SU463264A3 - The method of obtaining the polymer composition - Google Patents

Description

(54) METHOD FOR OBTAINING A POLYMER COMPOSITION

yl methacrylates, ohlmethacrylates, amilmetic crylates and hexyl methacrylates; methyl alloracrylate, ethyl-to-chloro-acrylate, etc. Preferred l: ethyl acrylate, ethyl acrylate, MCI acryl plat and ethyl methacrylate lat.

Plenism composition 110 of the invention r (vrc) i) HT by polymerizing an emulsion or euspen; ; puttel: simultaneous, continuous or 1 () dichss {) th addition of monomers and other components into the reaction zone. Poly iepH: uiii .Hio (go to emulsifier ij and polymerization generating С1н emulsifier) bodys radicals, at temperature O - ifl () C in the absence of molecular oxygen.

The polymer compositions according to the invention are obtained by measuring them to about 707 (i-Hoii by weight, conversion rate, iOO wt. H, c. Change., Consisting at least 70 w / w,%, at least 11 unsaturated) nitrile and 30 wt. %, lower: v; epe, od1)) layer / kn ether, followed by extrusion into the environment in which the polymerization occurs and, from 1 to 40 weight. including monomeric ivOMKOiieirra, which contains at least one conjugated diene, contains butadiene or isoprene, and continues to polymerize to 80-100% monomer conversion.

G1) with a preferred and polymerized mixture consisting of acrnlopitrile and methyl methacrylate, to a degree of at least 80 isee. % followed by the addition of butadiene-1, 3 and completion of the polymerization reaction to obtain a polymer having () high toughness and good impermeability to gases and vapors (when cured under the action of said gases or vapors) in the form of a film or thin sheet material. The polymerization process is carried out in the presence of an emulsion in the presence of free radical: 1 cal1 rrrrrrrrrrrrrr.

The half-fat composition obtained by the proposed method is well processed, has a high toughness (i.e., when tested by the notched cut method, the ductility is 2.7 kg-slg / cm notch. The composition is thermoplastic, it can be molded under heating conditions to make products with any of the methods used in the processing of known thermoplastic materials, such as continuous pressing, rolling, pressing, stretching, blowing, etc.

Polymeric compositions in accordance with the invention of the region; 1 are resistant to solvents; the high toughness and low permeability to vapors and gases make them very suitable for the packaging materials industry, and also suitable for the manufacture of bottles. lujenoK n other types of containers for liquids and solvents. Pizka the gas permeability of the polymer composition, obtained and the use of, in relation to such gases, PDA, oxygen and carbon dioxide, allows

use it for making bottles for tazirovannyh nanotek and vegetable. PRI me R 1.

A. The resin no lime method is prepared by polymerizing a mixture of the following ingredients (in weight parts):

Distilled water 250

Ammonium emulsifier salt of sulfated iopilfepoxypoly- (ethyloxy) ethanol ("Alipal CO 436) 1.5 Acrylonitrile75

Methyl acrylate25

Limopendimercaptan 0.5

Ammonium persulphate 0.06

Butadiene 12.0.

The polymerization is carried out at a temperature of 60 ° C, first the above ingredients are loaded into the polymerization reactor, then air is removed from the reactor by blowing the reactor with gaseous nitrogen. The polymerization is carried out in continuous dislocation. The total polymerization duration is 16 hours. The product is a latex solid resin. The conversion rate of monomers in the polymer is 85.5%.

The resin is isolated by coagulation by meta-moles with subsequent rinsing and by live Koi in vacuo. Then from the resin by the method of pressing made from the bars, which are subjected to the test. The impact viscosity of the bars using the notched Pzod method is 1 kg-cm / cm notch, the torque measured in the Brabepder device (230 ° С and 35 rpm upon reaching the low-speed torque), 3250 m-g ( the resin decomposes or burns when tested and tested for 5 minutes). This indicates that emola cannot be processed in conventional equipment used to process thermoplastic resins.

B. The resin is prepared by the proposed method in the same way as Test A, but the butadiene is polymerized and the mixture is introduced in one portion after the degree of conversion of the mixture of monomers consisting of acrylonitrile and methyl acrylate is reached to the polymer of 89.5%. Further, the polymerization is continued until a degree of conversion of the monomers into a 93% iolimer is reached. Salul is recovered from latex by coagulation, washing, and drying.

The resultant resin is characterized by the following P1. IMP indicators:

Impact viscosity according to the Pzo.ta method with a notch, kg-cm / cm padreza3,4

Cool moment, measured in Brabender plastometer (at CMenia and for 5 min), m-1890

Warp temperature

according to ASTM method, ° С70

Resistance to bending,

kg-cm

910

Bending modulus, kgf / cm 32600

Tensile strength, kgf / cm

623 69

Rockwell hardness, M scale

Permeability to water vapor (90% relative humidity, ASTM Method D-1434-66) 5.0 g / 2.54-10-3 cm / 642 cm2 / hour / 37.8 ° C

Permeability to oxygen (ASTM method

D-1434-66) 1.0 ml / 2.54.10-3

cm / 642 cm2 / 24 h / at / 22.8 ° C

B. A resin according to a known method is prepared according to claim B, but butadiene is introduced into the reaction mixture upon reaching approximately a 50% degree of conversion of the monomer mixture consisting of acrylonitrile and methyl acrylate into a polymer.

The conversion of monomers to polymer is 86.4%. The resin is recovered from latex.

Resin values:

Impact viscosity according to the Izod method with notch, kg-cm / cm notch1,9

Torsional torque in the Brabender plastometer (the resin burns in the Brabender instrument), m-2420.

G. The resin is prepared according to the proposed method, repeat experiment B, but a mixture of monomers consisting of acrylonitrile and methyl acrylate is polymerized to 100% for 16.1 hours, then butadiene is added (11.6 hours) and the reaction is carried out 6 o'clock The conversion of monomers to polymer is 91.0%. The resin is recovered.

The characteristic of the resin is as follows: Impact viscosity according to the Izod method with a notch of 3.5 kg-cm / cm notch3.5

Twisting moment in Brabender plastometer, m-d2690.

Example 2

A. A copolymer of acrylonitrile and methyl acrylate is prepared according to example 1 of the following ingredients (in weight parts):

Water156

Acrylonitrile75

Methyl acrylate25

Emulsifier ("GAFAC .RE 610) 3

Modifier ("Mercaptat

Q-43) 1.05

Ammonia0.06

The agent for the formation of an intracomplex compound (" Nag-rape R-4-100) 0.05.

The emulsifier is a mixture consisting of R-0 (SP2CH20-) PROZM2 and (CH2CH2O-) n 2-PO2M, where n 1-40;

R is an alkyl or alkaryl group, preferably nonylphenyl;

M is a hydrogen atom, an ammonium group or an alkali metal atom.

The modifier is tetraester of pentaerythritol and p-mercaptopropionic acid, and the agent for the formation of an intracomplex compound is the tetrakalium ethylenediaminetetraacetate acid salt.

The polymerization is carried out to a conversion of 99%. The resulting latex is diluted with water so that the solids content is 31%. A part of the latex is coagulated, the polymer is isolated, dried and

its parameters are determined: the impact toughness of the polymer, measured by the cut Pzod method, is 2 kg-cm / cm cut, and the torque measured in the Brabender plastometer, 1300 M-g.

B. To a part of the latex obtained in experiment A, is added on the basis of 100 weight. including resin 11.7 wt. including butadiene and 0.05 wt. ammonium persulfate. The polymerization is carried out for 7 hours at a temperature of 60 ° C. The finished polymer is isolated,

they are dried and their indicators are determined: impact viscosity, measured by the P1 method with a notch, 0.8 kg-cm / cm notch, and a torque component measured in the Brabender plastometer, 2040 m-g.

Example 3. Experiment 1B is repeated, but 95 wt. Is replaced by acrylonitrile. including methacrylonitrile, and Methylacrylate - 5 wt. including methyl methacrylate. Upon reaching a conversion degree, the monomer mixture consisting of methacrylate and

methyl methacrylate, 83% added 19 wt. h. butadiene. The polymerization is carried out until reaching a conversion degree of 90%. A polymer having a impact strength, measured by the Pzod notched method, 16 kg-cm / cm is obtained.

the incision, and the torque measured in the Brabender plastometer, is 2400 m-g.

Example 4. Example 3 is repeated, but methacrylonitrile is replaced by 70 wt. including Acrylonitrile, and methyl methacrylate 30 weight. h of ethyl acrylate; 11.1 weight. including butadiene, upon reaching the degree of conversion of the monomer mixture, consisting of acrylonitrile and ethyl acrylate, to the polymer 94.5%. The final polymerization is 95% conversion. Get

a polymer having a toughness, measured by a notched Izod method, 32 kg-cm / cm notched, and a torque measured in a Brabender plastometer, 1470 uM. Example 5. The experiment is carried out according to the example.

1B, but when the degree of conversion of the mixture of acrylonitrile monomers and methyl acrylate to the polymer was 92%, 17.85 wt. h. butadiene. The polymerization is carried out to a conversion degree of about 83%. The resulting polymer has a notch impact strength, measured using the Izod method, 1.1 kg-cm / cm notch and a torque measured in the Brabender plastometer, 1520 m-g.

Example 6. The experiment was carried out according to Example 5.

but upon reaching the degree of conversion of the mixture

/

tilacryl a, in polymer b // with butadiene. Polymerization isl g to fieiicini 11 | 1eventsii 92 ;;). The resulting lio.riH.icp has a shock LJ,)) according to the method of method 11 of the year, 5.37 kg / i.i of the notch and the torque mole, e 1t, nthc and r; Brabepder plastometer, 21,590 m-g.

The projection of this iio.Ti -: epa for Kielorod (measured by Aieixxiy ASTM) 1.2 ml / 2.54-10-3 cm / 642 cm2 / 24 tea / at and for water vapor (measured by ASTM method) 4.2 172.54-10-3 eat / 642 CMV24 tea / 37.8 ° C {90% of the total number of 15L 1 of my).

PRI} .1 e r 7. rioBTOpsiiOT experience, omieapia in iipH-Mciie G, 1H to reactiopioG eMeei, io doetk / keiii 95% dk) essioii ii) eBpameKini has my own components, and consists of acryloidtrile and methydacrylate, in and () vioe -i 9.8 voi. h. butadiene. I am leading the final imerimerization 1 to the extent of rotation, which is monomerosis li nol1Y1er 93.3o. B1 1 Deleted1 full) and: .1 (; em shock vkoet1, H3MepeiHiyi (): io by the cut method, 8.0 kg-em / e.m cut and torsional torque H3: icpeiniBiii with the Brabeider nlastometer, 2150 m- year

Example 8. Latex eo11odk} ,; e) a, nscchuchennn | but the irimer is 2 A, the content of P1 is 0.7% of the nonioradiated monomer, the substrate is in vacuum n) and the temperature) 0 ° G - for an enrichment of the total monomer to 0.05 wt. % relative to latex and) 1 bavl 10.2 weight. h. butadiene from Racheta 100 weight. h. pitches, lead to numbering; practically irenraschei in nolme

The resulting product has a torque measured on a Brabender plastometer, 2180 MT, and impact strength measured using a notched 11Sod method, (3.4 kg-e / c on; 1 cut).

PRI me R 9.

L. Full methacrylonitrile is prepared by polymerization at a temperature of 60 ° C mixed. It consists of the following contingents (in all.); Water 250

"Aliaal CO, 5

Methacrylointrnl100

Ammonium persulphate 0.05

Lm and endimercite and 0.5.

eight

B. At 250 pes. including latex, obtained in experiment A, 1 was 0.05 wt. including persulphate am1: oii and: 0.33 wt. including butadiene and 11 | K) c () d t; ihtn “ernzannyu at a temperature of 60 ° C in the absence of a slurry during iri.merio 24 hours before the injection into a polymer of 95.4%. A resin is made, .a) an aerating effect of .. and i 3 and 3 bodies:

Cool moment, measured on a Brabender's plastometer,

m - g 2350

Impact viscosity, measured by the method Izod e nadre about. i, k g s / m m n a d r ez a5,37

Temnerura deformanin but

; rrody - STM, ° С97

Co; rotary bending, kg / cm 1050, ib, kg / sl 30800

Co-ordinating i) a%, kg / meal 2700.

The method of obtaining and polymerisation

with a HIGH-shock impact of low gas yields) 1K1: aelty, containing 1 N of the most saturated, and itnl i eoir female diene to zoolynerns:; state ni-, 1e proximately in irO, if it is full: mernza, ai, about tl and h and about y and ii with tsl,

, pp. 1, e.tyo of the rode of those processes of the process of learning, the process of distillation, the water of the first, the carrier1) IO in two stages: from the beginning of the year. .40 70% or more of the iepB3ni version is a monomeric component consisting of

70 weight. / (, and bo, 0 of one unassigned general formula CH2 CR-CN, where R is hydrogen. C) -C4-alkyl or -halogen, n O-30 ne. % but extreme Aiepe with; Common Efnra Formulas

CHa CRi-COOR2, where Ri is hydrogen or,; - alk 1l 1 R2 - Ci-Cb-alkyl, then BTopoii may be added to the index and OI 1y 0 medium, containing, but most of the same, 1 intermediary of 1you ads or isonrene, 13 number 1-40 carried. hours and 100 weight. part of the first monomeric component, and so forth () is 5 years of totalization 0 to 80-100% 4 oi of mono-ers, and the process ns)

medium, water emulsion mediator, at a temperature of 0 ~ iOO ° C R Presence of free-motion radiation. , 1ato) K) p.