CS209259B1 - Manufacturing method of porous flat and shaped figures - Google Patents

Abstract

A macromolecular material with fibrous or flakey structure is produced in the form of a thin sheet. It is strong and has a good feel and flexibility. A soln./dispersion of a cpd. with >=2 reactive H atoms and di- or poly-isocyanate plus catalyst are reacted in a thin layer at a low temp. such that the solvent/dispersant crystallises.

Description

The invention relates to a process for the production of porous sheets and shaped bodies, in particular with properties similar to those of textiles and leather.

It is known that microporous sheets are produced by polyaddition of two compounds with two or more reactive hydrogens to diisocyanates or polyisocyanates in liquid media. The liquid phase is selected such that the polyadduct is insoluble therein or at least contains a false solvent for the polyadduct. The untreated solvent is removed after reaction and forming, leaving a microporous structure. However, surface formations produced in this manner often have the disadvantage that they are poorly permeable to air and water vapor. In addition, the roughness and texture of the surface can be little influenced.

Macromolecular products with a fibrous structure are formed by polymerizing an olefinic monomer in a crystalline matrix. The monomers are dissolved or emulsified in the liquid. By cooling, the spread liquid freezes on the crystalline matrix; The monomers are located between the crystals and are polymerized by irradiation with UV rays, optionally using a redox system. Subsequent melting of the crystalline matrix leads to flat fiber products, as can be accepted by the velvety hand, but only with very low strength, for which it is necessary to insert the textile sheet.

SUMMARY OF THE INVENTION It is an object of the present invention to produce macromolecular porous sheets and shaped bodies, preferably with a fibrous or scaly structure, directly from monomers or prepolymers I in a thin layer. This production and other resulting tasks are solved by the invention.

Porous sheets are formed by polyaddition reactions in fully or partially crystalline solidified liquids when solutions or dispersions; compounds with at least two reactive atoms hydrogen and diisocyanates or polyisocyanates having a molar mass of between 500 and 10,000 or molar masses of 100 to 800, preferably with the addition of catalysts, spread out in thin layers and, upon cooling, fully or partially crystallize. The crystal system remains at least until the main reaction is complete. Thereafter, the crystalline substance (s) is removed in a known manner and the resulting sheet is optionally subjected to a final thermal treatment.

It has been shown that the polyaddition reactions can take place in crystalline solidified liquids and the reaction does not start during the production of the reaction mixture at temperatures above the freezing point of the crystallizing liquid, but only after formation of the crystal system at deeper temperatures and without further initiation. Further, surface forms of polyaddition are formed if solutions or dispersions of diisocyanates or polyisocyanates I or dispersions of compounds with at least two reactions209253

They are sprayed simultaneously or sequentially on the surface of which the hydrogen atoms, in particular the diamines, or even water, optionally with the addition of catalysts, are added. ; Even the temperature lies below the crystallization point or below 10 ° C. in the melt crystallization area so that these liquids. completely or partially crystallize before or during the spontaneously running reaction. and if the solutions or dispersions of the polyaddition reactants are allowed to solidify fully or partially crystalline in the layer and on the surface. The catalyst or catalyst system is sprayed onto the substance, solution or dispersion. The crystalline substance (s) is removed after the reaction and the reaction product is optionally subjected to an additional heat treatment. As diisocyanates or polyisocyanates having a molar mass of 100 to 800 can be left. :! . react, for example, the commercially available compounds I. j and ^k o ^ '- ^ ^ sokyanáto phenylindene ^4,4' -diisok anatomically ^y I i. i-diphenylmethane, 1,5-diisocyanatonaphthaline, 2,4-diisocyanatotoluene, or 2,6-diisocyanatotoluene, ii p-xylylene diisocyanate and o-xylylene diisocyanate, ii. . 1,4-diisocyanato-benzene, tetramethyleptriphenylmethyl. tan or reaction. product diisocyanatotoluene? and glycerin. j [Diisocyanates or polyisocyanates with molecular weights between 500 and 10 000. NCOs are known: - precursors with at least two end-standing isocyanate groups; they are formed by addition with the advantage of diisocyanates to prepolymers having two or more reactive hydrogen atoms. Such pre-. polymers are, for example, high molecular weight compounds containing OH groups as precursors: densates of polyesters with OH - terminated polymers,.

* polyethers, polyacetals, polythioethers and polyesteramides; they may also have branched chains. Pro ί; the production of NCO-precedents is allowed to react; [‘Prepolymers · especially with diisocyanates in molar I · ratio. 1: 2.05 to 1: 6, preferably molar ' 1: 2.2 to 1: 4.5.

It serves to extend the chain of NCO products. | compounds with at least two reactive hydrogen atoms such as diols, diamines, aminoalcohols and water; j · da, such as diethylene glycol, triety- ¹ i. ... · Propylene glycols, butanediols, cyclohexyl-

I xanediols, ethylene glycol esters of dicarboxylic and polycarboxylic acids, ethanolamines, 4,4'-dihydroxydiphenylpropane, hydroquinone-bis (β-hydroxyl; tylether), p-aminobenzyl alcohol, hydrazine and hydrazides, ethylenediamine, hexamethylenediamine N-di- [minodiphenylmethane, benzidine and dianisidine. The molar ratio of NCO - diisocyanate precursors may vary over a wide range, which is primarily determined by the one used. means of extension. strings.

Meanwhile, preferably mixtures of the composite are allowed to react. of . NCO - precursor, polyisocyanate! with weights of 100 to 500; for extending. of chains, is a special variant 2. The process according to claim 1, wherein the prepolymer mixtures are at least two reactive. hydrogen atoms, as well as polyisocyanates having a molar mass of 100 to 800 [a. the means for extending the strings leave it react in crystalline solidified liquids in a one-step manner. . In this process, the separate production of NCO pre-products is eliminated.

Conventional catalysts such as triethyleneamine, N, N'-dimethylpiperazine, N-ethylmorpholine, triethylenediamine, di-n-butyltin diacetate and tin octoate are often used in the polyaddition reactions to accelerate the reaction in fully or partially crystallized liquids.

For production . The porous sheets according to the invention dissolve or disperse in such liquids. which solidify completely or partially by crystallization upon cooling. The freezing point of the liquids used should be within the range of from. 100 to + 200 ° C, preferably between. —25 to. + 120 ° C. The amount of dissolved or dispersed starting products may vary between 0.5 and 80. weighting. %, but is preferably 3. to. 35% by weight. i The characteristics of the products, especially their structure and strength, are. determined decisively depending on; the concentration of the reactants in the crystalline solidified liquid 1a at the rate of crystallization. The term "main reaction" in the present case means reaction a degree of polyaddition reactions in which the formed sheet is solidified to such an extent that the porous structure is retained even after removal of the crystal system. After the reaction, the liquids used for crystallization are removed, which is achieved, for example, by elongation, sublimation, dissolution; after appropriate processing, 90 to 100% can be recovered. liquid. Suitable products for forming the crystalline system are, for example, p-dichlorobenzene, naphthalene, dioxane, diphenyl, water and t-butanol. L In the manufacture of dispersions are preferably added emulsifying agent ^tor y. |

Various additives may optionally be added to the solutions or dispersions of the reactants during the production of the porous sheets according to the invention. dyes, for example, reactive; dyes or pigment dyes, low molecular weight. or high molecular weight fillers, products for. flame-retardant treatment, glidants or surfactant coating.

I. Pro. further improving mechanical '' properties, '' in particular, to increase tear resistance and shape stability, they can be inserted into. porous sheets formed in accordance with the invention; textile or [other planar shapes such as fabrics, knitted fabrics, nonwovens and foils; to this end, before forming a crystal system. They also impregnate or superimpose the textiles and / or other sheet-like formulations with the solutions or, if appropriate, the reactant dispersions. Also, fiber reinforcement results in an additional improvement in properties.

If the dissolved or dispersed reactants are allowed to react after the reaction. forming a crystalline system in the. shaped or profiled. containers. on the polyadduct, then correspondingly shaped or. profiled porous products. Continuous. carrying out the method. it is possible to carry out crystallization and reaction on smooth I or profiled cooling rolls, optionally on suitably temperable endless belts. To make the crystallization process in the production of porous! of flat or shaped bodies accelerated, can According to the invention, the starting solutions or starting dispersions can be introduced for crystalline solidification, either discontinuously or continuously, between the temperature ranges. and then or simultaneously to react.

The porous sheets obtained have, in addition to advantages; mechanical properties pleasant feel and excellent flexibility. Since the properties, especially the feel and structure can vary widely, there are numerous applications, 1 including synthetic leather products as well as ΐ decorative textiles, clothing textiles and technical textiles, moreover, it seems that use as sealant and insulating material is also conceivable.

The invention will be further elucidated on the basis of examples, in which a series of NCO precursors, whose composition is shown in Table 1, were used for the reaction.

To produce NCO precursors, the precondensates of polyester or polyethers were heated with 1,6-hexamethylenediisocyanate or

2,4-diisocyanatotoluene for two hours with stirring: at 80 or 70 ° C.

Table 1

Number A high molecular weight compound with at least two active hydrogen atoms Polyisocyanate Molar ratio AND a polyester of adipic acid and diethylene glycol; OH number 65 (acid number 1) 1,6-hexamethylenediisocyanate 13 II a polyester of adipic acid and diethylene glycol; OH number 122 (acid number 11) >> 1: 3 III polyester of adipic acid and diethylene glycol; OH Number 122 (Acid number 11) 1: 2.6 IV branched polyester of adipic acid, diethylene glycol and glycerin; OH - number 128 (acid number 1) » 13 in adipic acid polyester with diethylene glycol; OH number 140 (acid number 1) n 13 VI linear polytetramethylene glycol ether; OH - number 55 2,4-diidoocyanatotoluene 13 VII linear polytetramethylene glycol ether; OH - number 52 2,4-diisocyanatotoluene 13

(Example 1 i

In 30 g of the 25% naphthalene solution of the NCO 1 -products obtained in accordance with I are stirred under stirring.

! disperse 1.2 ml of water at 90 ° C. After addition of 0.2 g;

The 1,4-diaxa- (2,2,2) -bicyclooctane was stirred for a further 15 seconds and the reaction mixture was poured onto a tempered 80 cm ² metal plate. Pó>

With a reaction time of 15 minutes at 65 ° C, the polyaddition is complete. The naphthalene is then taken up by dissolution in acetone. After drying at 60 ° C, a shaped fibrous sheet is obtained.

Example 2

In 30 g of a 25% p-dichlorobenzene solution

Of the NCO - precursors obtained according to II are at at 64 ° C, with stirring, disperse 1.2 ml of water and 4 g of magnesium oxide. After addition of 0.2 g of triethyl The amine was stirred for a further 15 seconds and the reaction mixture was poured onto a tempered, 80 cm ^2, large metal plate. After a reaction time of 15 minutes at 45 ° C, the polyaddition is complete. The p-chlorobenzene is then removed by dissolution in chlorobenzene. After drying at 4600 ° C, a shaped, fibrous sheet is obtained.

Example 3.

1.2 ml of water and 4.5 g of asbestos are dispersed with stirring in 30 g of a 25% diphenyl NCO pre-product obtained according to III at 85 ° C with stirring.

1.2 g of bromo polycarbonate. After the addition of 0.2 g of triethylamine, it is stirred for a further 15 seconds and then the reaction mixture is poured onto a tempered, 80 cm @ ² large metal plate. After a reaction time of 15 minutes at 60 ° C after removal of the diphenyl and subsequent drying at 60 ° C, a shaped, fibrous sheet is obtained.

Example 4

1.2 ml of water are dispersed in 10 g of a 25% dioxane solution of the NCO pre-product obtained according to IV at 20 ° C and stirring. After the addition of 0.4 g of triethylamine, it is stirred for a further 20 seconds. The reaction mixture is then converted by cooling below the melting point of dioxane to a tempered, 80 cm ^2, large metal plate for crystalline solidification. After a reaction time of 45 minutes at -5 ° C, the polyaddition is terminated. After evaporation of the solvent, a solid formation corresponding to the wild leather type is obtained.

Example 5

In 30 g of a 25% naphthalene solution of NCO _s -products produced according to I, at 90 ° C, | ; Dissolve 1.2 ml of water with stirring and pour the mixture onto a ΐ tempered, 80 cm ² large, metal plate. After the crystal system was formed at 65 ° C, 1 g of a 20% acetone solution was sprayed onto this plate! triethylamine. After a reaction time of 20 minutes the oil 'only taken up by dissolving in acetone and the reaction product ^{* 1} was dried at 60 ° C. A sheet corresponding to that of Example 1 is obtained.

Example 6

In 20 g of a 25% naphthalene solution of the NCO-precursors produced according to II at 90 ° C, the following is added: | mixing 1.2 g of benzidine, the mixture was poured ^{J 1} and malleable, a large 80 cm ^2, and a metal plate. After a reaction time of 15 minutes, the polyaddition is complete. After removing the naphthalene and final usu-ΐ! The suture is obtained in a brown-colored, textured, fibrous form >> surface. EXAMPLE 7 1.4 g of NCO precursor prepared according to V, 0.69 g of butane-1,4,4.4 g of 1,6-hexamethylenediiso-; I ^ky diisocyanate - 22 ^{g f} naphthalene were mixed ^{at 90} ° C. After the addition of 0.2 g of triethylamine, 15 seconds

I ball ^{h a} . ^p Otom Rea ^to Eni poured onto temperová- ¹ 'Nou -cm2 80 - a large metal plate and processed for 60 minutes d. at 70 ° C and for another 60 minutes - at 80 ° C. Upon removal of the naphthalene and subsequent drying at 60 ° C, a formed, fibrous, low strength structure is obtained.

Example. 8 g of a 25% dioxane solution of the precursor product produced according to H and a solution of 0.29 g of ethylenediamine as well as 0.2 g of triethylamine in 10 g of dioxane are sprayed simultaneously over 3 minutes onto the metal;

a plate cooled below -15 ° C; after 5 minutes, the formed, "crystalline solid" formed; The dioxane is melted by heating and the porous material is dried at 60 ° C.

Example 9.

Glycene is treated with dieeylene glycol. with a hydroxyl number of 140, 2.6 g of 2,4-diiso- cyanatotoluene and 0.69g of butanediol-1.4 were added at room temperature;

° C, while stirring, dissolve in 21.6 g of naphthalene. 'Po ί: the addition of 0.2 g of triethylamine is stirred for a further 15 seconds, and the reaction mixture is poured onto a tempered 80 cm @ ² ; • large metal plate. The mixture is worked at 65 ° C for 1 hour and at 75 ° C for 3 hours.

After removal of the naphthalene, a shaped, resilient sheet is obtained.

Example 10 In 2 g of water and 2 g of 1,6-hexamethylenediisocyanate are dispersed at 90 DEG C. with stirring in 30 g of a 25% naphthalene solution - NCO @ ^{-1 of the} precursor produced according to VI. - After addition of 0.1 g of triethylamine, the mixture is stirred. After stirring for 15 seconds, the reaction mixture is poured onto a tempered, 80 cm @ 2 large metal plate. It is then heated at 70 ° C for a further 30 minutes. After removal of the naphthalene by ejection and after drying at 60 ° C, a slightly yellow colored sheet is obtained.

Example 11.

gNCO - precursor product obtained according to V, 3.5 g - i NCO - precursor product obtained according to VII and 1.6 ml, water is dissolved at. 90 ° C - stirring at 22.5 g '; naphthalene. - Stir for 15 seconds after adding 0.2 g of triethylamine. The reaction mixture is then poured onto

Claims (5)

! SUBJECT ; tempered, 80 cm2 large, - - metal plate coated with warp-knit of polyamide and viscose fibers. Low viscosity reaction solutions. the flux partially penetrates the carrier, so that a bilaterally overlaid material is obtained after the reaction. The reaction is complete after 65 minutes at 65 ° C. Naphthalene. The reaction product was dried at 60 ° C. Gets. with a soft, textured, fibrous, sheet-like structure with a water permeability of vodu 1200 mm / 10 - cm ² .24 h. . EXAMPLE 12 In 30 g of a 25% naphthalene solution of the pre-product produced according to V, 1.2 ml of water are dispersed at 94 DEG C. with stirring, and 0.2 g of triethylanunu is poured onto a tempered, 80 cm ^2, large metal I ^D ES ^to U, ^{the Ter} is povtečena fleece ^ESI mixture. ^p o ^ly - • amide and polyester (basis weight 80 - g / m ^2). -Po ·. Even at a reaction time of 15 minutes at 65 ° C the polyaddition, terminated and naphthalene can be removed. After drying even at 60 ° C, a molded, fibrous formation with high strength is obtained. Example 13 The reaction mixture, as described in Example 12, is poured onto a tempered, 80 cm ² large, metal plate that has been coated with an unpaved pulp of nonwoven web (basis weight 80 g / m ² ) under the conditions described therein. After removal of the crystallizing substance, a similar sheet as in Example 12 is obtained. Example 14 In 170 g of a 25% p-dichlorobenzene solution of a mixture composed of 20 g of the precursor produced according to IV and 25 g of the precursor produced according to I are used. at 60 DEG C., with stirring, disperse 7.2 ml of water. After addition of 1 g of triethylamine, it is stirred for a further 20 seconds and the reaction mixture is uniformly dispersed in a tempered bath. After a reaction time of 30 minutes, p-dichlorobenzene is removed; a shaped, fibrous formation is obtained corresponding to the shape of the mold. Example 15 In 30 g - 25% p-dichlorobenzene solution. 0.048 g of Remazol-brilliant blue R, 1.2 ml of water and 0.2 g of triethylamine, are dispersed at 64 DEG C. in the NCO product obtained according to III. stirring. After a reaction time of 20 minutes at 35 ° C, p-dichlorobenzene was removed with chlorobenzene. After drying at 60 ° C, a uniformly colored, shaped product is obtained. .. ....... OF THE INVENTION [ 1. A process for the production of porous, planar and shaped structures, in particular having properties similar to those of textiles and leather, characterized in that they are melt. or ^D is ^{a p} ersion stoučenín ^- with a minimum ^{of, and} LN ^{- i.e.} two - at reactive hydrogen atoms and diisocyanates or polyisocyanates with - 500- molecular weights between 10 000 or molecular weights of 100 800 _ -up to spread in - TLC preferably with the addition of catalysts and by cooling, they are allowed to solidify completely or partially crystalline, whereby the crystal system remains at least until the main reaction takes place, or that - solutions or dispersions of diisocyanates, optionally polyisocyanates, and solutions and optionally dispersing compounds with at least two reactive hydrogen atoms, especially diamines. . or water, If appropriate, with the addition of catalysts, they are simultaneously or sequentially sprayed onto the tempered surface such that the liquids solidify fully or partially crystalline before or during the spontaneously running reaction and then the crystalline substance or substances are removed in a known manner and the porous sheet formed additional thermal treatment. 2. Process according to claim 1, characterized in that the solutions or dispersions of the polyaddition reagents are solidified in whole or in part in the layer and the catalyst or catalyst system in the substance, solution or dispersion is sprayed onto the surface. 3. Process according to claim 1, characterized in that the solutions or dispersions of the reactants in the composition additionally contain dyes, low and high molecular weight refractive fillers, flame-retardant products or other refining agents. . AND 4. A process according to claim 1, characterized in that the textile or other surface formations are impregnated or overlaid on one or both sides with solutions or dispersions of the reactants and allowed to crystallize before or during the reaction. 5. Process according to claim 1, characterized in that the solutions or dispersions of the polyaddition reactants, optionally after addition of catalysts, are left completely or partially crystalline between two flat or shaped surfaces continuously or discontinuously.