Modified halogenated and halosulfonated butene-1 (co)

FIELD: plastic, rubber, chemical, petrochemical, paint-vehicle, air and other industrials.

SUBSTANCE: halogenated or halosulfonated butene-1 (co)polymer is obtained in tetrachloroethane or chlorobenzene solution and contains chemically coupled chlorine and/or bromine, or chlorine and sulfur, or bromine and sulfur, or simultaneously chlorine, bromine and sulfur in form of groups -SO2Cl and -SO2Br, wherein content of chlorine and/or bromine and sulfur is 1-73 mass % and 0,2-4,0 mass %, respectively. Also disclosed are polymer, elastomer composition, binding agent and articles based on halogenated and halosulfonated butene-1 (co)polymer.

EFFECT: butene-1 (co)polymer, article and composition therefrom with increased controlling strength, elasticity, fire-retarding, as well as controlling flow point, percent elongation, etc.

9 cl, 19 tbl, 6 dwg

 

The invention relates to plastic, rubber, chemical, petrochemical, paint, aviation and other industries, processing and use of plastics, rubbers, lacquers, adhesives, and more particularly to polymers, rubbers, rubbers, lacquers and polymer compositions on the basis of plastics, rubbers and synthetic resins.

Known chlorinated polyethylene (CCE)containing 1-72% chlorine (Ronkin G.M., Plastics, 1980, No. 8, p.16-20; Ronkin G.M. Jntem. Polym. Sci. and Technol, 1981, v.8, No. 2, pp.33-39).

The disadvantage of the CCE is their low strength, low elasticity and low resistance.

A mixture of rubbers and plastics with the CCE have insufficient strength, elasticity and resistance.

Used in the production of varnishes, paints and adhesives industrial CCE with high chlorine content (type CPE-10, CPE-20, FS: England) have low temperature fluidity - just 105-110°C.

From US 5668220, 16.09.1997 known chlorinated and chlorosulphurized polyolefin polymers, in particular a copolymer of ethylene and 1-octene containing chemically combined chlorine (2,0-23,0 wt.%) or chlorosulphurized containing chemically bonded chlorine in the amount of 20-50 wt.% and sulfur in a quantity of 0.8-2.5 wt.% on their basis, as well as on the basis of polymer compositions containing halogenated this and halogensulphonylphenyl copolymer of ethylene and 1-octane, get the hypoxia products for example the film.

Their products have low Flammability, but do not have the required strength properties, in addition, the copolymer sparingly soluble in organic solvents, which limits its use.

From US 4379882, 12.04.1983 known polyolefin compositions based on halogenated polyolefin polymers and copolymers of C2-C8olefins and dienes, polybutene-1, poly-4-methyl-1-penten). The halogenation agent is specified chlorine and bromine but does not specify the amount of chemically bound halogen in the polyolefin, as this patent primarily relates to the use of the catalyst for polymerization of aluminum-magnesium hydroxide Mgl-xAlx(OH)2+xmH2O. Known composition used for the manufacture of molded articles, films with good corrosion properties, but not good enough strength and elasticity.

From US 5449833, 12.09.1995 known chlorinated and chlorosulphurized polyolefins (polyethylene, copolymers of ethylene with propylene, copolymers of ethylene and butene-1)obtained in the presence of catalysts, organic peroxides or azocompounds and in a solution of dichloromethane. The content of chemically bound chlorine in the chlorinated copolymer of ethylene-butene-1 is 27,2-a 27.4 wt.%; the content of chemically bound chlorine is and sulfur in chlorosulphurized copolymer, ethylene-butene-1, respectively 29,7-35,4 wt.% and 0.9 to 1.0 wt.%. The obtained copolymers are used for various products, adhesives and coatings. The obtained chlorinated copolymers of ethylene-butene-1 have a relative elongation 360-370%, chlorosulphurized copolymers, ethylene-butene-1 have a relative elongation 521-538%.

The technical objective of the claimed invention (group of inventions is getting halogenated and halogencontaining (co)polymers of butene-1 and its compositions, and products with high adjustable strength, elasticity, resistance, and adjustable temperature yield strength, elongation and softness.

The goal of the project is achieved by a group of inventions, including halogenated or halogensulphonylphenyl (co)polymer of butene-1, obtained in the solution of tetrachlorethane or chlorobenzene containing chemically bonded chlorine and/or bromine, or chlorine, and sulfur, or bromine and sulfur, or simultaneously, chlorine, bromine and sulfur in the form of SO2Cl - and SO2VG-groups, the content of chemically related chlorine and/or bromine is 1-73 wt.%, sulfur 0.2 to 4.0 wt.%.

Thus preferably halogenated and halogenalkane (co)polymers of butene-1 contain 1-73 wt.% chemically combined chlorine, or 1-70 wt.% chemically bound bromine, or 1-73 wt.% at the same time chemically related chlorine and bromine, or one who temporarily chemically related 10-65 wt.% chlorine or bromine, and 0.2 to 4.0 wt.% sulfur in the form of SO 2Cl - and SO2VG-groups, or simultaneously chemically related chlorine and bromine in an amount of 1-70 wt.% and 0.2 to 4.0 wt.% of sulfur.

Thus, the technical problem is also achieved and compositions containing the above (co)polymers (halogenated and halogenalkane) of butene-1 as a binder for paints, adhesives, coatings, etc.

In the claimed group of inventions is an elastomeric composition comprising halogenated or halogensulphonylphenyl (co)polymer of butene-1, claimed as inventions in the amount of 1-99 wt.% and 99-1 wt.% a rubber composition based rubber selected from the group comprising styrene-butadiene rubber, butyl rubber, ethylene-propylene rubber, isoprene rubber, CIS-1,4-polybutadiene rubber.

In the claimed group of inventions is cohesive to adhesive-glue or paint compositions, which represents a modified halogenated or halogensulphonylphenyl obtained in the solution of lorenzana or tetrachlorethane (co)polymer of butene-1 containing chemically bonded chlorine and/or bromine and sulfur in amounts respectively 58-73 wt.% chlorine, or 56-70 wt.% bromine, or 56-70 wt.% chlorine and 0.3 to 4.0 wt.% sulfur, or 58-70 wt.% bromine and 0.2 is 3.76 wt.% sulfur, or both chlorine and bromine when the total content of their 58-70 wt.%, or both chlorine and bromine content of total chlorine and bromo-73 wt.% and 0.2 to 4.0 wt.% sulfur in the form of SO 2Cl - and SO2Br-group.

In the claimed group of inventions also includes a polymer composition for the manufacture of films, molded articles, comprising from 0.5 to 99.5 wt.% halogenated or halogencontaining (co)polymer of butene-1, claimed as the invention, and from 0.5 to 99.5 wt.% shared with him polymer selected from the group including polyethylene, polystyrene, polypropylene, polyvinyl chloride or mixtures thereof.

Meanwhile combine the polymer may be a secondary polymer (non-conforming), for example, in the form of waste polymer, for example in the form of different scraps of products (film, pipes, cable sheath).

The polymer composition may further comprise catalysts intermolecular dehydrocorydaline, or it can also be subjected to cross-linking γ-radiation with a dose of up to 70 Mrad, or both.

In the claimed group of inventions also includes products derived from halogenated and halogencontaining (co)polymer of butene-1 according to this invention, the surface of these products is subjected to chlorine and/or bromine or both chlorine and/or bromine and sulfur dioxide.

In the claimed composition of the invention also includes various products (coatings, films, molded products, traditionally made and the rubber mixtures sealants, adhesive coating and so on).

Manufactured using halogenated or halogencontaining (co)polymers of butene-1 according to this invention, and compositions containing, which is also one of the inventions claimed in the group.

The rubber compositions when receiving elastomeric compositions according to the invention is used, for example, various traditionally made of rubber mixtures containing various conventional additives target (vulcanizing additives, stabilizing additives, antioxidants, fillers, etc.), such as carbon black, zinc oxide, captax, diphenylguanidine, 4-mercaptobenzthiazole, burnt magnesia, and others (see “Handbook of reinsta” edited Piechaczek etc., M., Chemistry, p.32, 51-52, 61-68, 101-111).

In particular, as the rubber composition of styrene-butadiene rubber (example 14) using the composition of the rubber mixture comprising butadiene-styrene rubber is 100 parts by weight of 2-mercaptobenzthiazole to 0.6 parts by weight, sulfur is 0.1 to 0.8 parts by weight, thiuram of 0.3 to 0.6 parts by weight, zinc 3-6 parts by weight, stearin 6-8 parts by weight, phenyl-2-naphtylamine of 0.8-1.2 parts by weight, paraffin 10,4 by 20.8 parts by weight of the bitumen 5-10 parts by weight of rosin 1-2 parts by weight of chalk 50-100 parts by weight, talc 50-96 parts by weight, sodium tetraborates 10-15 parts by weight, carbon black 30-60 parts by weight, dibutyl phthalate to 0.23 parts by weight of

As a rubber composition based on isopre the new rubber using the rubber composition of the mixture, including isoprene rubber 100 parts by weight, zinc 4-8 parts by weight, captax 0.3 to 1.0 parts by weight, diphenylguanidine of 0.8 to 1.8 parts by weight, burnt magnesia 0.5 to 0.8 parts by weight, stearin 8-10 parts by weight, paraffin 10-15 parts by weight, carbon black 20-40 parts by weight(example 15).

As a rubber composition based on ethylene-propylene rubber is used, for example, the composition of the rubber compound, including parts: ethylene-propylene rubber-10, softner 6,0-8,0, filler 20,0-76,0, polyorganosiloxane 1,0-2,5, zinc oxide 5,0-10,0, stearic acid, 0.8 to 1.5 (example 17).

As a rubber composition based on butyl rubber using the rubber composition mixture comprising in parts by weight: butyl rubber 100, sulfur 2,0, thiuram 0,65-1,3, captax 0,65-1,3, zinc oxide 5,0, stearic acid 2.0 to 3.0, channel carbon black 50,0 (example 16).

As a rubber composition based on CIS-1,4-polybutadiene using the composition, for example, a rubber mixture comprising in parts by weight: butadiene rubber (SKD-II, ACS-I, SCDL) 100, oil MO-6 15-40, soot PM-100 60-80, sulfur 1,95-2,4, centocor-MT 1,15-1,4, stearic acid 2,0, zinc oxide 5.0, antilux 1,5, paraphenylenediamine 1,0 (example 18).

Below are specific examples of making halogenated and halogencontaining (co)polymer of 4-methyl-pentene-1, their properties, their properties as a binder for adhesive-adhesive and coatings, preparation and properties of the compositions and the products based on them.

The content of chemically related chlorine, bromine and sulfur in the polymer expressed in wt.%.

Polybutene and SB are known polymers of the class of polyolefins and production are on the 3rd place after polyethylene and polypropylene. The difference between IB and SB is that their strength is 29-26 MPa, while the strength of LDPE 10-12 MPa. This is the difference. as well as the structure of the circuit PB and SB was possible to achieve increased strength, elasticity and resistance of the modified PB and SB and mixtures thereof with other polymers, as evidenced by the following examples.

Chlorination, bromination, chlorbromuron, chlorsulfuron, prosultiamine and chlorobromomethane with PB PTR-0.14 to 15.6 g/10 min was performed in a solution of chlorinated solvents (tetrachlorethane or chlorobenzene) at the facility, consisting of a 2-liter round bottom reactor equipped with a bubbler for submission of cylinders of gaseous chlorine and gaseous sulfur dioxide, a stirrer, condenser, sootvetstvujushej valves and communications. Exhaust gases neutralized in the absorption column.

When bromirovanii, chlorbromuron and bromsulphalein liquid bromine was introduced directly into the reactor through an addition funnel. Sulfur dioxide was applied from a container through a bubbler. Chlorbromuron PB and SB was obtained by bromirovanii polymers in solution is liquid bromine, and then chlorination with gaseous chlorine.

Chlorosulphurized PB and SB received simultaneous chlorination and sulfonation of polymers when applying the polymer solution of chlorine and sulfur dioxide.

Prosultiamine PB and SB received simultaneous bromirovanii liquid bromine and sulfonation with gaseous SO2in the reaction mixture.

Upon completion of the reaction (obtaining a specified number of modifiers in polymer) solution of the modified polymers was otdovali nitrogen from acid gases, polymers were planted from a solution of ethanol, was pressed and dried in a vacuum oven at 40-60°until the volatile content is not more than 0.3%.

Determination of halogen conducted according to the method of Saniger.

Determining the level of highly elastic to plastic deformation of polymers and temperature yield strength was performed according to standard method of determining the degree of elasticity of polymers thermo-mechanical curve (PMC), filmed on the device for the removal of thermomechanical curves weights Zeitlin, uniaxial compression and heating of the samples from -50 to +180°C at a heating rate of 2°C/min with automatic recording of results. Rod load was 2 MPa (Ronkin G.M. Rubber & rubber, 1979, No. 7, p.5-11). The method of determining other characteristics of the modified polymers of butene and the security specified in the table is, described in this source.

It should be noted that the level of highly elastic deformation HPB obtained by chlorination in chlorobenzene, higher than HPB,

chlorinated in tetrachlorethane, but with equal concentrations of chlorine strength characteristics at them below.

The table below shows the level of highly elastic to plastic deformation, defined by TMK in the middle of the plateau viscoelasticity.

Figure 1. Thermomechanical curves of the source (1) and halogenated PB with chlorine content, %: 2-1,52 (bromine 1,71);3-7,70 (bromine 8,43); 4-13,16; 5-23,54 (bromine 26,45); 6-40,42 (bromine 44,68 and sulfur 1,32); 7-54,43; 8-61,83 (bromine 61,93 and chlorine 1.87); 9 63,83 (bromine 66,82); 10-69,71; 11-72,93.

Figure 2. The characteristics of the original (1) and halogenated PB with chlorine content, %: 2-4,31 (bromine 6,93); 3-7,70 (bromine 8,43); 4-11,42 (chlorine 10,61 and bromine 3,41); 5-23,54 (bromine 26,45 and sulfur 0,39); 6-33,16 (bromine at 36.91); 7-40,42 (bromine 44,81); 8-54,46; 9-58,23 (bromine 60, 11).

Figure 3. The resistance change of the gap (1), and elongation (2) and temperature fluidity according to thermomechanic (3) for halogenated PB varying degrees of halogenation.

1.. - chlorinated PB, Δ octabromodiphenyl PB,

2. x - chlorinated RO,octabromodiphenyl PB,

3. on - chlorinated IBoctabromodiphenyl IB.

Figure 4. Change the values of the TPP mixtures of polymers with HPB (14,63% chlorine) depending on the content HPB in the mixture.

1 - LDPE; 2 PP; 3 - PS.

Figure 5. The resistance change of the gap (a) and relative elongation (B) mixtures of polymers with HPB (14,63% chlorine) depending on the content of the project HPB in the mixture.

1. - HDPE; 2. 0 - PP; 3. x - PVC; 4.- PS.

6. Thermomechanical curves of the original polymers and mixtures of polymers with additives HPB (14,63% chlorine).

1.. - HDPE:, 2. x - HDPE with 3% HPB, 3.0 - PP.

4.Sections with 3% HPB. 5. Δ - SS. 6 ▿ SS with 7% HPB.

7.- PVC. 8. ⊘ - PVC with 10% HPV.

1. Halogenated or halogensulphonylphenyl (co)polymer of butene-1, obtained in the solution of tetrachlorethane or chlorobenzene containing chemically bonded chlorine and/or bromine, or chlorine, and sulfur, or bromine and sulfur, or simultaneously, chlorine, bromine and sulfur in the form of SO2CL - and SO2VG-groups, the concentration of combined chlorine and/or bromine is 1-73 wt.%, sulfur 0.2 to 4.0 wt.%.

2. Halogenated or halogensulphonylphenyl (co)polymer of butene-1 according to claim 1, characterized in that it contains 1-73 wt.% chemically combined chlorine, or 1-70 wt.% chemically bound bromine, or 1-73 wt.% at the same time chemically related chlorine and bromine, or simultaneously chemically related 10-65 wt.% chlorine or bromine, and 0.2 to 4.0 wt.% sulfur in the form of SO2Cl - and SO2Br-groups, or simultaneously chemically related chlorine and bromine in the total amount of 1-70 wt.% and sulfur, 0.2 to 4.0 wt.% in the form of SO2Cl - and SO2Br-groups.

3. An elastomeric composition comprising halogenated or halogensulphonylphenyl (co)polymer of butene-1 to p is .1 and 2 in the number 99-1 wt.% and 1-99 wt.% rubber compositions based on rubber, selected from the group comprising the best choice rubber, butyl rubber, ethylene-propylene rubber, isoprene rubber, CIS-1,4-polybutadiene rubber.

4. Binder for adhesive-glue or paint compositions, which represents a modified halogenated or halogensulphonylphenyl (co)polymer of butene-1, obtained in the solution of chlorobenzene or tetrachlorethane and containing chemically combined chlorine and/or bromine and sulfur in amounts respectively 58-73 wt.% chlorine or 56-70 wt.% bromine, or 56-70 wt.% chlorine and 0.3 to 4.0 wt.% sulfur, or 58-70 wt.% bromine and 0.2 is 3.76 wt.% sulfur, or both chlorine and bromine when the total content of their 58-70 wt.%, or chlorine and bromine when the total content of their 56-73 wt.% and sulfur in amount of 0.2 to 4.0 wt.% in the form of SO2Cl - and SO2Br-groups.

5. Polymer composition for the manufacture of films and molded articles, comprising from 0.5 to 99.5 wt.% halogenated or halogencontaining (co)polymer of butene-1 according to claims 1 and 2, and 0.5 to 99.5 wt.% shared with him polymer selected from the group including polyethylene, polystyrene, polypropylene, polyvinyl chloride or mixtures thereof.

6. Polymer composition according to claim 5, characterized in that the matching of the polymer represents a secondary polymer in the form of waste polymers.

7. Polymer composition according to claim 5 or 6, characterized in that it contains additionally the preliminary catalyst dehydrochlorinating and/or subjected to dihydrochlorides and cross-linking γ -radiation with a dose of up to 70 Mrad.

8. The product of a (co)polymer of butene-1 according to claims 1 and 2, the surface of which is subjected to the action of chlorine and/or bromine or both chlorine and/or bromine and sulfur dioxide.

9. The product of a halogenated or halogencontaining (co)polymer of butene-1 according to claims 1 and 2 or of the composition containing it, one of PP-7.



 

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