillers, should be neither too thin nor too large. According to a representative, but not limiting example, intended for a better understanding of this criterion, the filler may be substantially represented in terms of particle size distribution average diameter d50. This average diameter of the mineral fillers according to the invention is from 0.1 μm to 15 μm, preferably from 0.1 μm to 10 μm and more preferably from 0.3 μm to 8 μm. In addition, the specialist will be able to choose the fillers that meet this condition.

The invention relates also to mineral fillers special is erali and, if necessary, stage selection with lesser duration of mixing the thus treated filler with a polyhydric alcohol, and other reagents and intended for suspension in the polyhydric alcohol for use in the manufacture of polyurethane foams or by foaming without auxiliary blowing agent, either by aeration with an auxiliary blowing agent such as methylene chloride, acetone or CO2or others, or composite PUR, in particular mineral fillers carbonate type handled by this method and with this purpose.

The invention also relates to suspensions in polyatomic alcohols of these thus treated mineral fillers received for introduction into the manufacturing process of polyurethane foam or by foaming without auxiliary blowing agent, either by foaming with auxiliary blowing agent such as methylene chloride, acetone or CO2or other, and to their use in the production of flexible, semi-rigid or rigid polyurethane foam method or by foaming without auxiliary blowing agent, either by aeration with an auxiliary blowing agent such as methylene chloride, acetone or CO2or other, and for the manufacture of polyurethane composite.

The invention of the pore-forming, either by foaming with an auxiliary blowing agent such as methylene chloride, acetone or CO2or others, or cellular or neatzistam composite polyurethanes containing processed according to the invention, the fillers are mixed with a polyhydric alcohol.

The invention relates also to the use of the thus obtained flexible, semi-rigid or rigid, or cellular, or nechastyh composite foams in the manufacture of molded or unmolded products.

The invention also applies to pre-mixtures prepared according to the invention of the fillers with the polyhydric alcohol and, in particular, in proportions suitable for the manufacture of polyurethanes and, in particular, polyurethane foams or composite PUR.

The preferred method of carrying out the invention are used directly filler coming out of the production plants, the moisture content is at a level appropriate to its use.

The preferred way to carry out processing of mineral filler acidic phosphate aliphatic alcohol with C8-C20branched or unbranched chain, on which the envelopes.

Processing according to the invention can be carried out dry or wet method.

Thus treated mineral fillers according to the invention, providing a stable and homogeneous suspensions in polyatomic alcohols are chosen from among the mineral fillers that give the polyurethane foam and pour within the structure of composite materials with mesh or pacaisti matrix PUR, physico-chemical properties, the appropriate use of these materials for the manufacture of molded or unmolded products, and, in particular, are chosen from among natural or synthetic carbonates, phosphates and sulfates of alkaline earth metals, such as, in particular, calcium carbonates natural or synthetic origin, magnesium carbonate, zinc carbonate, mixed salts of magnesium and calcium, such as dolomite, lime, magnesia, barium sulphate, calcium sulphate, magnesium hydroxide, aluminum, dvuoksid silica, wollastonite, clays and other silicophosphate materials, such as kaolin, kremnevye compounds such as talc, mica, hollow or solid glass beads, metal oxides, such as, for example, zinc oxide, iron oxides, titanium oxide, and especially hydroxid aluminum, magnesium hydroxide, talc or mixtures thereof.

Mineral fillers according to the invention differ from prior art in that they retain a hydrophilic, with a polyhydric alcohol consumption by at least 15% and preferably at least 20% lower compared to the raw mineral filler, and, in particular, the fact that they are received by the processing method according to the invention.

Under the "preferred" mean the fact that the invention also covers values from 15 to 20%, it is natural that the efficiency of the results is higher, the greater the decline in the consumption of a polyhydric alcohol.

The polyhydric alcohol consumption, which is expressed through the absorptive capacity of fillers, represents by definition the number of milligrams or grams of a polyhydric alcohol used per 100 g or 100 ml of the substance of the filler in the measurement conditions of the test, determined by the method arising from the norms ISO 787/5.

Used polyhydric alcohols belong to the family of polyether and polyester - polyethers and polyesters.

Among the usual simple polyether polyols can be named, for example, products presolol, in the presence of ethylene oxide or without him. But can also be given special simple politically, such as, for example, polyether-based amines obtained by the addition of propylene oxide or ethylene oxide to amines, simple halogenated ethers, simple graft-copolymerizable esters obtained by copolymerization of styrene and Acrylonitrile in suspension in a simple polyester, or polytetramethylene.

Among the complex polyether polyols can be mentioned, for example, those that get in the polycondensation polyalcohol with policestate or their anhydrides, such as decollate, such as, for example, adipic, phthalic or other, interacting with dialami (for example, ethylene glycol, propylene glycol, butyleneglycol or other) and trioligy (for example, glycerin, trimethylolpropane or other), and tetralone (for example, pentaerythritol or other, either alone or in a mixture).

However, among the polyhydric alcohols may be called different gidroksilirovanii compounds such as, for example, gidroksilirovanii polybutadienes, prepolymers with hydroxyl ends (resulting from the reaction of an excess of a polyhydric alcohol with a diisocyanate) or W is Rostami the polyether polyols or alcohols, or complex polyether polyols to increase the education of a mesh structure.

Suspensions of mineral fillers in polyatomic alcohols according to the invention can moreover contain other mineral and/or organic compounds such as catalysts, and/or antioxidants and/or other, differ in that the dry matter content of processed mineral materials can be up to 80 wt.%, and the fact that these suspensions are not fatal decantation, sedimentation or thickening after exposure for 7 days for production of flexible, semi-rigid or rigid polyurethane foams, i.e., having a stable apparent viscosity Brookfield, below, in whose suspensions raw mineral fillers, and the fact that they contain 0.5-3 wt.% in relation to the weight of mineral filler, at least one processing agent of General formula (1).

An additional object of the invention to provide a homogeneous, stable suspension of low viscosity of these treated mineral fillers in polyatomic alcohols, characterized in that the concentration (by weight) of mineral fillers can reach 80%, and the content processing SS="ptx2">With these homogeneous, stable suspension of low viscosity according to the invention is easy to operate, because they do not have in common specialist operating conditions neither phenomenon decanting, i.e., separation into two phases, nor the phenomenon of sedimentation, i.e. the presence of sediment on the bottom of the tank in which is stored the suspension or thickening that cannot be eliminated, and therefore achieve a flexible, semi-rigid or rigid polyurethane foams or cellular or nechastyh PUR composite with high physical-chemical properties.

Finally, another subject of the invention is the use of these stable homogeneous dispersions of low viscosity mineral fillers in the production of flexible, semi-rigid or rigid polyurethane foams or cellular or nechastyh composite materials, and the use of these pins or named composite materials in the manufacture of molded or unmolded products.

Filled in this way a homogeneous, stable suspension of low viscosity suitable for use in the manufacture of polyurethane foams, regardless of whether they are flexible, semi-rigid or rigid, or in the manufacture of aerated iritani or cellular or NeatSuite composite polyurethanes, derived from the use of suspensions in polyatomic alcohols according to the invention prepared according to the invention, fillers are used in the manufacture of molded or unmolded products.

Other distinctive features and advantages of the invention will be better understood when reading the following description.

The scope and value of the invention will be better understood through the following examples, which do not bear any restrictive.

EXAMPLE 1

A. the experimental production of various processed fillers

With this purpose, conducted experiments 1-10, using three different bases for filler and a processing agent, a phosphate type, referred to below and in the various tables "AGT".

Experiments 1-4:

These experiments serve to illustrate the invention, and as a processing agent in them use a complex mixture of mono - and diesters of acid phosphate delovogo alcohol with 5 moles of ethylene oxide, and as filler chalk of champagne, the average diameter of which is 2 μm (product A),

Experience 1:

In this experiment, prepare the filling, prepared according to the method according to the invention, by injecting the agent from the La which is used as a selector with 24 blades.

Experience 2:

In this experiment, prepare the filling, prepared according to the method according to the invention, by introducing the agent according to the invention (AGT) before operation desagglomeration and selection described in experiment 1.

Experience 3:

In this experiment, prepare the filling, prepared according to the method according to the invention, by introducing the agent according to the invention (AGT) before operation desagglomeration in rod mill followed by a thin selection, which is used as a selector with 16 blades.

Experience 4:

In this experiment, prepare the filling, prepared according to the method according to the invention, by introducing the agent according to the invention (AGT) before operation desagglomeration in rod mill without surgery selection.

Experiments 5-7:

These experiments serve to illustrate the invention, and as a processing agent in them use a complex mixture of mono - and diapir acidic phosphate delovogo alcohol with 5 moles of etilenoksida, and as filler - calcite, the average diameter of 1.8 μm (product).

Experience 5:

In this experiment according to the invention apply the same method of manufacture of processed according to the invention the filler, as in experiment 4.

Experience 6:

In about and experience 2.

Experience 7:

In this experiment according to the invention apply the same method of manufacture of processed according to the invention the filler, as in experiment 1.

Experience 8:

This experience serves to illustrate the prior art, and as a processing agent uses a complex mixture of mono-and diapir acidic phosphate delovogo alcohol with 5 moles of ethylene oxide, and the filler is chalk champagne a mean diameter of 2.4 μm (a product).

To accomplish this, enter in a laboratory ball mill with a capacity of 15 liters, containing 9 kg of grinding load 3 kg of product (chalk) and 30 g AGT, then grind the mixture for 4 hours to obtain a particle size of the product And without the stage of disagglomeration.

Experience 9:

This experience serves to illustrate the invention, and it is used as a processing agent, a complex mixture of mono - and diapir acidic phosphate delovogo alcohol with 5 moles of ethylene oxide, and the filler is chalk champagne a mean diameter of 2.4 μm (a product).

To accomplish this, mix 3 kg of Product With 1.6 kg of water and 30 g of AGT and introducing this mixture in a laboratory ball mill with a capacity of 15 liters, containing 9 kg of grinding load, electio in laboratory selector with 24 blades.

Experience 10:

This experience serves to illustrate the invention, and it is used as agent complex monoether acid phosphate christianfree with 60 moles of ethylene oxide, and as a filler - calcite average diameter of 1.8 μm (product).

For this experience according to the invention applies the same method of manufacture of processed according to the invention the filler, as in experiment 1.

The results are shown in table I for experiments 1-4 and 5-7 and table II for experiments 8-10.

The thus treated fillers, and other processed or unprocessed fillers are used below when tested on their dispersion in the polyhydric alcohol, which allows you to simulate the speed and ease of dispersion of the filler in this polyhydric alcohol.

C. Experiments on dispersion in the polyhydric alcohol

For this weigh in a metal container with a height of 105 mm and a diameter of 90 mm 250 g of triol with a hydroxyl number equal to 48 mg/g, and a viscosity equal to 750 mPas, which is subjected to stirring using a stirrer brand Pendraulik equipped delocalise blade diameter of 50 mm and a speed controller. Control IC is RT and include the chronometer at the end of the introduction of the powder. Select 2 or 3 g of the dispersion using a Pasteur pipette periodically depending on time. Put the sample on the caliber of the North (0-100 μm) and conduct measurements, as described in the norm ISO 1524. Marked by the reading of the gauge is a scale value, where the first point redispersion mineral. The North caliber cleaned with isopropyl alcohol and dried between tests.

For each of the experiments 11-28 used polyhydric alcohol described below, in tables III-1, III-2, III-3, which shows the results.

In these tables AGT means the agent according to the invention the phosphate type, GUEDU - known type of mixer, and IOH - hydroxyl number.

Experience 11:

This experience represents the variance of the raw chalk champagne average diameters of 2 μm in the above polyhydric alcohol.

No caliber, i.e., there is no obtain homogeneous and without agglomerates of the mixture.

The result is low; this control experience.

Experience 12:

This experience is an example according to the invention, in which the Product is used And from experience 1. The gauge shows 4, 5 after 8 minutes

Thus, it is a good mixture after 8 Minoborony stearic acid, an average diameter of 2 μm, and a commercially available (Product D).

The result is bad.

Experience 14:

This experience consists of adding a processing agent used in experiments 1-9, not for processing of filler, as in experiments 1-9, and as a dispersant, as it is added to the mixture of filler-polyhydric alcohol.

The result is bad and confirms the importance of processing performed at any stage of the invention.

Experience 15:

This experience similar to the experience of 14 except share agent (insignificant) and the speed of mixing to obtain a mixture (almost twice) in order to provide a higher energy dispersion.

The result is also low.

Experience 16:

This experience similar to the experience of 11 except speed mixing to obtain a mixture (almost twice) that indicates that you need more than 20 minutes in order to have a high quality mix (calibre = 3), therefore, with a much larger number of mechanical energy.

Experience 17:

This experience similar to the experience of 13 except speed mixing to obtain a mixture (almost twice) that indicates that you need more than 20 minutes on the energy.

Experiments 18 and 19:

In these experiments use a simple mixer type Guedu and get poor results, proving the fact that held on one of the stages of processing according to the invention is not simple mixing.

Experience 18:

This experience is carried out with the raw chalk champagne a mean diameter of 2 microns. When mixed in the mixer used Guedu processing agent type complex mono - and diapir phosphate Nonylphenol containing 30 units of ethylene oxide.

Experience 19:

This experience is carried out with untreated calcite average diameter of 1.8 μm. When mixed in the mixer used Guedu processing agent type complex mono - and diapir acidic phosphate delovogo alcohol containing 5 parts of ethylene oxide.

Experiments 20-23:

In these experiments consistently use the products of experiments 1-4, and they are variants of the method according to the invention, showing that desagglomeration sufficient, and selection is not required.

Experience 24:

This experience according to the invention is carried out with calcite instead of chalk (use the product experience 5).

The result (calibre = 4 after 10 min) can be considered good.

The Experience Of 25:

In atbas desagglomeration does not give satisfactory results.

Experience 26:

In this experiment use the product experience 9 and get the best results (calibre = 3 after 15 min); this experience demonstrates thus the possibility of processing according to the invention by a wet method.

Experience 27:

In this experience using the product experience of 10 and get the best results (calibre = 3 after 5 min); this experience illustrates the use of another type of agent according to the invention.

Experience 28:

In this experiment, the use of processed according to the method of the invention in experiment 1 calcite (product) using 1 wt.% a mixture of complex mono - and diapir acidic phosphate smoothietrouble alcohol.

This experience gives the best results (calibre = 4 after 2 min) that illustrates the use of another type of agent according to the invention.

EXAMPLE 2

This example relates to the use of different fillers, processed according to the method of experiment 1.

Used the following different fillers:

- Product R: marble with an average diameter of 8 μm.

- The product's technical magnesium hydroxide with an average diameter of 1.4 to 1.8 microns.

- Product T: talc with an average diameter of 2.5 μm.

- The product U: dolomite medium is aolin with an average diameter of 0.50 μm.

- Product W: precipitated calcium carbonate with an average diameter of 0.30 μm.

Experience 29:

This experience is the control experiment, which consists in the dispersion of the raw kaolin kaolin with an average diameter of 0.50 μm in the above polyhydric alcohol.

Caliber is not, therefore, do not have any get smooth and free of agglomerates of the mixture.

The result is poor.

Experience 30:

This experience is an experience according to the invention, which is used by way of experiment 1 kaolin with an average diameter of 0.50 μm, treated with 1.5 wt.% agent used in experiment 1.

The caliber is good in comparison with the control sample.

Experience 31:

This experience is the control experiment conducted with the product U. Caliber no.

Experience 32:

This experience is an experience according to the invention is carried out with the product U, processed according to the method of experiment 1 with 1.5 wt.% agent used in experiment 1. The caliber is good in comparison with the control sample.

Experience 33:

This experience is the control experiment conducted with the product W. Caliber no.

Experience 34:

This experience is an experience according to the invention is carried out at about the control sample.

Experience 35:

This experience is the control experiment conducted with the product R. Caliber no.

Experience 36:

This experience is an experience according to the invention is carried out with the product R treated according to the method of experiment 1, with 1 wt.% agent, which is a complex of mono - and fluids acidic phosphate Nonylphenol with 10 moles of ethylene oxide. The caliber is good in comparison with the control sample.

Experience 37:

This experience is the control experiment carried out with a mixture (Product A + Product Tonnes) with an average diameter of 2.5 μm with a mass ratio of 50/50. Caliber no.

Experience 38:

This experience is an experience according to the invention is carried out with the product experience 37 treated by the method of experiment 1, with 0.5 wt.% agent used in experiment 1. Caliber good compared to control.

Experience 39:

This experience is the control experiment conducted with the product V. Caliber no.

Experience 40:

This experience is an experience according to the invention is carried out with the product V, prepared according to the method of experiment 1, with 1.2 wt.% agent used in experiment 1. The caliber is good in comparison with the control sample.

Experience 41:

This experience is the experience according to the invention, conducted product's treated by the method of experiment 1, with 1.5 wt.% agent used in experiment 1. The caliber is good in comparison with the control sample.

The results are shown below in tables IV-1 and IV-2.

The analysis of table IV shows that the method according to the invention allows to obtain suspensions of various mineral fillers in the polyhydric alcohol, which are homogeneous and contain particles of size less than 70 μm after 15 minutes

EXAMPLE 3

This example relates to the preparation of the preliminary mixtures of mineral fillers with a polyhydric alcohol, with different percentages of fillers.

Experience 43:

This experience serves to illustrate the invention, and it is used as a filler product And processed according to the experiment 1, and as the polyhydric alcohol is a polyhydric alcohol with a hydroxyl number equal to 48 mg/g, and a viscosity equal to 700 mPas at 20°C, With a mass ratio of 60% of a polyhydric alcohol - 40% of calcium carbonate.

Experience 44:

This experience serves to illustrate the invention, and in use as a filler product And processed according to the experiment 1, and as mno°C, when the mass ratio of 50% of a polyhydric alcohol - 50% of calcium carbonate.

Experience 45:

This experience serves to illustrate the invention, and it is used as a filler product And processed according to the experiment 1, and as the polyhydric alcohol is a polyhydric alcohol with a hydroxyl number equal to 48 mg/g, and a viscosity equal to 700 mPas at 20°C, With a mass ratio of 40% of a polyhydric alcohol - 60% calcium carbonate.

Experience 46:

This experience serves to illustrate the invention, and it is used as a filler product And processed according to the experiment 1, and as the polyhydric alcohol is a polyhydric alcohol with a hydroxyl number equal to 48 mg/g, and a viscosity equal to 700 mPas at 20°C, With a mass ratio of 90% of a polyhydric alcohol - 10% of calcium carbonate.

Experience 47:

This experience serves to illustrate the invention, and it is used as filler kaolin processed according to the experience of 30, and as the polyhydric alcohol is a polyhydric alcohol with a hydroxyl number equal to 56 mg/g, and a viscosity equal to 300 mPas at 25°C, With a mass ratio of 50% of a polyhydric alcohol - 50% kaolin.

The results are shown in table V.

EXAMPLE 4

This example shows getting a PUR foam containing fillers, processed according to the invention.

Foam PUR get well-known manner, using a preliminary mixture of filler treated according to example 3 (experience 44 of 50% calcium carbonate), with different density PUR foam and different percentages of filler according to the invention.

Experience 48:

For this experience the expected density of 25 kg/m3and the proportion of the filler is 10 parts with respect to the polyhydric alcohol.

Experience 49:

For this experience the expected density of 35 kg/m3and the proportion of filler to 20 parts with respect to the polyhydric alcohol.

Experience 50:

For this experience the expected density 40 kg/m3and the proportion of the filler 5 pieces with respect to the polyhydric alcohol.

The results are shown in table VI.

Analysis of table VI shows that it is possible to obtain PUR foams according to the method, including the improvement of the invention.

1. The method of processing mineral fillers designed the ASS="ptx2">a) process the at least one processing agent of the General formula (1)

in which R1represents H, C8-C40alkyl, aryl, alkylaryl or arylalkyl with6-C40;

r2is8-C40alkyl, aryl, alkylaryl or arylalkyl with6-C40;

X is-CH2-CH2-, or-CH(CH3)-CH2- or-CH2-CH(CH3)- or -(CH2)5-CO-;

Y is-CH2-CH2or-CH(CH3)-CH2- or-CH2-CH(CH3)-, or - (CH2)5-CO, while X and Y are the same or different;

(m+n) is changed from 0 to 60 (inclusive), as (p+q), with 0m+n60 and 0p+q60, when X=Y=-CH2-CH2(1m10 and R) and (0n59 and 0q59), when X is different from Y,

b) subjecting the stage of disagglomeration.

2. The method according to p. 1, characterized in that the said filler optionally subjected to a stage of selection, the next stage b) desagglomeration.

3. The method according to p. 1 or 2, characterized in that the said processing agent is acidic phosphate aliphatic alcohol with8-C20-a branched or unbranched chain, which condense 0-12 s a complex mixture of mono - and diesters.

5. The method according to any of paragraphs.1-4, characterized in that the said processing agent is a complex mixture of mono - and diapir acidic phosphate delovogo alcohol with 5 moles of ethylene oxide.

6. The method according to p. 1 or 2, characterized in that the said processing agent is a complex monoether acid phosphate christianfree containing 60 moles of ethylene oxide.

7. The method according to any of paragraphs.1-4, characterized in that the said processing agent is a complex mixture of mono - and diapir acidic phosphate smoothietrouble alcohol.

8. The method according to p. 1 or 2, characterized in that the said processing agent is a complex mixture of mono - and diesters of acid phosphate of Nonylphenol with 10 moles of ethylene oxide.

9. The method according to p. 1 or 2, characterized in that the said treatment is carried out by a dry method or a wet method.

10. The method according to any of paragraphs.1-9, characterized in that the said filler selected from natural or synthetic carbonates, phosphates and sulfates of alkaline earth metals, zinc carbonate, mixed salts of magnesium and calcium, dolomite, lime, magnesium oxide, barium sulfate, the sulfates callow, kaolin, kremnekislyh compounds, talc, mica, solid or hollow glass beads, metal oxide: zinc oxide, iron oxide, titanium oxide and mixtures thereof.

11. The method according to p. 10, characterized in that the said filler selected from natural calcium carbonate selected from chalk, calcite, marble, precipitated calcium carbonate, dolomite, hydroxides of aluminum or magnesium, kaolin, talc, wollastonite and mixtures thereof.

12. The treated mineral filler special particle size distribution for the manufacture of polyurethane foams according to the method by which the above mentioned filler is mixed with at least one polyhydric alcohol in the reaction leading to the formation of the polyurethane, and has a shorter mixing time with a polyhydric alcohol, and other reagents, characterized in that it

a) processed at least one compound of General formula (1)

in which R1represents H, C8-C40alkyl, aryl, alkylaryl or arylalkyl with6-C40;

R2is8-C40alkyl, aryl, alkylaryl or arylalkyl with6-C40;

X is-CH2-CH22-CH2or-CH(CH3)-CH2- or-CH2-CH(CH3)-, or -(CH2)5-CO, while X and Y are the same or different,

(m+n) is changed from 0 to 60 (inclusive), as (p+q), with 0m+n60 and 0p+q60, when X=Y=-CH2-CH2(1m10 and R) and (0n59 and 0q59), when X is different from Y,

b) subject to the stage of desagglomeration and

in prone, if necessary, the stage selection.

13. The filler under item 12, characterized in that the aforementioned processing agent contains a complex mixture of mono - and diapir.

14. The filler under item 12 or 13, characterized in that the said processing agent is a complex mixture of mono - and diapir acidic phosphate delovogo alcohol with 5 moles of ethylene oxide.

15. The filler under item 12, characterized in that the said processing agent is a complex monoether acid phosphate christianfree with 60 moles of ethylene oxide.

16. The filler under item 12 or 13, characterized in that the said processing agent is a complex mixture of mono - and diapir acidic phosphate smoothietrouble alcohol.

17. The filler under item 12 or 13, characterized in that the aforementioned processing agent submitted the preserver according to any one of paragraphs.12-17, characterized in that to be processed filler selected from natural or synthetic carbonates, phosphates and sulfates of alkaline earth metals, zinc carbonate, mixed salts of magnesium and calcium, dolomite, lime, magnesium oxide, barium sulfate, sulfates of calcium, magnesium hydroxide, alumina, silica, wollastonite, clays and other siliconinsulated compounds, kaolin, kremnekislyh compounds, talc, mica, solid and hollow glass beads, metal oxide: zinc oxide, iron oxide, titanium oxide and mixtures thereof.

19. The filler according to any one of paragraphs.12-17, characterized in that to be processed filler selected from natural calcium carbonate selected from the chalk, calcite, marble, precipitated calcium carbonate, dolomite, hydroxides of aluminum or magnesium, kaolin, talc, wollastonite and mixtures thereof.

20. The filler according to any one of paragraphs.12-19, characterized in that it is a material with an average diameter of 0.1-15 μm.

21. The filler according to any one of paragraphs.12-19, characterized in that it is a material with an average diameter of 0.1-10 microns.

22. The filler according to any one of paragraphs.12-19, characterized in that it represents Omnitel choose from marble with an average diameter of 8 μm, of magnesium hydroxide with an average diameter of 1.4 to 1.8 μm, talc with an average diameter of 2.5 μm, dolomite with an average diameter of 3 μm, the aluminum hydroxide with an average diameter of 0.8 μm, kaolin with an average diameter of 0.5 μm, precipitated calcium carbonate with an average diameter of 0.30 μm.

24. The filler according to any one of paragraphs.12-23, characterized in that it retains its hydrophilic nature, with the polyhydric alcohol consumption by 15% and preferably 20% lower compared with untreated mineral filler.

25. Suspension of mineral fillers in polyatomic alcohols, characterized in that the filler is a filler according to any one of paragraphs.12-24.

26. Suspension of mineral fillers in polyatomic alcohols on p. 25, characterized in that the polyhydric alcohols belong to families of polyether and polyester-polyethers, and polyesters, simple polyether polyols selected from the products of accession of propylene oxide and simple polyhydric alcohol, glycol, glycerol, trimethylolpropane, sorbitol, in the presence or without ethylene oxide, or special simple polyether polyols, such as polyether amine-based, policemilitary, simple craftsperson polyesters obtained by copolymerization of styrene and Acrylonitrile, and in suspension in a simple polyester, or polytetramethylene, complex polyether polyols, those who get in the polycondensation polyalcohol with policestate or their anhydrides, such decolletage as adipic, phthalic, and other acids interacting with dialami, such as ethylene glycol, propylene glycol, butyleneglycol and other trioligy, such as glycerin, trimethylolpropane and others, and tetralani, such as pentaerythritol and others, one or mixtures or various gidroksilirovanii compounds, such as gidroksilirovanii polybutadienes, the prepolymers with hydroxyl terminations resulting from the reaction of an excess of a polyhydric alcohol with a diisocyanate, or a simple polyhydric alcohols such as glycerin, aminoalcohols used in small quantities with a simple polyether polyols or complex polyether polyols.

27. Suspension under item 25 or 26, characterized in that it contains other mineral and/or organic compounds such as catalysts and/or antioxidants.

28. The suspension according to any one of paragraphs.25-27, wherein the content is a fatal decanting, sedimentation or thickening after exposure for 7 days, has an apparent viscosity at Brookfield lower viscosity raw mineral fillers, contains 0.5-3 wt.% at least one processing agent of General formula (1) in relation to the weight of mineral filler.

29. Preliminary mixture of mineral fillers with a polyhydric alcohol, in particular, in proportions suitable for the manufacture of polyurethanes and especially polyurethanes, or by foaming without auxiliary blowing agent, either by aeration with an auxiliary blowing agent such as methylene chloride, acetone or CO2or composite polyurethanes, characterized in that the filler is pre-treated by the method according to any of paragraphs.1-11.

30. Preliminary mixture of mineral fillers with a polyhydric alcohol under item 29, wherein the filler is a filler according to any one of paragraphs.12-22 selected from natural calcium carbonate selected from the chalk, calcite, marble, precipitated calcium carbonate, dolomite, hydroxides of aluminum or magnesium, kaolin, talc, wollastonite and mixtures thereof.

31. Flexible, semi-rigid Il is m with auxiliary blowing agent, selected from methylene chloride, acetone or CO2or other, characterized in that they contain pre-treated filler according to any one of paragraphs.12-24.

32. Cellular or NeatSuite composite materials, characterized in that they contain pre-treated filler according to any one of paragraphs.12-24.

33. Molded or unmolded products, characterized in that they are produced from polyurethane foam or composite polyurethanes obtained by p. 31 or 32.



 

Same patents:

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FIELD: chemistry.

SUBSTANCE: invention pertains to the mixture for obtaining flexible polyurethane foam and can be used as mastic for hydro and thermal insulation of foundations, buildings, pipelines, as well as for filling cavities in building structures. The mixture contains defined ratios of the following components: a hydroxyl containing oligomer-copolymer of butadiene and piperylene with molecular mass of 2100 and containing 0.92% hydroxyl groups; isocyanate component - polymethylene polyphenyl isocyanate with 29-31% content of isocyanate groups; catalysts: dibutyl tin dilaurate and N,N,N- triethylamine; water; glycerine; polydimethyl siloxane and polydimethyl siloxane modified by a polyester in the form of foam stabilisers and extra bitumen. Use of bitumen considerably lowers moisture absorption of the material and increases viscosity of the foam systems. This also enables the material to retain the density attained during foaming. Use of defined foam stabilisers in the mixture enables formation of more fine cells, with high stability and attainment of low density of the polyurethane foam.

EFFECT: lower density and moisture absorption of flexible polyurethane foam.

10 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention refers to method for making bulk, high resilience slabstock or moulded foam, used for upholstery, automobile seats and panel cushions, for packing, other applications to softening and energy management, for sealing and other applications. The presented method involves as follows. Organic polyisocyanate contacts with polyol compound containing high mass equivalent polyol or mixed polyols with foaming agent, gelling catalyst and surface-active substance added. At least 10 wt % of high mass equivalent polyol (polyols) represent one or more equivalent mass hydoxymethyl-containing polyesterpolyols at least 400 up to 15000 produced by interaction of hydoxymethyl group containing fatty acid with 12-26 carbon or this acid ester atoms and compound initiator polyol or polyamine, thereby polyesterpolyol contains as follows: [H-X](n-p)-R-[X-Z]p, where R is residual compound initiator, X is independent, -O-, -NH- or -NR'-, while Z- represents linear or branched chain containing one or more groups A, independently chosen of groups A1, A2, A3, A4 and A5, expressed by formulas (II), (III), (IV), (V) and (VI), respectively. Besides there is disclosed polyurethane foam made by the declared method. Declared method ensures making polyurethane foams with using polyol from renewable source.

EFFECT: improved UV resistance and heat stability, and improved gas-invoked discoloring resistance.

9 cl, 8 tbl, 41 ex

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining compounded foam polyurethanes for operation as shock, heat and sound absorbing layers. Compounded foam polyurethanes are obtained by interaction of 100 weight parts of polyol component and 20 weight parts of polyisocyanate component, where polyol component is mixed preliminarily with 70-100 weight parts of rubber chips, and reaction mix is foamed and solidified at 160°C or higher to component destruction temperature. Butadiene and piperylene copolymer with 1200-3200 molecular weight and 0.8-1.1% content of hydroxylic groups is used as polyol component, and polymethylenepolyphenylisocyanate with 29-31% content of isocyanate groups is used as polyisocyanate component.

EFFECT: simplified composition and technological process for mix processing in elastic foam material production, facilitated utilisation of rubber industry waste, particularly rubber chips, and higher compounding degree and tension at 40% compression of foam polyurethanes obtained by the claimed method.

2 ex, 3 tbl

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