The method of stabilization of organic phosphite and/or phosphonite from the effects of hydrolysis and stable composition

 

(57) Abstract:

The invention relates to a method of stabilizing organic phosphite and/or phosphonite from exposure to hydrolysis by adding them sterically constrained amine containing group of the formula (II) or (III) where G is hydrogen, methyl; G1and G2is hydrogen, methyl or both together represent = 0, in an amount to provide content in stable organic phosphite and/or phosphonite of 0.1 to 25.0 wt.% the amine in the calculation of the organic postit and/or phosphonic. The proposed stabilized composition containing organic postit or phosphonic and sterically hindered amine with the following content, wt.%: postit or phosphonic 80 to 99.9, sterically hindered amine is 0.1 - 20. Thanks additives sterically obstructed amines increases the hydrolytic stability of organic phosphites and phosphonites. 2 c. and 7 C.p. f-crystals, 2 PL.

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m

Called steric employed amines are known compounds; in addition, many of them available on the commercial market.

In the method according to the invention particularly preferred stabilizing phosphites or phosphonites, the formula of which is relevant to the means 2, 3 or 4; p denotes 1 or 2; q represents 2 or 3; r - 4 or 12; I denotes 1, 2 or 3; and z represents a number from 1 to 6;

A', if n'=2, denotes alkylene with the number of carbon atoms from 2 to 18;

broken-S-, -O - or-NR'4-alkylene with 2-12 carbon atoms; a group of the formula

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or phenylene;

A', if n'=3, denotes a group of formula CrH2r-1;

A', if n'=4, denotes a group of the formula-C(CH2)4;

A is A', if n'=2;

B' represents a group of formula-CH2-; -CHR'4-; -CR'1R'4-; -S-or a direct bond; or C5-C7-cycloalkylation or cyclohexylidene substituted from 1 to 4 groups C1-C4-alkyl at position 3, 4 and/or 5;

D', if p=1, denotes methyl and, if p=2, denotes-CH2OCH2-;

E', if y=1, is an alkyl with a number of carbon atoms from 1 to 18, a group of the formula-OR'1or halogen;

E', if y=2, represents a group of formula-O-A-O-;

E', if y=3, is a group of the formula R'4C(CH2O)3;

Q' represents a group of at least z-valent alcohol or phenol, and this group is associated with a P-atom (atoms) through the O-atom (atoms) alcohol (spirits) or phenol (phenol);

R'1, R'2and R'4, -CN, or - CONR'4R'4alkyl with the number of carbon atoms from 1 to 18; broken-S-, -O - or-NR'4-alkyl with a number of carbon atoms from 2 to 18; phenyl-C1-C4-alkyl; cycloalkyl with the number of carbon atoms from 5 to 12; phenyl or naphthyl;

substituted with halogen, 1-3 alkyl or alkoxygroup with the total number of carbon atoms from 1 to 18 or phenyl-C1-C4the alkyl phenyl or naphthyl; or a group of the formula

< / BR>
where

m denotes an integer from 3 to 6;

R'4or group R'4independently of one another denote hydrogen; alkyl with the number of carbon atoms from 1 to 18; cycloalkyl with the number of carbon atoms from 5 to 12; or phenylalkyl with 1-4 carbon atoms in the alkyl chain;

R'5and R'5independently of one another denote hydrogen; alkyl with the number of carbon atoms from 1 to 8 or cycloalkyl with 5 or 6 carbon atoms;

R'7and R'8if q=2, independently of one another denote C1-C4-alkyl or together are a group of 2,3-degidro-pentamethylene; and

R'7and R'8if q=3, denote methyl;

the substituents R'14independently of one another represent hydrogen, alkyl with the number of carbon atoms from 1 to 9, or cyclohexyl;

semestered or C1-C4-alkyl, and provided that there are several groups R'16group R'16have the same or different values;

X' and Y' each represent a direct bond or-O-; and Z' represents a direct link; -CH2-; -C(R'16)2- or-S-.

Particularly preferred manner in which postit or phosphonic has the formula(1), (2), (5) or (6), where

n' denotes the number 2, and y denotes 1 or 2;

A' represents alkylene with the number of carbon atoms from 2 to 18; p-phenylene or p-biphenylene;

E', if y=1 represents C1-C18-alkyl, -OR1or fluorine; and if y=2, then p-biphenylene;

R'1, R'2and R'3independently of one another denote alkyl with the number of carbon atoms from 1 to 18; phenyl-C1-C4-alkyl; cyclohexyl; phenyl; substituted by 1-3 alkyl groups with a total number of carbon atoms from 1 to 18 and phenyl;

the substituents R'14independently of one another denote hydrogen or alkyl with the number of carbon atoms from 1 to 9;

R'15represents hydrogen or methyl;

X' represents a direct link;

Y' represents-O-; and

Z' represents a direct bond or-CH(R'16)-.

Of particular technical interest is the way stabiliy a p-biphenylene;

E' represents C1-C18-alkoxy, or fluorine;

R'1, R'2and R'3independently of one another denote alkyl with the number of carbon atoms from 1 to 18; substituted 2 or 3 alkyl groups with a total number of carbon atoms from 2 to 12 phenyl;

the substituents R'14independently of one another represent methyl or tert.-butyl;

R'15represents hydrogen;

X denotes a direct bond;

Y' represents-O-; and

Z' represents a direct bond, -CH2- or-CH(CH3)-.

Particularly preferred phosphites, in particular, formulas (1) and (5).

Listed at the end of the description (Ph-1 - Ph-10) compounds can serve as examples of the phosphites and phosphonites, stability from the effects of hydrolysis which can be improved significantly thanks to the method according to the invention.

Mentioned phosphites and phosphonites are already known compounds; partly they are available for sale.

Some of the commercially available compounds are represented as mixtures or in a pre-stabilized form; as a means of pre-stabilization is often used traditional Amin about 1% concentration. Resistance similar productdata, obtained using the method according to the invention, can with great advantage be used as stabilizers of organic materials, in particular organic polymers, for example, synthetic polymers against the harmful effects of heat, oxygen and/or light. Examples of such polymers are described in U.S. patent 4855345, beginning with column 4, line 63 to column 7, line 54.

The above objective is also achieved stable composition containing organic postit or phosphonic and Amin, which according to the invention as an amine contains a sterically hindered amine with the following content, wt.%:

postit or phosphonic - 80-99,9

sterically hindered amine is 0.1-20

(in each case relative to the weight of the composition).

In the compositions according to the invention sterically hindered amine is primarily contained in an amount of from 0.1 to 13 wt.%; the preferred composition, in which the sterically hindered amine is contained in an amount of from 0.1 to 7.4; especially from 0.1 to 4.8; primarily in the amount of from 0.2 to 2.4 wt. % (in each case relative to the weight of the composition).

Preferably the composition in addition to organic phosphite and/or is in on the basis of organic polymers with a molecular weight of more than 5000.

Especially preferred compositions, in addition to components (a) and (b) does not contain compounds, the molecular weight of which exceeds 2000.

Component (a) at a temperature of 20oC preferably is a solid.

Stabilized according to the invention phosphites and/or phosphonites are characterized by excellent resistance to hydrolysis and have a high storage stability in high humidity conditions.

Steric employed amines, especially sterically difficult amines with a molecular weight or average molecular weight in the range from 1500 to 10000, used as stabilizers of organic phosphites and/or phosphonites from the effects of hydrolysis, in particular, from hydrolysis when stored in contact with moist air. Preferably used as hydrolysis stabilizers of organic phosphites. To achieve the desired improved hydrolytic stability it is possible to use any number of amine, for example, from 0.01 to 200 wt.%, especially from 0.1 to 100 wt.%, first of all, from 0.2 to 25 wt.% in relation to the number of phosphite or phosphonite.

For storage of solid organic phosphites or phosphonites in the last in the flax from 0.1 to 8 wt.%, especially from 0.1 to 5 wt.%, most preferably 0.2 to 2.5 wt.% (in relation to phosphite or phosphonite).

The following examples illustrate the method according to the invention. All data in fractions and percentages given in the examples with respect to the total mass used phosphites or phosphonites, unless otherwise noted. Structural formulas used in the examples of phosphites and amines listed above, and at the end of the description.

Example 1. 300 g of phosphite Ph-1 are dissolved in 300 g of isopropanol at 50oC. Under stirring solution was added 15 g of amine P; then the solution is cooled to 10-15oC, and postit crystallizes together with the amine. After that, the crystalline product is filtered and dried under low pressure at 60oC.

Elemental analysis reveals the content in the dry product (1.6 wt.% Amin P (with respect to phosphite) or of 0.98 wt.% in the calculation of the total mass of the composition.

Is used for the comparison sample, crystallized without additives amine.

In another comparative test, 300 g Ph-1 process known used for hydrolytic stability triisopropanolamine and crystallized as described above.

Then an equal share of the product Poti air time is fixed, when you start the visual flow of the original powder (transition p-k), and is measured period of time, after which the material becomes fluid and forms a transparent solution (transition k-f).

b) after storage for 8 h at 70oC and air humidity of 100% using liquid chromatography to determine the content of phosphite Ph-1; in table. 1 shows the percentage of decomposed (hydrolyzed) phosphite.

The results are shown in table. 1. All percentages are relative to the mass of phosphite available at the beginning of the test.

Examples 2-9. Compound Ph-1 stabilized as described in example 1 way amines C, E, H, J, K, P, Q and U. the resulting product are tested for resistance to hydrolysis as described in example 1.

Examples 10-11. Compound Ph-1 stabilized as described in example 1 way amines N and O. the resulting product are tested for resistance to hydrolysis as described in example 1.

Examples 12-15. Compound Ph-3 stabilized as described in example 1 way amines C, J, N, and O. the resulting product are tested for resistance to hydrolysis as described in example 1.

Examples 16-17. With pytyvaya resistance to hydrolysis, as described in example 1.

Examples 18-19. Compound Ph-6 stabilized as described in example 1 way amines N and O. the resulting product are tested for resistance to hydrolysis as described in example 1.

In all the examples of the phosphites, stabilized according to the invention, provide excellent resistance to hydrolysis.

Examples 20 and 21. The homogeneous composition of organic phosphite Ph-1 and amine N prepared by extrusion blending the two components in the ratio given in the table. 2, when 100oC) under conditions preventing access of air and moisture. Crystallization of the desired product is carried out in a cooled zone of the extruder. The obtained stabilized composition experience as described in example 1, with the percentage of hydrolyzed phosphite was determined by the method 31P NMR after storage for 66 h at 50oC and air humidity of 75%. All quantities are given as mass parts (wt.h.) (PL. 2).

The amine content in the compositions according to examples 20 and 21 in the calculation of the total mass of the composition ranges from 9.1 and 16.7 wt.% respectively.

1. The method of stabilization of organic phosphite and/or phosphonite from near atroveny Amin, which is added in an amount to provide content in stable organic phosphite and/or phosphonite of 0.1 to 25.0 wt.% the amine in the calculation of the organic postit and/or phosphonic.

2. The method according to p. 1, characterized in that the number of sterically constrained amine in the final product is 0.1 - 8 wt.% in relation to organic phosphite or phosphonite.

3. The method according to p. 1, in which the sterically hindered amine is added to the solution or melt of the organic phosphite or phosphonite to crystallization of the latter.

4. The method according to p. 1, characterized in that get stable organic postit and/or phosphonic not containing in addition to the sterically constrained Amin no other components based on organic polymers.

5. The method according to p. 1, in which the molecular weight sterically constrained amine is in the range 1500 to 10000.

6. The method according to p. 1, in which the sterically hindered amine is a cyclic sterically hindered amine containing at least one group of formula (II) or (III):

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< / BR>
where G is hydrogen or stands

G1and G2denote hydrogen, methyl, or both together predstavldata fact, as Amin it contains a sterically hindered amine with the following content, wt.%:

Postit or phosphonic - 80 to 99.9

Sterically hindered amine is 0.1 - 20

8. The composition according to p. 7, characterized in that in addition to organic phosphite and/or phosphonite and sterically constrained amine contains no other components based on organic polymers, mol.m. more than 5000.

9. The composition according to p. 7, containing sterically hindered amine in the amount of from 0.1 to 7.4 wt.% in relation to the weight of the composition.

 

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