The adhesion promoter for plastisols based on polyvinyl chloride or copolymer of vinyl chloride with vinyl acetate and plastisol based on polyvinyl chloride or copolymer of vinyl chloride with vinyl acetate

 

(57) Abstract:

The invention relates to polymer chemistry, in particular to the synthesis of adhesion promoters based on polyethylenepolyamine for polyvinyl chloride (PVC) plastisols and to the composition of the adhesion of the PVC plastisols used as adhesives for oil, fuel, air filters car, for sealing and protective coatings for metal surfaces. The adhesion promoter is a product of the interaction of polyethylenepolyamine and epoxidations resin, obtained when the equivalent ratio between 7.4 to 12.4:1 with amine number 600-806 mg KOH/g and viscosity 103-300 Pass. Plastisol based on PVC or copolymer of vinyl chloride with vinyl acetate (100 m h) includes the plasticizer is an ester of phthalic acid or its mixture with dioctyladipate, dioctylsebacate or plastification brand "ADOS" 85-100 m H.; lead stabilizer 3-7 m H.; calcium carbonate 45-150 m H.; calcium oxide 5-25 m H. ; phenol-formaldehyde resin grade SF A 5-25 m h and above, the adhesion promoter of 0.8 and 5.6 m H. Plastisol according to the invention has high adhesive strength and thermal stability. 2 C. p. F.-ly, 3 tables.

The invention relates to the field of synthesis promoters hell is stezala, used as adhesives for oil, fuel, air filters car, for sealing and protective coatings for metal surfaces.

The main requirement of the PVC plastisols of the above applications is high adhesion to metal.

Adhesive PVC plastisols, mainly determined by the promoter of adhesion, i.e. additive, giving adhesion.

Recently, as adhesion promoters PVC-plastisols are widely used polyamine and polyaminoamide ["Plastic", 1988, 10, S. 43-45].

It is known the use of PVC plastisols as adhesion promoters of polyethylenepolyamine ["Plastic", 10, 1988, S. 43-45), the product of the interaction of amines and carboxylic acids. [Application WO 94/18261, 08 G 69/34, 1995], the reaction product demonizovana esters of fatty acids of vegetable oils with polyethylenepolyamine (EN 2074214, 08 L 27/06, 1997).

Comparative evaluation of adhesion of the above adhesion promoters was conducted on the example of PVC-plastisol of the following composition, wt.h.:

PVC - 100

The dioctylphthalate (DOP) - 70

Trehosnovnoy sulphate of lead - 5

Carbonate ka="ptx2">

From the above table. 1 data shows that the use of the above additives increases the adhesion of the PVC plastisol is insignificant and practically does not increase its thermostability.

An object of the invention is the creation of effective adhesion promoter for plastisols based on PVC or copolymer of vinyl chloride, which increases the adhesion strength and thermal stability plastisol based on PVC or copolymer of vinyl chloride with vinyl acetate.

This task is solved in that the proposed adhesion promoter for plastisols based on PVC or copolymer of vinyl chloride with vinyl acetate, which is a product of the interaction of polyethylenepolyamine and epoxidations resin, obtained when the equivalent ratio between 7.4 to 12.4:1, respectively, with an amine number 600-806 mg KOH/g and viscosity 103-300 Pas.

The technical problem is solved by the fact that the plastisol based on PVC or copolymer of vinyl chloride with vinyl acetate contains the plasticizer is an ester of phthalic acid or its mixture with dioctylphthalate, dioctylsebacate or plasticizer brand "ADOS", lead stabilizer, calcium carbonate, calcium oxide, phenol-formaldehyde resin, representing the FDS is the product of the interaction of epoxygenase resin and polyethylenepolyamine, if the equivalent ratio between 7.4 to 12.4:1 with amine number 600-806 mg KOH/g and viscosity 103-300 Pass, with the following content of components plastisol, wt.h.:

Polyvinyl chloride or copolymer of vinyl chloride with vinyl acetate - 100

Plasticizer - 85-100

Lead stabilizer - 3-7

Calcium carbonate - 45-150

Calcium oxide - 3,5-15

Phenol-formaldehyde resin brand SFA - 5-25

The adhesion promoter is 0.8 and 5.6

As PVC is used paste PVC brands MSC (TU 6-01-2-533-80), EP S (GOST 14039-78), LacovyI PB 1302 (f. The elf Atochem, France), Solvic 372 LD, 372 NA, MD 373, 374 MB (F. Solvay, Belgium). As a copolymer of vinyl chloride (I) with vinyl acetate (VA) use the emulsion copolymer brand Vestolit V 5% VA (F. Hoechst AG, Germany).

As the plasticizer used esters of phthalic acid: dioctylphthalate (DOP), dibutyl phthalate (DBP), diallylphthalate (DAP 8-10, GOST 8728-88) and their mixtures with dioctyladipate (OSTEOARTHRITIS, GOST 8728-88), dioctylsebacate (DOS, GOST 8728-88) or with a mixture of dioxane alcohols and their high-boiling esters (plasticizer grade ADOS THE 2493-003-13004749-93).

As a lead stabilizer is used, for example, dibasic phthalate lead (TOFTS, THE 6-09-600-76), trehosnovnoy the use chalk fine (dpi) for Noblestown (TU 6-18-18-38-85), calcium carbonate (GOST 12085-88).

Used in the plastisol composition phenol resin is the condensation product of phenol and aniline with formaldehyde, taken in the ratio of 80:20: 44,4 has a name - formaldehyde resin SF-A(GOST 18694-80).

Calcium oxide is used for THE 6-18-197-74.

The plastisol may further comprise 5-40 wt.h. PVC extender brand Solvie 266 SF (f. Solvay, Belgium), 2-10 wt.h. white spirit (GOST 3134-78), 2-10 wt. including a mixture of Aerosil a-175 (GOST 14922-77) with glycerol (GOST 6259-75) in the ratio of 4:1, 15-25 wt.h. epoxygenase resin brand ED-16 or ED-20 (GOST 10587-84).

The invention is illustrated by the following examples.

Synthesis of adhesion promoter.

Example 1. In a reactor equipped with a stirrer, thermometer, heatable dropping funnel and air with alkaline protection from acid fumes in the air, put 183, (3,43 EQ.) polyethylenepolyamine. Include a mixer and add 72 g (0.36 EQ.) heated to 50oepoxy resin ED-20) with such speed that the temperature in the reactor was in the range of 60o. The equivalent ratio of polyethylenepolyamine and epoxy resin is equal to 9.5:1. After adding the epoxy resin is of amine number (and.h.) and when reaching the value and.h. 600-800 mg KOH/g of the product the contents of the reactor is drained into a clean container. Get 279 g of a viscous transparent mass of yellow, 6 g remains on the walls of the reactor. The viscosity of the product 160 Passing, and.h. 778 mg KOH/g

Amine number is determined by the method developed at the Institute of polymers, which consists in the following.

A portion of the adhesion promoter 0,02-0,15 g placed in a titration flask, dissolve in 15 cm3isopropyl alcohol, ethylene glycol (1:1), add 1 drop of color indicators methyl orange indicator and titrate with hydrochloric acid in a mixture of isopropyl alcohol and ethylene glycol concentration of 0.2 mol/DM3to first change the yellow color of the indicator in orange. In parallel to control the experience. Amine number (and.h.) calculated by the formula

< / BR>
where V', V k is the volume of hydrochloric acid used for titration of the promoter and the control experiment, cm3;

M - concentration hydrochloric acid, mol/DM3;

56,1 molecular weight of potassium hydroxide, g;

m is the mass of an adhesion promoter, was

For the analysis of the arithmetic mean of the results of at least two parallel definitions. Measurement error is 3.5%.

Visco is with the rotor 7 when the rotor speed 10 rpm

Example 2. Prepared as in example 1, but take 43 g (0,807 EQ.) polyethylenepolyamine and 13 g (0,065 EQ.) ED-20, i.e., the equivalent ratio of 12.4:1. The viscosity of the product 103 Pas, and.h. 806 mg KOH/g

Example 3. Prepared as in example 1, but take 38 g (0,72 EQ.) polyethylenepolyamine and 19.5 g (0,0975 EQ.) ED-20, i.e., the equivalent ratio of 7.4:1. The viscosity of the product 300 Pas, and.h. 675 mg KOH/g

Thus, synthesis of the proposed adhesion promoter lead by the interaction of polyethylenepolyamine and epoxidations resin in an equivalent ratio of between 7.4 to 12.4: 1, respectively, and the temperature not exceeding 60oC. the Process is a waste-free technology.

The test obtained in examples 1-3 of the product, which is the object of the invention, comprising the above PVC-plastisol led to the results given in table. 2.

Comparison of the adhesion of the known adhesion promoters (see tab. 1) the product of the interaction of polyethylenepolyamine and epoxy resin (see tab. 2) show that the proposed adhesion promoter known for superior adhesion and in addition increases thermostability of PVC plastisol.

The comparative result.

The selected ratio polyethylenepolyamine and epoxide-Vodianova resin between 7.4 to 12.4: 1 is because when the ratio is less than 7,4 dramatically increases the viscosity promoter, and when the ratio is larger than that of 12.4 increases dramatically amine number that koreanum ultimately affects product properties as adhesion promoter.

Getting PVC plastisols.

Example 1.

In the mixer planetary mixer download 100 wt.h. PVC brand MS S, 85 including DOP, 3 wt.h. LOFTS, 45 wt.h. chalk fine, 5 wt. including calcium oxide, 5 wt.h. onlinephenterminesales resin SF-A. Mix the components for 30 min with rotation speed planetary mixer 60 rpm Then dispersed mixture on a three-roll pasterka at minimum (50 μm) gap between the rollers.

Predispersion plastisol is loaded into the mixer, add 0,8 wt. am a product of the interaction of polyethylenepolyamine with epoxy resin, taken in an equivalent ratio of 9.5:1, respectively, with and.h. 778 mg KOH/g and a viscosity of 160 Passing, stirred for 15 min and vacuum for 30-40 min at a residual vacuum of not more than 10 mm RT.article.

The temperature of the plastisol at all stages of its photobleachable.

Preparation of samples for testing

Two plates, pre-wiped with ethanol, stick together among themselves lapped the plastisol with an area of overlap 25x25 mm2and to hold paper clips. Prepare 5 samples.

The sample is placed in a heat chamber, heated to a temperature (1973)oWith, stand in it for 5 min and cooled at room temperature.

Tension shear (adhesion strength) of the bonded wafer is determined using a bursting machine (the speed of sliding clamps 10010 mm/min) and calculated by the formula

< / BR>
where P is the breaking load, N;

F - area overlap, mm

Determination of thermal stability of the plastisol

In a glass test tube with 1 g of plastisol at a distance of 7.5 cm from the bottom of the test tube is placed a strip of indicator paper "the Congo". The tube is installed in a cell of a thermostat heated to a temperature of 200oC. Record the time since the installation of the tubes in thermostat until the color changes of indicator paper. At the same time test 5 samples plastisol.

The results are given in table. 3.

Example 2-16

Method of preparation of plastisols and methods the comparison (prototype)

From the above table. 3 data shows that the use of the plastisol composition based on PVC or copolymer of vinyl chloride as a promoter of adhesion of the product of the interaction of polyethylenepolyamine and epoxy resin in an equivalent ratio of between 7.4 to 12.4:1, respectively, with an amine number 600-806 mg KOH/g, viscosity 103-300 Pas and at 0.8 and 5.6 wt.h. on 100 wt. including the polymer allowed to increase adhesive strength under shear to 7.8 and 9.0 MPa, a thermal stability up to 40-50 min at 200oC. the prototype, these figures respectively of 4.5 to 7.7 MPa and 20-30 minutes

The selected amount of adhesion promoter in the plastisol (0.8 to 5.6 wt.h. on 100 wt.h. PVC) due to the fact that when the content of the adhesion promoter is less than 0.8 wt. including sharply reduced adhesive strength of the glue, and when the content is more of 5.6 wt.h. the adhesion strength of the adhesive layer practically does not change, and thermal stability of the composition falls.

A significant increase in the adhesion of the plastisol with the introduction of the proposed promoter adhesion is achieved by a much smaller quantity (0.8 to 5.6 wt. hours at 100 wt.h. PVC) than the additives used in the prototype, the total number of which is 10-50 wt.h. on 100 wt.h. PVC.

1. The promoter ADI a product of the interaction of polyethylenepolyamine and epoxidations resin, if the equivalent ratio between 7.4 to 12.4:1, respectively, with an amine number 600-806 mg KOH/g and viscosity 103-300 Pas.

2. Plastisol based on polyvinyl chloride or copolymer of vinyl chloride with vinyl acetate containing plasticizer is an ester of phthalic acid or its mixture with dioctyladipate, dioctylsebacate or plasticizer brand "ADOS", lead stabilizer, calcium carbonate, calcium oxide, phenol-formaldehyde resin, which is a product of condensation of phenol, aniline and formaldehyde brand SF A and the adhesion promoter based on polyethylenepolyamine, characterized in that the adhesion promoter based on polyethylenepolyamine it contains the promoter of adhesion under item 1 in the following plastisol components, wt.h.

Polyvinyl chloride or copolymer of vinyl chloride with vinyl acetate - 100

Plasticizer - 85-100

Lead stabilizer - 3-7

Calcium carbonate - 45-150

Calcium oxide - 3,5-15

Phenol-formaldehyde resin brand SFA - 5-25

The adhesion promoter is 0.8 - 5.6 t

 

Same patents:

Polymer composition // 2186802
The invention relates to polymeric compositions used in the repair of oil and gas pipelines both in summer and winter conditions, the use of metal couplings, as well as casting compounds in electronics, electrical engineering, construction and other purposes

Epoxy composition // 2186801
The invention relates to epoxy compositions of cold hardening and can be used for the manufacture of epoxy self-leveling flooring, protective and decorative coatings, potting compounds, etc

Epoxy composition // 2186077
The invention relates to epoxy compositions used for gluing repair linings for pipes, metal structures for filling small defects, as anti-corrosion coatings

Repair part // 2186076
The invention relates to filled with metal compositions based on epoxy resins intended for repair of metal surfaces, in particular pipelines

The invention relates to the field of creation of high-strength composite materials on the basis of fibrous fillers and epoxy resins, which can be used in machine building, shipbuilding, aviation industry and other fields

The invention relates to polymeric compositions used in nuclear engineering, namely for the conditioning of radioactive waste with high fluence induced activity

The invention relates to woodworking industry, in particular the production of Board materials, and can be used in the manufacture of combustible materials

The invention relates to the manufacture of compositions that can be used for the manufacture of GRP pipes, automotive compressed gas cylinders, tanks for storing liquids for the formation of protective corrosion-resistant coatings and various products made of composite materials

Epoxy composition // 2160291
The invention relates to compositions of polymer compositions based on epoxy Dianova resins and their hardeners which can be used as a binder for the production of GRP materials, in particular of shell structures

The invention relates to the chemical, petrochemical, rubber, aircraft, etc

The invention relates to the field of composite materials, in particular antifriction compositions based on phenolic resins and fillers, suitable for the manufacture Bolotnikova pairs of gas meters

The rubber modifier // 2118969
The invention relates to the rubber industry, in particular to the modification of rubbers to improve their hardness and strength characteristics, and can be used in tire and rubber industry

The invention relates to the rubber industry, in particular the production of reclaim and rubber mixtures based on it for the manufacture of soles

The invention relates to the manufacture of polymeric materials on the basis of phenol-formaldehyde resins rezol type and can be used in the construction industry

The invention relates to the manufacture of polymeric materials on the basis of phenol-formaldehyde resins rezol type and can be used in the construction industry

Composite material // 2104875
The invention relates to composite materials designed for the production of interior parts in aviation, shipbuilding, automotive and other industries, including the manufacture of products of complex configuration

Plastisol // 2074214
The invention relates to compositions of polyvinylchloride (PVC) plastisols used as adhesives for oil, fuel and air filters car

The rubber mixture // 2036939
Up!