SU1705305A1 - Method of producing polymers based on cyclopentadiene - Google Patents

Abstract

The invention relates to the preparation of polymers, in particular to the preparation of cyclopetitadiene oligomers used as film-forming agents in the paint industry. The goal is to reduce the cost of obtaining polymers by using cheaper reagents, increasing the hardness of coatings based on the polymers obtained from 0.40 to 0.72, expanding the field of application of polymers as film-forming (it is possible to use as an independent film-forming oil without additives) obtaining by copolymerization of cyclopentadiene with a diene comonomer in the presence of an additive, methyl sec-pentenyl ether, taken in an amount of 0.1-1.0 wt.% from co-monomers. The catalyst used in the process is the Friedel-Crafts catalyst. taken in an amount of 0.1-0.3 wt.% of the co-rooms. 4 tab. yo

Description

The invention relates to the preparation of oligomers, in particular copolymers of cyclopentadiene with diene hydrocarbons.

Cyclopentadiene based low molecular weight copolymers are used as substitutes for vegetable oils and film forming materials. Due to the high content of double bonds, these polymers are capable of undergoing three-dimensional crosslinking with atmospheric oxygen to form protective coatings.

A known method for the preparation of an oligomer of cyclopentadiene, which has an increased compatibility with oils. The reaction is carried out by the interaction of cyclopentadiene with 10-40 mol.% (Per monomer) trifluoroacetic acid, taken as a solution in

organochlorine or aromatic solvent. An oily liquid is obtained with number average mol. Ma. 400, the yield of the finished product to 100%.

The known method is expensive due to the use of an expensive catalyst, the resulting film-forming agent is an additive used in combination with vegetable oil. Although the known polymer can replace up to 90% of the oil, it is not used as an independent film-forming agent. Coatings based on the known film-forming agent do not have sufficiently high hardness.

The purpose of the invention is to reduce the cost of the process, increasing the hardness of coatings on the basis of the obtained polymers,

eight

SL SO O SL

 polymers and polymer applications as film-forming.

This goal is achieved by the fact that the preparation of copolymers of cyclopentadiene with diene hydrocarbons is carried out by copolymerization in the medium of an organic solvent in the presence of a Friedel-Crafts catalyst using an additive, methyl sec-pentenyl ether (2-methoxypentene-3; 2-MOP-3 ), taken in an amount of 0.1-1.0% by weight of comonomers.

Chlorinated or aromatic hydrocarbons (chloroform, chloroethyl, benzene, toluene, xylene) are used as organic solvents.

2-MOP-3 is obtained by reacting piperylene with methanol in the presence of ionized molded catalysts; used for the synthesis of trans-piperylene and as a high-octane gasoline additive.

The process of copolymerization in the presence of 2-MOP-3 allows to increase the yield of oligomers, to improve their physicochemical properties. When less than 0.1 wt.% Is added to the reaction mixture, a small amount of gel is formed in the copolymer; more than 1.0 wt.% leads to a decrease in the yield of the copolymer.

The method is carried out as follows.

For polymerization, a glass reactor is jacketed to provide coolant or preheat. The grinded top cover has openings for the agitator, thermocouple, reflux condenser, capillaries for feeding the charge and blowing nitrogen. All parts of the reactor are thoroughly rinsed and drained. The polymerization is carried out in a chlorinated medium (chloroform, hporethyl) or aromatic hydrocarbons (benzene, toluene, xylene) at a temperature of from -10 to 30 ° C under the action of Friedl-Crafts catalysts (chlorine tin, aluminum chloride, titanium chloride, boron trifluoride etherate and others).

While stirring, the solvent, the catalyst solution are loaded into the reactor, then a mixture of monomers and a modifier is fed through a capillary funnel.

Depending on the set temperature, coolant is supplied to the jacket of the reactor or heated. After completion of the reaction, the polymer is precipitated from the solution with ethanol. Filled with antioxidant, dried to constant weight, and characteristics determined.

PRI me R 1. The recipe of the mixture, mac.ch .:

Cyclopentadiene70

Butadiene 2-methoxypenthen-3

Chloroform

TiCh (catalyst)

thirty

0.1-1.0 per monomer

100 0.3 by 2. monomers

The reaction temperature is 10 ° C; reaction time 1.2 h; polymer yield 98 mas.%.

0 Dependence of average viscosity mol.mae. from the content of 2-MOP-W are presented in Table. one.

Example 2. The recipe of the mixture, may, h .: Cyclopentadiene 90 5 Isoprene "10

2-Methoxypentene 30.1-1.0 at

monomers

p-Xylene 100 SnCU 0.2 to 0 monomers

The reaction temperature is 0 ° C; the polymer yield is 97 wt.%. The reaction time is 2 hours.

Dependence of average viscosity 5 mol.mae. from the content of 2-MOP-W is presented in Table 2.

Example 3. The recipe of the mixture, mph.: Cyclopentadiene85 Piperylene 15 0 2-Methoxypenten-C 0.1-1.0 per

monomers

100 0.1 per

monomers 5 Reaction temperature 30 ° C; reaction time 1 hour; polymer yield 99 wt.%.

Dependence of average viscosity mol.mae. from the content of 2-MOP-W is presented in Table. 3

Thus, using 2-methoxypentene-3. It is possible to obtain cyclopentadiene-based oligomers with good physicochemical properties, which do not contain a gel, with a high yield. The resulting substances can be used as film-forming materials.

When used as an independent film-forming copolymer 0, it is diluted with xylene to a working viscosity of 18–20 s according to VZ-4, applied to the working surface by pouring or dipping. At 20 + 2 ° C, a hard elastic film is formed and for 15-20 hours. The coating is smooth, smooth, transparent, has a faint yellowish tint, which allows it to be used to obtain enamels of a wide color range.

In tab. 4 shows the properties of coatings based on vegetable oil, known

Toluene BF30 (C2H5) 2

film-forming (mixed with 17, linseed oil and 83% copolymer of tsh. oopstadiene) and proposed (copolymer of cylopentadienes in xylene without adding oil) Properties for hardness and resistance to resistance to impact are determined with a coating thickness of 25 μm, adhesion and elasticity with a thickness of coatings of 100 microns. An inventive method for the preparation of cyclopentadiene-based polymers by polymerization of cyclopentadiene in the presence of a catalyst, characterized in that. what. with the aim of

cheaper process, increasing the hardness of coatings based on the polymers obtained, expanding the field of application of polymers as film-forming. The polymerization is carried out in the presence of a diene comonomer and the addition of methyl sec-pentenyl ether in an amount of 0.1-1.0% of the mass of comonomers, while the catalyst Fridel Crafts is used as a catalyst, taken in an amount of 0.1 -0.3% by weight of comonomers.

Table 1

table 2

Table 3

Table 4

Continuation of table 4

Claims (1)

Foomula inventions A method of producing polymers based on cyclopentadiene by polymerizing 10 cyclopentadiene in the presence of a catalyst, characterized in what. in order to reduce the cost of the process, increase the hardness of coatings based on the obtained polymers, expand the field of application of polymers as a film-forming one, the polymerization is carried out in the presence of a diene comonomer and methyl-sec-pentenyl ether, taken in an amount of 0.1-1.0% by weight of comonomers, at in this case, the Friedel-Crafts catalyst, taken in an amount of 0.1-0.3% by weight of comonomers, is used as a catalyst.