UA137220U - POLYMER COMPOSITION - Google Patents

Abstract

The polymer composition contains a vinyl chloride polymer, plasticizers, stabilizers, lubricants, pigments, fillers and polyurethane and / or polyurethaneurea in fine form, synthesized by dispersing the isocyanate component in an aqueous medium in the presence of surfactants. As the isocyanate component, a block oligomer containing 0.8-6.0% of free isocyanate groups is used, which is obtained on the basis of oligoetherdiol, diisocyanate and a low molecular weight chain extender with an active hydrogen atom.

Description

The utility model belongs to polymer compositions based on vinyl chloride polymer (VCP) and polyurethane and/or polyurethane urea in finely dispersed form using low molecular weight organic and inorganic compounds that can be used to produce film materials, artificial leather, adhesives, binders, coatings, construction materials, medical products.

Known thermoplastic compositions based on vinyl chloride polymers (polyvinyl chloride, chlorinated polyvinyl chloride, copolymers of vinyl chloride with vinyl acetate or copolymers of vinyl chloride with vinylidene chloride) and polyurethanes (PU) of various chemical structures, which are obtained on the basis of 4,4-diphenylmethanediisocyanate (DFMDI) and oligobutylene glycol adipinate (PBA) PI ; PBA and toluidinediisocyanate (TDI) (21; polyisocyanates, polyetherdiols and low molecular weight compounds with an active hydrogen atom |Z). The compositions contain thermal and light stabilizers, lubricant, pigments and fillers. The compositions include low molecular weight (esters of phthalic, adipic, sebacic acids, etc.) and oligomeric plasticizers.

The disadvantage of these compositions is the production of materials with strength properties below the additive values due to their microsterogenicity, and the maximum reduction in strength characteristics is observed when adding 20-50 906 PU to PVC. For PU based on oligoesters, the reduction in breaking strength is 20-40 95 (0 28-40 MPa), and based on oligoesters - 40-80 95 (with 10-30 MPa). The introduction of low-molecular plasticizers (LP) also leads to a decrease in the mechanical characteristics of materials.

The closest analogue to the composition, it is claimed, is the composition |4| on the basis of polymers and/or copolymers of vinyl chloride (polyvinyl chloride, copolymers of vinyl chloride with vinyl acetate), polyurethanes and/or polyurethaneurea in powder form with a particle size of "0.6 mm.

The composition of the composition (parts by weight): polyvinyl chloride 100

PU and/or polyurethane urea 5-100 plasticizers 35-65 stabilizers 1-2.5 grease 0.6-1.5 pigments 0.01 0.5 fillers 0.5-2.5.

PU with a softening temperature of 130-230 "C is obtained by dispersing the isocyanate component (prepolymer) synthesized on the basis of oligoetherdiol and diisocyanate, which contains 1.5-2.5% of free isocyanate groups in an aqueous medium (water is a chain extender of the isocyanate component ) in the presence of surfactant (polyvinyl alcohol) followed by filtering and drying. The components are mixed in a rotary mixer heated to 90 "C, into which PVC, PU, wax, stabilizer, filler are loaded. After

After short-term mixing, plasticizers are introduced and the mixture is homogenized. When a temperature of 75"C is reached, the mixing is finished and the mixture is poured onto tin trays for cooling. The dry mixture is rolled for 5 minutes at a temperature of 175"C, and samples 6.5mm thick are pressed from the obtained film with a thickness of 0.6mm. Properties of the obtained materials: tensile strength (c) 12-14 MPa; relative elongation (is) 280-340 9o. However, the disadvantage of this composition is the low strength properties of the obtained materials.

The task of a useful model is to create a polymer composition with increased strength properties of materials based on it due to increased compatibility of polymers.

The problem is solved by the fact that in a polymer composition containing a vinyl chloride polymer, plasticizers, stabilizers, lubricants, pigments, fillers and polyurethane and/or polyurethane urea in finely dispersed form, synthesized by dispersing the isocyanate component in an aqueous medium in the presence of surfactants, according to a useful model as the isocyanate component uses a block oligomer with a content of 0.8-6.095 free isocyanate groups, which is obtained on the basis of oligoetherdiol, diisocyanate and a low-molecular chain extender with an active hydrogen atom, with the following ratio of composition components (parts by weight): vinyl chloride polymer 5-100 polyurethane and/or polyurethaneurea 5-100 plasticizers 0.01-65 stabilizers 0.01-3.0 lubricant 0.01-1.5 pigments 0.01-0.5 fillers 0.01-2.5.

Polyvinyl chloride (PVC), chlorinated polyvinyl chloride (CPVC), copolymers of vinyl chloride with vinyl acetate, copolymers of vinyl chloride with vinylidene chloride (VCVD) are used as a vinyl chloride polymer.

For the synthesis of PU and polyurethaneurea (PUM), oligoetherdiols of molecular weight 800-2000 with the functionality of hydroxyl groups g 2 are used. These include oligoethers (oligooxy-tetramethylene-, oligooxyethylene-, oligooxypropylene glycol), oleisters obtained by polycondensation of aliphatic diols and dicarboxylic acids (oligodiethylene glycol adipinate , oligoethylene glycol adipinate, oligobutylene glycol adipinate), oligolactones.

Aromatic and cycloaliphatic diisocyanates are used as diisocyanates (toluene diisocyanate, naphthylene diisocyanate, hexamethylene diisocyanate, 4,4- diphenylmethane diisocyanate).

Aliphatic diodes (1,3-propanediol, 1,4-butanediol), diamines (ethylenediamine, 2,4-toluenediamine, 4,4"-diaminodiphenylmethane, cyanethylated ethylenediamine, oxypropylated ethylenediamine, M-methyldiethanolamine) are used as a chain extender with an active hydrogen atom. ), hydrazine, hydrazineethanolamine.

The synthesis of the polymer in a finely dispersed form is carried out as follows: a reaction between oligoetherdiol, diisocyanate and a chain extender is first carried out to obtain a block oligomer (isocyanate component) with the presence of free isocyanate groups 0.8-6.0 905, which is then dispersed in an aqueous medium in the presence of a surfactant . By lengthening the block oligomer with water, the polymer is obtained either in powder form with a particle size of 0.02-1.00 mm, or in the form of microfibers (average particle diameter (D) 0.05-0.10 mm, average length (I) 0.05 -1.00 mm.

Phthalic, adipic, and sebacic acid esters (dioctyl phthalate, dibutyl phthalate, dioctyl adipinate) are used as a plasticizer.

Metal and organotin thermostabilizers (tribasic lead sulfate, calcium stearate, calcium and zinc stearates, barium and cadmium stearates, tin dibutyl dilaurate, CM 7105) and light stabilizers (benzophenone, beisotriazole) are used as stabilizers.

Polyethylene wax (PEW), montan wax, glycerine ether (GLE), stearic acid (STK) are used as lubricants.

Chalk, aerosol, kaolin, aluminum hydroxide, aluminum oxide and pigments (titanium dioxide, carbon black) are used as fillers.

The technology of preparing the composition consists in preliminary mixing of the initial components in a rotary mixer, then the mixture is homogenized by rolling at a temperature of 155-170 "C and a film with a thickness of 0.1-0.6 mm is obtained or extruded at a temperature of 135-170 "C.

By dissolving the polymer composition in an organic solvent (dimethylformamide, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, tolublue, it is possible to obtain a polymer solution for various technical purposes.

The essence of a useful model is confirmed by examples. Composition and granulometric characteristics

PU and PUM are given in Table 1, the composition of the composition in finely dispersed form - in Table 2, and the properties of materials obtained by rolling, extrusion or from solutions in an organic solvent - in Table 3.

Example 1.

The synthesis of PU-1 is carried out as follows: 67.4 g of dehydrated oligobutylene glycol adipinate (dried for 3 hours at 100 "C in a vacuum of 133 Pa) with a molecular weight of 2000 (PBA-2000), 23, is loaded into a 500 ml reactor equipped with a propeller stirrer. 5 g of toluene diisocyanate (TDI) and 5.1 g of 1,3-propanediol (PD). The mixture is heated for 3 hours at 807C and a block oligomer with free isocyanate groups of 2.95 95 is obtained, then it is dissolved in 20 g of methyl ethyl ketone and until 120 g of a 2.595 aqueous solution of a copolymer of styrene with maleic anhydride (STM) is added to the solution with intensive stirring (the number of revolutions of the stirrer is 20 rpm). After stirring at a temperature of 60 C for 1 hour, the resulting dispersion is diluted with 100 ml of water, filtered, washed and dried A powdery product with a particle size of 0.1-0.4 mm is obtained.

In a closed rotary mixer with a capacity of 5 l, heated to 90-95 C, 1000 g of suspended PVC of the C 7059M brand, 5 g of polyethylene wax (PEW), 30 g of stabilizer (art. Са, 2п) are gradually introduced through the loading device, after mixing for 10 min. inject 400 g of a mixture of dioctyl adipinate (DOA), dioctyl phthalate (DOF), dibutyl phthalate (DBF) and a plasticizer based on adipic acid (PE) in a ratio of 3:1.5:1:2, then the mixture is homogenized. When the temperature of the mixture reaches 75 "C, the heating is stopped. After the mixture has cooled to 30-40 C, 200 g of powdered PU-1 is loaded into the mixer, mixed for 15 minutes.

Then the mixture is rolled for 5 minutes. at a temperature of 155-170 "С and obtain a film with a thickness of 0.1-0.8 mm. The mechanical properties of the composition were determined according to GOST 11262-80 (Table 3).

Synthesis of PU and PUM in powder form, as well as polymer compositions for rolling and extrusion in the last examples 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16 are prepared similarly to example 1.

Table 1-

Composition and properties of PU/PLUM in finely dispersed form

The composition of the block oligomer Granulometric p. ply Extender and characteristics

MSO- | dl/g| "C Dimension of mass t limit mass mara mass th

For Porosh proto- PBA TDI 1.70 11.14) 150 | copo- | 0.1-0.4 type of days

PBA-

PU-1 2000 67.40 TDI 23.50 Pd 510 2.95 |1.11 | 120 0.05-0.30 pFf- TDI 15.66 J

Micro-

PEBA-d-0.07

PEBA-d-0.10

OKLlvo 00 Powder

PUM-6 | 2000 ' 13.92 | М-М 2.00 1.95 10.80 100 | copo- I0.10-0.40 10.00 pd: l-1052 days

PDA-

PUM-7 800 60.00 TDI 39.00 GE 7.50 140 0.10-0.50 te ns no| but that doesn't bother Gog

PEBA-2000 - polyethylene butylene glycol adipinate M.M. 2000

PF-1000 polyoxytetramethylene glycol M.M. 1000

L-1052 - polyoxypropylene glycol M.M. 1050

OKL-2000 - polycaprolactone M.M. 2000

PDA-800 - polyethylene glycol adipinate M.M. 800

MDI - 4,4"-diphenylmethanediisocyanate

GE - hydrazineethanolamine

CED - cyanethylated ethylenediamine

BDI1,4 - butanediol

М-М - M-methyldiethanolamine

Table 2

The composition of the polymer composition adj. 1 time- Type time- Type time- Type time- | Type of time- Type of time- tyna and tyna tyna tyna tyna tyna tyna

DOA

For PVC For Montan proto-| (biomypiy 100 Iproto-| 20 DB. PE 40 spsai 3.0 - wax oo type 683) type 1 r.4. SEE ' 371,571:2

DOA

Montan PVC DOF, art. Sa, - 0.50 1 Istohom| 100 | PUL 20 |dBFffpv| 0) in | 59 tk | 040 3:21,5:11:2

M

Soot -

PVC with 7049 art. Ba, kaolin |0.01 100 0 dob | lo |В 30 0 peVO o5o po; battles are not scattered

PVC b holo st.Va,| 2.0 -

Sen liu tv in | dov | with |toso

J

M

M.

J

PVC b tolo

Y dOF, сM7o pM-

Av 9010 |PUM-6| 40 DOA (3-1) 25 in 20 | PEV ) 050 | 500) 0.01 | ABO» |0.01

PVC eevgvo to" 11 zho | 8020 | PUM-7 to the Federal District | 25 spa at PEV 0.50 | PM-oi maiy oo peoh-lo , 100 ; raid | 0. PVC E 6250 12 x 4010 |PUM-8| 50 DEF 0.01 |St.Sa| 2.0 | stkK | 0.01 | TiO5| 0.5 |) Chalk | 0.01 input-40 input-40!| 60 (|PUM-8 A-175 14 | Al | 5 |pU2gu| 700 | dBF | 001) BF | 001 | StkK | 0.01 | Tib 0.01 | ОО» |Т00)

M

M

A-15 - copolymer of vinyl chloride with vinyl acetate, VKHVD-40 - copolymer of vinyl chloride with vinylidene chloride, PE - plasticizer based on adipic acid, TOSS - tribasic lead sulfate, st.Ca, 2p - calcium and zinc stearate, st.Ba, Ca - stearate barium and cadmium;

BF - benzophenone, BF - benzotriazole, AI29Oz - aluminum oxide, TiO" - titanium dioxide

Table C

Mechanical properties of film materials obtained from the polymer composition

Me ne SHU VOYEN PNO FIELD FIGHTING FIELD prototype 17123 | 2801 - | 1-1 - 1 - 2 | 27 | 301 - her - 1 - 1-1 3 | 96 | 375 | Sh - | - her - Her - 1 - 741 24 | 2901 Shshch- | - th - Her - 1 - | 42 | 4001. - | - | DMFA | 45 | 450 76 | 935 | 3501. - | - 1 шЩщф- Her - 1 - 78 | 48 | 325 | 38 | 325 | DMFA | 49 | 400 79 | 45 | 420 1 - | - her - Her - 1 - 10, 30 | 300 1 sh- | - her - Her - 1 - 1138 1 330 | .- | - 1 - 1-1 - 712. 7-1 - 1 30 | 600 DMFAEA(IL) 32 | 700 13 7-11 -17171117 17111111 BA | 35 | 400 714 7-1 - 1 40 | 830 | mmEK | 45 | 850 15 | 25 | 550 17-17 - 1-1 - 16 | 16 | 2801 - | - her - her - 1 -

EL - ethyl acetate, MEK - methyl ethyl ketone

Example 7.

The synthesis of a polymer with the shape of particles in the form of microfibers (PUM-4, PUM-5) is carried out as follows: 120 g of Z 95 aqueous solution of STM are loaded into a 500 ml reactor equipped with a propeller stirrer and with intensive stirring (the number of revolutions of the stirrer is 20 rpm /s) at a temperature of 20 "C, add 7095 of a solution of the block oligomer (composition in Table 1) in dimethylformamide (DMF). After stirring for 5 minutes, the resulting dispersion is diluted with 200 ml of water and after standing for 3-4 hours, it is filtered, washed with water and dried.

The polymer is obtained in the form of fibrous particles with the following characteristics: D-0.07 mm, D-0.7 mm (PUM-4) or D-0.1 mm, D-0.6 mm (PUM-5).

The polymer composition for rolling and extrusion is prepared similarly to example 1.

As can be seen from the examples given, the materials obtained on the basis of the proposed polymer composition have higher strength characteristics due to the improvement of the compatibility of polymers (the dependence of the tensile strength on the composition is additive in nature). This expands the areas of their application, in particular for the production of artificial leather, film and duplicated materials for various technical purposes. In addition, they can be used to obtain coatings, glues, binders, structural materials, and medical products.

Sources:; 1 US patent Mo 3204013 2. Japanese application Mo 59-184240)

Z Application of Japan Mo 57-43570 4. Patent of the Czechoslovak SSR Mo 200025 - the closest analogue.

Claims (1)

UTILITY MODEL FORMULA A polymer composition containing a vinyl chloride polymer, plasticizers, stabilizers, lubricant, pigments, fillers and polyurethane and/or polyurethaneurea in finely dispersed Zo form, synthesized by dispersing an isocyanate component in an aqueous medium in the presence of a surfactant, which differs in that as an isocyanate component use a block oligomer with a content of 0.8-6.0 95 free isocyanate groups, which is obtained on the basis of oligoetherdiol, diisocyanate and a low-molecular chain extender with an active hydrogen atom, with the following ratio of composition components (parts by weight): vinyl chloride polymer 5-100 polyurethane and/or polyurethaneurea 5-100 plasticizers 0.01-65 stabilizers 0.01-3 lubricant 0.01-1.5 pigments 0.01-0.5 fillers 0.01-2.5.