Stable composition and its preparation

 

(57) Abstract:

Use: for the manufacture of constructional products with high heat resistance, resistance to hot water and re-forming. The inventive stabilized composition comprises an aromatic polycarbonate contains at least 85% of the chains on the basis of bisphenol a, max 0,00005 wt. chlorine ions and not more than 0.001 wt. chlorine atoms and stabilizing system. The stabilizing system includes 0,005-0,01 wt.h. on 100 wt. including polycarbonate, at least one diapir phosphorous acid and 0.001 to 0.08 wt.h. at least one compound selected from the group comprising phenolic antioxidant, triavir phosphorous acid, aromatic phosphonic. The composition is prepared by mixing the components, granulation and processing of granular molding. 2 S. and 3 C.p. f-crystals, 1 table.

The invention relates to stabilized compositions based on polycarbonate, which finds application as a structural material, and to a method for producing stabilized polycarbonate composition. In polycarbonate, processed by molding the melt, add the stabilizers to eliminate okrashivaemoy and anteanna of 0.02-5 wt.h. on 100 wt.h. polycarbonate diapir phosphorous acid. The diesters of phosphorous acid have a significant effect on the resistance in a short period of time refining of the melt, however, their drawback is the low resistance to hydrolysis of the formed products under the action of hot water and water vapor and staining polymer with long-term heat aging. These unwanted effects depend on the amount added of thermo stabilizer, and with the increase in the number of reduced resistance to hot water and increases the degree of okrashivaemoy polymer.

Closest to the technical essence is a stabilized composition comprising an aromatic polycarbonate and a stabilizing system. The method of obtaining the composition consists in mixing components of the composition.

Stabilizing system contains the ester of phosphorous acid (tiefer) and phenolic antioxidant. The disadvantages of the composition is a low resistance to hot water, re-molding, the heat resistance.

An object of the invention is to improve the heat resistance, resistance to hot water and re-forming.

This task Reshma, as the aromatic polycarbonate comprises polycarbonate containing at least 85% of the chains on the basis of bisphenol a, max 0,00005 wt. chlorine ions and not more than 0.001 wt. chlorine atoms, and as a stabilizing system of 0.0005-0.01 wt. hours at 100 wt.h. polycarbonate of at least one aromatic diapir phosphorous acid and 0.001 to 0.08 wt.h. on 100 wt.h. polycarbonate, at least one compound selected from the group comprising phenolic antioxidant triavir phosphorous acid, aromatic phosphonic.

As the aromatic polycarbonate composition contains vysokokritichnyh polycarbonate with property acquisitions, determined with a spectrophotometer using a solution of 1 g of polycarbonate in 7 ml of methylene chloride, placed in a cuvette with an optical path length of 1 cm, less than or equal to 0.01 at 400 nm.

The technical problem is solved in a method of producing a stabilized composition consisting of a mixture of aromatic polycarbonate and a stabilizing system, and as an aromatic polycarbonate using a polycarbonate containing at least 85% of the chains on the basis of bisphenol a, max 0,00005 wt. chlorine ions and not more than 0.001 wt is wow aromatic diapir and 0.001 to 0.08 wt.h. on 100 wt.h. polycarbonate, at least one compound selected from the group comprising phenolic antioxidant, triavir phosphorous acid, aromatic phosphonic. It is preferable to use as the aromatic polycarbonate by solid state polymerization of the crystalline aromatic polycarbonate prepolymer.

Obtaining an aromatic polycarbonate.

Polycarbonate A.

Diphenylcarbonate get from dimethylcarbonate and phenol using lead oxide as a catalyst known method. The resulting diphenylcarbonate contains not more than 0,00001 wt. chloride ions and not more than 0.001 wt. chlorine atoms.

Crystalline aromatic polycarbonate prepolymer with srednekamennogo mol. m 4100, containing as end groups of 34% of the hydroxyl end groups and 66% of the limit phenylcarbamate groups receive from diphenylcarbonate and bisphenol A. 11 kg of the prepolymer is subjected to solid-phase polymerization using a 70-liter solid-phase polymerizate reversible type. Under a small amount of nitrogen, which is introduced into the system, the polymerization is performed under high temperature (th 1-2 mm RT.article created by a vacuum pump, resulting in a gain aromatic polycarbonate Mn12500 and 28000 Mw.

The polycarbonate contains no more than 0,00001 wt. chlorine ions and not more than 0.001 wt. chlorine atoms.

Polycarbonate Century

Solid-phase polymerization is conducted similarly to obtain a polycarbonate And, except for the fact that this use of the crystalline polycarbonate prepolymer with srednekamennogo mol.m. 4200, containing as end groups of 37% of the end hydroxyl groups and 63% of the limit phenylcarbamate groups, which is derived from bisphenol a and diphenylcarbonate. The result is an aromatic polycarbonate Mn 13400 and Mw 33400. The obtained polycarbonate does not contain more than 0,00001 wt. chlorine ions and not more than 0.001 wt. chlorine atoms.

Polycarbonate With.

Diphenylcarbonate containing not more than 0,00002 wt. chlorine ions and not more than 0.001 wt. chlorine atoms, receive distillation purification of diphenylcarbonate obtained from phenol and phosgene. Solid-phase polymerization of this diphenylcarbonate carried out similarly to obtain a polycarbonate And except that use crystalline aromatic polycarbonate prepolymer containing 28% limit Mw 23300. The obtained polycarbonate contains no more than 0,00002 wt. chlorine ions and not more than 0.001 wt. chlorine atoms.

Polycarbonate D.

Polycarbonate receive volgenau method.

This polycarbonate Mn 10800 and 28000 Mw, and it contains about 0.001 wt. chlorine ions and 0.004 wt. chlorine atoms.

The polycarbonate that is

Polycarbonate receive volgenau method.

This polycarbonate is characterized by Mn 9200 and 23000 Mw, and the fact that it contains 0,0008 wt. chlorine ions and 0.003 wt. chlorine atoms.

Polycarbonate F.

Polycarbonate receive method from the melt using bisphenol a and the same diphenylcarbonate that was used to obtain polycarbonate C. as the catalyst add sodium salt of bisphenol a in an amount of 5 wt. hours 1000000 wt.h. bisphenol A. Driving phenol, which is released as a product of condensation, the temperature of polymerization is gradually increased from 180aboutWith up to 310aboutOn the final stage. Srednekislye mol.m. the obtained aromatic polycarbonate is 10500 and srednevekovaja mol.m. 28300. This polycarbonate contains no more than 0,00002 wt. chlorine ions and not more than 0.001 wt. chlorine atoms.

1.5 g of this polycarb the go with the help of a spectrophotometer to measure the light absorption, having 0,013 at 400 nm.

Polycarbonate G.

An aqueous solution prepared by dissolving 64,8 g of the hydrate of oxide of sodium in 800 g of water, 137 g of 2,2-bis-(1 oksifenil)-propane, 400 g of methylene chloride and 1.1 g of phenol are mixed, prepared emulsion. After the emulsion is gradually passed by blowing in air for 1 h at 10-20aboutWith and with stirring 58.5 g of phosgene, completing the reaction.

After that, in such reaction mixture was added a solution prepared by dissolving 1.7 g of methylchloroform in 40 ml of methylene chloride, and then for 5 minutes through a mixture miss an additional 6 g of phosgene. Next add in the reaction mixture of 0.15 g of triethylamine, followed by stirring for 2 hours Then the reaction mixture is divided into methylenchloride phase containing the prepolymer, which was washed with 0.1 G. of aqueous solution of hydrochloric acid, and then sufficiently washed with distilled water, and the operation continues until, while in the wash liquid is stopped to detect chloride ions. Methylene chloride is distilled off under reduced pressure at room temperature, to obtain a prepolymer, which contained about 100 wt. chloride methylene. Further, this forpol the tone as long while in the wash acetone liquid is stopped to detect ions of chlorine atoms. The resulting prepolymer was crystallized, and the degree of crystallinity of 15% and srednevekovaja molecular weight equal to 6300.

After this, the thus obtained prepolymer is loaded into the flask vacuum evaporator with heater and the prepolymer is heated to a temperature of 190aboutWith a speed of 5aboutWith/H. the Reaction is carried out with flow into the flask with dry nitrogen under reduced pressure (2-5 mm RT.CT.) while stirring by rotation of the flask. After the temperature reaches 220aboutSince the reaction is carried out for an additional 7 h, resulting in a gain polycarbonate with srednevekovoi mol.m. 27000 (Mw/Mn 2,23). This polycarbonate contains no more than 0,00003 wt. chlorine ions and not more than 0.001 wt. chlorine atoms.

Polycarbonate N.

Solid-phase polymerization is conducted similarly to obtain a polycarbonate A, except that in this case the use of the crystalline aromatic polycarbonate prepolymer, obtained from bisphenol a, 0,4 mol. (in terms of bisphenol a) ,',"-Tris-(4 oksifenil)-1,3,5-triisopropylbenzene and diphenylcarbonate. The result is an aromatic polik the CLASS="ptx2">

Polycarbonate I (a).

Solid-phase polymerization is conducted similarly to obtain a polycarbonate And except that in this case, use bisphenol a, diphenylcarbonate and 0.0002 mol. (based on bisphenol a) of sodium phenolate. The result is an aromatic polycarbonate Mn 12400 and Mw 27900. This polycarbonate contains no more than 0,00001 wt. chlorine ions and not more than 0.001 wt. chlorine atoms.

Polycarbonate I (b).

The polymerization is conducted similarly to obtain a polycarbonate A, except that in this case, use diphenylcarbonate obtained using phenol and phosgene and subsequent simple distillation.

The result is an aromatic polycarbonate Mn 12400 and Mw 27900. This polycarbonate contains no more than is 0.0002 wt. chlorine ions and not more than 0,0015 wt. chlorine atoms.

Polycarbonate K.

Solid-phase polymerization performed in the same manner as when receiving polycarbonate, but use crystalline aromatic polycarbonate prepolymer with srednekamennogo mol.m. 4100 containing 34% of the end hydroxyl groups and 64% of the limit phenylcarbamate groups, prepared from bisphenol a and bisphenol Z (molar ratio 27600 w and contains not more than 0,00001 wt. chlorine ions and not more than 0.001 wt. chlorine atoms.

Polycarbonate L.

Solid-phase polymerization carried out analogously to the preparation of the polycarbonate, but use crystalline aromatic polycarbonate prepolymer with srednekamennogo mol.m. 4200, containing 28% of the end hydroxyl groups and 72% of the limit phenylcarbamate groups derived from bisphenol a and bisphenol S (molecular ratio between bisphenol a and bisphenol S is 98: 2), and diphenylcarbonate. Get aromatic polycarbonate Mn 10500 and Mw 24000.

The obtained polycarbonate contains no more than 0,00001 wt. chlorine ions and not more than 0.001 wt. chlorine atoms.

Polycarbonate M

Polycarbonate D obtained in accordance with poshtovam way, purified, comprising dissolving it in tetrahydrofuran, the deposition of n-hexane and drying the precipitated polycarbonate under vacuum three times to remove the contained chlorine. Thus purified polycarbonate contains less than 0,00001 wt. ion chloride and 0.001% wt. chlorine atom.

Polycarbonate n

Repeat the method for producing polycarbonate F except that the reactor maintained under nitrogen atmosphere with pre order Srednekislye mol.m. and srednevekovaja mol.m. accordingly 10400 and 28000. Thus obtained polycarbonate dissolved in methylene chloride and the resulting solution was washed with an aqueous solution of 0.01 N. HCl and then washed with distilled water continue up until the chlorine ions in the wash solution cannot be determined. The resulting product is subjected to distillation under reduced pressure for removal of the methylene chloride. Thus obtained polycarbonate cleaned three times by repeating a series of stages consisting of polycarbonate in tetrahydrofuran, precipitation of the dissolved polycarbonate of n-hexane and drying the precipitated polycarbonate in a vacuum. Then the obtained polycarbonate washed with acetone until no chlorine ion or a chlorine atom is not defined. Thus the treated polycarbonate contains is 0.0002 wt. or less chlorine ion and 0.001 wt. or less of the chlorine atom. The absorbance at 400 nm of the thus treated polycarbonate equal to 0.01 or less.

Preparation of stabilized compositions.

P R I m e R 1. 0.15 g of the secondary acid phosphite bis-(nonylphenyl) and 2.0 g of Tris-(2,4-decret.butylphenyl)-phosphite mixed with 10 kg of polycarbonate And, in the mixer hensely, then granularit the mixture is extruded through the EC for testing are tested for heat stability, resistance to hot water and re-formovaniya, the results of which are summarized in the table.

P R I m e R s 2-22. Carried out analogously to example 1. The composition and properties of the compositions are given in the table.

Comparative examples 1-17.

Carried out analogously to example 1. The composition and properties shown in the table.

The measurements of properties carried out by the following methods:

1. The coloring. Determine by the method of CIELAB. The thickness of the test sample was 3.0 mm

2. Test the heat.

Test sample (ASTNo 4 "dumbbell") were placed in a furnace Gere, where was kept at a temperature of 140aboutWith within the specified period, after which the determined color and elongation at tensile (ASTM d-638) of the test sample.

3. The test for resistance to hot water.

The test sample was immersed in boiling water, which was passed during this period, after which it was extracted and determined the molecular mass, the elongation at tensile strength (ASTM-D638) and characteristic Izod test specimen with a thickness of 3.0 mm

4. Test re-shaping

The test consists in grinding the test sample, made the five times. Defined color and elongation at tensile made so test sample.

5. Molecular mass.

Srednevekovoy molecular weight (Mw) and srednekamennogo molecular weight (Mn) was determined by gel chromatography (GPC) (detector refractive index Shodex RI SE-51 manufactured by a company "Showa the den com K. K."), column: TSK-GEL.

Abbreviations used in table:

BNP secondary acid bis-(nonylphenyl)-hospit;

NP Tris-(nonylphenyl)-hospit;

P 168-Tris-(2,4-decret.butylphenyl)-hospit;

WRR secondary sour biphenylphosphine;

Q tetrakis-(2,4-decret.butylphenyl)-4,4'-diphenylpropionic;

VVR secondary acid bis-(2,4-decret.butylphenyl)-hospit;

Irganox 1010 pentaerythritol-tetrakis-[3-(3,5-decret.butyl-4 oksifenil)-propyl-NAT]

Irganox 1076 of octadecyl-3-(3,5-decret.butyl-4 oksifenil)-propionate;

BDNP bis(dinonylphenyl)postit hydrogen;

BNAP bis(naphthyl)postit hydrogen.

Thus, the proposed composition containing an aromatic polycarbonate with a minimum content of ions and atoms of chlorine and stabilizing system containing fluids of phosphorous acid and a phenolic antioxidant, triavir phosphorous acid idorname formation.

1. Stabilized composition comprising an aromatic polycarbonate and a stabilizing system, characterized in that the aromatic polycarbonate it includes polycarbonate containing at least 85% of the chains on the basis of bisphenol a, max 0,00005 wt. chlorine ions and not more than 0.001 wt. chlorine atoms, and as a stabilizing system of 0.0005 to 0.01 wt. hours at 100 wt.h. polycarbonate of at least one aromatic diapir phosphorous acid and 0.001 to 0.08 wt.h. on 100 wt.h. polycarbonate, at least one compound selected from the group comprising phenolic antioxidant, triavir phosphorous acid, aromatic phosphonic.

2. The composition according to p. 1, characterized in that the aromatic polycarbonate contains vysokokritichnyh polycarbonate.

3. The composition according to p. 1, characterized in that the aromatic polycarbonate contains polycarbonate with property acquisitions, determined with a spectrophotometer using a solution of 1 g of polycarbonate in 7 ml of methylene chloride, placed in a cuvette with an optical path length of 1 cm, less than or equal to 0.01 at 400 nm.

4. A method of obtaining a stable composition by mixing and the carbonate is used polycarbonate, containing at least 85% of the chains on the basis of bisphenol a, max 0,00005 wt. chlorine ions and not more than 0.001 wt. chlorine atoms, and as a stabilizing system of 0.0005 to 0.01 wt.h. on 100 wt.h. polycarbonate of at least one aromatic diapir phosphorous acid and 0.001 to 0.08 wt.h. on 100 wt.h. polycarbonate of at least one compound selected from the group comprising phenolic antioxidant, triavir phosphorous acid, aromatic phosphonic.

5. The method according to p. 4, characterized in that the aromatic polycarbonate used polycarbonate by solid state polymerization of the crystalline aromatic polycarbonate prepolymer.

Priority signs:

18.08.89 in respect of a stabilizing system comprising diverfostering acid and Trevira phosphorous acid or aromatic phosphonite;

23.08.89 in respect of a stabilizing system comprising diesters of phosphorous acid and a phenolic antioxidant.

 

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