DE2120416A1 - Fluorine-containing polyurethanes and processes for their manufacture - Google Patents

Description

3e description of the patent application relating to FLUORHAL? IGE POLYURETHANE AND METHOD OF MANUFACTURING THE SAME The invention relates to polymeric fabrics, and more particularly fluorine-containing polyurethanes and processes for their preparation.

The substances mentioned are used for the production of foam plastics, Varnishes, adhesive and sealing compounds, etc.

The known fluorine-containing polyurethanes are reaction products of glycols or polyesters containing a hydroxyl group, or bisphenols, or Fluorine derivatives of the compounds mentioned with fluorine-containing aliphatic diisocyanates, or aromatic diisocyanates, fluorinated in the core (see for example U.S. Patent No. 2911390, 1959; U.S. Patent No. 3121764, 1964; briti ce Patent No. 994411, 1965; U.S. Patent No. 3398182, 1968; USA patent No. 3413271, 1968; R. Gosnell, I. Hollander, I. Macromolec. Sci. Phys., 1 B, 831, 1967).

Processes for the production of the polyurethanes mentioned are also known by reacting said components containing a hydroxyl group with the mentioned fluorine-containing diisocyanates in the medium of an organic solvent at a temperature of 20-150 ° C (see the same publications).

A disadvantage of the known fluorine-containing polyurethanes is their low level Resistance to temperature changes as well as insufficient hydrolytic resistance. Many of the known fluorine-containing polyurethanes tend to decompose at low temperatures with excretion of hydrogen fluoride.

The present invention aims to avoid the disadvantages mentioned.

The invention is based on the object of a new type of To develop fluorine-containing polyurethanes, the reaction products of glycols or Polyesters containing a hydroxyl group, or bisphenols, or fluorine derivatives represent the compounds mentioned with fluorine-containing diisocyanate.

According to the invention, this object is achieved in that fluorine-containing polyurethanes are proposed1 which represent polymers which consist of the following members: where R is a radical of glycols or hydroxyl-containing polyesters, or bisphenols, or fluorine derivatives of the compounds mentioned and which have a degree of polymerization n = 7-20.

The proposed fluorine-containing polyurethanes are under preservation of properties that are characteristic of ordinary polyurethanes,. (high adhesion and cohesion, elasticity, wear resistance, frost resistance i.a.) excellent by. a high hydrolytic resistance and increased Resistance to temperature changes, vras the proposed fluorine-containing polyurethanes allowed to be added to the number of temperature change-resistant polymers.

The fluid polyurethanes mentioned can be obtained by reacting glycols or hydroxyl-containing polyesters which contain a hydroxyl group, or bisphenols, or fluorine derivatives of the compounds mentioned with fluorine-containing diisocyanate in the medium of an organic solvent at a temperature of 20-150 ° C. According to the invention, the fluorine-containing diisocyanate used is flexafluoroisopropylidene p, p'-diphenyl diisocyanate of the following formula: and the process .. carried out at a molar ratio of the said hydroxyl-containing reagents to the diisocyanate, correspondingly equal to 1: 1-1.5.

The introduction of fluorine atoms into the polyurethane molecule leads to a significant change in the strength of the urethane bond. One plays the position of the fluorine atoms in relation to the urethane bond plays a decisive role. The application of diisocyanate with the formula mentioned above for the synthesis of polyurethanes allows a significant number of fluorine atoms in the macromolecule of the polymers introduce, which leads to a substantial strengthening of the urethane bond. sufficient. Increase the electronegative substituents in the molecule of the diisocyanate mentioned the proportion of positive charge on the carbonyl atom of the hydrogen of the isocyanate group, whereby they. facilitate its attack by the nucleophilic reagent, and the speed accelerate the formation of polyurethane. The presence of fluorine atoms in the side substituents at the central carbon atom in the molecule of the mentioned Diisozyanats and the related removal of the fluorine atoms from the Isocyanate group close the Possibility of excessive enlargement the reactivity of these groups and thereby eliminate technological Difficulties encountered in the industrial use of fluorine-containing diisocyanates Pop up.

The polyurethanes produced according to the invention significantly outperform non-fluorinated analogs, as well as the known fluorine-containing polyurethanes with regard to the thermal shock resistance and the physical-mechanical properties. The possibility of obtaining high molecular weight polymers and their increased solubility in a number of organic solvents significantly expands the possibility of Use of such polyurethanes.

The production of the proposed fluorine-containing polyurethanes is as mentioned above, accomplished in the medium of an organic solution. as Solvents can be used such anhydrous inert solvents such as dimethyl sulfone, cyclohexanone and dimethyl sulfoxide, the latter is preferable.

The synthesis is carried out in a temperature range of 20-150 ° C depending carried out by the nature of the starting reagents. Starting reagents containing the hydroxyl group For example, the following can be used: 2,2-bis (p-oxyphenyl) propane; 2,3-bis (p-oxyphenyl) hexafluoropropane; Ethylene glycol; Diethylene glycol; α, α, #, # - tetrahydrohexafluoropentadiol; Polyester, obtained on the basis of the esterification of adipic and phthalic acid by glycerine and Diethylene glycol; Polyester, obtained on the basis of an esterification of the perfluoradipine and phthalic acid by a mixture of Gly-.

cerin and diethylene glycol or a mixture of glycerin and α, α, #, # - tetrahydrohexafluoropentadiol.

For a better understanding of the present invention, the following the following examples of the production of fluorine-containing polyurethanes according to the invention cited.

Example 1 To a solution of 1 mol of hexafluoroisopropylidene-p, p'-diphenldiisozyanate (HFDI) in 300 ml of dry dimethyl sulfoxide (DMSO) is at ~ room temperature and Stir the solution of 1 mol of ethylene glycol in 100 ml of DMSO was added. The mixture was heated at a temperature of 11000 and stirring over the course of two hours, then DMSO diluted to a 5% concentration and poured into water. That Precipitating polymers were filtered off, washed with water, from a The solution was reprecipitated in acetone, filtered off, washed with water and dried at 100.degree.

The polymer yield was 85% of theory 4 reduced. = 0.76 dl / g (in dimethylformamide at 25 ° C); the softening temperature is equal to 285 ° C; the onset of weight loss on heating in the air is set according to the thermogravimetric Analysis (TGA) at 300 ° C. The polymer is indefinitely soluble in acetone, cyclohexanone, Dimethylformamide, dimethyl sulfoxide and forms solid elastic films, (see table 1).

Example 2 The synthesis of the fluorine-containing polymer was carried out as in Example 1 described, carried out except the temperature of the synthesis, the same Was 60 ° C and the duration of the process was equal to 3.5 hours.

The polymer yield was reduced by 70% of theory. = 0.60 dl / g (in dimethylformamide at 25 ° C) The other data for the polymer are the same as with the polymer obtained in Example 1. The properties of the free Films formed by the polymer are listed in Table 1.

Example 3 The synthesis of the polymer was carried out as in Example 1, besides the temperature of the synthesis, which was equal to 15000, and the duration of the process, equal to 40 minutes.

The polymer yield was 80% of theory 7 reduced. = 0.80 dl / g (in dimethylsormamide at 2500). The other data for the polymer are the same as in the case of the polymer obtained in Example 1. The properties of the free Foils, which were formed by the polymer are listed in Table 1.

Example 4 The polymer was made from 1 mole of HFDI and 1 mole of diethylene glycol Obtained analogously to Example 1. The polymer yield was 82% of theory # reduced = 0.87 dl / g (in dimethylformamide at 25 ° C) The softening temperature is equal to 273 ° C; the onset of weight loss when heated in the air according to the TGA at 309 ° C. The polymer is unlimited in the example 1 listed solvents. The properties of the free foils, formed by the polymer are listed in Table 1.

Example 5 The polymer was made from 1 vol HFDI and 1 mole diethylene glycol under conditions similar to those described in Example 2, obtained.

The yield of polymer was 75% of theory # reduced. = 0.65 dl / g (in dimethylformamide at 25 ° C); the softening temperature is equal to 25,000. The onset of weight loss when heated in the air is set according to the TGA at around 300013. The polymer is indefinitely soluble in the example 1 given Solvents. the Properties of the free foils, formed by Polymer are given in Table 1.

Example 6 The polymer was made from 1 N: oi HFDI and 1 liter of diethylene glycol obtained under the conditions described in Example 3.

The polymer yield was reduced by 60% of theory. = 1.1 dl / g (in dimethylformamide at 25 ° C); the softening temperature = 310 ° C. The beginning of the According to the TGA, weight loss when heated in the air begins at 32,000. The polymer is indefinitely soluble in the solvents listed in Example 1 are. The properties of the free films formed by polymer are in table 1 specified.

Example 7 The polymer was synthesized starting from 1 col HFDI and 1 mole of α, α, #, # - tetrahydrohexafluoropentadiol, under conditions as in example 1.

The polymer yield was 61% of theory #reduced. = 0.43 dl.g (in dimethylformamide at 25 ° C; the softening temperature is 17700;; der According to the TGA, the onset of weight loss when heated in the air is around at 200 ° C. The polymer is indefinitely soluble in acetone, cyclohexanone, dimethylformamide, Dimethyl sulfoxide and from these solutions forms solid and elastic ones Foils.

(see table 1).

Example 8 The polymer was made from 1 sl HFDI and 1 ol 2,2-bis- (p-oxyphenyl) propane, obtained similarly as in example 1.

The polymer yield was 87% of theory #reduced. = 0.62 dl / g. (in dimethylformamide at 25 ° C); the softening temperature is equal to 205 ° C; the onset of weight loss when heated in the air is set according to the TGA at around 220 ° C. The polymer is readily soluble in the solvents in example 1 are listed. The properties of the free foils, formed by polymer, are given in Table 1, Example 9 The polymer was made from 1 mole of HFDI and 1 Moles of 2,2-bis (p-oxyphenyl) hexafluoropropane. obtained similarly as in Example 1.

The polymer yield was 78% of theory. ~~~ # reduced. ~ 0.58 dl / g (in dimethylformamide at 25 ° C); the softening temperature is 2060C * the onset of weight loss when heated in air is set according to the TGA around 22000 a. The polymer is readily soluble in the solvents in example 1 are listed. The properties of the free foils, formed by polymer, are given in Table 1 Example 10 '1 kol of hexafluoroisopropylidene-p, p'-diphenyl diisocyanate was dissolved in 1 l of cyclohexanol and at room temperature with a 20% solution in polyester cyclohexanone based on adipic and phthalic acid, diethylene glycol and glycerin (molecular weight # 800, hydroxyl number 300 mg KOH / g, acid number 4 mg KOH / g mixed. The amount of diisocyanate and polyester corresponded in the reaction mixture the NCO / OH molecular ratio = 1.4: 1. The obtained solution was on a steel support applied and dried at 120 ° C over the course of an hour. The properties of the Protective films formed by polymer are given in Table 3.

Example 11 1 col of HFDI was dissolved in 1 1 of cyclohexanone and at room temperature with a 20% solution in polyester cyclo hexanone based on adipine and Phthalic acid, glycerine and α, α, #, # tetrahydrohexafluoropentadiol mixed. (Molecular weight 550, hydroxyl number - 400 mg KOH / g, acid number 3 mg KOH / g). The amount of diisocyanate and polyester in the reaction mixture corresponded to the molecular ratio nis NCO: OH = 1.5: 1. The obtained solution was applied to a steel support and dried at a temperature of 120 ° C for one hour. The properties of the protective films formed by polymer are given in Table 3. Tabel 1 PROPERTIES OF THE FREE POLYURETHANE FILMS Serial No. 20 ° C 100 ° C 150 ° C 200 ° C 250 ° C elementary polyurethane link game # # # # # # # # # # 1,2,4 -OCHN-C6H4-C (CF3) 2-C6H4-NHCOO (CH2) 2-O- 610 30 510 52 470 68 310 87 220 190 4,5,6 -OCHN-C6H4-C (CF3) 2-C6H4-NHCOO (CH2) 2O- (CH2) 2-O- 580 34 440 58 340 75 220 112 170 210 7 -OCHN-C6H4 (CF3) 2C6H4-NHCOO-C6H4C (CH3) 2-C6H4-O- 530 28 210 72 - - - - - -8 -OCHN-C6H4 (CF3) 2C6H4-HCOO-C6H4 (C3) 2-C6H4-O- 480 21 180 89 - - - - - -9 -OCHN-C6H4C (CF3) 2-C6H4-NHCOO-CH2 (CF2) 3CH2O- 400 52 310 95 140 280 # - ultimate tensile strength, kp / cm² # - related elongation For comparison Table 2 shows the strength data of free films made from polymer based on methylene-p, p'-diphenyl diisocyanate and diethylene glycol (elementary Polyurethane member - COHN-C6H4-CH2-C6H4NHCOO - (CH2) 2O (CH2) 2-O-; # reduced = 0.65 dl / g Dimethylformamide at 250C) are formed.

Table 2 Strength data for free 20 ° C 100 ° C 150 ° C 200 ° C 250 ° C polyurethane films Tear Resistance, kp / cm2 480 350 260 melts related elongation,% 25 42 67 melts Table 3 Mechanical properties 30 µm thick protective Polyurethane lacquer foils Polyurethane (starting compounds) Type of sample HFDI and HFDI and fluorine-ethylene-p, p'-polyester containing poly-diphenyldiiso- (example ester (Example cyanate, poly-10) 11) ester from Example 10 (comparative etalon) impact test (direct hit / recoil), agreed units 50/50 50/50 50/50 impact test (direct blow / kickback, after holding at 2000C for 300 hours, agreed Unit 50/50 30/20 20/20 hardness, relative units 0.88 0.72 0.6 Specific weight wear with a load of 1.9 2.5 3.0 2 kg, mg / m.cm2

Claims (2)

PATENT A- NSPRÜ CHE 1. Fluorine-containing polyurethanes, which represent a reaction product of glycols or a hydroxyl group-containing polyesters, or bisphenols, or fluorine derivatives of the compounds mentioned with fluorine-containing diisocyanate, as characterized in that the polyurethanes are polymers which consist of the following members : where R - is a residue of glycols or hydroxyl group-containing polyesters, or bisphobnols, or fluorine derivatives of the compounds mentioned. and which have a degree of polymerization n = 7-20. 2. Process for the preparation of fluorine-containing polyurethanes according to claim 1 by reacting glycols or polyesters containing a hydroxyl group, or bisphenols, or fluorine derivatives of the compounds mentioned with fluorine-containing diisocyanate in the medium of an organic solvent at a temperature of 20-150 ° C., characterized in that as the fluorine-containing diisocyanate, hexafluoroisopropylidene-p, p'-diphenyl diisocyanate of the following formula is used and the process is carried out at a molecular ratio of the said reagents containing a hydrocyclic group with the diisocyanate corresponding to 1: 1-1.5.