DE1131179B - Process for making cellulosic material resistant to putrefaction - Google Patents

Description

Process for obtaining rot resistance in cellulosic material It has been found that cellulosic material, such as fabric, is protected from putrefaction can by treating it with a liquor containing haloacetamide and formaldehyde in a molar ratio of 1 to not more than 1 or methylolhaloacetamide and optionally contains a curing catalyst and the impregnated dried out Cellulose material subjected to post-heating at 120 to 150 ° C. With others However, halocarboxylic acid amides by no means achieve the same favorable result as with haloacetamide. The same applies to the unsubstituted acid amides. It was Among other things, the effect of the methylol compounds of the following substances was tested: Acetamide, butyramide, capronamide, ß-chloropropionamide, dichloroacetamide; was doing it however, hardly any effect was found. Treatment with formaldehyde alone was just as ineffective a rot resistant product.

Since the presence of 1 mole of formaldehyde per mole of chloroacetamide is sufficient for the reaction and thus an excess of formaldehyde would not only mean waste but would even be harmful, no more than 1 mole of formaldehyde or a formaldehyde-producing substance such as paraldehyde should be per mole of haloacetamide , be applied. Example normal fabric made of 1001 / o calico weight per square meter 270 g number of threads per 10 cm; Chain 334; Weft 198 yarns: warp yarn NE 31, 3/2 (18, 9 - 2) weft yarn NE 21, 2/2 (27, 9 - 2) A padder was used for the impregnation. Cloth speed ..... 0.7 m / minutes Press result. . . . . . . . . . about 60% Impregnation agent Drying temperature ...... 70 ° C Dry season . . . . . . . . . . . . . 10 mins Post-heating time ...... 41 / z minutes The calico was impregnated with a solution of methylolchloroacetamide in water to which oxalic acid had been added as a curing catalyst. After drying, the treatment followed at a higher temperature, the actual reaction taking place. In order to completely remove material that may not have reacted, the padding was rinsed a few times with cold water at 70 ° C.

The calico treated in this way was subjected to a burial test. To At 1, 2 and 4 weeks a number of strips were removed and the tensile strength certainly. "Residual strength" means the ratio of the tensile strength after and before burial, expressed as a percentage. The burial tests and the tensile strength were according to »Voorschriften voor de biological testing of textiel en others materials «by Dr. H. J. Hueck, editor: CentraalLaboratoriumT.N.0. (Rapport No. Cl. 58/9) Julianalaan 134, Delft, Netherlands.

The result of a series of tests is recorded in the table below: Table 1 Burial attempts concentration Sample No. Methylolchloric Substitution Tensile Strength Residual Strength ('%) after acetamide grade in o7o bath (kg / 25 mm) 1 week I 2 weeks I 4 weeks R31-40 ................ 2 0.5 46 61 7 0 R31-41 ................ 5 1.2 39 92 56 36 R31-42 ................ 10 2.2 38 105 61 32 Z2-17 ................ 13.3 3.1 39 85 67 41 Z 2-18. . . . . . . . . . . . . . . . 16.7 4.2 37 95 92 62 Z2-19 ................ 20 5.8 35 94 100 83 R31-53 ................ 20 5.9 26 100 85 92 Untreated ........... - - 44 10 0 0 1) Expressed in the number of side groups per 100 glucose units. From these results it can be concluded that there is a clear connection between the degree of substitution and the resistance to the action of microorganisms. Complete resistance during a burial of 4 weeks was obtained with a degree of substitution of about 6. If one takes burial during one week as a criterion, a degree of substitution of 1 to 2 is sufficient. These degrees of substitution are extremely low compared to other methods of making cellulose material resistant to rot by means of chemical modification, such as e.g. B. acetylation, and cyanoethers, but in which at least a third of the total number of OH groups of the cellulose must be substituted if you want to be successful, but this brings about a profound change in properties.

In addition to a burial sample, some specimens of treated calico were subjected to the action of an enzyme solution for 2 weeks. The result can be summarized as follows: Table 2 Enzyme treatment attempts Concentration tensile strength residual strength residual strength Sample no. Methylolchlor- degree of substitution according to enzyme- after burial acetamid in'o / o bath (kg / 25 mm) treatment (o / o) for 1 week Untreated .... - - 44 44 0 to 40 R31-40. . . . . . . . 2 0.5 44 63 61 R31-41. . . . . . . . 5 1.2 36 89 92 R31-42. . . . . . . . 10 2; 2 39 89 105 R 31-53. . . . . . . . 20 5.9 25 96 100 For purposes of comparison, the result after burial during one week has been included in this table.

In these experiments, too, it was found that the reaction the calico is made resistant with methylolchloracetamide. It continued to be examined what effect the post-heating in the context of the method according to the invention had on the resistance of calico. Here calico was mixed with solutions of methylolchloroacetamide impregnated in water.

The impregnated fabrics were subjected to a burial test. Table 3 Comparison of "bound" and "loose" methylol chloroacetamide Number of molecules residual strength Sample No. Treatment with (° / o calculated on bath) chloroacetamide 100 glucose units each 1 week I 2 weeks L4 weeks R31-50 ........ methylol chloroacetamide 2.6% 3.0 52 1 0 R 31-51:. . . . . . . Methylol chloroacetamide 6.6% 5.4 96 30 0 R31-42. . Methylol chloroacetamide 10% 2.2 105 61 32 R31-53. ....... methylol chloroacetamide 20% 5.9 100 I 85 92 Samples R31-50 and R31-51 were only dried after impregnation, but not reheated at higher temperatures; so there is no "bond". Samples R31-42 and R31-53 were post-heated at 130 to 140 ° C for about 41/2 minutes.

It is clear that hardly any effect can be achieved without post-heating. at The following variables occur in the reaction of cellulose with methylolchloracetamide: 1. Concentration of methylol chloroacetamide in the impregnation liquid; 2. Art and amount of catalyst used; 3. Temperature and duration of post-heating.

The amounts of bound chloroacetamide in this reaction are a Criterion for the degree of implementation. In addition, this type of reaction requires that the mechanical properties of the calico should not or hardly change. One criterion for this is the tensile strength. It was now examined what influence some of the above variables on the degree of substitution achieved and on had the loss of tensile strength.

1. Relationship between bath concentration, degree of substitution and tensile strength Reaction conditions: pH of the impregnation bath .. 2.5 Catalyst ............. oxalic acid Dry . . . . . . . . . . . . . . . 70 to 80 ° C Post-heating. . . . . . . . . . . . 5 minutes at 140 ° C Table 4 Loss of methylolchlorine Sample No. acetamide (° / o) Degree of substitution (O / o) Tensile strength to tensile strength (aqueous solution) (kg / 25 mm) (° / o) R31-40. . . . . . . . 2 0.5 46 - R31-41. . . . . . . . 5 1.2 39 11 R31-42. . . . . . . . 10 2.2 38 14 Z2-17. . . . . . . . 13.3 3.1 39 11 Z2-18. . . . . . . . 16.7 4.2 37 16 Z2-19. . . . . . . . 20.0 5.8 35 20 2. Influence of the type and amount of the catalyst used and the post-heating temperature Oxalic acid was chosen as the catalyst. The pH was adjusted to 4.5 and 2.5 using oxalic acid as the catalyst. In addition, a sample was also made with a pH of 6.5, which was obtained by adding a few drops of NaOH to a methylolchloroacetamide solution, which itself had a pH of about 5.5. So no oxalic acid was added here.

Reaction circumstances: bath concentration 16.7%.

Post-heating at 130 or 140 or 150 ° C for 5 minutes. Table 5 Tem sub-loss Sample no. PH value temperature stitution at FeZirß degree (0 / a) gkei ° C (%) Z2-26-1 a 130 0.5 4 b 6.5 140 3.0 10 c 150 2.8 29 Z2-26-2 a 130 0.7 6 b 4.5 140 1.6 8 c 150 5.5 40 Z 2-26-3 a 130 0; 7 0 b 2.5 140 4.2 10 c 150 7.8 60 From all these samples it follows; that by the treatment according to the invention an excellent, rot-resistant product is obtained.

Some samples were taken to compare the present Procedure with known procedures.

1. Influence of repeated washing and dry cleaning on rot resistance of calico treated in the following manner: a) According to the invention (degree of substitution 6; see table 1).

b) copper naphthenate (about 0.7% Cu).

c) Laurylpentachlorophenol (water repellent) (about 20/0).

These three swatches were washed five times and five times next to each other dry cleaned. The two treatments were in a household washing machine made. A commercially available detergent in an amount was used for washing of 10 g / 1 used. The liquor ratio was 1:20. It was during one Washed for 15 minutes at 80 ° C. This was followed by twice 5 minutes in distilled Rinsed with water and dried at 60 ° C. The dry cleaning took place in trichlorethylene at 20 ° C for 10 minutes. It was then air dried. After completion After the washing test, the samples were subjected to a burial test for 2 and 4 weeks.

Table 6 below shows the percent residual strength of the strips after burial. Table 6 After being buried for 2 weeks After being buried for 4 weeks Pattern five times five times five times chemically five times chemically wash immediately I wash immediately Clean clean According to the invention. . . . . . . . . . 93 84 98 85 73 84 Copper naphthenate ......... 98 83 96 99 44 81 Lauryl pentachlorophenol .... 100 0 0 48 0 0 Untreated .............. 0 0 0 0 0 1 0 According to this, washing and dry cleaning have only a very slight influence on the rot resistance of calico treated according to the invention. Calico treated with copper naphthenate can be dry cleaned, but is less washable. The effect of lauryl pentachlorophenol disappears completely, both with dry cleaning and washing.

From these results the difference between the Effect of the chemical reaction with the cellulose according to the invention and the effect from "loose" impregnation with the usual fungicides. Some exposure samples were also made.

A comparative sample was placed on a number of bars on the roof of a building made, with a number of strips of calico treated in different ways have been exposed to sunlight. Here, half of the stripes were behind Plexiglass panes, whereby the influence of sunlight is not that of rain was probably turned off.

After the end of the suspension (1, 2, 4 and 8 months) a Number of strips subjected to a grave test (2 weeks).

The following treatments took place: a) Treatment after the Invention (degree of substitution 6).

b) Treatment with copper naphthenate (0.8% Cu). c) treatment with lauryl pentachlorophenol and water repellent.

d) Treatment with copper-8-oxyquinoline (0.7% Cu).

The residual strengths (in percent) are shown in Table 7 below. Table 7 Originally exposed Pattern borrowed not covered covered 1 month 1 2 months 14 months 18 months, 1 month 1 2 months 1 4 months 18 months Untreated. . . . . . . . . . . . 0 0 j 14 18 2 0 3 7 8 Treated after the finding .............. 89 81 98 63 38 86 85 84 74 Cu naphthenate .......... 97 96 98 25 4 93 89 93 88 Laurylpentachlorophenol. 97 20 21 11 6 48 37 32 47 Cu-8-oxyquinoline ....... 100 69 18 15 3 94 94 '88 92 It is clear from these results that calico treated according to the invention loses its resistance to rot on exposure to atmospheric influences much less quickly than after the usual methods of treating impregnated calico. This is due to the chemical reaction that took place during treatment with methylolchloroacetamide.

Claims (1)

PATENT CLAIM: Process for achieving rot resistance in cellulose material, characterized in that this material is mixed with a liquor, the haloacetamide and formaldehyde in a molar ratio of not more than 1.0 or methylolhaloacetamide and optionally contains a curing catalyst, impregnates, dries and subjected to post-heating at 120 to 150 ° C.