The method of graft copolymer

 

The invention relates to the field of polymer chemistry, in particular to a method for obtaining graft copolymer of (meth)acrylic monomer in the copolymer of butadiene with styrene modifier for polyvinyl chloride (PVC), and can be used to create composite materials based on plasticized and unplasticized PVC, recyclable, for example, profiles, films, sheets, etc. To reduce the mass fraction of elastomer in the resulting graft copolymer while maintaining the degree of crosslinking him, as well as improving the impact strength of the modified PVC polymerization in aqueous medium of a copolymer of butadiene with styrene and grafted monomer in the presence of oil-soluble radical initiator and high-molecular dispersant pre-mixed without heating the copolymer of butadiene with styrene and acetone at a mass ratio of 1:1.5 to 3, respectively, of oil-soluble initiator and grafted monomer, and then distilled acetone, enter the aqueous phase and carry out the grafting polymerization when the mass ratio of the copolymer of butadiene with styrene, grafted monomer, equal 10-35:90-65, as grafted monomer used (meth)acrylic monomer. In the result, the wt.%, average particle size of 40-110 μm and impact strength with notch standard unplasticized PVC compositions using the obtained graft copolymer 30-88 kJ/m2. 4 C.p. f-crystals, 1 table.

The present invention relates to the field of polymer chemistry, in particular to a method for obtaining graft copolymer of (meth)acrylic monomer in the copolymer of butadiene with styrene modifier for polyvinyl chloride (PVC) with a reduced share of the elastomer, thereby reducing its cost, and an increased degree of crosslinking, and can be used to create composite materials based on plasticized and unplasticized PVC, recyclable, for example, profiles, sheets, films, etc. with improved toughness.

Currently, the solution to the problem of creating modifiers for PVC materials aimed at synthesizing modifiers, which can improve a number of properties of materials based on PVC. For example, composite materials based on PVC can be used in different high-speed (up to shock and temperature regimes. When increasing the speed of loading to impact the ability to maintain the integrity of the material for which the usage is toughening the conditions under shock loading.

A method of obtaining a modifier for PVC (Patent RF 2074202, 08 F 279/02, 1977) by mixing vinyl chloride (I) or methyl methacrylate (MMA) latex of copolymer of butadiene and Acrylonitrile with subsequent graft polymerization in the presence of a radical initiator at a mass ratio of monomer : copolymer of equal 5-30:95-70, characterized in that the polymerization is carried out in the presence of 0.1 to 1.3% by weight of copolymer of a substituted phenol selected from the group comprising 4-methyl-2,6-di-tert-butylphenol, 4-methoxymethyl-2,6-di-tert-butylphenol, 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol), and use a copolymer of butadiene and Acrylonitrile in weight ratio of butadiene : Acrylonitrile, equal 80-55:20-45. The implementation of this method yields a powdery graft copolymer I or MMA rubber elastomer with an average particle size of the powder 10-96 μm, the content of the elastomer 69-95 wt.% and the degree of crosslinking 20-35 wt.%. Standard composition comprising 100 wt.h. PVC 0.6.h. of barium stearate, 0.8 wt.h. of cadmium stearate, 0.5.h. calcium stearate and 8 wt.h. the obtained graft copolymer, mixed at 90oC for 30 min, rolls 6 min at 175oWith and pressed by the plate thickness of 4 mm with shock is the way of the graft copolymer I (RF Patent 2070209, C 08 F 279/02, 1996 - prototype) in the presence of a copolymer of diene with styrene, a radical initiator, high-molecular dispersant and stabilizer, in which as indicated copolymer used is a copolymer of butadiene with styrene in a mass ratio 67-74:33-26 accordingly, the stabilizer is used in 0.1 to 1.3% by weight of copolymer of a substituted phenol selected from the group comprising 4-methyl-2,6-di-tert-butylphenol, 2,2-methylene-bis-(4-methyl-6-tert-butylphenol) and polimerizuet when the mass ratio of I : copolymer, equal 90-98,5:10-1,5. The process leads to the production of grafted copolymer BX rubber elastomer containing elastomer 38-98 wt.% and the degree of crosslinking 15-78 wt.%, average particle size of 20-200 μm. Impact strength with notch above standard unplasticized PVC composition with the use of the final modifier is 10-19 kJ/m2(see table, example 26).

It was interesting reproduction of this method using as the grafted monomer is (meth)acrylic monomers, since their production, in contrast to the production of I, is more simple technological schemes, which generally simplifies the process of gaining the roll in the way the prototype leads to be prone to lumping in the polymerization process.

To reduce the mass fraction of elastomer in the resulting graft copolymer while maintaining the degree of crosslinking, and improved toughness of the modified PVC method for obtaining a grafted copolymer by the polymerization in aqueous medium of a copolymer of butadiene with styrene and grafted monomer in the presence of oil-soluble radical initiator and high-molecular dispersant, wherein the pre-mixed without heating the copolymer of butadiene with styrene and acetone at a mass ratio of 1: 1.5 to 3, respectively, of oil-soluble initiator and grafted monomer, and then distilled acetone, enter the aquatic environment and carry out grafting polymerization when the mass ratio of the copolymer of butadiene with styrene: grafted monomer equal 10-35:90-65, whereas the grafted monomer is used (meth)acrylic monomer.

When using a copolymer of butadiene with styrene in a mass ratio 67-74:33-26.

As oil-soluble initiator is used 0.1 to 1.5% by weight of a copolymer of butadiene with styrene, benzoyl peroxide or peroxide of Laurel.

As (meth)acrylic monomer is used, a monomer, selected from the group of climara of butadiene with styrene and acetone, oil-soluble initiator and grafted monomer is carried out at a temperature of 18-22oC for 22-30 minutes.

Comparative analysis of the prototype allows us to conclude that the claimed method of the graft copolymer differs from the known prior mixture of a copolymer of butadiene with styrene and acetone at a mass ratio of 1: 1.5 to 3, respectively, of oil-soluble initiator and grafted (meth)acrylic monomer evaporation of acetone and conducting graft polymerization with the mass ratio of the copolymer of butadiene with styrene, grafted monomer, equal 10-35:90-65. Thus, the proposed technological solution meets the criterion of "novelty."

The technical result of the invention is to obtain a grafted copolymer with a mass fraction of elastomer 10-35 wt.%, the degree of crosslinking 41-99 wt.%, average particle size of 40-110 μm and impact strength with notch standard unplasticized PVC compositions using the obtained graft copolymer 30-88 kJ/m2(see table of examples 1-25).

Improved characteristics of the resulting grafted copolymer modifier for PVC compared with the grafted copolymer, synthesizing these characteristics to improve the given set of properties is not detected from the prior art, that will allow the authors to conclude that under their proposed technical solutions to the criterion of "inventive step".

The essence of the invention is illustrated by the following examples.

Example 1 (invention) In a glass reactor with a capacity of 4 l load 100 g chips ranging in size from 1 to 5 mm, rubber elastomer, butadiene - styrene copolymer mass ratio of links 70: 30, 200 g of acetone, 0.7 g of benzoyl peroxide, 900 g of methyl methacrylate and stirred at room temperature for 25 minutes Heat the reactor up to 50oWith, evaporate the acetone and return it in the recycling. After that, the reactor add the aqueous phase, consisting of 1800 g of water and 0.08 g of methylcellulose. Heat the reactor to 70oWith and carry out the process for 5 h, then the product of copolymerization is separated from the aqueous phase, for example, by centrifugation and dried in a vacuum Cabinet at 80+5oC.

Free elastomer and the free methyl methacrylate) in the final product there that is determined by fractionation of the dichloromethane, the number of cross-linked copolymer - extraction in dichloroethane, the average size of the particles using an electron microscope.

The obtained partially crosslinked graft copolymer of (meth)acrylic monomer, wt.h.: PVC (GOST 14332-78) - 100, stearate barium (TU 6-19-283-88) - 0.6 stearate cadmium (TU 6-09-17-318-96) of 0.8, calcium stearate (TU 6-14-722-76) - 0,5, modifier - 8. The composition is mixed at 90oC for 30 min, rolls 6 min at 175oC. and Then pressed the squares of a size of 140 mm, a thickness of 4 mm at 180oC for 5-7 min and determine the impact strength notched at 20oWith GOST 4647-80. The process conditions of grafting polymerization, the properties of the modifier and the modified PVC in the table.

Examples 2-25 (invention) is carried out as in example 1. The process conditions of grafting polymerization, the properties of the modifier and the modified PVC in the table.

Example 26. The reproduction of the prototype Property of the modifier and the modified PVC in the table.

Examples 27-37 (for comparison).

Carried out as in example 1. All examples are summarized in table. Example 1-25 table shows that the implementation of the method of graft copolymer by pre-mixing without heating the copolymer of butadiene with styrene in a mass ratio of 1:1.5 to 3, respectively, 0.1 to 1.5% by weight of a copolymer of butadiene with styrene, benzoyl peroxide or peroxide of lauroyl and grafted (meth)acree when the mass ratio of the copolymer of butadiene with styrene, grafted monomer, equal 10-35:90-65, leads to the production of grafted copolymer of (meth)acrylic monomer in the copolymer of butadiene with styrene, with a mass fraction of elastomer 10-36 wt.%, the degree of crosslinking 41-99 wt.%, the average particle size is 40-110 μm. Impact strength with notch standard unplasticized PVC composition with the use of the final modifier is 30-88 kJ/m2.

The process of grafting polymerization of (meth)acrylic monomer, for example, MMA in the copolymer of butadiene with styrene in a mass ratio that is different from the claimed results of the grafted copolymer with a degree of crosslinking from 13 to 30 wt.%, impact modified PVC 15-18 kJ/m2(see examples 27, 28).

The process of grafting polymerization, for example, MMA on GP in the presence of benzoyl peroxide in the amount, less the present invention leads to the production of grafted copolymer with a degree of crosslinking 11 wt. %, toughness of the modified PVC 13 kJ/m2(see example 29), the process in the presence of benzoyl peroxide in a quantity greater offer, leads to the destruction of the grafted copolymer (see example 30). The process of grafting of polymerise the acetone in the process (while maintaining other equal conditions) leads to be prone to lumping in the synthesis process (see examples 31, 37) or the increase in energy consumption per reconcretion acetone from the reactor (see example 32).

The process of grafting polymerization, for example, MMA on GP at the time and the temperature of the pre-mixing GP, acetone, initiator and MMA than claimed, leads either to an increase in energy consumption for mixing (see examples 33, 34, 36), or to be prone to lumping in the polymerization process (see example 35).

Thus, the proposed method allows to obtain a graft copolymer of (meth)acrylic monomer with a reduced share of elastomer and an increased degree of crosslinking, which, when used as a modifier for PVC, it is possible to improve the impact strength of the composition.

Sources of information 1. RF patent 2074202, 08 R 279/02, publ. 1997.

2. RF patent 2070209, 08 R 279/02, publ. 1996 - the prototype.

Claims

1. The method of graft copolymer by polymerization in the aqueous phase of a copolymer of butadiene with styrene and grafted monomer in the presence of oil-soluble radical initiator and high-molecular dispersant, wherein the pre-mixed without heating the copolymer of butadiene with styrene, Aceto the ATEM distilled acetone, enter the aqueous phase and carry out the grafting polymerization when the mass ratio of the copolymer of butadiene with styrene, grafted monomer, equal 10-35: 90-65, whereas the grafted monomer is used (meth)acrylic monomer.

2. The method according to p. 1, characterized in that use is a copolymer of butadiene with styrene in a mass ratio 67-74:33-26, respectively.

3. The method according to p. 1, characterized in that as the oil-soluble initiator is used 0.1 to 1.5% by weight of a copolymer of butadiene with styrene, benzoyl peroxide or peroxide of lauroyl.

4. The method according to p. 1, characterized in that as (meth)acrylic monomer is used, the monomer is selected from the group comprising methyl methacrylate, methacrylate, methacrylic acid, acrylic acid.

5. The method according to p. 1, characterized in that the mixture of a copolymer of butadiene with styrene and acetone, oil-soluble initiator and grafted monomer is carried out at a temperature of 18-22oC for 20-30 minutes

 

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