UA68406C2 - Method for producing composites based on chlorvinyl polymers and polyurethanes - Google Patents

Abstract

The method for producing the composites based on chlorvinyl polymers and polyurethanes, the low-molecular plasticizers, the stabilizers, and the special additives in granulated form employing the extrusion technique. The composites thus obtained are suitable for being processed by the rolling, the extrusion, the pressure casting and may be used for manufacturing the elastic film materials, the imitation leather, the coating, the adhesives, the binding materials, the shoe soles, the hoses, and the medicinal products.

Description

Description of the invention

The invention relates to the method of obtaining composites based on chlorovinyl polymers (CVP) and polyurethanes 2 (PU), which are processed by rolling, extrusion, injection molding or by solution technology, and can be used to obtain film materials, artificial leather, coatings, adhesives, binders, shoe soles, hoses and medical products, etc.

There are known methods of obtaining composites based on chlorovinyl resins and polyurethanes by mixing starting polymers, low molecular weight plasticizers, special additives and various fillers, which can be processed on rollers or by the extrusion method at a temperature of 160-180 "C. Polyurethanes are added to the composition in powder form (A.c ChSSR Mo200025) or in granular form (Federal patent Mo1193241).

Composites that are insoluble in dimethylformamide (US patent Mo4347338) with improved strength properties are obtained by mixing 5-100 (wt. parts) of polyisocyanate with »2 functional MSO - groups with 100 (wt. parts) thermoplastic polymer (polyvinyl chloride). Then the obtained concentrate in the amount of 1-100 (parts by weight) is mixed in an extruder or mixer with 100 (parts by weight) of thermoplastic polymer and processed by injection molding, ending with curing at a temperature of 1007C for 2 hours. The material with a content (wt. parts) of 100 polyvinyl chloride (PVC), 20 naphthylenediisocyanate, 100 polyester polyurethane is characterized by tensile strength (5)-32.3(19.6)MPa, relative elongation (E) -500(546)96, modulus of elasticity at 10095 elongation (E100)-4.8(2.7) MPa. The characteristics of the sample obtained without the use of polyisocyanate are given in quotation marks.

There are known methods of obtaining composites by mixing powdered HVP and reactive isocyanate and hydroxyl-containing components to obtain PU. So, for example, (Japanese application Mob2-1715, published in 1987) by mixing polyvinyl chloride with an isocyanate component, a heat stabilizer and a catalyst at a temperature of 707C for 15 minutes. powder A is obtained. Then PVC is mixed with a polyol, a catalyst at 1007C for 20 minutes, obtaining powder B. Composites are obtained by mixing powders A and B at a molar ratio of 29 MSO:OH-O,5-10 at room temperature and then processed by rolling at temperature (U 1857"C. This method produces rigid plastic with up to 41MPa and E up to 5095. Compositions with a content of 5-5590 fractions insoluble in tetrahydrofuran (Japanese application Mo3294326 published in 1991) are obtained by mixing in a PVC melt with a polymer polyol of molecular weight (MM)300-10000, which contain 5-2 OH groups, and compounds containing 53 isocyanate groups. Composites based on polymers of vinyl chloride, polyols, isocyanates, plasticizers, stabilizers (US patent Mo5929153) are obtained by reaction in the melt under the action | "c) of a catalyst with simultaneous mixing of components under shear loads. 200-800 (wt. parts) of polyols and isocyanates are used in such quantities that the ratio is MSO-:OH-groups equals 0.3-0.8:1.0. The disadvantage of known methods of obtaining composites is the lack of manufacturability of the starting materials (ge) from compositions that include isocyanate and hydroxyl-containing components, since they are not stable in air. with

The reaction of isocyanate groups with moist air leads to a violation of the ratio of functional groups, which in turn reduces the stronger indicators of the final material.

The method of obtaining composites based on chlorovinyl polymers, polyurethanes, stabilizers and special additives using a prepolymer as an isocyanate "20 component, which is cured with moist air (Ass. of the Czechoslovak SSR Mo211067), is the closest to the stated solution. Prepolymer (FP) is synthesized on the basis of polyol and diisocyanate, which contains 0.1-1095 free isocyanate groups (better with 0.5-2.595). Compositions are obtained in a mixer, homogenized powdered HVP, stabilizers, special additives and previously heated to 907 FP in the amount of 2-4595, preferably 5-2595. From the obtained compositions, first by rolling at a temperature of 1757C for 5 minutes. form a film with a thickness of 0.bmm, and then by casting under

Tskom - sheet material with a thickness of 4 mm. With the help of this method, a hard impact-resistant composite material is obtained (impact strength-20-45 kJ/m?). Composites containing 25-4596 PU are characterized by a relative elongation of 160-30095, and a modulus of elasticity at 10095 elongation of 32-16MPa. The method of obtaining co-composites according to the prototype has a number of technological disadvantages: their 1. instability of the original compositions in air; 2. high stickiness to rolls of compositions with a content of more than 4595 FP, which makes it impossible to obtain elastic materials by rolling.

Ф The task of the proposed invention is to create a method for obtaining composites, which ensures the improvement of the technological properties of composites in granular form, stable in air, processed by methods of rolling, extrusion, injection molding, according to soluble technology and obtaining 8pastic materials with a polyurethane content of 25-95 (wt. .parts) and low molecular weight plasticizer 0.01-40 (parts by weight). (F. The task is achieved by the fact that in the known method of obtaining composites based on chlorovinyl co-polymers, polyurethanes, stabilizers and special additives, in accordance with the proposed invention, 25-95 (wt. parts) of oligourethane synthesized on based on oligodiol, in the action of isocyanate and a low-molecular chain extender with an active hydrogen atom, which contains 0.8-6,090 free isocyanate groups, 0.01-40 (wt. parts) of a low-molecular plasticizer and mix the original components by the extrusion method and obtain a composite in the form of rods with a diameter of 3-4 mm, cool them in a water bath, granulate and harden in air for 22-24 hours.

For the synthesis of oligourethanes, oligodiols of molecular weight 800-2000 with 65 functionality according to hydroxyl groups can be used »2. These include simple polyesters (polyoxytetramethylene, polyoxyethylene, polyoxypropyl glycol), complex polyesters obtained by polycondensation of aliphatic diols and dicarboxylic acids, and polylactones.

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

Aliphatic, cycloaliphatic, aromatic diols (ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,4-butanediol, cyclohexanediol), diamines (ethylenediamine, toluenediamine, 4,4-diaminodiphenylmethane, cyanethylated ethylenediamine, hexamethylenediamine, oxypropylated ethylenediamine, etc.) amino alcohols, hydrazine. 70 The synthesis of oligourethanes based on oligodiol, diisocyanate and a low-molecular chain extender is carried out in a reactor at a temperature of 75-807C for 2-3 hours. before reaching the theoretical value of isocyanate groups (0.8-6.0905).

Polyvinyl chloride, perchlorvinyl resins (PSC), copolymers of vinyl chloride with vinyl acetate, vinylidene chloride (VCHVD), butyl acrylate, acrylonitrile, /5 methyl acrylate, etc. can be used as chlorovinyl polymers. monomers

Phthalic, adipic, sebacic acid esters, etc., can be used as low molecular weight plasticizers (LP).

As heat and light stabilizers, you can use stearates (St) of cadmium, barium, zinc, lead, thioalcophene MVP, thioalcophene C, phosphite NF, benzol OA, phenozal 23,30, forstab K-21, epoxy compounds, etc.; 2 o lubricants - polyethylene wax (PEW), chloroparaffin. stearic acid (STK) and oleic acid; fillers - pigments, chalk, aerosol, kaolin, graphite, aluminum hydroxide, stibium oxide, etc. flame retardants, pigments.

The composite preparation technology consists in pre-mixing the powdered components in a rotary mixer for 15-20 minutes. When using low-molecular weight plasticizers, the mixer is heated to 90°C and the mixture is homogenized until it reaches a temperature of 75°C, and then cooled. The mixing of powdered components with the isocyanate component, preheated to 50-80°C, is carried out in a disk extruder to obtain rods with a diameter of 3-4 mm, which then cooled in a water bath to i) a temperature of 20"C, granulated, hardened in air for 22-24 hours. The resulting composite in granular form, stable in air for a long time, is processed by methods of rolling, extrusion, and pressure casting in the temperature range of 140-1757C. By dissolving the granulate in an organic solvent (dimethylformamide, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, toluene, etc.), a polymer solution for various technical purposes can be obtained. at

The essence of the invention is confirmed by examples. The composition of oligourethanes (OU) is presented in Table 1, the composition of polymer compositions - in Table 2, the properties of film composites obtained by rolling, extrusion, or from solutions in an organic solvent - in Table 3.

Example 1. "Fr

The synthesis of OU-1 (example 1, Table 1) is carried out as follows: 1000 g of dehydrated polybutylene glycol adipinate (dried for 3 hours at 1007"C in a vacuum of 133 Pa) with a molecular weight of 2000 (PBA-2000) is loaded into a 2000 ml reactor equipped with a propeller stirrer. , 110.5 g of toluene diisocyanate (TDI) and 3.4 g of 1,3-propanediol (PD). The mixture is heated for 3 hours at 807C and a block oligomer with free isocyanate " groups of 1.2595 is obtained. shsh s In a closed rotary mixer with a capacity of heated to 90"C, 1000g (44.4 mass parts) of suspension PVC brand So 7059, 5g (045 mass parts) are slowly introduced through the loading device;" polyethylene wax, 30 g (1.34 parts by weight) of zinc and calcium stearate stabilizer), after stirring for 10 minutes, add 200 g (8.9 parts by weight) of dioctyl phthalate (DOF) and then homogenize the mixture. Upon reaching a temperature of 757C, the heating is stopped and the mixture is cooled to 2570. Mixing the powdered components with

He» 1000g (44 b4 mass.h.) heated to 807"С SU-1 is carried out in a disk extruder to obtain rods with a diameter of

Zmm, which harden after cooling in a water bath. Then they are granulated, hardened in air for 22 hours. and dry. The absence of isocyanate groups in the composite is confirmed by IR spectroscopy. Next, their granulate is rolled for 5 years. at a temperature of 155-1657C and obtain a film with a thickness of 0.1-0.bmm. Physical and mechanical properties of the film; 5-34MPa, El00-6.5MPa, Е-52095. By dissolving the granulate in dimethylformamide, a Z0956 solution was obtained with a dynamic viscosity of 250 pz and the properties of the film material: C-Z35MPa,

F Echo 0-6 MPa, E-600905.

Composites in examples 2, 3, 5, 6, 7, 8, 9, 10 are prepared similarly to example 1.

Example 4.

Synthesis of OU-4 and preparation of the composition is carried out similarly to example 1. Mixing of powder-like components from SU-4 and 8 OU| Oligodiol | Diisocyanate Chain extender Content MSO-corpse, 95

Zaprotyuttyum ev (ma uz pe leyuitdimtje) wdo 02200293 vv S mdovo 01101

OSU-A PEBA 1000 MDI 261.0). CED 85.0 312 su8| layui |, 11113 1 lova zobotdozaez| opvdo vv 297 ut pdA soyuitdovzhye) To 00025 0000600 was payu! 11 approx. voo tdunole hydrazino/ 064 ol

PEB - oligodiol based on ethylene glycol and adipic acid (acid number mg KOH/g-56) 70 PEBA - polyethylene butylene butylene glycol adipinate molecular weight (MM) 2000

Laprol 1052 - polyoxypropylene glycol MM1O5O

PDA - polydiethylene glycol adipinate MM8OO

PF - polyoxytetramethylene glycol MM1Т0О0О

BD - 1,4-butanediol

MDI - 4,2-diphenylmethanediisocyanate

CED - cyanethylated ethylenediamine

GL - glycerin

OPED - oxypropylated ethylenediamine

ГД - hydrazineethanolamine 2 order pc kish o part /table.1 (part part part part part Ge) se MN ey totype Ziomipu! 7p,Sa Helaton 0.84 683 Р-26 g 7059М sh 2 | it's easy! | 001) 2oo | PEV | this | o z pehvbavozh vezo ouz BO doF bo vo 20030 « 11pdvyu voi 111111 i pvhstvom lvoo oul lvoo do 2207 15730050 so zv 5 | polo village su toso dvo, 0lo0 30 Azoyu ol o 6 | dl lvoo ouye vosodoFi 001 || At oyu 7 enter ovooo sut zvo two 00107100 80199 in pszhle 340 sold|vvoo| 7: 001 АЮ 055 Z s ovo mo you my de vo and t 7p,Sa ;"

KC - stable icon KC-05 with

F so nn to pteeovuioiv mov movi i ukdyumo tererovyts ho mla/ el type vozchinina o. Mpa Is Mpa,

FD gives 10001161 levs

F 1 rovvyev with | entered! 17771717171717171117111111111111171dmeya | 35) in bob) 80 voyatv yav in" zvo 000 allows 0 45 region 00000080 in vh vva import 01000010 0174111 zvayu | i vvolv0000pvoluv | 42 voi 07300049 82 in mk o vviv, yu i quooyuv, kov, in 81 vm | wow 01010 1 olo | yavovovyu in 0450090 vvoy 1717 -1717111717711717717711111 molvv t vovoy! 17111111

Example 2" - processing of the composite by injection molding in the temperature range of 145-1557С, properties: 5-27MPa, v5 E-1oMPa, Е-40095 is carried out in a disk extruder to obtain bars with a diameter of 4 mm, which, after cooling in a water bath, are granulated and hardened in air for 24 hours and dried.The properties of the film materials are given in Table 3.

As can be seen from the examples given, the proposed method is technological, because it allows you to obtain air-stable composites in granular form based on chlorovinyl polymers, polyurethanes, / low-molecular plasticizers, stabilizers and special additives, expands their processing methods and allows you to obtain elastic materials with a wide range properties (E 400-4-10MPa, 0-17-55MPa, Е-350-85095), which significantly expands the areas of their application, in particular, for obtaining artificial leather, film and duplicated materials for various technical purposes. In addition, they can be used to obtain coatings, adhesives, binders, shoe soles, hoses and medical products.

Claims (1)

The formula of the invention The method of obtaining composites based on chlorovinyl polymers, polyurethanes, stabilizers and special additives, which is distinguished by the fact that 25-95 wt. oligourethane synthesized on the basis of oligodiol, isocyanate action and a low-molecular chain extender with an active hydrogen atom, which contains 0.8-6.095 free isocyanate groups, 0.01-40 wt.h. low molecular weight plasticizer and mix the original components by the extrusion method and obtain a composite in the form of rods with a diameter of 3-4 mm, cool them in a water bath for 2o, granulate and harden in air for 22-24 hours. Official bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated microcircuits", 2004, M 8, 15.08.2004. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. 6) (Se) «c) « (ee) (Se) - and? (o) (ee) sh" ("c) 4) name) 60 b5