SU817027A1 - Method of preparing reactive polymers - Google Patents

Description

one

The invention relates to polymer chemistry, in particular to a method for producing polymers with terminal peroxide functional groups, and can be used to obtain block copolymers, multicomponent polymer systems, as well as to obtain structured unsaturated polymeric xixpositions agents without additional introduction of radical initiators or curing agents. Due to the ability to self-structure the products of this method can be used as sealants.

(A known method of producing polymers with terminal peroxide groups is the polymerization of dienic monomers or their mixtures with vinyl in an organic solvent medium in the presence of trifunctional peroxides containing peracil and peiberol groups, as well as peracil and primary tertiary peroxide groups

one.

However, this method has disadvantages, due to the complexity of the synthesis of the original trifunctional peroxides, their relatively weak resistance to heat, impact and

friction, as well as the tendency to hydrolysis by ester bond. The final product has insufficient functionality.

Closest to the present invention is a method for producing reactive polymers by radical polymerization of butadiene or by copolymerizing it with acrylonitrile in

10 environment of an organic solvent in the presence of diperoxide initiator - bifunctional peroxide 1BPI) of the formula

15 (cH5) j- с - o - o - С (С (СНз) 2- UN 2}

However, this method is carried out with, which leads to such a decomposition of BPI, in which half of the surrounding formations do not contain peroxide groups, but is involved in initiating polymerization and other radical processes. This, in turn, leads to the formation of per25 oxide oligomers with low functionality.

The purpose of the invention is to increase the functionality of the final product with an adjustable molecular weight and

30 simplified process technology.

This goal is achieved by the fact that in a process for the preparation of reactive polymers by radical polymerization of butadiene or its copolymerization with acrylonitrile c. an organic solvent in the presence of a diperoxide initiator, an initiating system consisting of tert-butylparaisopropylcumylperoxide hydroperoxide, benzoin and naphtha bivalent iron at a mole ratio of 1: 1: 0.001 to 1: 1: 0.010, respectively, and the process With the SOA-CB of the proposed method, the initiation of the polymerization occurs due to the decomposition of only the hydroperoxide group, and it is not the OH radical that forms, but the OH-ion that is not capable of radical mutual action.

The tert-butyl paraisopropyl cumyl peroxide hydroperoxide contains an active oxygen hydroperoxide group of 5.39 wt.% (Theory 5.60 wt.%). 1.3 butadiene before the experiments is distilled. Acrylonitrile before experiments cleaned. The copolymerization is carried out in a solvent (benzene, acetone). The rate and depth of polymerization is calculated according to dilatometry and checked by dry residue. At the end of the polymerization, the monomer is distilled off. For the purpose of purification, oligomers are re-precipitated from benzene to ethanol three times. Drying is carried out in vacuum (2-3 mm Hg) at 30-40 ° C.

The presence of peroxide groups in the polymer structure is confirmed by iodometry, IR and PMR spectroscopy. The molecular weight is determined by a cryoscopic method, and the content of active oxygen is calculated by applying elemental analysis and iodometric titration.

Example 1. 2.3.3 g (0.132 mol / l) of tert-butyl para-isopropyl-cumyl peroxide (BPI) hydroperoxide, 2.75 g (0.132 mol / l) of benzoin and O, About g (9.110 mol / L) of iron naphthenate are dissolved in 24.6 g benzene and the solution is placed in a graduated ampoule. The vial is cooled (-5 ° C) and 20 g (6.0 mol) of butadiene are introduced. The polymerization is carried out at. For $ 5 h, the conversion depth reaches $ 3, 1%.

the purified polymer has a mol.m. 49.70, contains 0.65% by weight of active oxygen, and its number average functionality is 2.02.

In the IR spectra of the polymer, there are absorption bands in the region of 870 cm, which confirm the presence of a peroxide bond in the PMR spectra of butadiene, signals of methyl (cf 1/13 and 1.45 ppm) and aromatic (cg 7.15 m) were found. e.) protons due to the presence of FIPs of the di-oxide initiator BPI.

SP R and m 2. 2.22 (0.132 mol / BPI hydroperoxide, 1.67 g (0.132 mol / l) of benzoin and 0.01 g (1, b10 mol / l) of iron naphthenate are dissolved in 23.3 g of benzene, 19 g of butadiene (6.0 mol) are also added thereto. The polymerization is carried out at, and in 55 hours the conversion reaches 39%. The purified polymer has a molecular weight of 4120 and contains 0.79% by weight of active oxygen, and its number average functionality is 2.03.

IR and PMR spectra are similar to example 1.

Example 3. 1.75 g (0.1 mol / BPI hydroperoxide, 1.32 g (0.1 mol / l) benzoin and 0.046 g (7, O-10 mol / l) iron naphthenate are dissolved in 24.6 g of benzene. 20 g (6.0 mol / l) of butadiene are added in. The polymerization is carried out at 50 ° C and in 90 hours the conversion reaches 29.4%.

The purified polymer is mol.m. 3530, contains 0.91% by weight of active oxygen, and its number average functionality is 2.01. .

IR and PMR spectra are similar to example 1.

Example 4.1, bbg. (0.1 mol / l) of BPI hydroperoxide, 1.26 g (0.1 mol / l) of benzoin, 0.021 (3.410 4 mol / l) of iron naphthenate are dissolved in 23.3 g of benzene. 19 g (6.0 mol / l) of butadiene are also added there. The polymerization is carried out at 50 ° C, and in 90 hours the conversion depth reaches 23.8%.

The purified polymer is mol.m. 4170, contains 0.76% by weight of active oxygen, and its number average functionality is 1.98.

IR and PMR spectra are similar to example 1.

Example 5. 2., 33 g (0.132 mol / L) of BPI hydroperoxide, 1.75 g (0.132 mol / L) of benzoin and 0.06 g (9.110 mol / L) of naphthenate are dissolved in 22.16 g 20 g (6 mol / L; butadiene. Polymerization is carried out at 50 ° C. In 60 hours the conversion is 42%.

The purified polymer is mol.m. 2100, contains 1.52 wt.% Active oxygen and srednekamennogo functionality 2.0.

IR and PMR spectra are similar to example 1.

Claims (1)

Example 6. 2.32 g (0.132 mol / l) of BPI hydroperoxide, 1.75 g (0.132 mol / l) of benzoin and 0.06 g (9.1-10 mol / l) of iron naphthenate are dissolved in 22.4 g of benzene 20 g (6 mol / l) of butadiene and 2.22 g (0.6 mol / l) of acrylonitrile are also added thereto. The copolymerization is carried out at, and in 42 hours the copolymer yield is 35.6%. The purified copolymer has a mole, m, 4900, 0.65 mass, h. active oxygen, and the number average functionality is 1.99,. It can be seen that The proposed method produces low molecular weight polymers and copolymers containing at the ends of the macromolecules, tertiary peroxide groups. Moreover, the average number of functional peroxide groups per oligomer macromolecule is approximately 2, OiO, 02, In addition to TO1U, the method provides the ability to control the molecular weight of the final product , the ability to isolate and purify the polymer obtained under stringent conditions due to the high stability of the di-tertic peroxide end groups. Used in the BPI method is available, the process temperature is low. The invention The method of obtaining reactive polymers by radical polymerization of butadiene or copolymerization of it with acrylonitrile in an organic solvent medium in the presence of a di-oxide initiator, characterized in that, in order to increase the functionality of the end product with an adjustable molecular weight and simplify the process, as a di-oxide initiator, initiating system consisting of tert-butyl paraisopropyl cumyl peroxide hydroperoxide, benzoin and naphthenate d uvstshentnogo iron at a molar ratio of from 1: 1: 0.001 to 1: 1: 0.010, respectively, and the process is carried out at 50-60 ° C. Sources of information taken into account during examination 1, USSR Copyright Certificate 500214, C, 08 F 36/04, 1976, 2, USSR Copyright Certificate No. Application No. 2549537/05, class C 08 F 36/04, 1977 (prototype).