Liquid hardener of prepolymers with terminal isocyanate groups

 

(57) Abstract:

The invention relates to liquid hardeners of prepolymers used to obtain molded products of polyurethane elastomers, polyurethane coatings and others, the Invention is directed to receive liquid hardener of prepolymers with good aggregate stability at temperatures below 90oWith and providing a high level of properties obtained on the basis of polyurethane elastomers. Liquid hardener for prepolymers with terminal isocyanate groups include 3,3'-dichloro-4,4'-diaminodiphenylmethane and the non-volatile solvent. As a non-volatile solvent curing agent contains polyols mol.m. 2100-5000 in the following ratio of components, wt. h: 3,3'-dichloro-4,4'-diaminodiphenylmethane. -20 - 50, non-volatile solvent 80 - 50. 1 Il., table 1.

The invention relates to liquid hardeners of prepolymers with terminal isocyanate groups, ispolzuemyi to obtain molded products of polyurethane elastomers, polyurethane coatings, etc.

Used as a hardener of prepolymers with terminal isocyanate groups of the aromatic diamine 3,3'-dichloro-4-4'-diaminodiphenylmethane (bargaining which is a crystalline substance with a high melting temperature (about 105oC), which creates difficulties in processing (large energy consumption for heating equipment, high toxicity vapor Diamete X at temperatures above 100oC, the danger of formation of tubes from napravlennogo of Diamete X in the circulation channels, equipment and other) (Wright P., Cumming A. Polyurethane elastomers. Leningrad. Chemistry, 1973).

It is important to develop methods of modification of Diamete X to translate it in a liquid state of aggregation in the field of low temperatures (20-90oC) without significantly affecting the properties of polyurethane elastomers.

A known solution to this problem is to use as a liquid hardener solution of a mixture of aromatic diamines, 3,3'-dichloro-4-4'-diaminodiphenylmethane and 3,3'-dichloro-4-4'-diaminodiphenylmethane at a molar ratio of 1:1, in the amount of 60-75 wt.h. in the non-volatile solvent (polyol or oligoadenylate mol.m. 90-2000) in an amount of 40-95 wt.h. (and.with. USSR N 615095 class. C 08 G 18/32, 1978). Such a composition liquid hardener provides a good aggregate stability of a solution of the diamine in the non-volatile solvent at a temperature below 90oC, including the high concentration of the diamine.

However, use is also creates an irregular structure moonwing hard blocks obtained polyurethane elastomers, which leads to the reduction of their properties (hardness, strength and other).

Another way to solve this problem, the closest offer, is used as a liquid hardener solution Diamete X in the non-volatile solvent-polyoxyethyleneglycol mol.m. 500-1000, in the following ratio, wt.h.

Diameter X OF 2.6 - 50

The non-volatile solvent of 97.4 - 50

(U.S. patent N 3718624, class C 08 G 22/14, 1973).

The disadvantages of this liquid hardener should be attributed to the instability of the aggregative state of the system Diameter X polyoxyethyleneglycol at temperatures below 90oC and the content of Diamete X more than 30 wt.h., and, consequently, the impossibility of obtaining liquid hardener with a high concentration of Diamete X that is necessary to ensure the properties of polyurethane elastomers, approaching the properties of elastomers on the basis of the net Diamete X.

The aim of the invention is to provide a liquid hardener of prepolymers with terminal isocyanate groups, representing a solution of Diamete X in the non-volatile solvent with good aggregate stability at temperatures below 90oC and providing a high level sinovich elastomers based prepolymers with terminal isocyanate groups and mixed hardeners, representing a solution of Diamete X in the hydroxyl-containing compound different chemical structure depending on the composition of the hardener. In this surprisingly it was found that the dependency of the properties of elastomers on the composition of the mixed curing agent may be selected critical concentration of hydroxyl-containing compounds where mYESand mGSS- the content of Diamete X and hydroxyl-containing compounds in the mixed curing agent, by weight.h. The drawing shows the dependence of hardness of polyurethane elastomers based prepolymer (the product of the interaction of polyoxyethyleneglycol mol. m 1000 and TDI) and the mixed curing agent that includes a Diameter X and a hydroxyl-containing compound, the composition of the hardener. View hydroxyl-containing compounds: curve 1-1,4 butanediol (CCRGSwith= 0,09), curve 2-polyoxyethyleneglycol mol.m. 1000 (CRGSwith= 0,38) , curve 3-polyoxyethyleneglycol mol.m. 2000 (CCRGSwith= 0,53). From the data obtained it follows that in the region CGSS< CCRGSwithproperties of polyurethane elastomers as growth CGSSlittle change and approach the properties of elastomers on the basis of h is based properties of polyurethane elastomers. The value of CCRGSwithdepends on the molecular weight hydroxyl-containing compounds and increases with increasing. From this it follows that with increasing molecular weight hydroxyl-containing compounds its content in the mixed curing agent can be increased without significant damage to properties of the polyurethane elastomers.

Thus, the goal can be achieved through use as non-volatile solvent in the composition of the liquid hardener polyols in mol.m. 2100-5000 in the following ratio of components, wt.h.

3,3'-dichloro-4,4'-diaminodiphenylmethane - 20-50

The non-volatile solvent - 80-50.

According to the invention uses the following raw materials:

The aromatic diamine is 3,3'-dichloro-4,4'-diaminodiphenylmethane (Diameter X h)

THE 6-14-980-84

The non-volatile solvent:

- polyoxyethyleneglycol mol.m. 1000 (polyphonic) THE 6-02-646-81

- polyethylenbutylenglycoladiapinate mol.m. 2100 (complex polyester P5 14) - THE 2226-206-21081385-96

- polyethyleneglycoladipinate mol. m 2200 (complex polyester P6) THE 38.103582-85

- polydiethyleneglycoladipinate mol. m 3200 (complex polyester B) THE 6-05-221-687-86

- polyoxypropyleneglycol mol.m. 1000 (supraoccipital mol.m. 3500 (Laprol 3502-2B-20)

THE 2226-318-10488057-94

Polyoxypropylenediamine mol.m. 5000 (Laprol 5003-2B-10)

THE 2226-0008-10488-057-94

- mixture of isomers 2,4 and 2,6-diisocyanate (product KZT80) THE 113-03-12-17-85.

As prepolymers end of oceantype groups can be used prepolymer-based polyols and diisocyanate.

Liquid hardener can be obtained by mixing Diamete X with non-volatile solvent at a temperature of 90oC until completely dissolved with stirring. Subsequently the solution is cooled to a predetermined temperature (20-90oC).

The mixture of liquid hardener with prepolymers when molding the polyurethane elastomer can be performed at a temperature of from 20 to 90oC.

The invention is illustrated by the following examples:

Example 1.

Liquid hardener contains 20 wt.h. Diamete's and 80 wt.h. polyethylenbutylenglycoladiapinate mol.h. 2100.

100 wt.h. Prepolymer with terminal isocyanate groups, which is the product of interaction of polyethyleneglycoladipinate mol.m. 2200 with a mixture of isomers 2,4 and 2,6 TDI, mixed with 36,23 wt.h. the specified liquid hardener (NCO : NHoC, then define its properties (table).

Example 2.

Liquid hardener containing 30 wt.h. Diamete's and 70 wt.h. polyethylenbutylenglycoladiapinate mol.h. 2100.

100 wt. hours of prepolymer with terminal isocyanate groups used in example 1, utverjdayut 24,47 wt.h., the specified liquid hardener and get a sample of the elastomer of example 1. The properties of the elastomer are shown in table.

Example 3.

Liquid hardener contains 40 wt.h. Diamete X and 50 wt.h. polydiethylene adipate mol.m. 3500.

100 wt. hours of prepolymer with terminal isocyanate groups used in example 1, utverjdayut 24,38 wt.h. the specified liquid hardener and get a sample of the elastomer by the procedure analogous to example 1. The properties of the elastomer are shown in table.

Example 4.

Liquid hardener contains 40 wt.h. Diamete's and 60 wt.h. Polyoxypropylenediamine mol.m. 5000.

100 wt.h. prepolymer with terminal isocyanate groups, which is the product of interaction polyethylenebutyleneglycoladipinate mol.m. 2000 is ocedure, similar to example 1. The properties of the elastomer are shown in table.

Example 5.

Liquid hardener contains 50 wt.h. Diamete X and 50 wt.h. polydiethylene adipate mol.m. 3500.

100 wt. hours of prepolymer with terminal isocyanate groups used in example 4 is mixed with 26,11 wt.h. specified hardener and get samples of the elastomer by the procedure analogous to example 21. The properties of the elastomer are shown in table.

Example 6.

Liquid hardener contains 50 wt.h. Diamete X and 50 wt.h. polyethylenbutylenglycoladiapinate mol.m. 2100.

100 wt.h. prepolymer with terminal isocyanate groups, which is the product of interaction of polyoxyethyleneglycol mol.m. 1000, mixed with a 21.6 wt. including the specified curing agent and get samples of the elastomer by the procedure analogous to example 1. The properties of the elastomer are shown in table.

Example 7.

Liquid hardener contains 40 wt.h. Diamete's and 60 wt.h. Polyoxypropylenediamine mol.m. 3500.

100 wt. hours of prepolymer with terminal isocyanate groups used in example 6 are mixed with 35,77 wt.h. specified hardener and get samples of elastomer according to claim what cue hardener contains 50 wt.h. Diamete X and 50 wt.h. polyethylenbutylenglycoladiapinate mol.m. 2100.

100 wt.h. prepolymer with terminal isocyanate groups, which is the product of interaction of polyoxypropyleneglycol mol.m. 1000, mixed with 28,74 wt.h. specified hardener and get samples of the elastomer by the procedure analogous to example 1. The properties of the elastomer are shown in table.

Example 9.

Liquid hardener contains to 44.5 wt.h. Diamete X and of 55.5 wt.h. polyoxyethyleneglycol mol.m. 1000.

100 wt. hours of prepolymer with terminal isocyanate groups used in example 6 are mixed with 20,76 wt.h. specified hardener and get samples of the elastomer by the procedure analogous to example 1. The properties of the elastomer are shown in table.

Liquid hardener of prepolymers with terminal isocyanate groups, including 3,3'-dichloro-4,4'-diaminodiphenylmethane and polyol as a non-volatile solvent, characterized in that as a non-volatile solvent it contains polyols mol.m.2100 - 5000 in the following ratio, wt.h:

3,3'-Dichloro-4,4'-diaminodiphenylmethane - 20 - 50

The non-volatile solvent - 80 - 50

 

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FIELD: new associative amphiphilic cationic polymers.

SUBSTANCE: polymers of formula I dissolvable or dispersible in water, as well as method for production and application thereof are disclosed. Claimed polymers are useful as thickening agents in cosmetic and therapeutic compositions. Composition containing polymers of present invention also are disclosed.

EFFECT: polymers of improved thickening ability and cosmetic quality.

13 cl, 4 ex

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