SU857161A1 - Transparent copolyamide containing butyladipic acid units for construction and electroinsulating materials and its preparation method - Google Patents

Description

(54) TRANSPARATION OF THE SUSPENSION with aliphatic diamines, which can be used as a constructional and insulating material. Transparent copolyamndas are known, which are obtained by copolyrnensation of non-branched salt. lifatane with a number of people of sixteen and more aliphatic diaphragm; with copolyamide; and copolyamide; etc., however, amorphous and non-volatile; or alicyclic diamines 2

PREPARATIONS These polyamides have low softening temperatures and are designed as adhesives for scoops. In addition, new amorphous and transparent half-mounds, half-full of 3-tert-butt case of acid in a high-grade diaphragm, sphc lagic, alicyclic vpc arvpalve of Efat h. These polymers also have glass transitions (60,), softenings (lO2–15O t) cannot be used for preparing molded battles with vyfvkk fvskkomekhancheskvmvvvokaatetel mv. The most bvcv Aksy Alv-386 phagic, alshiklicheskikh, and aromatic dicarboxylic acid. Fvfkolkmer by a known method receive, heating together a mixture of acids and diamines, taken in equimolecular ratios of $ 1x or in the form of salts, in the presence or absence of water, preferably in the absence of oxygen at elevated pressure and temperature, then condensation is continued, heating the prepolymer at atmospheric and then under reduced pressure to remove the reaction water and obtaining the polymer of the required molecular weight. copolyamide, soluble in cold in alcohol and having a softening temperature of 128 ° C 4; Known polyamides also have a low softening temperature due to the high content of links; hydrochloric dicarboxylic acid in the copolyamide. Such polyamides are also unsuitable for processing into molded products with high physicomechanical indicators. The purpose of the invention is to obtain a transparent copolyamide with high physicomechanical and dielectric indices suitable for structural and electrical insulating products. This goal is achieved by using an amorphous transparent copopyamide of the general formula. HO-CCOCCH7) nCO-NH (CH2) KM NHlo, —CO — R — co — NHCCH2.) —CO — CH — CH — CCH2VCO — NH (CH2) yyi NH ccctH H where -11 4 - 12, - 12; a 1 - 15, in - I00; i with 1 - 55; L-1. I With a small mass of 15,000 - ZOOOO. Unlike the well-known copolyamide, the components are used in a new qualitative and if one natural combination, which ensures the production of a molding material with the required temperature range of the metal and high physicomechanical indicators. The content of the links in copolyamide I is in the following order: taXCHa, -CO-NHtCH2) iH 30-60% by weight -tCO-R-CO-NH (. 10-5 O-wt.% ICO-CHi-CH- (CMi) 2-CO -NH (CHiVf Hl: - Bec.% Cc) s Copoliamvd is obtained by joint polycondensation of a mixture of diamine salts and 1 dicarboxylic acid in the presence of water and a molecular weight regulator in a nitrogen atmosphere to form a prepolymer at a temperature of 220 ° C and a pressure of up to 18 atm and then dopolix "densation is carried out at a temperature of 265 tS С followed by vacuuming of the reaction mass. As dicarboxylic acids, besides 3-tert-butyl adipovinic acid lots, use aliphatic dicarboxylic acids with the number of carbon atoms from 4 to 12, mainly adipic, sebacic, dodecanedicarboxylic and aromatic dicarboxylic acids (iso- and terephthalic). As diamines use aliphatic diamines with a number, carbon atoms from 6 to 12, such as hexamethylenediamine, nsamethylenediamine, dodecamethylenediamine. Diamines and dicarboxylic acids are used in the form of salts, some of which (salts of AG, SG) are produced on a trial or industrial scale, others are manufactured Special, as indicated in examples 1-3. . A molecular weight regulator is used; aliphatic dicarboxylic or monocarboxylic acid in an amount of 0.1-0.2 wt.% to the total mass, and acetic acid is used in the polycondensation of the AH salt, and in the polycondensation of salts of other acids. and diamines use adipic acid. The specified amounts of molecular weight adjustments provide a copolyamide with a molecular weight from 15OOO to ZOOOO. The structure of the obtained copolyamides is confirmed by the data of elemental analysis, IR spectroscopy, and d-magnetic resonance. In the NMR spectra of polyamide solutions, SWCs are observed at 178.22 and 177.28 ML, which belong to carbonyl carbon atoms of the residue tert.-butyl adipine acid in the copolymer. In the IR spectra of the polyamides obtained, there is an absorption in the region of 148 O15OO and 1590-1610 corresponding to the vibrations of the aromatic nuclei. There is an absorption in the region of 1460-1470, 2850-286O, 2925-293O, corresponding to the scissor, symmetrical and symmetric valence cocks of the MSN groups. There is an absorption in the region of 79О-84О, 925-935 cm, corresponding to the vibrations of the C-C bond of the tert-butyl group. There are absorption bands of 58 1200-1210, 1393-1405, 13GO1370 cm, co-intangible and deformational oscillations of the scareclad bump. The physicomechanical and dielectric properties of the copolymers are given in the table. The abbreviations used in the examples are: SG coagent of sebacic acid and hexamegylene diamine, AH salt of adipic acid and hexamethylenediamine, IG-SAL salt of isophthalic acid and hexamethylene diamine, TG salt of terephthalic acid and hexamegylenediamine. PRI me R 1. Getting salt IG. A 5 liter of ethanol, 3.2 l of water, and 5.1 kg of hexamethylenediamine (HMDA) are loaded into the apparatus equipped with a jacket, a stirrer and a refrigerator under a stream of nitrogen. The dissolution of HMDA is carried out by stirring at a temperature of 55-6 ° C for 1 hour. Upon completion of the dissolution, the resulting solution is cooled to. Then, the isotphthalic acid in an amount of 7 kg is added in portions over a 1 hour portion of the working stirrer in an amount of 7 kg. In a side view of a webgall8S1 | HMDA acids come with heat release, the reaction mixture is cooled, maintaining the temperature in the reactor not exceeding 6 ° C. After loading all the acid, the solution is stirred in a stream of nitrogen for 30 minutes. The salt solution is cooled at the temperature of the stirrer to 1 ° C, 16 liters of ethanol are added, and the B mixture is stirred for 5 minutes, filtered and the crystallization is poured into it for crystallization, which is placed in a refrigerating chamber. After 1.5 to 2 hours at a temperature, the cobalt crystallizes out, it is filtered and washed with ethyl alcohol. The salt is dried in air at a temperature of 20-25i C for 24 hours. 11.5 kg of white cryetallic acid with an melting point of 212-214 ° C are obtained and the pH of the solution of 7.5 ml is obtained. j Calculated,%: C 59.5; H 7.82; 9.95. Found,%: C 6O, 2; H, 7.95; lO, 12. “Example 2. Getting salt TG. in the apparatus described in example 1, under a stream of nitrogen load 8 l of ethanol and 5.1 kg of HMDA. Next, the process is carried out as described in example 1, loading 7 kg of Tvrefat of LevsL instead of isophthalic acid. 11.0 kg of a white crystalline salt TG are obtained with a melting point and pH of aqueous solution T-Sa. 61 Elemental composition: Calculated,%: C 59.5; H 7.82j 9.95. Found: С 6О, 15гН 7.98iNlO, O7, Example 3. Preparation of the salt of 1-1О deca of dicarboxylic acid and 1-12 of decamethylenediamine. In the apparatus described in 1, under a stream of nitrogen, 8 l of ethyl alcohol and 5.1 kg of 1-12 dodecamethylene are loaded. amine. Next, the process is carried out using the following procedure: Example 1, loading 5.6 kg 1–10 with isophthalic acid (decandicarboxylic quolts). 11.5 kg of white crystalline salt with a melting point of 175177 ° C are obtained to a pH of the aqueous solution of 7.6. : C 62.5; H 1O, 98; M 8.1. Found: C 62.75; H H, 1; N8.35. P and m in p 4. 18OO g (6O wt.%) salts SG, 45Og (15 wt.%) salts IG, 75Og (25 wt.%) salts of 3-tertbutylaminimic acid in x xamethylenediamine, 16Cyu grams of water and 6 g (0.2 V9C. adipic acid is loaded into the autoclave. After purging with nitrogen, the autoclave is hermetically sealed, heated to temperature tours for 1.5–2 h. The pressure rises to 18 atm. Then, “the atura rate rises to 265; 5 ° C. Then the reaction mass is evacuated by the RW of 100 mm Hg in 2O mvv, after which the melt is discharged half a kilogram into a cooling bath. 2.5 kg of a bespachny prostfnogo kitchenware with the following characteristics are obtained: absorptive viscosity measured in 1% - polymer solution, in 93% - sulfuric acid 1,95, temperature softened 185 C. Vychispvvo,%: C 62,88; H 8.65; 1a 10,78. Found,%: C 62.35; H 8.53; N10.95. Molvkud moat mass 15SOU. PRI me R 5. 18OO g. (6O wt.%) Soot Cft ZOO g (1O wt.%) Soy TG, 9OOH. (ZO wt.%) Sobi Z-tertbutvladvvvsykh acid in hexamethyldiamine, 16OO g of water, And 6 g (0.2 wt.%) Of the adiphenous CVC is loaded into the autoclave and the process is carried out as described in Example 4. 2.5 kg of transparent polyme is absorbed, together with the measured viscosity measured in 19U8OM polymer solution, in 93) Your gray serpent is 2.02, the temperature is mag. Vychv (with eno,%: C 63.O5; H 8.7; H 11.45. Found: C 62.58; H 8.71; N11.07.

Molecular weight 180OO. In the example, 1350 g (45 wt.%) Of sobi AG, 150O g (5O wt.%) Of sobi IG, 15O g (5 wt.%) Of sobi 3-gretbugiladipnnovoy knslogy and 1-12-dodecamethylenediamine, 16OO g of disgunnogo water and 3 g (OD wt.%) Vinegar acid is loaded into the autoclave. Next, npwecc is a guide, as described in lrimer 4.

2.5 kg of clear polyme pa having an oisite viscosity measured in 93% sulfuric acid are obtained, 2.27, softening temperature 2OO C.

& D,%: C 64.73; H 9.25; By 11.35.

Found,%: C 64,12; H 9, O1; N11.5. Molecular weight 21000. Pr and m and p 7. 900 g (30% by weight.%) Salts of 1-10 decanedicarboxylic acid and 112-dodecamethylenediamine, 1500 g

(5O wt.;%) Copoly terephthalic acid and 1-12-dvkametsh1diamsha, 6OO g (2O wt.%) Salts of 3-t-butyl adipic acid and 1-12-dodecamethylenediamine, 160O g of distilled water and 6 g (0.2 weight. %) adnpinovoy booths are loaded into autzhzlav. Prsadesses are conducted as

described in example 4.

 2.5 kg of a transparent polymer are obtained with a relative viscosity measured in 93% sulfuric acid, 2.05 and a softening temperature of 175 ° C.

Calculated,%: C 7O, 85; H 9.85; N8.24 Found,%: C 71.52; H 9.7; N 8.14 Molecular weight 26,000.

about

EXAMPLE 8. 15OO g (5O wt.%) Salts of adipic acid and nonamethylenediamine, 12OO g (4 O wt.%) Salts of isophthalic acid and nonamethylenediamine, ZOO g (1 O wt.%) Copium 3-tert6 ethyl acetate and ivoic acid and nsiamethylenediamine, 16OO g of distilled water and 6 g (0.2 wt.%) of acetic acid are loaded into an autoclave and the process is carried out as described in Example 4.,

2.5 kg of transparent polymere are obtained with a relative viscosity of measured 93% sulfuric acid, 2.12 and a softening temperature of 190 ° C.

Calculated,%: C, 67.38; H, 9.25; N9.28. - Found,%: C 67.57: H 9, 9.56. Molecular weight ZOOOO.

PRI me R 9, 1500 g (5O wt.%) Soybean dodecanedicarboxylic acid and hexamethylenediamine, 900 g (30 wt.%) Of salt G, 6OO g (20 wt.%) Salts of 3-tert.-butyl-dipipic acid and hexamethylenediamine- , 16OO g-distilled water and 6g (0.2 wt.%) Of adipic acid are loaded into an autoclave and the process is carried out as described in example 4.

2.5 kg of a transparent polymer are obtained with a relative viscosity measured in 93% sulfuric acid, 2, O9 and softening temperature of 195 ° C.

Calculated,%: C 69.7O; H 9.65; N8.95.

Found,%: C 69.45; H 9.87; M-9.15.

Molecular weight 28 °.

High physicomechanical and dielectric properties {{iraic properties} make it possible to use copolyamides as transparent construc- tion and electrical insulating products manufactured by the method of drinking under pressure for making caps of instruments, lanterns, portholes and other transparent products for various branches of engineering .

Due to their high chemical resistance, copolyamides can also be used for parts working in aggressive media.

The process for the preparation of transparent copolyamides can be easily carried out in industrial production, since it does not require special equipment. By comparison with the known method, polyamide can be obtained within a shorter time, the stage of vacuumization is significantly reduced (from 2 hours to 20 minutes), which reduces the energy costs of the process. Structural and Nizaachene electrically insulating materials Melting point, C, GOST 21553.3-76 Relative viscosity 1.952, О7 GOST 18249-72 Transparent Clear Transparency

Destructive stress during stretching, kg / cm GOST 11262-76

Spike elongation 1FI rupture, N, GOST 11262-76

Well child volume resistance. Ohm cm GOST

45О

38О

530

120

100

33 Structural Adhesives in Electro-Collision Photographic Materials 1.99 2.242.2 He.nposps “Not everything is different

Claims (4)

Invention Formula Jl. transparent copolyamide containing 3-t-butyl adipic acid, formulas .n N: soChSN1.1u, CO-HNSN2% "MN a-CO-R-CO-14H (. PSS-Cs-CM-CCHi l-CO-NH-CCH.) where .h 4-12, s 6 - 12, a 1-15, in 3-100, K-fll / C molecular weight 15OOO-ZOOOO for structural and electrical insulation materials. 2. A method of obtaining a transparent solamide by copolycondensation of 3-tert.butyl-diaminoic acid and diamine salt and an aliphatic or aromatic dicarboxylic acid and diamine salt when heated by pressure in the presence of a low molecular weight regulator, differing from 4rov with oroosfener flow regimenter, an increase of 4o with an acceleration rate of an oisosphane flow regimenter, an increase of 4rov with an accelerator oro-oxidizer. carried out at the time of a total period of 4–4.5 h with subsequent vacuum 1fv 4O-1OO mm rg.st. during leaking 152O min. 3. The method volucheni provrachnogo sopodiamida claim. 2, characterized in that, in order to narrow ioluchevi volvamidov Molek ifno weight raspredv SO fiBeM, as regulators mopekUl torus angles Classes ispalazgyut aaifatvchyusvuyu dvkarbonovuyu or movszharboaovdgyu acid Colville "ETS 0.1 -O, 2% by weight to both of the mass, taking half of the condensation into a vacuum (acids and hexametes of the endkamp all over acetic acid, and other salts of other acids use two salts of acetic acid). 11 857161 1 Sources of information services, 3. Pageng France number 2202112, accepted in expertise under expert judgment. C 08 g 2O / OO, publ. 1974. 1. Patent Yapovv M 21116, onyfSnBK. 197O. 4. .Patent of France M 213OO28,  2. Frantsvv No. 2079969, j «« С O8 gf 20/00, pubic. 1972 cl. From Oag 20/00, pubpick. 1971. (prototype).