Suitable for printing swelling paste and its application for cable insulation and manufacture of nonwoven materials
(57) Abstract:Described is suitable for printing, consisting of two components swelling pasta-based superabsorbent, characterized in that the component 1 contains (a) water, pre-crosslinked poly(meth)acrylic acid and/or (b) water, pre-crosslinked poly(meth)acrylic acid represented in certain cases, in the form of a salt, preferably in the form of potassium, sodium or ammonium salt, and/or C) a copolymer of at least 50 mol.% water, pre-crosslinked poly(meth)acrylic acid with acrylamide, and component II contains as reactive crosslinking agent is at least di - or polyfunctional epoxide and/or aziridine, and/or simple polyglycidyl ether, and/or polyfunctional isocyanate, and/or polyester monoatomic alcohols with a low-boiling carboxylic acids, and/or epichlorohydrin, either himself is such a crosslinking agent, and its use for isolation of cables and manufacture of nonwoven materials. 4 C. and 8 C.p. f-crystals. The invention relates to suitable for printing swelling of the paste and its application for the insulation of cables and manufacture of nonwoven materials.Cables predstavljauwego they must meet high requirements regarding their durability and reliability in operation. Damage to the cables caused by the penetration of water can be prevented by using insulation, protects them from water. In the journal "Drahtwelt" 5 1992 describes the different methods of insulation of power cables, communication cables and siteprovides designed for leak protection against penetration of water along their entire length. The main attention is paid to the problem of applying swelling powders or swelling natkaniec materials based on polyacrylates, closed up in the cables.With overabsorbed ability polymers have long been known and some of them come on the market in the form of powders, in particular under the trademark FAVORor CABLOC. However, it should be noted that the processing of powders involves considerable technical difficulties, and because the manufacture and processing of the product due to abrasion produces fine dust that can penetrate into the respiratory tract occur to the same problems associated with health, and it is therefore desirable to avoid if possible operation of this product.The right to pursue alternative means of polymerization of a solution of monomers on in the private gas and the need to comply with relevant security measures granted only to enterprises of the chemical industry and can not be implemented at the enterprises of other industries, such as printing industry, cable industry and textile. It is necessary to further develop this technology, which would provide the product with the highest possible solids content and the ability to quickly swelling with the aim instant sealing of the cable in the event of water penetration of the latter and limit its further spread.One solution to this problem is suggested, as it may seem, in European patent application EP 188091. According to this publication aqueous solution seamless prepolymer put method plyaski on a non-woven material. In order to achieve desired to plyaski viscosity molar mass prepolymer choose relatively high. Due to this factor, the yarn tension leads to coverage of all fiber membrane from a solution of prepolymer. Therefore, upon completion of the fusion process is getting very hard, inflexible, non-woven material that makes it extremely difficult for further technical processing of the product, such as, for example, rolling for storage or transportation.In European patent application EP 269778 describes capable of swelling by non-woven cloth made of the Oka absorbent capacity of the particles with the penetration of water swell, thus preventing its further spread along the length of the cable. The proposal does not, however, offered no solution to the problem of dust.In European patent application EP 271171 describes intended for cable insulation banding containing microcapsules, which expand at different temperatures, thereby providing a hermetic protection for the cable. Expansion microcapsules is already in the process of manufacture of cables, but the application is not listed, what should be provided to seal the cable against leakage during operation.In European patent application EP 357474 describes a method of applying a dispersion of low viscosity aqueous solutions of unstitched polyacrylic acids on textile fabrics and subsequent thermal crosslinking with the formation capable of swelling under the action of water gels due to the simultaneously applied cross-linking agents. Problematic in the implementation of the proposed method is that the coating leads to uneven distribution of the polymer on the surface of the canvas, and other application methods, such as printing or coating using a doctor blade, only briefly mentioned in this publication is the IR.In European patent application EP 391012 describes intended for the insulation of cables extrudable mixture based on butyl rubber containing synthetic swellable powder based on polyacrylate. This mix allows you to abandon the sealing gap between the rubber membrane and the outer conductive layer, however, it requires use of special devices.Proposed in EP 397410 technical decision regarding the application polyglycolic of profirov (meth)acrylic acid, which at first due to the embedding in the polymer structure, and then use the free alcohol group during the subsequent heat treatment can form a network structure by binding esters, has the decisive disadvantage that for carrying out the described process of stitching with acceptable material temperatures of the order of 200oWith an interval time more than half an hour. For reasons of economy, this duration has not been satisfactory.In European patent application EP 645429 describes miscible with water thickener for printing pastes based emulsion of the type oil-in-water". As the polymer used in this mixture of carboxylic thus obtained paste, contributing to its swelling in the specified publication no.Based on the above the basis of the invention was based on the task to create a suitable for printing, is capable of swelling the paste on the basis of superabsorbent, which could in a single operation apply to pre-made textile fabrics of any type, such as fabric or non-woven materials, and which, through subsequent heat treatment could in the presence of water or aqueous solutions quickly to swell and increase its original volume several times. This paste should not contain easily inflammable or dangerous substances and should have at room temperature with simultaneously low tension wires required for the environment printing viscosity. The fusion process may be carried out at temperatures of about 200oWith taking into account thermal load on the base material and for reasons of economy within a maximum of 5 minutes Then subjected to the printing process, the fabric should have the ability to ruanruan without showing trends for bonding. And, finally, it was necessary to provide the method with CLASS="ptx2">The task according to the invention has been unexpected way to solve it using the swelling paste based on superabsorbent containing two components, and component I is a water pre-crosslinked poly(meth)acrylic acid and/or water, pre-crosslinked poly (meth)acrylic acid represented in certain cases, in the form of a salt, preferably in the form of potassium, sodium or ammonium salt, and/or a copolymer of at least 50 mol. % water, pre-crosslinked poly(meth)acrylic acid with acrylamide, and component II contains reactive crosslinking agent or such. In a preferred embodiment, the paste contains component I in the amount of 95-99,9 wt.% and component II in an amount of 0.1-5 wt.% in terms of the total weight of the mixture. In the preferred embodiment, component (I additionally may contain a cationic surfactant.Degree primary staple, providing the desired printing or coating using a doctor blade viscosity should be selected differ depending on the respective application quantity and the selected template, and depending on the purpose prego structure of the additive, but have a positive impact on the process. First of all it is in these cases, the substances that contribute to reducing fragility (stiffness) of the dried product, and such substances, which help to reduce the stickiness.As substances intended to reduce brittleness of the product may be used, in particular, polyethylene glycols, polypropylenglycol or mixed polyalkoxyalkyl, in addition, polyalkoxyalkyl based on polyhydric alcohols, such as glycerin, trimethylolpropane and butanediol. Next can be considered surfactants with index products HLB (hydrophilic-lyophilic balance) more than 10, such as alkylpolyglucoside or ethoxylated sugar esters, such as Polysorbate supplied to the market by the company ICI under the name Tween.As substances intended to reduce the stiffness of the product, you can offer cationic detergents (surfactants), such as, for example, chlorides of alkyltrimethylammonium or chlorides of dialkyldimethylammonium or chloride of dimethyldodecylamine, further, the chloride of alkylbenzyldimethylammonium or appropriate methosulfate or quaternion imidazolinone ¬ before or after polymerization, and they join during the exchange interaction between the cations and anions to polycarboxylates circuit, thereby plasticizing effect and simultaneously increasing the rate of absorption of aqueous solutions (see the comparison of example 1 with example 2). Another advantage of these substances is their biocidal action that can prevent biodegradable agents swelling. This property is especially important for cables buried under the ground.As anti-adhesive substances may be used, for example, inorganic or organic melkoporistaya antiadhesive funds in the amount of from 0 to 2 wt.% in terms of component I. as such is acceptable, for example: powder wood powder and wood products such as wood flour, cellulose fiber, bark, cellulose flakes, cotton linters, etc., mineral fillers, such as perlite, synthetic fillers, such as nylon cereal, small pieces of viscose filament yarn and so on, then, diatomaceous earth, slag, talc, clay, fly ash, coal dust, magnesium silicates, fertilizers, or mixtures thereof. Preferably use highly dispersed pyrogenic silicic acid, some of which comes on the market, in particular p is Menno reduce the stickiness of the products, due to the plasticizing effect of cationic surfactants (see the comparison of example 1 with example 3).As agents of primary stitch used in quantities of 0.05 to 1.0 wt. %, preferably in the range of 0.1-0.5 wt.% in terms of the actual monomer or Monomeric mixture component, can be applied in connection with at least two embedded in the polymer structure groups. As such crosslinking agents acceptable among others, but not only they, di-, tri - or polyvinyl compounds such as divinylbenzene and dividercolor. In addition to them, can be applied di-, tri - or polyesters of unsaturated carboxylic acids, such as acrylic acid, methacrylic acid or maleic acid with di-, tri - and polyols, in particular ethylene glycol, trimethylacetyl, trimethylolpropane, glycerin, or ethoxylated di-, tri - or polyols. Among other acceptable agents primary staple can be called, for example, alkyltrimethylenedi, such as N, N'-methylenebisacrylamide or N,N'-methylenebismethacrylamide, complex carbamylate esters obtained by reaction of polyisocyanates containing hydroxyl group of substances, or a simple di-, tri - or poly the unsaturated carboxylic acids, in particular allylacetate and alismataceae, as well as di-, tri - and polyallylamine esters of polycarboxylic acids, such as diallylphthalate or dellilachip. In addition to the above, as agents of primary staple acceptable di - or trialkylamine. These agents are the primary staple can also be used in the form of their mixtures. Preferably used trimethylolpropane, N, N'-methylenebisacrylamide, the ethoxylated trimethylolpropane and triallylamine or mixtures of the above compounds.As component 2 swelling paste is used in an amount of 0.1-5 wt.%, preferably 0.5 to 3.0 wt.% in terms of the total weight of component 1 actual reactive crosslinking agent, which is injected immediately before the printing process and intensively mixed with component 1 before the formation of a homogeneous mass. As specified reactive crosslinking agent may be applied in connection with at least two functional groups capable under thermal initiation after a short interval of time to react with carboxylate or carbenoxolone functional groups. As such compounds include, N. the mixture of these substances. Between the functional groups of the crosslinking agent can be embedded with different length polietilenglikoli chain. I prefer simple bisglycinate esters of (poly)etilenglikola and especially bisglycinate esters of etilenglikola, as well as mixtures of these compounds. These compounds come on the market, for example, the firm Nagase Chemicals Ltd. under the trademark Denacol.As reactive crosslinking agents can offer further water-soluble or polyisocyanates water-soluble polyesters of polyglycols with carboxylic acids having a low boiling point, such as formic acid or acetic acid.Unsuitable for use as the second component are compounds, in which the mesh structure should be built by esterification or amidation of the free alcohol or amine functional groups, as these groups during the drying time, which is usually provided in the printing or textile industry for reasons of economy, is not sufficient to fully react (see comparative example 3).Components I and II shortly before the deposition process (a maximum of 48 h, Pres who're asked to formation of a homogeneous mixture. Because depending on the temperature and duration of storage may occur solidification initially low viscosity mixture, it is recommended to continue with this two-component mixture without a long break, usually the same day. Preferably a two-component mixture is supplied in a combination package. One part (section 1) this package contains a pre-crosslinked polymer, while the second part (section 2) is exactly the specified number of reactive crosslinking agent. The total amount of product in a combined package form, for example, so that the mixture can be processed in one day.Thus obtained swelling paste can be applied using known methods for pre-made textile fabrics or yarns. It is preferable to obtain the uniformity of the pattern or drawing to apply the method of printing or coating on a substrate using a doctor blade, using the appropriate template and substrate for applying the paste may be, for example, fabrics, nonwovens, paper or film.Then caused by the polymer should be pederasty heat treatment will depend on:
- used temperature and
- reactivity of selected actual reactive crosslinking agent,
- as well as the degree of neutralization of the polymer corresponding carboxylic functional groups.The heat treatment can be carried out in the temperature range from 100 to 200oC, preferably from 150 to 200oC. In all cases the temperature of the stitching must be above the boiling point of the solvent (e.g. water) and below the temperature of the shrinkage of the fabric, respectively, of non-woven material. For reasons of economy to conduct the heat treatment given to no more than 5 minutesNonwovens according to the invention can find wide range of application.So, for agricultural purposes can be applied in the form of "irrigation" mats (for irrigation in greenhouses, irrigation plants grown outdoors and in special containers); and landscaping can be applied in the form of manufactured accordingly textiles (for example, for ornamental planting hanging plants to create a natural barrier to greening the roofs of buildings, etc); as in the first and in the second case, mats and CLASS="ptx2">In the garment industry made according to the invention nonwoven materials can be designed to absorb the secretions of the sweat be used, for example, in the manufacture of insoles for shoes and working clothes.Declared paste can also be used to make a waterproof bandage.In the field of funeral services, they can be used in the form of appropriate textile linings inside the tomb to absorb excreted by the body of the deceased liquids.For experimental studies swelling paste using the appropriate template in each case was applied by printing on polyester canvas and then were dried. In all experiments, except for comparative examples 1 and 2 (unstitched the polyacrylates), received a uniform dot pattern. For drying the products within 3 min were subjected to thermal influence of the IR emitter (manufacturer: company Elstein).Determination of the technical characteristics
Determination of the degree of swelling and speed of swelling
To determine the degree of swelling and rate of swelling of the sample round shape (50,9 cm2) cut from textile fabrics coated, placed the achala thin polyester non-woven fabric (thickness 0.05 mm), and then squeeze a round punch with a diameter of 80 mm and a weight of 100, This punch has over 60 of the through holes, each with a diameter of 2 mm In the measurement process observing the height of the upper edge of the punch. Then in a vessel add 75 ml of fully desalted water (8 Ás) and record the height of the upper edge of the plug, respectively, after 1 and 10 min (double measurement).Measuring thread tension
For measuring thread tension use a round glass rod 6 mm thick, at room temperature, immersed in the product to a depth of 5 cm and after 30 movement vertically upwards with a speed of 10 cm/s is extracted from the product. Removing the rod stop when thread breakage, measuring in cm the length of its stroke (three-dimension).Example 1
Component I received the following way: 2034 g of acrylic acid, 79,2 g sodium lye (50%), 4296,6 g of water, 16.2 g of trimethylolpropane-triacrylate and 13.2 g of mercaptoethanol in conjunction load at 30oWith and introduction of 13.8 g of hydrogen peroxide (35 wt.%-tion) and 60 g of 1 wt.%-aqueous ascorbic acid solution initiate the start of the reaction. The temperature of the mixture then increases for 11 min 90oC. When this those is eroxide hydrogen and 53 g of 20 wt.%-aqueous solution of hydroxylamine hydrochloride stirring is continued for one hour. After cooling the mixture to 35oWith its neutralized by adding 2455 g 44 wt.%-aqueous sodium liquor, and the temperature does not rise above 40oC. At the same temperature, stirred into 80 g Marlazin KS 30/50 (quaternionic polyglycolic ether fatty amine) (company Huls AG) and 16 g of Aerosil 200 (superfine silicon dioxide) (company Degussa AG). The viscosity, determined using the apparatus Brookfield, depends on the frequency of rotation of spindle:
the spindle 4; 1 rpm: 22700 mPas
the spindle 4; 5 rpm: 18600 mPas
the spindle 4; 10 rpm: 16200 mPas
thread tension: 8 seeThe product was thoroughly mixed with 3 wt.%-the principal component II, namely DGEEK (diglycidyl ether of ethylene glycol, supplier Contract Chemicals) and after 30 min by means of a perforated pattern was applied by printing onto polyester fabric in the amount of 120 g/m, then for 3 min was subjected to drying at 190oC. the Finished canvas was dry to the touch and when ruanruan agglutination.The degree of swelling: after 1 min: 10 mm; 10 min: 11 mmExample 2
Worked similarly to example 1, however, a difference that did not use any Marlazin KS 30/50 or Aerosil 200. Aqueous polymerization solution was somewhat b mPas
the spindle 4; 10 rpm: 17900 mPas
thread tension: 15 seeThe product was made similarly to example 1. Ruanruan non-woven material lightly glued and swollen with lower speed.The degree of swelling: after 1 min: 8 mm; 10 min: 11 mmExample 3
The polymerization process was carried out analogously to example 1, however, the difference is that after adding the sodium liquor was mixed into 80 g Marlazin KS 30/50 (company HUls HELL, Marl) without the introduction of Aerosil 200.The viscosity Brookfield:
the spindle 4; 1 rpm: 22700 mPas
the spindle 4; 5 rpm: 18600 mPas
the spindle 4; 10 rpm: 16200 mPas
thread tension: 12 seeProduct with perforated pattern was applied by printing onto polyester fabric in the amount of 120 g/m2, and then for 3 min was subjected to drying at 190oC.The degree of swelling: after 1 min: 10 mm; 10 min: 11 mmThe dried cloth after rolling glued.Example 4
The polymerization process was carried out analogously to example 1, however, the difference is that instead of trimethylolpropane used 2.8 g of triallylamine, and the polymerization was started at 30oC.The viscosity Brooke is ethylene glycol) trademark of Nagase), then use the template was applied by printing on polyester canvas in the amount of 95 g/m, then for 3 min was subjected to drying at 190oC. in This way got dry to the touch non-woven material, which even after rolling agglutination.The degree of swelling: after 1 min: 8 mm; 10 min: 9 mmExample 5
339 g of acrylic acid, 368,25 g sodium lye (50 wt.%-tion), 762 g of water, 0.5 g of trimethylolpropane-1530-triacrylate (Showpop 435 firms Cray Vally), 6.0 g of mercaptoethanol in conjunction load at 30oAnd the addition of 2.18 g of hydrogen peroxide (35%) and 10 g of 1% aqueous solution of ascorbic acid initiate the start of the reaction. After that, the temperature rises within 12 min to 82oC. At this temperature, continue to mix for another 30 minutes Then after you have added 6.2 g of 35% hydrogen peroxide solution and 5 g of 20 wt.%-aqueous solution of hydroxylamine hydrochloride stirring is continued for one hour. Then add 5 g Marlazin UC 30/50 (firm uls HELL) and 1 g Aerosil 200 and the mixture during cooling to 40oTo continue carefully to mix.Viscosity:
the spindle 4; 1 rpm: 40000 mPas
the spindle 4; 5 rpm: 29000 mPas
the spindle 4; 10 rpm: 22,000 mPas
The polymerization process was carried out analogously to example 1, with two differences: worked without the use of trimethylolpropane or any other reactive crosslinking agent and at the same time reduced the amount of mercaptoethanol to 3 gThe viscosity Brookfield:
the spindle 4; 1 rpm: 24000 mPas
the spindle 4; 5 rpm: 23500 mPas
the spindle 4; 10 rpm: 23400 mPas
thread tension: 80 cmWhen applying product to the canvas with a perforated pattern because of the high thread tension was not possible to obtain a uniform pattern.Comparative example 2 (unstitched polyacrylate low viscosity): according to EP 307474
The polymerization process was carried out analogously to example 1, with two differences: worked without IP is the number of mercaptoethanol were doubled, bringing to 26.1 g, and the polymerization was started at a temperature of 30oC.The viscosity Brookfield:
the spindle 1; 5 rpm: 620 mPas
thread tension: 5 seeWhen applying this product using the same perforated pattern as in comparative example 4, it was not possible to obtain a dot pattern. Applied product spread, forming a thin layer. After drying at 190oSince the fabric was so stiff and bulky that it was almost impossible to romaniawith for storage or further processing.Comparative example 3 (the proof of the unfitness of the diols as reactive agents stitching)
100 g of the product from example 1 was mixed not with bisglycinate ether of ethylene glycol and 3 g of ethylene glycol and with a perforated pattern was applied by printing in the amount of 118 g/m2. The fabric with the coating was dried for 3 minutes at 190oC.The degree of swelling: 0 mm after 1 min and 0 mm in 10 minutes 1. Suitable for printing, consisting of two components swelling pasta-based superabsorbent, characterized in that component I contains (a) water, pre-crosslinked poly(meth)acrylic acids form salts, preferably in the form of potassium, sodium or ammonium salt, and/or C) a copolymer of at least 50 mol. % water, pre-crosslinked poly(meth)acrylic acid with acrylamide, and component II contains as reactive crosslinking agent is at least di - or polyfunctional epoxide and/or aziridine, and/or simple polyglycidyl ether, and/or polyfunctional isocyanate, and/or polyester polyols with a low-boiling carboxylic acids, and/or epichlorohydrin, either himself is such a crosslinking agent.2. Swelling paste according to p. 1, characterized in that component I has been sewn of 0.05-1 wt. %, preferably 0.1 to 0.5. % agent primary staple in terms of the number of monomer component I.3. Swelling paste under item 1 or 2, characterized in that component I additionally comprises a cationic surfactant.4. Swelling paste according to any one of paragraphs. 1-3, characterized in that the component 1 additionally contains an inorganic anti-adhesive agent.5. Swelling paste according to any one of paragraphs. 1, 2 or 3, characterized in that the component 1 further comprises in its composition organicheskaia stitched trimethylolpropantriacrylated, and/or N, N' - methylenebisacrylamide, and/or trialkylamine, and/or the ethoxylated trimethylolpropane.7. Swelling paste according to p. 1, characterized in that it contains 95-99,9 wt. % component 1 and 0.1-5 wt. % component II, respectively, calculated on the total weight of the mixture of components I and II.8. Swelling paste according to p. 1, wherein component II comprises a reactive crosslinking agent is at least (poly)ethylene glycol with two epoxy functional groups or himself is such a crosslinking agent.9. Swelling paste according to p. 8, wherein component II comprises a reactive crosslinking agent bisglycinate ether of ethylene glycol and/or bisglycinate ether (poly)ethylene glycol or himself is such a crosslinking agent.10. Swelling pasta in the form of a two-part package consisting of separately packaged components I and II according to any one of paragraphs. 1-9, and component II is a reactive crosslinking agent in an amount of 0.1-5.0 wt. % in terms of the number of component I.11. Waterproof bandage, made using the swelling paste according to any one of paragraphs. 1-10.
FIELD: polymer materials.
SUBSTANCE: composition comprises polyolefin A, containing anhydride function and having viscosity at least 20 g/10 min measured at 190°C and loading 2,16 kg, and epoxy function-containing product B destined for cross-linking polyolefin A. Relative proportions of A and B are such that for each epoxy function there are from 0.1 to 1.5 anhydride functions. Composition can be used in slush molding process, in thermal molding of sheets, or in on-rod casting process.
EFFECT: increased flowability resistance and wear resistance.
6 cl, 1 tbl, 6 ex
FIELD: organic chemistry, polymers, chemical technology.
SUBSTANCE: invention relates to new high-molecular cross-linked polyvinyl butyrals, to a method for their synthesis and to their applying also. Invention describes high-molecular cross-linked polyvinyl butyrals prepared by cross-linking polyvinyl butyral with diethyl- and/or dimethyl oxalate. Method for preparing indicated polyvinyl butyrals involves addition of a cross-linking agent and, if necessary, a plasticizing agent to the parent polyvinyl butyral, homogenization of the mixture and thermal cross-linking at temperature from 80°C to 280°C. Polyvinyl butyrals prepared by such method are components of films useful for manufacturing the triplex. Films made by using such polyvinyl butyrals show the rupture strength value at the level 29 N/mm2 and glasses made of such films show stability against the impact in F- and Sn-directions as 8 and 4, respectively.
EFFECT: improved preparing method, improved and valuable properties of films.
9 cl, 2 dwg, 13 ex