Method of producing mixture for impregnating polyamide fibre containing perfluoroalkyl groups, epich

专利摘要:
The invention relates to derivatives of carbamic acids, in particular, a method for producing a mixture for impregnating polyamide fibers, the general formula (CHi) j ..- CH (CH2 Cl) -C (0) (0) - (OK) -0-B1, (1), where R CgFij is C, 2.F2, or CgF, 7 is C gFj5 perfluoroalkyl; 1.8-3; z 1-10; m 1-2; n 1-1, 5, moreover, with (m + n) -and 3 A:; C Nd-CH3, diphenylmethane-4, 4 j dicyclohexylmethane-4, 4, triphenylmethane-4,4,4, D (CH2) b - -NH-C (0) N- (cnj) g-; R -CII (CKjCl) - —CHj.-, Cj-C-alkylene, -CH (CHj) -CH2-, -CH (CH20C H C9F, -,) -CH2-; BH, C-C-alkyl, -C (0) MH-B-HMHS (0) - OCH (CHiCl) CnJ-, OCn2, (CsFn -C, bG „) (11) .- ССО) КК 19 КНССО } - ocn () -cnJ.-ocHiCH ,, - (CaF, 7 -CjgFj, (III), D - (SP) N-
公开号:SU1445555A3
申请号:SU864028507
申请日:1986-11-12
公开日:1988-12-15
发明作者:Веховски Франк；Клебер Рольф；Йекель Лотар
申请人:Хехст Аг, (Фирма)；
IPC主号:

专利说明:

(OCHCN) s-OCH2SI2- (CaIp C | yGsz) 2,
CH2C
-COWH-Yol-NHCO-lOCHCH lj-OCH CHv-fcgFn-CisfVi) (b).
CHnCl
CH3 D- (CH, 1,
The aim of the invention is to develop an affordable method for obtaining the above mixture of compounds, which significantly improves the oil and water repellency properties of the impregnated fibers.
The proposed method proceeds through the steps of preparing an additive compound 1 of the formula
Р1 (СН2) 201СН2СНО) у-Н
and the additive compound 2 of the formula. Rr (CH2) 20 (CH2CHO) y-C01JH-А-ШСО)) -; ,
CHjCl
where Rp, A, y, n have the indicated meanings.
45
Example 1. In a glass flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a heating bath, 527.9 g (1.0 mol) of a commercially available perfluoroalkyl ethanol mixture are placed.
C (0) H (CH2) perfluoroalkyl: ohm-CBS, (hydroxyl number 106) 5 380 ml, - trifluorotrichloetaka (CFCl2 CF gCl., Kip, 48 ° C) as solvent V 5.0 g of bortrifluoroethyl ether in quality of catalyst (1 wt.% of catalyst, attributed to perfluoroalknl-; 1 tanol), 166 was added to this solution at 1: 0 drops, 5 g (1, - (1.8 mol) of epichlorohydrin, after which the mixture within 3 The solvents are kept at the boiling point and then the solvent used is distilled off in vacuo (vacuum obtained by means of a water-jet pump). A yellow-colored wax is obtained. brazny product - additive compound 1. This compound is ET with perftoralkiletanol-epihlorgidri- HOBbiM additive compound with a molar ratio of epichlorohydrin to perftoralkileta- nol 1; 1 | 8 (this zna50
55
cheat that y in formula I is equal to 1.8),
cheat that y in formula I is equal to 1.8),
.14
The same technology was used to prepare the additive compounds used in the following examples.
The starting mixture is shown below for further transformations to produce compounds according to the invention. These transformations are carried out in a stirrer equipped with a reflux condenser with a drying tube, a thermometer and a heating bath of a glass flask.
The initial mixture:
100.0 g (0.144 mol) of additive compound 1;
25.1 g (0.144 mol) of toluylene diisocyanate, namely, mixtures of about 80% by weight of 2,4-toluene diisocyanate and 20% by weight of 2,6-toluene diisocyanate (commercially available product);
 g (O, 144 mol) of hexaepichlorohydrin
CH, C1
n (main) -one
Thus, the additive Compound 1, toluylene diisocyanate and hexa-epichlorg idrin are used in molar ratio of 1: 1: 1: 1,
Carry out the conversion.
An additive compound is placed in a glass flask: e} ie 1 and toluene diisocyanate. The mixture is heated to 100-110 C. The mixture is heated at this temperature for 3 hours while stirring and then cooled (first step of the reaction). The resulting perforal alkyl acetate compound epichlorohydrin-toluene diisocyanate is a yellow colored waxy product. To the product hexa-epichlorohydrin is added to the product in the glass jolba. The mixture is heated to i00-110 ° C, held at this temperature for 3 hours with stirring, and then cooled (second step of the reaction). A brown colored waxy product is obtained (yield 206.1 g, 99.3 wt.% Of theory). The composition of the compound obtained in accordance with the invention, expressed by the gross formula, corresponds to the formula given in Table 1, with sequence number B1.
PR, and measure 2.
Initial mixture: 69, 4 g (0.1 mol) of additive compound 1B according to example 1
55
with
five
0
0
„
50
55
17.4 g (0.1 mol) of tolylethmisocyanate in accordance with Example 1,
20.3 g (0.1 mol) of dipichloroplich,
Thus, the additive compound 1, toluene diisocyanate and diapichlorohydrin are used in a molar ratio of 1: 1: 1.
The conversion was carried out by analogy with iepo 1. A brown wax-colored product was obtained (yield 105.2 g, 98.1 wt.% Of theory). The composition of the compound obtained corresponds to the formula with the serial number B2 in Table 1,
PRI i e p 3.
The initial mixture:
133.2 g (0.2 mol) of additive compound 1 according to example 1;
54.4g (0.2 mol) diphenylmethane-4, 4 -diisocyanate (product available),
5 114.6 g (0.2 mol) of hexazpichlorohydrin.
Thus, the additive compound 1, diphenylmethane diisocyanate and hexaepichlorohydrin are used in a molar ratio of 1 M t 1.
Carrying out the transformation;
Put in a glass flask; diuthocyanate ayut. melted by heating and molten addition compound 1 is added to the molten diisocyanate while stirring. The mixture is heated to 110-120 ° C, kept at this temperature for 3 hours while combing, and then cooled (first step of the reaction). The resulting perfluoroalkyl-ethanol-epichlorohydrin-diphenylmethanediisocyanate additive compound is a yellow colored waxy product. To the product in the glass flask, hexaepichlorohydrin was added. The mixture is heated to 110-120 ° C, kept at this temperature with stirring for 4 hours and then cooled (second reaction step). A wax-colored product is obtained in brown. (yield 298.6 g, 98.8 wtL from theory). The composition of the obtained compound corresponds to the formula with the serial number of the OT in the table. one .
Pr 4 and p 4. The initial mixture:
310jO I (0.442 mol) additively ;;;;
compounds 1 according to nj-ii; - measure om 1 j
377.0 g (0522; mol) tripheny.g: yy-tan-A h, 4 tritzocia11at l H
24.4 g (0,221 mol) -chloromel -1,2-dihydroxyethane CH, C1
wear SI 2.-on
Thus, the addition of the compound; - nenie 1 in triisocyanate and dio.g; a new combination is used in a mono ::: a 2: 1: 1 ratio.
Transformations make analogies to frost; 3 ,, prt-tchgp at the g. Of the first step of the reaction mixture nt: h; : 1; 1h: 5 h is kept at 10-120 s. E: -iec-then hexa-epichlorohydrin is added the above chlorine; po-a1; ld 5ol and on the second cTyiieKH rsaclet MIXTURE bb live for 8 hours at 120-130 ° C; get cKpai; | eni ;;: ri; in measles Chievyk Ui; wax-like 1; product (09 g, 99.7 wt.% of theory), The compound of the obtained compound corresponds to pho; a mule with a gur number B4 t table about 1 ..
Pr and m with p 5.
The initial mixture:
150.0 g (0.225 nil) a.editive compound: 1 according to rum 1 I
115.3 g (0.150 mol) CMecvi triiso cyanate containing a group
And OH, 1 -:
- (CHjg.,) ,: -, - (SP /; ,, N-LH BUT N
-N- (CH2) g -fr-C-N-CCH,) ,. - g (UK) AND O (CH) g-N-C.
P h and L and pate cool the first. c-: viieHTj reaction) „poluchn: -o ald, -ggivenop perfluoroalkyl compound -; i; -aac, r; - :: And ;; x; / orgidrin-nzop1--; aty -; ts painted yellow dvk1 zosko-,: Sra ve ve ;; EC; O. To khodl T (l ..:: i; O: TUS to the product, add: r 1; x :; .1eg; them, m org1- Drin, Cr ess J o: JO-1 I.);:, B1 .i; СРЖ - vag) Г i-pn this
one: : ; G; bishop. (Pf a h)), o; jy4aKjT о:; tr ashen-, In which l and h; product NR: O, G. ::. h g; .- pHii). {.:. :; : -i1eni corresponds / chluy: /: tabl, 1.
,;, GI I O:; . rg) T (1 -.
-and;:
-SSND-KN About
129.0 (0.225 mol) -xa hydrin
In this way; Addithigiguidin a compound 1 5 isodian n hexazpichlorgs: - rin is used in molar -. ratios ;, SRI 3; 2: 3.
Carrying out the transformation
Isocyanate n 1.2 g dibutshsh - layi. ; The tin of tin as a catalyst (this is 1 wt.%, related to the amount of isocyanate used) is placed in a glass flask.
/ le b
From,.: Remaining semi-: .- D1-; neg-and gabl. one,.
P p and; S p 7, Yas-course; -a mixture;
81.3 g (0.10 mol) of an additive compound of IG according to with
28.5 g (0.05 mol) of triisocyanate in accordance with example 5j
31.7 g (0.05 mol) of polytetrahydrofuran in accordance with Example 6
Thus, the additive compound 1, triisocyanate and polytetragi irofuran are used in a molar ratio of 2: 1: 1,
The conversion is carried out by analogy with example 1 ,. but instead of hexahaphlorohydrin, polytetrahydrofuran is added, and in the second step of the reaction, the mixture is held for 7 hours at 100-1. A brown wax-colored product is obtained (yield 138j4 g, 98.2 wt.% Of theory). The composition of the obtained compound corresponds to the formula B7 in Table 1.
Example 8,
The initial mixture:
97.5 g (0.12 mol) of additive compound 1 according to example 6;
34.2 g (0.06 mol) of triisocyanate in accordance with example 5J
58JO g (0.06 mol) of one-way etherified diol of formula
H (OCHCH2.) Io - OCitH9
sns
Thus, the additive compound 1, the triisocyanate and decapropylene glycol mono p-butyl ether are used in a molar ratio of 2: 1: 1.
The conversion is carried out by analogy with example 1, the mixture being incubated for 6 hours at 100-1 ° C in the first stage of the reaction, the mentioned diol mono ether is added instead of hexa-epichlorohydrin and the mixture is maintained for 100 hours at the second stage at 100-110 ° C . A brown colored wax product is obtained (yield 184 g, 97.2% by weight of theory). The composition of the obtained compound corresponds to the formula B8 in the table. one.
PRI me R 9.
The initial mixture:
81.3g (0.10 mol) of additive compound 1 in accordance with example 6j
28.5 g (0.05 mol) of triisocyanate in accordance with Example 5;
54.7 g (0.05 mol) of unilaterally esterified diol of the formula
H (OCHCH,) io- (OCH, CH,) jo-OC, H9

SNS
Thus, the additive compound 1, triisocyanate and deca (propylene-ethylene) glycolmones-butyl ether are used in a molar ratio. 2: 1: 1.
The conversion is carried out by analogy with Example 5, the mixture being incubated for 6 hours at 100-110 ° C in the first step of the reaction; . A brown-colored wax-like product is obtained (yield 161.7 g, .98.3 wt.% Of theory). The composition of the obtained compound corresponds to the formula B9 in the table. one.
Example 10
The initial mixture:
162.6 g (0.20 mol) of additive compound 1 in accordance with Example 6;
57.0 g (0.10 mol) of triisocyanate; in accordance with example 5
64.1 g (0.05 mol) of polytetrahydrofuran in accordance with Example 6 of.
Thus, the molar ratio of the compounds used is 4: 2: 1.
Carry out the conversion.
The additive compound 1 and the triisocyanate are placed in a glass flask. The mixture is heated to 100-110 ° C and maintained at this temperature for 3 hours while stirring (first step of the reaction). Polytetrahydrofuran is added to the resulting waxy yellow colored perfluoroalkylethanol-epichlorohydrin-isocyanate additive compound. The mixture was incubated for 4 hours at 100 with stirring and then cooled (second reaction step).
g
A brown colored wax product is obtained (yield 278.2 g, 98.1% by weight of theory). The composition of the obtained compound corresponds to formula B10 in Table 1.
PRI me R 11. The original mixture:
. 81.3 g (0.10 mol) of an additive in accordance with Example 6;
RCeFiv- С 1bGz3CHN2CH20- (passable) s- CONH
Molar ratio compounds used are 2: 1: 1: 1.
The conversion is carried out by analogy with Example 10, with monoethylene glycol being added in the second step of the reaction. To the obtained brown-colored, waxy product (which corresponds to the PMI compound in Example 7) was added 0.05 mol of the said perfluoroalkyl-ethanol-epichlorohydrin-isocyanate compound, which is obtained by converting 0.1 mol of the additive compound 1 with 0.05 mol of toluene diisocyanate, the mixture is maintained at 100-110 ° C for 3 hours with stirring and then cooled (third reaction step). A brown colored wax product is obtained (yield 160.7 g, 99.1% by weight of theory). The composition of the obtained compound corresponds to the formula B11 in the table. one
Example 12,
The initial mixture:
81.3 g (0.10 mol) additive compound in accordance with Example 6J
28.5 g (0.05 mol) of triisocyanate in accordance with Example 5,
5.8 g (0.05 mol) of 1,6-hexanediol.
Thus, the molar ratio of compounds used is 2: 1: 1.
. The conversion is carried out by analogy with Example 7, with the aforementioned 1,6-hexanediol being used together with the polytetrahydrofuran. A brown colored wax product is obtained (yield 114.3 g,
98.8 wt.% From theory). The composition of the obtained compound corresponds to the formula B12 in the table. 1 g
144555510
28.5 g (0.05 mol) of triisocyanate in accordance with Example 5}
3.1 g (0.05 mol) monoethylene glycol
49.3g (0.05 mol) of the compound of the following formula:
  0
PRI me R 13.
The initial mixture:
162.6 g (0.20 mol) additive compound in accordance with Example 6J
57.0g (0.10 mol) of triisocyanate in accordance with Example 5;
9.0 g (0.10 mol) 1,4-butanediol
The molar ratio of compounds used is 2: 1: 1: 1.
The conversion is carried out by analogy with example 12. A wax-like product colored in ocher color is obtained (yield 226.5 g, 99.1% by weight of theory). The composition of the obtained compound corresponds to the formula B13
in tab. one.
Example 14
The initial mixture:
162.6 g (0.20 mol) of additive compound 1 according to example 6;
 57.0 g (0.10 mol) of triisocyanate in accordance with Example 5,
27.1g (0.05 mol) of a fluorinated dihydric alcohol compound
formula os-engon
SNGOSN-sn2SeR17
The molar ratio of compounds used is 4: 2: 1.
Conduction transformation.
The additive compound 1 and the triisocyanate are placed in a glass flask. The mixture is heated to 110 ° C and kept at this temperature for 4 hours with stirring, then 4 drops of tin dibutyl dylurinate are added and the mixture is held at 110 ° C for 3 hours with stirring ( first reaction step, example 10). To the resulting yellow-colored waxy compound perfluoroalkyl ethanol-epichlorohydrin-isocyanate was added a fluorinated dihydric ester compound, solution 1445555
renny in 55 g of di-p-butyl ether
with
adipic acid. The mixture is kept under stirring for 5 hours and then cooled (second reaction step). A brown colored wax product is obtained (300 g weight, 99.5 wt.% Of theory). The composition of the obtained compound corresponds to the formula B14 in Q table, 1.
Symbol B. -СОМН-А5-ГЫНСО- (ОНСНН2) з-ОСН2СН2- (С9Рп-С1бГзЗЯ
CHjCl
Symbol Bj,: - CONH
Symbol B. -CONH
-A9- mNSO- (OCHC) s-OCH2CH - (SzG „-Cb%) 2
(OCHCN2) s-OCH2CH2, - (S8G "-S1bGzz). CH2Cl

SNS
The use of compounds in accordance with the invention.
Examples I-XIV. Compounds B1-B14 are tested in these examples.
In Examples I-VI, compounds B1-B6 were tested using a specially prepared solution, which consisted of approximately 1.2 g of the compound according to the invention and 250 g of acetone (acetone-based cleaning solution). Each of the six acetone-based detergent solutions was treated with the same fabric from polyamide-6 complex yarns so that the fabric had 0.05 wt.% Fluorine (fluoride coating), the weight percentages are related to the fabric weight. To do this, the fabric is immersed in the usual way into the washing solution, the bath is absorbed from 30% to 40% by weight, the fabric impregnated with acetone is first dried in air and then held at 200 ° C for 30 seconds (heat treatment, also called condensation) . After this treatment, six tissues treated with compounds B1-B6 in accordance with the invention were obtained, each tissue was impregnated with fluorine in 0.05 wt.%, The weight percentage was related to the weight of the tissue.
The oil-repellent properties in accordance with the AATCC 118-1966 control standard and its water-repellent properties were tested on six pieces of fabric.
In formulas B5 and B7 - B14, the symbols A - A are used to denote
- (CH2)
.
N- (CH2.) 6- (cH le NHCo
in formulas B10, B14 and B11, S1 tmvoly means:
0
0
5 in accordance with DIN 53888-1965, namely in accordance with the described condensation and with a three-hour treatment of the condensed fabric with an alkaline liquid at the boiling point. In this treatment, the individual tissues are boiled in the usual manner for 3 hours in an alkaline washing liquid and then dried. The washing liquid consists of 1 l of water, 1 g of trisodium phosphate and 2 g of po-
liglycolic ester of the ester ester, which is obtained by oxyethylation of 1,4-butanediol with 15 mol of ethylene oxide, and then esterifying oxyethylate with 1 mol
oleic acid.
I
In Examples VII-XIV, Compound B7-B14 was tested using a conventional spin preparation of polyamide fibers, which per 1000 g of spin preparation contained about 150 g of the compound in accordance with the invention (thus, the spin preparation consisted of water in the main component, pure ethoxylated fatty alcohol spirits and a long chain containing amine oxide as a formulation and about 15% by weight of the compound according to the invention). : Using each of the eight spinning preparations, identical polyamide-6 multifilament yarns were processed so that the multifilament yarn was 5
0
five
carried with only the compound of the preparation composition, so that on the complex threads there was 0.05 wt.% of fluorine and 1 wt.% of the repair composition, the weight percent is related to the weight of the complex; To this end, complex threads
,about
In the usual way, they were drawn through a spinning preparation, dried and kept for 30 s at; 200 ° C (heat treatment, condensation). Of the threads treated in such a way, the fabric was fabricated. Bøsho eight were obtained.
pieces of cloth, impregnated with compounds - 4 g compound of general formula
 about
II
 (CH,) -CH CH O- (CH J. CH-0) -CNH
- „.i
f -CH-0) -CNH
S1TsS1
S02N (CHj) CH ,,
-CH ,, 0 (GI; L
The following describes the tests in accordance with the standard AAC TSS 118-1966 (American Society of Chemists and Artists - Colorists and the textile industry) and DIN 53888-1965 (German industrial standard)
To determine the oil loss of the following parameter, in accordance with the test of LATSS 118-1966, the limestone method was applied to the text to be checked by a known method: three drops of a certain control liquid were carefully spread.
The exposure time is 30 s. In the table. 3 indicates the value, which still does not cause visible wetting of the tissue under the drops (after), and the time of exposure).
The oil repellent rate 1 means the worst oil repellent indicator j 8 - the best tilt, -, nodding effect,
In order to determine the water repellency index in accordance with DIM 53888-1965 in a known manner, the tested textile material is sprayed under standardized conditions, at the same time lower II.
Rp- (CH2) (CH2-CH 0) LrC-N A--N-C- (OR)
CH2Cl
RP perfluoroalkyl group CgF ,, or REE; y = 1.8-3;
mi B7-B14 according to the invention, with each tissue having a fluoride coating of 0.05 wt.% and a preparative coating of 1 wt.%, the weight percentages are related to the tissue weight.
On eight pieces of fabric, oil-resistant and water-repellent properties were tested.
The results of examples I-XIV are presented in table. 2
As a comparison, use
- „.i
CH (II)
CH,; C1
Ron textile sample is trets mechanically. The water repellent effect is evaluated visually from 1 to 5. Estimation t means the worst, rating 5 is the best water repellent effect.
thirty
35
 -
 five
The test results show that i Ch1O with the help of urethanes in accordance with the invention achieves a very high oil repellency effect and in -to-repellency, especially after washing at high temperature, and that the urethanes are in accordance with. A shadow can also be added for treating the textile material of the preparations.
rti about rmu l invention
The method of obtaining a mixture for impregnation of polyamide fibers containing perfluoroalkyl groups, epichloro compounds, rinovye groups and residues of urethane dihydric alcohol, total forch mules I,
n o
II
-N A- -N-C- (OR)
552 Q.
m 1-2; n 1-1,5, and the sum m + p.maxim is equal to 3; A - group
I
-COMH-D- HCO- (OCHCH2VOCH2CH2- (C8Hj7-) 2 (a)
CH2C1
-C01SH t gv-NHCO- (OCHCH2) 3-OCH2CH2 .- (CgFi7-CisF33) (b)
a ™ 2Ct,
C- (.C (0) KN (SI21b with (OTi (CH2) b
characterized in that, in order to improve the oil and water repellency properties, fluorine-containing alcohol of the general formula II
Rp (CH5,) ,, OH,
where RP has the indicated values, is reacted with epichlorohydrin in the presence of a Lewis acid in an organic solvent at boiling point to obtain a compound of general formula III
Rf (CH2l20 (CH2CHO) y-H, CH2C1
where lip, y have the indicated meanings, which is then reacted with a diisocyanate or a triisoxy
Number Chemical formulas of compounds in accordance with the invention according to examples 1-14
B1 (C6Fi3-Ci2F) -CH2CHjO- (CH2CHO) i, 8-C013H-Y V 5HCO- (OCH2CH) 6-OH

AT 2
SSbGp-С u, r25) ,, 0- (1,8-CONH (ОННСНЧ г-ОН
CHjCl CH Cl
OT
CC6Fi3-Ci2F25bCH2CH20- (CH2CHO), 8-CONH- (
CHjCl
A45555
sixteen
ten
ČSN2) BM-1-С (0)
-N- (CH) 6-
- (CH VNH-ccor.
5 R - CK, CH, C-C-Alkapen, CH-CHo; .I,
CH-CH.,
I (.
CH20C2Hi CgHj.y
in - hydrogen, C, -Sf-alkyl.
3
at 100-120 ° C to obtain a compound of general formula IV
% 1СН2 гО (СН2СНО) у-СО№1-А-ШСО) п ICHjCl
where Rp, y, n have the indicated meanings,
which is then reacted with a dihydric alcohol or its monoester of general formula V
H (OROG.OH or H (OR) 2, OB, where R and Z have the indicated values |
B is hydrogen or C, -C4-alkyl, at 100-130 ° C and the compound of formula I thus obtained is isolated or the compound, where B is hydrogen, is treated with the appropriate, isocyanate at 100-110. C followed by isolation of a compound of formula I, where B takes on the values (a) or (b), as indicated above.
Table 1
-NHCO- (OCH2CH 6-OH CHjCl
VA
AT 5
AT 6
AT 7
AT 8
, CH-0-Shso- (Osngsn) -On
G (SbPz-S1g% LCH, CH20-1SNgSHO ,,
LcHjCi
Г (СБГ1з-С1, Г, 5) -СН2СНгОЧШГСНОСНО) and WITH Н1-Ai-rNHC040CH CH) 5 - OH j j
I j
-.CHjCl 2 - (С8Гп-С, b% СНгСН О- (СНгШО) з-СОШ-СНг-Х «) - МНСО- (ОS /, Н8) 8,5-ОН
Г (С8Г17-Сш зз) -СН2СНгО- (СI; СНО) AgrWiCO - {OC tH8) 8.S- OH
sire
(С8П1-С1бГзз) -СН ШгО - (СНгСМО) - Aj-WiCO - (OCHCH2) io-OC tH9
I-SHLGCHCHl
CHCt
SNS
B9
r (C8rn-- Ci6Fj3) -CH.CH20- (CH2CHO) 3-CONH 2 -A% -NHCO- (OCHCHi io (OC2H; i-) o-OCiiH9-CHiCt
AT 10
AT 11
AT 12
IN.
B14
r (C8Fi7 Ct6F3i) -CH2CH20- (CK2CHO) 3-CONHl-As-NHCO- (OCztH8) 8.5-OBi L J TH
. CHaCi
rCCgFn-CieFsshCHjCHiO-lCH CHOls-CONH j-Ae-NHCO-IOC Hii -OBa
G (S8G17-S1bGzz) -SNgShgO- (SI2, SIO) s-SOYn1 A7-INSO-(OSbN12) -OH
SNGSL 8G17 S15Gzz) -SNG20- (ShgSno) s-co NHJ -Ae-NHco-Coc Hg) - it
(S8G17-S1vGzzSNgSN 0- (SNGSNO) s -. SOKn1-A9-1CHSO- (OShSNg) -OVz
.CHaOCjH / tCePit
65
five
, CH-0-Shso- (Osngsn) -On
HCH
Chl
SNS
CHC
Table 2
l 5 5
55
5 5
55
Control fluid
Paraffin oil Paraffin oil; n-hexadecan 65:35
p-Hexadecane
p-tetradecane
p-dodecane
p-dean
p-octane
p-neptan
144555520
Continued tabl, 2
Table3
Indicator of oil repellency
one
2 3
four.
five
6
7
eight

权利要求:
Claims (4)
[1]
Claim
A method of obtaining a mixture for impregnation. · ’15 ki of polyamide fibers containing perfluoroalkyl groups, epichlorohydrin groups and the remains of a two-atomic alcohol of urethanes, general formula I '
H 'but where R _p is the perfluoroalkyl group Cg I and
[2]
2s or CgFjp- -
C 46 ^ 33 i
Y = 1,
[3]
3-3;
z is 1-10;
in = 1-2; η - 1-1.5, and the sum m + and the maximum is 3; ‘
A - group
fifteen
16
[4]
4CH ₂ ) ₆ -NH-C (O1
CSN _{2) 6} - H-C ^ (^ oy ^{(CIS) b} 5 R - CH ₂ SR, C ₄ -C ₆ alkylene, CH-CH SYo _g c1 I CH-CH, ^CH 3 _{sNgOSg'gTsSaNp}
B is hydrogen, C ^ Cd alkyl,
-CONH-D- ^ IHCO- (OCHCH ₂ ) ₃ -OCH ₂ CH ₂ - (C ₈ H ₁₇ - s ₁₆ f ₃₃ )] ₂ (01)
CH ₂ C1
-CONH-fgy-NHCO- (O <pHCH ₂ ) ₃ -0CH ₂ CH ₂ - (C ₈ F _{ 7-C _l6 F ₃₃ ) (b).
С% ^СН ^ ^С1 ...., d- (ch ₂ ) ₆ -n / С (О) КН (СН ₂ ) _b ^ сУЖнСсНг, characterized in that, 25 in order to improve the oil and water repellent properties of a fluorine-containing alcohol of the general formula II r _f (ch ₂ he, where Rp has the indicated meanings, is reacted with epichlorohydrin in the presence of a Lewis acid in an organic solvent at boiling point to obtain a compound of general formula ΙΈΙ,
R _F (CH ₂ ) ₂ O (CH ₂ CHO) yH
CH ₂ C1 where Il, y have the indicated meanings, which are then reacted with a diisocyanate or triisocyanate at 100-120 ° C. to give a compound of the general formula IV [R _f (CH ₂ ) ₂ O (CH ₂ CHO) ₃ —CONH] -A- (NCO) _n · ί CH ₂ C1 where D _p, y, η have the abovementioned meaning, 'which is then reacted with a dihydric alcohol or a monoester of the general formula V
H (OR) _Z OH or H (OR) _Z OB, where R and z have the indicated meanings;
B is hydrogen or C, -C ₄ -alkyl, at 100-130 ⁱⁿ C and the resulting compound of formula I is isolated, or the compound where B is hydrogen is treated with an appropriate one. ' isocyanate at 100-110 ° C, followed by isolation of the compounds of formula I, where B takes the values of (a) or (b), as described above.
blitz 1 '
room
The chemical formulas of the compounds in accordance with the invention according to examples 1-14
B1 (C ₆ G ₁₃ -C _and E _g5 ') - CH _g CH _g O- (CH ₂ CHO) ₁₁₈ -SOIN-g ^ MHCO- (OCH ₂ CH) b-OH
CH ₂ Cl R CH ₂ C1
SNZ
B2 (C ₆ F _n -C ₁₂ F ₂₅ ) -CH ₂ CH ₂ 0- (CH ₂ CHO) _li8 -CONH '"r"! YNHCO- (OCH2CH ') _2- OH, CH ₂ C1 CH _g C1
B3 (C ₆ F ₁₃ -C ₁₂ F ₂₅ ) -CH ₂ CH ₂ 0- (CH ₂ CHO) | _{B -CONH- (i ^ CH, -} / 3-NHCO- (OCH2CH) 6-OH cN _g and _g with 6N,
1 7
Number | ; AT 4
AT 5
AT 6
AT 7
B8
AT 9
AT 10
AT 11 ·
AT 12
B13.
B14
Continuation of table 1 |
The chemical formulas of the compounds in accordance with the invention according to examples 1-14 [(ss ^ - ^ cng ^
Rc ₆ f ₁₃ - c ₁₂ f ₂₅₎ -ch ₂ ch ₂ o clearly 4CH _{2) 11a} "somn1 - Αι - | mnsoChosn CH _{2) 6} - He] ^L. ₂ s ^5. .ci (CsFn-CBTajl-aijCHjO-fcHjCHojj-coNH- ^ j-CHj- ^ HyNHco-toc ^ Heje.j-OH
CH ₂ Cl 1 r (C ₈ Ft7-C ₁₅ F ₃ 3 ') - CH ₂ CH ₂ 0- (CH ₂ CH0) 3 “-CONHl -A ^ -SHFWOF ^ Not ^ d- he ¹ CHC1 - ² a
Г (С _in Гп- ^с 1бГ ₃ ЗСН ₂ СН _g О- (СН _г СНО) j-somn] - Az-MHCO - (OCHSN ₂ ) 1 ₀ -ОС ₄ Н9 ^L. С№1 ² Sn 3
Г (С ₈ Гп-С ₁₆ Гзз) -СН. ₂ CH ₂ O- (CH ₂ CHO) _3- СОМн] -a vNHCO- (OCHCH ₂ ) ₁₀ (ОС ₂ Н $) ₁₀ - ОС ^ Нд ¹ СН ₂ С1 sn ₃ pc ₈ F _l7 - _{с 16} f ₃₃ ) - sn ₂ sn ₂ o- (sn ₂ chs) ₃ - conh] ^ As-N-HCO- (ОС ₄ Н ₈ ) _8i5 - 0 Bi • .. СН _g С1 [(C ₈ F _l7 -C _i6 F ₃ 3) -CH ₂ CH ₂ O- (CH ₂ CHO) 3-CONH] -A6-NHCO- (0C ₂ H ^ -OB ₂
CH ₂ Ct ^ C ₈ G ₁₇ -C ₁₆ G ₃₃ ) -CH _g CH ₂ O- (CH _g CHO) s-SOKn1 - A7-MHCO- (OSbN ( ₂ ) -OH
CH ₂ Ct ^J2 | ^ 8Г17 “С ₁₅ Гзз) ~ СН _g СН _g О- (СН ₂ СНО) s-СОЫН'1-А ₈ -KHCO- (OS4Н ₉ ) -ОН
CH ₂ C1 ^Jz [(e ₀ F c _tB F ₃ j) - CH _g CH ₂ 0- (eH _g CH0) _3- CONH ^ - Ag-NHCO- (0CHCH ₂ ) - OB ₃ ^CH 2 ^C1 0Η ₂ 0Ο ₂ Ηί £ ₈ Γ ₁₇
---------------------_____----- (--- _: - _- --------: ----—
CH ₂ C1
Table 2
Example and verified connections Oil repellent Repulsive properties condensation ate boiling rinses after condensation after washing with boiling I / B1 6 ^{: #}5 5 5 II / B2 5 5 ' 5 5 III / B3 5 5 5 5
19
Continuation of the table, 2
“· ........Example and verified connections Oil repellentproperties Water Based Properties after condensation after washing with. boiling after condensation after rinsing while boiling IV / B4 6 5 5 4 V / b5 5 4 5 5 VI / B6 6 5 5 4 VII / B7 6 4 5 5 VIII / B8 5 4 4 4 IX / B9 5 4 4 4 X / B10 5 4 ' 5 4 ΧΪ / Β11 6 5 4 4 XII / B12 5' 4 4 4 XIII / B13 5. 4 4 4 XIV / B14 6 4 4 4 Compound 11 5 1 4 1
Table 3
Control fluid Oil repellent Paraffin oil 1 Paraffin oil: p-hexadecane 65:35 2 p-hexadecane 3 p-Tetradekan 4. p-dodecan 5 p-dean 6 ’ p-octane 7 p-neptan 8
ВНИИПИ Order 6517/59 Circulation 370 Subscribed
Custom polygr. ave, city of Uzhhorod, st. Project, 4

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同族专利:

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EP0222334A3|1988-08-03|

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JPS62120352A|1987-06-01|

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DE3540147A1|1987-05-14|

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AU589232B2|1989-10-05|

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DE3681250D1|1991-10-10|

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KR870004945A|1987-06-02|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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DE19853540147|DE3540147A1|1985-11-13|1985-11-13|PERFLUORALKYL GROUPS, EPICHLORHYDRINE GROUPS AND UALETHANE CONTAINING DIALCOHOL RESIDUES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE|

---