SU994472A1 - Process for producing grafted copolymers and process for preparing composition for bases of dentures - Google Patents

Description

emulsion polymerization of 62-75 wt.% olkylacrylate (C2-Cg), O, O4-O, 4 wt.% allyl (meth) acrylate and 24.6-31.96 May. % styrene and / or benzyl acrylate 2. The resulting graft copolymer is used as modifiers in PMMA composites or its copolymers. The coke positions contained in this modifier have good toughness, however, the breaking stress due to static bending is reduced compared to the unmodified poly C -. rum. Thus, the introduction into the PMMA composition of 25-37.5% of the copolymer obtained by the ethnm method leads to an increase in the impact strength of the composition to 8.3-22.7 kgf cm / cm gyu compared to 3.3 kgf cm / cm For unmodified compositions. In this raerushuyuschee. static stress decreases from 564 kg / cm to 4-0-853 kg / cm. The closest to the technical essence and the achieved result is smnaex-with the method of obtaining graft copolymers by emulsion polymerization of butylcrystal in an aqueous medium in the presence of a radical type initiator until complete conversion, followed by the addition of methyl methacrylate or its mixture with an allyl compound and dopolymerization. Known copolymers are used as modifiers in acrylic compositions ej. Typically, compositions for bases of dentures are obtained by mixing a polymer powder and a liquid — a monomer capable of polymerizing. The resulting mass swells within 10-15 minutes to a pasty consistency. Next, the molding mass is placed in a plaster or metal form, pressed under preos for 10-15 minutes and primed in a boiling water bath. The closest in technical essence and the achieved result is a method of preparing a composition for powder-liquid denture bases using a graft polymerization reaction followed by mixing the resulting graft copolymer with a methyl acrylate in a 2: 1 ratio, respectively. A copolymer of methyl methacrylate (MMA) ethyl methacrylate (EMA) and methyl acrylate (ML) is obtained by suspension polymerization of these monomers in the presence of benzoyl peroxide. After the polymerisation of the indicated composition, according to the usual technology, material of the brand Et Krill 4 is obtained. A disadvantage of the denture bases derived from this composition is the low toughness to fracture under static bending of the bases. So, the impact viscosity is 4.7 kgf cm / cm, the stress at static bending is 875 kg / cm {m, and this is measured by GOST 14235-69). The purpose of the invention is to increase the impact strength and destructive stress in the case of sugatic and dibebbaznos dentures. The supplied crop is achieved by agreeing that the preparation of grafted tolimers is obtained by emulsion polymerization of butyl acrylate in an aqueous medium in the presence of a radical type initiator before complete conversion, followed by the addition of methyl methacrylate or its mixture with an allylicomer and a polymerization with a monomer. the presence of allyl methacrylate, and butyl acrylate is used in the amount of 29.7-69.3 May. % methyl methacrylate - 30-7O May. % allyl methacrylate, 3-1 May. % In addition, according to the method of preparing a composition for powder-liquid denture bases using the graft polymerization reaction, followed by mixing the resulting copolymer with methyl methacrylate in a 2: 1 ratio, respectively, 9O-95 may be grafted. % methyl methacrylate in the presence of 5-1 O may. % grafted butyl acrylate copolymer (29.7 69.33 wt.% -) methyl acrylate (307O wt.%) and allyl methacrylate (0.3 1 wt.%). Example. Sytez graft copolymer of butyl acrylate, methyl methacrylate and allylmethacrylate. For the synthesis, 59.4 g of butyl acrylate (which corresponds to 29.7 May.%), O, 6 g of allyl methacrnlate (0.3 May.%) And 140 g of methyl methacrnate (70. May.%) Are used. Stage A - synthesis of latex elastomer. A reactor equipped with a stirrer, a tube for introducing nitrogen and a measuring device for dispensing monomers, as well as a reverse REFRIGERATOR, is charged with 0.6 i-emulsion sodium lauryl sulfate and 160 g

distilled water, heated with stirring to 8–5 ° C. Potassium persulfate initiator solution {O, OZ g in 2 O ml of water) is added to the reactor, then the mixture of monomers is metered: 59.4 g butylacr & Lata (BA) and 0.6 g of allyl megacrylate (AMA) for 2 hours. Conducting 5g polymers at 85 ° C for 3-4 hours, then raise the temperature in the reactor to 9-5 ° C and stir the reaction mixture at this temperature for 2 hours. Obtain 240 g of latex, containing 25 may. % dry matter. Conversion monomer is 99.8%.

Stage E - synthesis of a grafted concomitant.

240 g of latex containing 6O g of dry matter, 40O g of distilled water, 14O g of methyl methacrylate (MMA) are placed in a reactor equipped as in A. The reaction mixture is heated to 7SRc, then a solution of 0.28 g of potassium persulfate in 60 g of distilled water is added. Blend n & (Stir at for 5 hours. Latex is coagulated with 10% ammonium sulphate solutions, filtered and washed. The copolymer is dried at a temperature not higher than 6 ° C. Conversion of monomers 99.0%. A graft copolymer containing 29.7% by weight of butyl alcohol is obtained LVL 0.3% by weight of allyl methacrylate and 7% of% by weight of methylmethacrylate.

Obtaining compositions for bases dentures.

Stage C - synthesis of polymer powder for composite bases of dentures.

In a liter reactor equipped with a fridge and refrigerator for a thermometer, 2O g (Yumas.%) Of the copolymer obtained in step B, 180 g (9O may.%) Of methyl methacrylate are loaded, after the copolymer is completely dissolved, benzoyl peroxide, 400 g distilled water. The suspension is stabilized with a 1% starch solution in water.

The polymerization is carried out at 8 ° -9 ° C for 2 to 3 hours, then the temperature of the reaction mass is lowered to room temperature. Add 0.00078 May. % aminosubtilenum, stirred and left for 152 minutes. Then the reaction mixture is filtered onto a filter, washed

spray with water and dry at 70-75 ° C for 2-3 hours.

Stage D - Cooking Composites

for bezisov dentures.

May 2 including polymeric nqpoiUKa, half of a chenogo at stage C is mixed with 1 wt.h. methyl methacrylate. The resulting mixture swells within 1O-15 minutes to a pasty consistency. The molding mass is placed in a metal presso-form and polymerized at 1OO-1O5 ° C under a pressure of 20-25 kg / s.

Figurative for testing are plates of size (10x15 mm, 2.5 mm thick (method GOST 14235-69),

PRI me R 2.

 SSHVV7GOGO with € nypvm € ra gtyush rvlata, met megak shlata n allvmetakrzh lag.

For the implementation of a synthetic mixture, 59.4 g of butyllaciate (corresponding to 39.6 May.%), 0.6 g of allylmethacrylate (0.4 May.%) And 9O g of methyl methacrylate (6O May.%) Are used.

Step A is analogous to Example 1.

Stage B is analogous to Example 1, but to 240 g of latex obtained in Stage A and containing 60 g of dry matter, 90 g of methyl methacrylate are obtained.

Getting the position for denture bases. / Stage C is similar to example- 1.

Step 13 is similar to Example 1.

PRI me R 3.

Synthesis of PRTICTED copolymer of butyl acrylate, methyl methacrylate n allylmetry acrylate.

To carry out the synthesis and use

59.4g butylacnlate (which corresponds to

49.5 May. %), 0.6 g of allyl methacrylate (0.5 May.%) And 60 g of methyl methacrylate (50, May.%).

Step A is similar to Schaaler 1.

Stage B as in Example 1, but to 24O g of latex obtained in Stage A and containing 60 g of dry matter, 60 g of methyl metathyl acetate are added.

Obtaining a composite for bases of dentures.

Stage C is analogous to Example 1, but 10 g (5 may.%) Of the graft copolymer obtained in Step B is dissolved in 19 O g (95 May.%) Of methyl methacrylate.

Step D is similar to Example 1.

PRI me R 4.

Synthesis of graft copolymer of methyl methacrylate butyl acrylate and allyl methacrylate.

To carry out the synthesis using 59.4 g of butyl acrylate 59.4 May. %), 0.6 g of allshshkztakrilat (0.6 May.%) 40 g of methvol methacrylate (40 May.%). Stage A is analogous to Example 1. Stage B is analogous to Example 1, but 40 g of methyl methacrylate are added to 240 g of latex obtained in Stage A and containing 60 g of dry matter. Obtaining composition for bases of dentures. Stage C is analogous to example 3. Stage D is analogous to example 1. Tame. Synthesis of the graft copolymer of butyacrylate, methyl methacrylate and allylmethoxylate. To synthesize, use 59.4 g of butyl acrylate (69.3 May.%), 0.6 g of allyl methacrylate (0.7 May.%), 25.7 g of methyl methacrylate (30.me%.). Step A is similar to Example 1. Step B — according to example 1, but to 240 latex obtained at stage A and containing dry substance in g, was added 25.7 g of methyl methacrylate. Obtaining compositions for bases dentures. Stage C is similar to example 3. Stage D is similar to example 1. Example. Synthesis of a graft copolymer of butyl crylate, methyl methacrylate and allylmethacrylate. For the synthesis, 58.8 g of butyl acrylate (49 wt.%), 1.2 allyl methacrylate (1 May.%) And 6O g of methyl methacrylate (50 May.%) Are taken. Step A is analogous to Example 1, but taking 58.8 g of butyl acrylate and 1.2 g of allyl methacrylate. Stage B is analogous to Example 1, but 60 grams of methyl methacrylate is added to 24 grams of latex obtained in step A and to the total of 60 grams of dry matter. Obtaining a composition for denture bases. Step C is similar to Example 3. Step D is similar to Example. 1. PRI me R 7. Synthesis of a grafted copolymer of butsh-a-filate, methyl methacrylate and allylmeo acrylate. In order to carry out the synthesis, 59.4 g of buts1-acrylate (49.5 May.%), 1.2 g of all tsmethacrylate (1 May.%) And 59.4 g of methyl metrylate (49.5 may.% X and 0.6) are taken. g of allyl methacrylate (0.5%,% is introduced at stage A, and the rest is shorter at stage B. Stage A is added to the reactor, equipped according to example 1, 0.6 emulgator of sodium lauryl sulfate and 16O g of distilled water is heated under stirring Potassium persulfate solution (0.03 g in 2 O ml of water) is poured into the reactor, the monomer mixture containing 59.4 g of butyl acrylate and O, 6 g of allyl methacrylate is metered in, t & 2 hours. Polymerization is carried out at 85 ° C for 3-4 hours, then the temperature in the reactor is raised until the mixture is kept for 2 hours. Conversion of monitors is 99.8%. 24O g of latex is obtained with a dry matter content of 25%. In analogous to example 1, but to 24O g of latex obtained in stage A and containing .60 g of dry matter, 59.4 g of methyl methacrylate and O, 6 g of allyl methacrylate are added. Preparation of a composite for bases of dentures. Stages C and D are similar to Example 1. Example 9 (for comparison). Synthesis of grafted copolymer of methyl methacrylate butyl 1-formate and allylmethane acrylic. For the synthesis, 59.4 g of butyl acrylate (29.7 May.%), O are used in g of allyl methacrylate (O, 3 May.%) And 14O g of methyl methyl methacrylate (70 May.%), All the amount of allyl methacrylate (0.6 d) are introduced on V. prototype 3}. Step A is analogous to Example 1, but 59.4 g of butyl acrylate is taken instead of the monomeric dimethyl butyl acrylate and allylmeth | philate. Stage B is analogous to Example 1, but 14O g of methyl methacrylate and 0.6 g of allyl methacrnlate are taken. Obtaining a composite for bases of dentures. Step C is analogous to Example 3. Step D is analogous to Example 1. I will try on (for comparison). Synthesis of a graft copolymer of butyl acrylic, methyl methylate and allyl methacrylate. For the synthesis, 59.4 g of butyl acrylate (69.3 May.%), O, 6 g of allylmethyl 1-phylate (O, 7%) and 25, 7 g of methyl methacrylate (30% May.%) Are used, and allyl methacrylate (0.6 g) is introduced at stage B, i.e. prototype h. Step A is analogous to Example 1, but 59.4 g of butyl acrylate is taken instead of the monomeric butvrylate dimer with allyl methacrylate. . Stage C is analogous to Example 1, but 25.7 methylmetacrvpata is taken, and 0.6 g of the allele of crypate is taken. Preparation of a composition for bases of dental prostheses. Stage C is analogous to Example 3. Stage D is analogous to Example 1 "Example R 11 (only compare). Synthesis of 6nrE & grafted eopimer acrvlata, methylmeta ernpata and allhalmeph ahphylate. For implementation, 59.4 g of 6yTmiajqpffimTa (29.7 May.%), O, 6 g of allylmeasch} of elate (6.3 May.%) 14O g of methylmethine finite 47Q may be used. %). Stages A and B are the same as in size 1 Preparation of Echochysis for prototype dentures {. Stage C is missing. Stage D-to mV1S. . a polymer mixture consisting of 2O g (1O may.% graft copolymer obtained in stage B and 18O g (9O may.%} pypimyuylethacrylate is poured in May 1. part of methyl methacrylate and left to swell for mines to obtain testos;) Aanos consistency. The molding mass of a & ntaioT into a metal press is done under 1OO. under a pressure of 2–25 kg / cm. Example 12 (for sraoana). A total of 59.4 g bottles of AlfSh1ata (69.3 May.%), O, 6 g of allyl methacrylate (CV7 May.%) And 25.7 g of metal methacrylate ( ZO May.%). Stage A is similar to U) and 1. Stage B analogue 1 is Iphiqpy 5. Production of composites for bases of dental prostheses according to phototype 4J. Stage C oteutsteyugg. Stage D is similar to 9. The dependence of the properties of the bases of dental prostheses on the method of obtaining a primer of the copolymer is presented in Table. 1. The dependence of the properties of the bases of dentures on the method of obtaining the composite FDI for the bases is given in p. . As follows from the table. 1, the proposed method for producing grafted copolymers of butylavrylate, allyl methacrylate and methyl syngate allows to obtain high values of the destruction of the stress during static bending {up to 122 O-140 O kg / cm -) compared to 11OO kg / cm for the poor way (examples 1-7 for zbre-, NIJ and 3 for the prototype). In this case, KCYMPOSEAS for dental prosthesis bases are obtained according to the proposed method. Use of a grafted copolv obtained in 3, i.e., 3, i.e. by adding allyl methacrylate, not in elaostom, but in nassed monsmer, it is not possible to obtain high properties of the bases of dental preparations, although at the same time monitors take in the same quantitative context (examples 9-10 for comparison). Conducting a mixture of acrylate, allylmethacrylate and methylmethacrylate in the proposed method, but with a quantitative ratio of monomers, from the proposed method also does not allow obtaining the satisfactory properties of the basis of dental prostheses (measure 13). From tab. 2, it can be seen that the proposed method of a half way of dental protrusions increases the impact strength and the breaking stress during static bending of the bases of the dental prostheses. In this case, the graft copolymer is obtained according to the method specified in claim 1 of the formula of the invention w. In this way. Isofetoing allows graft copolymers to be obtained in denture bases with increased toughness and destructive pressure during static bending.

Table

Composites for dental dental care were obtained in examples 1-7, 9-10, 13-14,

Compoan for bases obtained by a known method 4

The co-polymer is a continuous mass, which must be introduced into

K (I | L1OOSHI

A and B)

.

«IKyurka 1 Copolymer

mixture (MMA (MMA

75% by weight 75% by weight

EMA 2O mvs.% EMA 2 O wt.%

MA S mvs.%} MA 5 wt.%)

MMA 1 Composition of solo-5-limer as in example 1, BUT- obtained by prototype

MMA 1 Composition of sopo S lkmer as in example 5 | but received

by PROUTOT

Table 11a2

124O

at

I23o

6.4

1220

6.4 6.4

13OO

1400 Gfl 6.4

1230

135О 6.8

4.7

875 101О

4.5

five

1050

4.3

The formula of acquisitions 1. The method of studying the grafted sons of measures by the emulsion polymerization of butyl acrylate in aqueous medium in the presence of a radical type initiator until complete conversion, followed by the addition of methyl methacrylate or its mixture with an allyl compound and a prepolymer of the resulting polymer to the resulting polymer, or a mixture of allyl compound and a prepolymer, which will be added to the resulting polymer, methyl methacrylate or its mixture with an allyl compound and a prepolymer that has been added to the resulting polymer, methyl methacrylate or its mixture with an allyl compound and a prepolymer that has been added to the resulting polymer, methyl methacrylate or its mixture with an allyl compound and a prepolymer that has been added to the resulting polymer, methyl methacrylate or its mixture with an allyl compound and a prepolymer that has been added to the resulting polymer, methyl methacrylate or its mixture with an allyl compound and a prepolymerized polymer, which will be added to one another. stress during static bending of products based on copolymers, the polymerization of butyl acrylate is carried out in the presence of allyl methacrylate, and butyl acrylate is used in an amount 29,7-69,3 wt% metilmetakrvlat -. LP-70 May. %, allyl methacrylate - 0.3-1 May. % 2. A method of preparing a composition for bases of dental prostheses such as powder-liquid using a graft polymerization reaction, followed by mixing the resulting graft copolymer with methyl methacrylate in a ratio of 2: 1, respectively, Q tl and h aych of Y and C Ya in order to increase the impact viscosity and destructive anesthesia during static bending of the prostheses, the grafted suspension of polymerization is carried out on 9O-95 May. % methyl methacrylate in the presence of 5-10 May. % grafted copolymer of butyl acrylate (29.769, 3 may.%), methyl methacrylate (ZO7O may.%) and allyl methacrylate (0.31 may.%). Sources of information taken into account in the examination 1. US patent number 41О8923, cl. 260-836, with a hub. 1978. 2.Patent of Great Britain No. 1431564, 1974. 3. USSR author's certificate in application No. 2711369, cl. C08F220 / 1O, 1979 (prototype). 4. P.Tanrykuliev. Clinical and experimental investigations of some of the potential properties of acrylic tampons used for denture bases. Dissertations, M., TsNIIS, 1968 (prototype).

Claims (2)

Claim 1. A method for producing grafted copolymers by emulsion polymerization of butyl acrylate in an aqueous medium in the presence of a radical type initiator until complete conversion, followed by the addition of methyl methacrylate or a mixture thereof with an allyl compound and additional polymerisation of the monomer, characterized in that, in order to increase tensile stress during static bending of copolymer-based products, butyl acrylate is polymerized in the presence of ⁵ allyl methacrylate, butyl acrylate being used in a quantity A total of 29.7-69.3 wt.% * methyl methacrylate - May 30-70. %, allylD methacrylate - 0.3-1 May. % 2. A process for preparing a composition ^{of 20} bases poroshokzhidkost type dental prosthesis using a graft polymerization reaction, followed by blending the resultant graft copolymer with methyl methacrylate in the ratio ²⁵ NII 2: 1, respectively, l and m of h and w schiysya in that, in order to increase . impact strength and tensile stress during static bending of prostheses, grafted suspension polymerization is carried out on May 90-95. % methyl methacrylate in the presence of May 5-10. % grafted copolymer of butyl acrylate (May 29,769.3.%), methyl methacrylate (May 3070.%) and allyl methacrylate (May 0.31.%).