SU1130574A2 - Liquid curing agent for fluoropolymer having isocyanate end radicals - Google Patents

Abstract

LIQUID HARDENER FOR A PREPOLYMER WITH ENDS OF ISOCIANATIC GROUPS on the autor. No. 806715, differing from the fact that, in order to increase its resistance to delamination while maintaining the reduced flammability of the final product, it additionally contains phosphorobromo-chloro-containing compound of the formula / / CH2I1 h ciCHg-CHBr-eHg-pos) o H2VG in the following ratio of components, May .ch .: A mixture of 3,3-dichloro-4,4-diaminodiphenylmethane and 3,3-dichloro-4,4 -diami: notriphenylmethane at a molar ratio of 1: 1100 Phosphorus i-polyol 67-230 kn Phosphorobromo-chloro-containing compound. 76-825.

Description

00 about pr | The invention relates to liquid hardeners used in the preparation of polyurethane coatings to protect metal products, fiberglass, etc. from various types of erosion wear, as well as for sealing products, making gaskets, molded products, etc., and can be applied in various areas of industry. A liquid hardener is known for the prepolymer with terminal isocyanate groups, comprising a mixture of 3.3 dichloro-4,4-diaminodiphenylmethane and 3,3-dichloro-4, 4-diaminotriphenylmethane at a molar ratio of 1: 1 and non-volatile solvent (polyoxypropylene glycol and others with the following ratio of components, wt.h .: Diamine mixture 100 Non-volatile solvent 33-67 1 Such a liquid curing agent is resistant to storage for at least 6 months, but it has too high reactivity, which makes coatings difficult , sealants and moldings of the compositions containing this hardener, due to their insufficient viability, which is no more than 30 minutes. According to the main author. Grade 806715 discloses a liquid hardener dp prepolymer with terminal isocyanate groups, which comprises a mixture of 3,3-dichloro4, 4-diaminodiphenylmethane and 3,3-dichloro-4, 4-diaminotriphenylmethane at a molar ratio of 1: L and a phosphorus containing polyol of the general formula HO -ROPOHOP-OR-OH II II OO where B is CH 2, —OH 2 —CH 5 R —CHg — CHf, —CHO — CH CH 2 OH R —H 3 C — C 2 CH 2 -, CH 2 OH (bH 2) 2 with the following ratio of components, wt. b .: Mixture of diamines 100 Phosphorous polyol 67-230. The use of the known liquid hardener for curing the prepolymer with terminal isocyanate groups provides an increase in the viability of the composition and a reduction in the flammability of the final product r2J. However, the stability of the known liquid hardener at room temperature (18-22 ° C) does not exceed 6 months, which is not enough under production conditions. After the specified storage period hardener. It does not provide coatings and sealants with the required physicomechanical properties and fire resistance. The purpose of the invention is to increase the stability of the liquid hardener to delamination while maintaining the reduced flammability of the final product. This goal is achieved by the fact that the liquid hardener for the prepolymer with terminal isocyanate groups additionally contains a phosphorus-containing compound of the formula. . CHoCl С1СН2- СНВР-СН2-Р () 2 with the following ratio of components, May. including: A mixture of 3,3-dioxl-4,4 diaminodiphenylmethyl and 3,3-dichloro-4,4-diaminotriphenylmethane in a molar ratio of 1: 1100 Phosphorus-containing polyol 67-230 Phosphorobromochloro-containing compound 76-825. Previously, such phosphorobromochloro-containing compounds under the trade arches of Bromphos-1 and Bromphos-2 were used as flame retardants. The use of the proposed liquid hardener provides for the possibility of introducing targeted additives of catalysts, fillers, etc. A liquid hardener can be obtained in advance. The mixture of diamines is melted at 90 ° C for one hour, mixed with phosphorus-containing polyol, phosphorobromochlorine-containing compound and heated at 903

100 ° C to dissolve the mixture of diamines in non-volatile solvents. The stability of the proposed liquid hardener for at least 1 year. The proposed liquid hardener can be used to cure prepolymers prepared in advance, for example, products, reacting toluene diisocyanate with hydroxyl-containing polyesters and polydiene diols. It is also acceptable for curing prepolymers obtained immediately before mixing them with a hardener, for example, the products of interaction of industrial polyisocyanates of the brands Surizon ML

sn-on-o-r-o-ssh-s-sno-0-p-o-sno-sn-one

  Ii.

oSnOon o

76 mach. phosphorobromochlorine

compounds, 100 ma.h. mixtures of 3,3 dichloro-AaA-diaminodiphenylmethane and 3, 3-dichloro-4,4-diaminotriphenylmethane in a molar ratio of 1: 1 (diamine-304),

For curing 100 mash. the prepolymer is a product of the interaction of polytetrahydrofuranI1lla etoluylsiidiisodianatom its mixes e 32 mah.h specified liquid hardener.

The resulting composition is nano-t on non-fat etal pletinki and washed down in a form at one time. The coating and the product are confirmed at 1822 ° C for 24 hours. Oenoids' physical and mechanical properties and combustibility of films according to the electrophore indenter method are determined after 14 days after their application according to GOST 209-75 and GOST 21793-76, respectively. The viability of the composition is evaluated according to GOST 13489-79. .

SNS

HO-CH2-CH2-0-P-0- (CH2) 20

300 ma.ch. fooforbromochlorine-containing compound and 100 wt.h. diamine-304. 100 ma.ch. the prepolymer, the product of the interaction of a hydrokeyl-containing isoprene and divinyl e copolymer with toluene diisocyanate, is cured 21 wt.h. this hardener is the same as in example 1. The position is applied ,;

744

(polyisocyanate-T. surizon P85, surizon M60, etc., with polyesters and polydiene diols.

In use, the curing agent with the prepolymer is mixed at room temperature, and the cured composition is cured both at room temperature and when heated.

An example. The liquid hardener, made I a year ago, contains 67 mach. phosphorus-containing polyol (the product of phosphorylation of pentaerythritol, subjected to hydroxypropylation) of the following structure;

SNGON SN.

HE.

Example 2. A liquid hardener, made 1 year ago, contains 230 mach. foreparent polyol used in Example 1, 825 wt.h. fooforbromochloro-containing compound SHO mac.h. diamina-304.

100 ma.ch. a prepolymer — a product of interaction of a liquid polybutadiene diol with toluene diisocyanate — cures 42 mas. of this hardener in the same way as in Example 1. The composition is applied, cured and tested as in Example 1.

Example 3. A liquid hardener, manufactured 1 year ago, contains 100 mach. the foreforce-containing polyol (the product of diethyleneglycol fooforilation, subjected to oxyethylation) of the following structure:

Нз СН2) 2-0-Р-0-СН2СН "ОН

II

about

cured and tested in the same way as in example 1.

Example 4. Liquid hardener, made 1 year ago, contains 67 Mad.ch. phosphorus-containing polyol used in the device, 1.76 wt.h. phosphorobromochlorine 51 containing compounds 100 mas. diamine-304 .; 100 ma.ch. the prepolymer is the product of the interaction of the liquid polybutadiene diisole with surizone II85 (polyisocyanate-T) - a mixture of isomers of diphenylmethane diisocyanate and polyphenylme; tanpolyisocyanates, which are confirmed by 25 wt. This hardener is the same as; as in Example 1. The composition is applied and tested in the same manner as in Example 1. Example 5 (KOHtponbHbm j “Liquid from the converter, prepared from 6 months ago. Contains 67 wt. Parts of a forcing-containing polyol used in example i and 100 parts of diamine 304. i 100 parts by weight of a prepolymer used in example 1, it is cured. 22 parts by weight of the specified liquid will cure L. Composition is applied, cured and tested as in example I. Example 6 (control. Liquid hardener, made 1 year ago, contains 67 parts. the phosphorus-containing polyol used in Example 1 and 100 parts by weight of diamine-304, 100 parts by weight of the prepolymer used in Example 1, 22 confirms mae.ch. said liquid curing agent. The composition is applied, cured and tested the same way as in Example 1. The test results of Examples 1-6 are shown in Table.

Strength at break, kgf / cm 37

Relative lengthening,%

Residual elongation

% 20 Oxygen index Gk),% 28.5 Viability of the composition using the proposed hardener, min310 Limestone liquid hardener after 6 months. after manufacturing, it provides films with a significantly lower oxygen index than the proposed one, but a sufficiently high oxygen index (example 5 y, but when using it a year after the production, the oxygen index of the films was only 19%, i.e. they became flammable their physical and mechanical properties and viability of the composition are significantly

43

100

69 85

880

460 308

506

25

13

13 30.5 31 28.5 295 309 deteriorate due to the insufficient stability of the hardener (Example 6J. Thus, as follows from the examples, only with the additional introduction of C. the known liquid hardener of the phosphorobromochlorine-containing compound as a non-volatile solvent while maintaining reduced flammability of the final product and increased viability of the composition to increase the hardener stability by 2 times (the period of possible storage: increases from 6 months. 7 to 1 year.) When using the proposed liquid hardener, even after a year. after fabrication, films with high physicostimulantry are obtained.

Claims (2)

LIQUID CURING AGENT FOR FORM POLYMER WITH END ISOCIANATIC GROUPS according to ed. No. 806715, characterized in that, in order to increase its resistance to delamination while maintaining reduced flammability of the final product, it C1CH ₂ -CHBg-CH _? -P ^{4 Z} II additionally contains a phosphorus bromochloride compound of the formula / H ₂ C1 CH ₂ BF in the following ratio of components. product, parts by weight: A mixture of 3,3-dichloro-4,4-diaminodiphenylmethane and 3.3 ¹ -dichloro-4,4'-diaminotriphenylmethane at a molar ratio of 1: 1 100 Phosphorus-containing polyol 567-230 Phosphorus bromochloride-containing compound 76-825. ^ SU., „1130574 1 1130574 7