Vinyl chloride resin composition

FIELD: polymers, in particular composition for molded articles useful in building materials.

SUBSTANCE: claimed composition contains (A) 100 mass pts of vinyl chloride-based resin; (B) from 1 to 30 mass pts of graft copolymer obtained by graft polymerization; (C) from 0.1 to 5 mass pts of methylmethacrylate-based polymer obtained by two-step method in presence of polymer, wherein 0.1 g of said polymer in 100 ml of chloroform has intrinsic viscosity (ηsp) at 30°C of 0.7 or more and contains 0-50 mass % of methylmethacrylate repeated units, and 0.1 g of in two step obtained polymer in 100 ml of chloroform has intrinsic viscosity (ηsp) at 30°C of 0.5 or more; and (D) from 1 to 20 mass pts of calcium carbonate.

EFFECT: articles with high processibility, whether resistance, impact resistance and luster.

5 cl, 19 ex, 3 tbl

 

The technical FIELD TO WHICH the INVENTION RELATES.

This invention relates to a resin composition based on vinyl chloride, which has extremely high performance in terms of weather resistance, impact resistance, gloss and molding of the extrudable blanks.

Prior art

Due to low cost and availability of favorable mechanical and chemical properties of molded products made from resins based on vinyl chloride, are widely used in various fields. However, these products have certain disadvantages, such as having insufficient impact resistance, the proximity of the temperature of the processing to the temperature of thermal decomposition and, thus, the possibility of formation only within a narrow temperature range and the need for a long period of time to achieve a molten state.

To solve the insufficient impact resistance to the present time, there have been several ways. Talking about them can be noted that the common practice was the use of MBS-resins (copolymers of methyl methacrylate, butadiene and styrene) and ABS resins (copolymers of Acrylonitrile, butadiene, styrene)obtained by graft-polymerization of resin-based butadiene rubbers with what amylmetacresol, with styrene or Acrylonitrile.

Although data mixing MBS-resins and ABS resins with resins based on vinyl chloride, the impact resistance can be improved, the weather resistance will deteriorate, and there is a problem, which consists in the fact that the thus obtained molded articles will demonstrate significantly degraded impact strength when used outdoors. Accordingly, it is proposed to improve the weather resistance of the MBS-resins and give them a good resistance due to graft-polymerization on the polymer-based alkylacrylate rubber, free from any double bonds, of methyl methacrylate, an aromatic vinyl compound and an unsaturated nitrile (JP-B-51-28117 and JP-B-57-8827; the term "JP-B" in accordance with the application approved in this document, refers to "the publication of the last examination of Japanese patent application").

In the case of a grafted copolymer obtained by this method produced thus molded product from the resin based on vinyl chloride have excellent weather resistance, and therefore, they are suitable for possible use in the manufacture of building materials that require long-term weather resistance, such as materials for window frames and sheets of siding.

As methods Ulu the decision processing AIDS data resins based on vinyl chloride suggested adding as technological additives from about 0.5 to 5% of the copolymer, containing a repeating element, formed from methyl methacrylate as the main component (JP-B-52-49020). Usually when you use this processing AIDS in the extrusion of window frames or sheets of siding in the resin based on vinyl chloride promoted gelation, and thus can be obtained useful molded products.

Some songs resins based on vinyl chloride to the field of building materials contain as filler calcium carbonate or titanium oxide. Among the fillers are widely used calcium carbonate because it is not only less expensive and thus allows to achieve the effect of reducing the cost of the final product, but it also contributes to raising the temperature of the beginning of thermal deformation, the improvement of the dielectric strength and improved dimensional stability. For example, in the case of window frames need to produce a molded product with a smooth and shiny surface, but so far have not suggested any way that would meet the needs of improving Shine. That is, although the use of large quantities of technological additives Shine improves, the effect of improving the gloss is still insufficient and, moreover, there is the additional problem of deterioration of impact resistance. If the ESC can be improved by reducing the content of calcium carbonate, this method is undesirable because it leads to increased cost. Although superior gloss can be obtained by increasing the temperature of the molding, and in this case, there are certain problems, such as reduced performance, due to the increase in torque during extrusion and thermal decomposition of vinyl chloride. Accordingly, it is very difficult to simultaneously achieve a satisfactory gloss, high impact resistance, high performance and low cost.

SUMMARY of INVENTION

The invention was made to overcome the problems arising at the present level of technology, aimed at creating a resin composition based on vinyl chloride, from which no deterioration of the impact resistance can be obtained molded articles with good surface properties and high gloss.

The inventors have conducted intensive studies to resolve the above problems. As a result, they found that without deterioration of the impact resistance of molded articles with high gloss can be obtained by using the hard polymer containing as the main components of the grafted copolymer based on acrylate rubber and duplicate link formed from metalmetal the ATA, with an extremely high molecular weight.

Accordingly, the present invention relates to a resin composition based on vinyl chloride, which may allow to achieve the purpose mentioned above.

1. The resin composition based on vinyl chloride, which contains:

(A) 100 mass parts of the resin based on vinyl chloride;

(B) from 1 to 30 mass parts of the grafted copolymer, which is obtained in the graft-polymerization, in the presence of from 70 to 95 mass parts of cross-linked polymer type acrylic rubber (b-1) from 5 to 30 mass parts of the vinyl monomer (b-2), despite the fact that the total number of (b-1) and (b-2) withstand equal to 100 mass parts;

(C) from 0.1 to 5 mass parts obtained in two stages polymer based on methyl methacrylate, which is produced in the presence of a polymer obtained by emulsion polymerization of from 50 to 100 mass parts of the monomer or monomer mixture (C-1)containing 50 to 100 wt%. of methyl methacrylate, 0 to 50 wt%. monomer selected from the group consisting of alkyl methacrylates other than methyl methacrylate, and alkylacrylate, and from 0 to 20% of the mass. vinyl monomer, copolymerizable with other components of the mixture, given that the total number of monomers withstand is equal to 100 wt. -%, a solution of 0.1 g of polymer in 100 ml of chloroform detects the characteristic viscosity of 0.7 or more at 30° With, by adding from 0 to 50 mass parts of the monomer or monomer mixture (C-2)containing from 0 to 50 wt%. of methyl methacrylate, from 50 to 100% of the mass. at least one monomer selected from the group consisting of alkyl methacrylates other than methyl methacrylate, and alkylacrylate, and from 0 to 20% of the mass. vinyl monomer, copolymerizable with other components of the mixture, given that the total number of monomers withstand is equal to 100 wt. -%, and the total number of (s-1) and (2) withstand equal to 100 mass parts, and a solution of 0.1 g of the obtained two-stage polymer in 100 ml of chloroform detects the characteristic viscosity of 0.5 or more at 30°and

(D) from 1 to 20 mass parts of calcium carbonate.

2. The resin composition based on vinyl chloride in the above claim 1, where the resulting two-stage polymer (C) on the basis of methyl methacrylate is obtained in two stages polymer based on methyl methacrylate, a solution of 0.1 g to 100 ml of chloroform detects the characteristic viscosity of 0.7 or more at 30°C.

3. The resin composition based on vinyl chloride in the above item 1 or 2, where the grafted copolymer (B) is a graft copolymer that is obtained in the polymerization, in the presence of from 70 to 95 mass parts sewn kauchukopodobnoe polymer containing from 70 what about the 99.99% of the mass. alkylacrylate, an alkyl group which contains from 2 to 8 carbon atoms, and from 0.01 to 5% by mass. polyfunctional monomer and from 0 to 30% of the mass. monomer, copolymerizable with other components of the mixture, given that the total number of monomers withstand is equal to 100 wt. -%, from 5 to 30 mass parts of the monomer component (component) for vaccinations containing from 60 to 100% of the mass. of methyl methacrylate and from 0 to 40 wt%. at least one monomer selected from the group consisting of alkyl methacrylates other than methyl methacrylate, alkylacrylate, unsaturated NITRILES and aromatic vinyl compounds, despite the fact that the total number of sustain is equal to 100 mass parts.

4. A molded product obtained by molding the composition according to any one of the above paragraphs. from 1 to 3.

5. Window frame or door frame, the resulting molding composition according to the above item 4.

The BEST WAY of carrying out the INVENTION

Resin (A) based on vinyl chloride, used in this invention include the vinyl chloride homopolymers and copolymers containing 70% of the mass. or more repeating units derived from vinyl chloride. Examples of monomers, which comprise the remaining 30% of the mass. or less and which have to be copolymerizable with vinyl chloride include vinylacetat is, finalproject, vinylboronate, vinylbenzoic, acrylic acid, methacrylic acid, methyl acrylate, acrylate, methyl methacrylate, ethyl methacrylate, methacrylamide and other copolymerizate monomers with one olefinic unsaturation of the type. Can be used either one of these comonomers, or a mixture of two or more compounds.

Graft copolymer (B)used in this invention may be obtained by polymerization of a monomer (b-2)containing the vinyl group, in the presence of cross-linked polymer type acrylic rubber (b-1).

Cross-linked polymer (b-1), type acrylic rubber, which is produced mainly from alkylacrylate and polyfunctional monomer synthesized using preferably from 70 to 99.99% of the mass. (even more preferably from 80 to 99.9 wt. -%) alkylacrylate, in which the alkyl group contains from 2 to 8 carbon atoms, preferably from 0.01 to 5% by mass. (even more preferably from 0.1 to 3% wt.) polyfunctional monomer and preferably from 0 to 30% of the mass. (even more preferably from 0 to 20 wt. -%) monomer, copolymerizable with other components of the mixture. If the content of alkylacrylate, in which the alkyl group contains from 2 to 8 carbon atoms, is less than 70 wt. -%, then there is a problem with resistance or change of color due to n is scoi weather resistance. If its content exceeds 99.99% of the mass, and the content of the polyfunctional monomer becomes excessively small, and thus as a result of its use can be achieved only minor effect. Also it is undesirable that the content of the polyfunctional monomer exceeded 5 wt. -%, since in this case will deteriorate the impact resistance.

Alkylacrylate, in which the alkyl group contains from 2 to 8 carbon atoms, represents the component that is used to obtain kauchukopodobnoe component having excellent weather resistance and improved impact resistance. Typical examples include acrylate, propylacetate, isobutylamine, n-butyl acrylate and 2-ethyl hexyl acrylate. Can be used either one of these alkylacrylate, or a combination of two or more compounds. Among all of them is preferred to use, for example, n-butyl acrylate or 2-ethyl hexyl acrylate, because when using data alkylacrylate due to the low value of Tg at kauchukopodobnoe component is easy to achieve high impact resistance.

Described above polyfunctional monomer component is used as a staple. Typical examples include aromatic polyfunctional vinyl compounds (e.g., divinylbenzene), methacrylate polyhydric alcohols (for example, dimethacrylate of polyethylene glycol, dimethacrylate 1,3-butanediol), complex allyl esters of unsaturated carboxylic acids (for example, alismataceae, allylacetate), diallele connection and triethylene connection (for example, diallylphthalate, treelistener). Among these polyfunctional monomers are preferred those in which at least one of the functional groups will have a reactivity different from reaktsionnosposobnykh other functional groups, such as a polyfunctional monomer, even in small quantities makes it possible for custom made kauchukopodobnoe polymer. As preferred examples may be mentioned alismataceae and diallylphthalate.

Examples of monomers copolymerizing with the above compounds include other copolymerizate monomers containing one vinyl group, and paired connection with two nenasyshchennosti olefinic type.

Specific examples of other copolymerizing monomers containing one vinyl group include alkylacrylate other than those in which the alkyl group contains from 2 to 8 carbon atoms, other acrylates, alkyl methacrylates, acrylic acid, acrylates metals, acrylamide, an aromatic vinyl compounds and derivatives thereof, Acrylonitrile, Methacrylonitrile, connect the Oia simple vinyl ether, compounds of vinyl ester, vinylchloride and vinylidenechloride. It is undesirable to use such a monomer in excess of 30 wt. -%, because the result will be degraded impact strength.

Specific examples of paired compounds with two nenasyshchennosti olefinic type include 1,3-butadiene and isoprene. It is undesirable to use such a monomer in excess of 30 wt. -%, because the result will be bad weather.

Moreover, as a monomer, copolymerizable with the compounds mentioned above may be used organosiloxane. Namely, it is advantageous to use koutsokoumnis a composite consisting of a component, which is a siloxane rubber derived from organosiloxane, and component, which is the acrylate rubber. Specific examples of organosiloxane include cyclic siloxanes (for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, Dodecamethylcyclohexasiloxane, Dodecamethylcyclohexasiloxane), alkoxysilane (for example, trimethoxysilane, tetraethoxysilane) and methacryloyloxy (for example, β-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane). As kauchukopodobnoe composite, consisting of a component, which is a siloxane rubber, and whom Oneonta, which acrylate rubber, it is possible to mention koutsokoumnis a compound having a chemical bond between siloxane rubber and acrylate rubber, koutsokoumnis composite, whose molecules siloxane rubber and acrylate rubber intertwined with each other, and koutsokoumnis composite, whose molecules siloxane rubber and acrylate rubber just coexist together without weave. It is undesirable to use organosiloxane monomer in excess of 30 wt. -%, as a result, this sometimes led to the deterioration of the working properties resin based on vinyl chloride.

Stitched koutsokoumnis polymer can be obtained by an arbitrary method without restriction. For example, it may be obtained using conventional emulsion polymerization method.

Examples of the polymerization initiator used in the polymerization include organic peroxides, such as peroxides, ketones or aldehydes (for example, cyclohexanone peroxide), diazepamonline (for example, acetylmuramic), hydroperoxides (such as, tert-butylhydroperoxide, cumene hydroperoxide), dialkylamide (for example, di-tert-butylperoxide), complex alkylpyridine (for example, tert-butylbenzoate) and percarbonate (for example, tert-butyl peroxy isopropyl carbonate), inorganic peroxides (EmOC is emer, hydrogen peroxide, potassium persulfate and azo compounds (e.g., 2,2'-azobisisobutyronitrile), although the invention these compounds and is not limited. In the case of using an organic peroxide and/or inorganic peroxide from the above compounds, these compounds may be used as initiators of polymerization, related to the type of compounds that decompose when heated. You can also use these compounds as polymerization initiators of redox type when creating combination with a reducing agent (e.g. sodium ascorbate, formaldehydefree sodium) is possible with the use of the activator (for example, iron sulfate(II)) or a chelating agent (for example, ethylenediaminetetraacetate).

The type of surfactant used for emulsion polymerization, a special limitation is imposed. That is, it is possible to use anionic surface-active agent, nonionic surface-active agent, cationic surface-active agent, a combination of anionic surfactants with nonionic surface-active substance or combination of cationic surfactants with nonionic surface-active agent. Examples of anionic surface is about-active agents include salts, formed from alkali metals and fatty acids (for example, potassium palmitate, sodium oleate, sodium stearate), salts of alkali metal, amine or ammonium salt in the form of sulfates of higher alcohols (for example, sodium dodecyl sulphate, triethanolamine dodecyl sulphate, dodecyl sulphate ammonium salts)salts formed from alkali metals and alkylbenzenesulfonic acids or alkylnaphthalenes acids (for example, dodecylbenzenesulfonate sodium, dodecylsulfonate sodium), salts formed from alkali metals (for example sodium salt) and condensation products of naphtalenesulfonic acid/formalin, salts formed from alkali metals (e.g. sodium salt) and diallylmalonate acids, alkylphosphate (for example, alkylphosphonate) and polyoxyethylenesorbitan salt (for example, polyoxyethylenesorbitan sodium), although the invention these compounds and is not limited. Examples of nonionic surfactants include polyoxyethylenesorbitan esters (for example, polyoxyethyleneglycol ether, polyoxyethyleneglycol ether), polyoxyethylenesorbitan esters (for example, polyoxyethyleneglycol ether), esters derived from sorbitan and fatty acids (for example, servicemonitor, sorbitanoleat, servicesecurity), esters obtained speleoklimaticheskaya and fatty acids, an example of which is polyoxyethylenesorbitan, complex polyoxyethylenated esters (for example, polietilenglikolmonostearat, polietilenglikolmonostearat), oksietilenom/oxypropylene block copolymer (molecular weight: from about 2000 to about 10000) and monoglycerides of fatty acids (for example, glycerylmonostearate), although the invention these compounds and is not limited. Examples of cationic surfactants include the salts of alkylamines followed (for example, acetate, dodecylamine), Quaternary ammonium salt (e.g. chloride of dodecyltrimethylammonium) and polyoxyalkylene, although the invention these compounds and is not limited. In addition to these surface-active substances may also be used and high-molecular surface-active substances.

Graft copolymer (B)used in this invention may be obtained by polymerization, in the presence of from 70 to 95% of the mass. (preferably from 75 to 92 wt. -%) polymer (b-1), type crosslinked acrylate rubber, from 5 to 30% of the mass. (preferably from 8 to 25 wt. -%) the vinyl monomer (b-2), despite the fact that the total number of (b-1) and (b-2) maintain 100% of the mass. It is undesirable that the amount of polymer (b-1), such crosslinked acrylate rubber, it would be less than 70% of the mass. or exceed the least about 95 wt. -%, since then molded products made from formed in the resin composition based on vinyl chloride, in respect of impact resistance can be obtained only very little effect.

As the vinyl monomer (b-2)used in the graft polymerization, there may be used monomers mentioned above as an illustration of the monomers forming the polymer, the type of cross-linked rubber. To strengthen the effect of toning impact resistance, it is necessary to carefully choose the monomer. Of all these monomers, it is preferable to use the monomer methyl methacrylate or a mixture of monomers containing methyl methacrylate as a main component. Namely, the content of methyl methacrylate in the monomer (b-2) preferably is in the range from 60 to 100 wt. -%, even more preferably from 70 to 100 wt. -%, despite the fact that the content of one or more monomers selected from alkyl methacrylates other than methyl methacrylate, alkylacrylate, unsaturated NITRILES and aromatic vinyl compounds (hereinafter in this document is sometimes referred to as "monomer component (component), polymerized with methyl methacrylate"), is preferably in the range from 0 to 40 wt. -%, even more preferably from 0 to 30% of the mass. It is undesirable that the content of matilla is relata in the monomer component (b-2) for vaccination would be less than 60% of the mass. (that is, the content of the monomer component (component), polymerized with methyl methacrylate, would exceed 40% of the mass.), because in this case, the effect of improving impact resistance is less pronounced.

When carrying out the graft polymerization of the monomer components for vaccination can be added all at once followed by the polymerization. Alternatively, it is possible to continuously or periodically adding and polimerizuet all the number of components or part of it. Data Monomeric components for vaccination can be mixed with each other with obtaining a whole. Alternatively, the polymerization can be carried out in two or more stages, adjusting at each stage of the composition of the monomer components for vaccinations so that he would fall in the above range of compositions.

Thus obtained graft copolymer typically has the form of a latex and the solid particles can be obtained, if the subject of the grafted copolymer type latex spray drying, salting out or precipitation of the acid followed by filtration, washing and drying. At the stage of obtaining solid particles can also be added stabilizer or absorber of ultraviolet rays, commonly used at the present level of technology.

The resulting two-stage poly is EP (C) on the basis of methyl methacrylate, used in this invention are the polymerization in the presence of the polymer obtained by polymerization of the monomer or monomer mixture (C-1)containing methyl methacrylate as a main component, monomer or monomer mixture (C-2). The monomer or monomer mixture (C-1) is a monomer or Monomeric mixture containing from 50 to 100% of the mass. (preferably from 60 to 90 wt. -%, even more preferably from 70 to 85 wt. -%) of methyl methacrylate and 0 to 50 wt%. (preferably from 10 to 40 wt. -%, and even more preferably from 15 to 30 wt. -%) monomer selected from alkyl methacrylates other than methyl methacrylate, and alkylacrylate, and from 0 to 20% of the mass. (preferably from 0 to 10 wt. -%, and even more preferably from 0 to 5 wt. -%) vinyl monomer, copolymerizable with other components of the mixture. The monomer or monomer mixture (C-2) is a monomer or Monomeric mixture containing from 0 to 50 wt%. (preferably from 20 to 49 wt. -%, and even more preferably from 30 to 45 wt. -%) of methyl methacrylate, from 50 to 100% of the mass. (preferably from 51 to 80 wt. -%, and even more preferably from 55 to 70 wt. -%) at least one monomer chosen from alkyl methacrylates other than methyl methacrylate, and alkylacrylate, and from 0 to 20% of the mass. (preferably from 0 to 10 wt. -%, even more preferably from 0 on the 5% mass.) vinyl monomer, copolymerizing with other components of the mixture. By the formation of a polymer part, derived from the monomer or monomer mixture (C-2) as the outer layer of polymer formed in the first stage, can be induced gelation of the resin based on vinyl chloride, if the resin based on vinyl chloride to add the polymer obtained in two stages. As a result, in significant degree may be enhanced by the effect of improving the gloss in accordance with this invention.

It is undesirable that the content of methyl methacrylate in the monomer or monomer mixture (C-1) would be less than 50 wt. -%, because in this case worsens Shine. When the content of the monomers (monomer)selected from alkyl methacrylates other than methyl methacrylate, and alkylacrylate will exceed 50% of the mass, the ability to stimulate the gelation of the resin based on vinyl chloride will be weakened. When the content of vinyl monomer, copolymerizable with other components of the mixture will exceed 20 wt. -%, the ability to stimulate the gelation of the resin based on vinyl chloride will be weakened.

Specific examples of alkyl methacrylates other than methyl methacrylate in the monomer or monomer mixture (C-1) include alkyl methacrylates having an alkyl group containing from 2 to 8 carbon atoms, such as those who methacrylate, propylbetaine, butylmethacrylate and 2-ethylhexylacrylate.

Examples of alkylacrylate include alkylacrylate having alkyl group containing from 1 to 8 carbon atoms, such as methyl acrylate, acrylate, propylacetate, butyl acrylate and 2-ethyl hexyl acrylate. Can be used either one of these alkyl methacrylates other than methyl methacrylate, and alkylacrylate, or a combination of two or more compounds.

Specific examples of the vinyl monomer, copolymerizable with other components of the mixture, the monomer or monomer mixture (C-1) include aromatic vinyl compounds such as styrene and α-methylsterol, and unsaturated NITRILES such as Acrylonitrile. Can be used either one of these vinyl monomers, or a combination of two or more compounds.

The solution, which is produced by dissolving 0.1 g of the polymer obtained by emulsion polymerization of monomer mixture (C-1), in 100 ml of chloroform, has a characteristic viscosity of 0.7 or more (preferably in the range from 0.8 to 1.9, and more preferably from 0.9 to 1.8) at 30°C. If the characteristic viscosity is less than 0.7, the effect of improving the gloss can be obtained sufficiently. If the characteristic viscosity will exceed 1,9, maybe not in the residual degree will be stimulated gelation and will probably deteriorate processability.

Specific examples of alkyl methacrylates other than methyl methacrylate in the monomer or monomer mixture (C-2) include alkyl methacrylates having an alkyl group containing from 2 to 8 carbon atoms, such as ethyl methacrylate, propylbetaine, butylmethacrylate and 2-ethylhexylacrylate. Examples of alkylacrylate include alkyl acrylates having an alkyl group containing from 1 to 8 carbon atoms, such as methyl acrylate, acrylate, propylacetate, butyl acrylate and 2-ethyl hexyl acrylate. Can be used either one of these alkyl methacrylates other than methyl methacrylate, and alkylacrylate, or a combination of two or more compounds. From all of these monomers is preferred to use butyl acrylate, as thus can be obtained a polymer with a low glass transition temperature.

Specific examples of the vinyl monomer, copolymerizable with other components of the mixture, the monomer or monomer mixture (C-2) include aromatic vinyl compounds such as styrene and α-methylsterol, and unsaturated NITRILES such as Acrylonitrile. Can be used either one of these vinyl monomers, or a combination of two or more compounds.

The solution, which is produced by dissolving 0.1 g of the polymer obtained by polymerization monomer the th mixture (C-2) in the presence of the polymer, obtained by polymerization of the monomer or monomer mixture (C-1), in 100 ml of chloroform, has a characteristic viscosity of 0.5 or more (preferably in the range of from 0.6 to 1.9, more preferably from 0.7 to 1.8, and more preferably from 0.8 to 1.8) at 30°C. If the characteristic viscosity is less than 0.5, the effect of improving the gloss can be obtained only insufficiently. If the characteristic viscosity will exceed 1,9, it is possible sufficiently to be stimulated gelation and will probably deteriorate processability.

For keeping the total amount of monomer or monomer mixture (C-1) and the monomer or monomer mixture (C-2), which are used to obtain the resulting two-stage polymer (C) on the basis of methyl methacrylate as technological additives suitable for the invention, to 100 mass parts of the monomer or monomer mixture (C-1) is used in an amount of from 50 to 100 mass parts, preferably from 60 to 95 mass parts, and even more preferably from 65 to 90 mass parts), while the monomer or Monomeric mixture (C-2) is used in an amount of from 0 to 50 mass parts, preferably from 5 to 40 mass parts, and even more preferably from 10 to 35 mass parts). In the present invention, the term "developed the first two-stage polymer based on methyl methacrylate includes a polymer, produced in one stage only of the monomer or monomer mixture (C-1).

When the amount of polymer obtained from a monomer or monomer mixture (C-1), (i.e., the polymer obtained in the first stage) is less than 50 mass parts, the gelation of the resin based on vinyl chloride may be stimulated sufficiently. When the amount of polymer obtained from a monomer or monomer mixture (C-2), (i.e., the polymer obtained in the second stage) will exceed 50 mass parts, the gelation of the resulting resin composition based on vinyl chloride may be stimulated sufficiently.

Obtained in two stages polymer based on methyl methacrylate can be obtained by way of conventional emulsion polymerization.

When polymerization of the above monomer or monomer mixture (C-1) a monomer or monomer mixture (C-1) can be added all at once followed by the polymerization. Alternatively, it is possible to continuously or periodically adding and polimerizuet the whole amount of the monomer or monomer mixture (C-1) or its part. The monomer or monomer mixture (C-1) can be mixed with obtaining a whole. Alternatively, the polymerization can be carried out in two or more stages, adjusting for each hundred is AI the composition of the Monomeric components so that he would fall in the above range of compositions.

By conducting the polymerization of the above monomer or monomer mixture (C-2), in the presence of a polymer obtained by emulsion polymerization of a monomer or monomer mixture (C-1), the monomer or monomer mixture (C-2) can be added all at once followed by the polymerization. Alternatively, it is possible to continuously or periodically adding and polimerizuet the whole amount of the monomer or monomer mixture (C-2) or its part. The monomer or monomer mixture (C-2) can be mixed with obtaining a whole. Alternatively, the polymerization can be carried out in two or more stages, adjusting at each stage of the composition of the Monomeric components, so that he would fall in the above range of compositions.

The resulting two-stage polymer (C) on the basis of methyl methacrylate in the form of the thus obtained latex is subjected to spray drying, salting out or precipitation of the acid followed by filtration, washing, drying and obtaining a polymer in the form of solid particles. At the stage of obtaining solid particles can also be added stabilizer or absorber of ultraviolet rays, commonly used at the present level of technology.

It is also possible that the latex described above vaccinated is polymera (C) of the present invention and the latex described above is obtained in two stages polymer (C) on the basis of methyl methacrylate present invention as such were mixed each other and then subjected to the spray drying, the salting out or precipitation of the acid followed by filtration, washing and drying to obtain a mixed resin.

The resin composition based on vinyl chloride, corresponding to this invention, can be obtained by mixing 100 mass parts of the resin based on vinyl chloride with the grafted copolymer (C) in an amount of from 1 to 30 mass parts, preferably from 3 to 20 mass parts)obtained in two stages polymer (C) on the basis of methyl methacrylate in an amount of from 0.1 to 5 mass parts, preferably from 0.2 to 3 mass parts) and calcium carbonate (D) in an amount of from 1 to 20 mass parts, preferably from 3 to 15 mass parts). When the content of the graft copolymer (B) is less than 1 mass part, no effect of improving the impact resistance will be impossible to get. It is undesirable that the content would have been more than 30 mass parts, since the thus obtained molded products will decrease the resistance. When the content obtained in two stages polymer (C) on the basis of methyl methacrylate is less than 0.1 mass part, no effect of improving the gloss will be impossible to get. It is undesirable that the content would have been more than 5 mass parts, as in this case will deteriorate the impact resistance. It is undesirable that the content of the description of the frame above the calcium carbonate (D) would be less than 1 mass part, since in this case will decrease the stiffness. Also it is undesirable that the content of calcium carbonate would have been more than 20 mass parts, as in this case worse gloss and impact resistance.

As calcium carbonate can be used, for example, heavy calcium carbonate, light calcium carbonate or adhesive calcium carbonate. To improve the affinity for the resin (A) based on vinyl chloride and improve the dispersive ability of the pigment in it can additionally be carried out surface treatment of calcium carbonate. In this case, can be used in the processing of fatty acids (e.g. stearic acid, oleic acid, linolenic acid), organic acids (for example, a resin acid, silicic acid), organic titanates (e.g., isopropylideneuridine) or wilanowie or phosphate coupling agents (for example, γ-ipropertysetstorage, monooctyltin). It is preferable to use calcium carbonate with an average particle diameter in the range from 0.2 to 5 microns, although the invention this range and is not limited.

The resin composition based on vinyl chloride, corresponding to this invention can optionally contain additives that increase the resistance, such as chlorinated polyethylene or styrene. This additional is on can be added technological additive, improving peeling from the hot metal surface. Optionally you can add a methyl methacrylate polymer with a molecular weight less than those obtained in two-stage polymer (C) on the basis of methyl methacrylate, suitable for the invention.

The resin composition based on vinyl chloride, corresponding to this invention, can be obtained simply by mixing the above materials, as in the case of conventional resin compositions based on vinyl chloride. That is, for a method of obtaining special limitation is imposed. At the stage of mixing the materials, if necessary, may be added additives commonly used in the compositions of the resins based on vinyl chloride (for example, stabilizers, oiling agents, plasticizers, dyes, fillers, absorbers of ultraviolet rays, light stabilizers, flame retardants).

Examples of stabilizers include stabilizers lead-based (for example, rejonowy the lead sulfate, dibasic postit lead, basic lead sulfite, dibasic phthalate lead, white lead, lead silicate); stabilizers on the basis of tin (for example, maleate butyanova, maleate Ochirova, demolet dibutylamine, mercaptide di-n-alkalolu, laurenmarie dibutylamine, dioctylamine-S,S'-bis-(isooctylphenyl citat)); metal-containing stabilizers related type to the Soaps derived from metals (e.g. potassium, calcium, magnesium, barium, zinc, cadmium, lead) and fatty acids (for example, 2-ethylhexanoic acid, lauric acid, stearic acid, ezoterikovou acid, hydroxystearates acid, oleic acid, ricinoleic acid, linoleic acid, beganovi acid); composite metal-containing stabilizers, concerning the type of the soap (for example, BA-CA series Ca-Zn-series, BA-CA series Ca-Mg-Sn-series, Ca-Zn-Sn-series, Pb-Sn-series, Pb-BA-CA-series), and stabilizers based epoxidizing oil (for example, epoxydecane soybean oil, epoxydecane linseed oil). Can be used either one of these stabilizers, or a combination of two or more compounds.

The resin composition based on vinyl chloride, corresponding to this invention, may be formed in various ways, such as the formation of an extrudable blanks, forming calandrinia, blow moulding or injection molding. Particularly preferred use of the method of molding of shaped extrudable blanks.

Now the invention will be described in more detail with reference to the following examples. However, it should be noted that the invention is not limited to data, p is kerami. Unless otherwise stated, all percentages are mass and mass are all part of. Each of the abbreviations used in the following examples, comparative examples and tables, has the following value.

MMA: methyl methacrylate.

MMA: butylmethacrylate.

BA: n-butyl acrylate.

AMA: alismataceae.

2-S: 2-ethyl hexyl acrylate.

In the following examples and comparative examples, evaluation was made as described in (3) in this document.

Example 1

(1) preparation of graft copolymer

In a glass reactor equipped with a thermometer, a stirrer, a partial condenser hot irrigation, a device for supplying nitrogen and boot device for the monomer and emulsifier, gave 200 parts of distilled water, 0.5 parts of potassium stearate, 0.2 part of formaldehydeinduced sodium, 0.01 part of disodium salt of ethylenediaminetetraacetic acid and 0.005 part of sulfate heptahydrate iron(II) and the resulting mixture was heated to 50° under stirring in a stream of nitrogen gas. After that here for 4 hours dropwise introduced a Monomeric mixture consisting of 79,2 part VA, 0.8 part of AMA and 0.1 part of cumene hydroperoxide. Simultaneously with the addition of the monomer mixture for 4 hours continuously added 5% of the mass. an aqueous solution of 2 parts is tarata potassium. After adding the monomer mixture, the resulting mixture was stirred for 1.5 hours. After that here for 1 hour continuously added 17 parts of MMA and 3 parts of VA, which was used as monomer components for vaccinations, and 0.01 part of cumene hydroperoxide. After addition was added 0.01 part of cumene hydroperoxide, and the resulting mixture was stirred for a further 2 hours to complete thus polymerization. The degree of conversion was 99.8%. Thus obtained latex grafted copolymer was vysalivanie of an aqueous solution of calcium chloride, was heated and then obezvozhivani/dried, thus obtaining a white powdery resin.

(2) the Receipt obtained in two stages polymer based on methyl methacrylate

In a glass reactor equipped with a thermometer, a stirrer, a partial condenser hot irrigation, a device for supplying nitrogen and boot device for the monomer, gave 200 parts of distilled water and 0.7 part of dioctylmaleate sodium. After removal of the volume of oxygen and water from the reactor by passing through the liquid phase of nitrogen content with stirring, they were heated to 70°C. After that, the reactor was immediately added to the Monomeric mixture consisting of 70 parts of MMA and 10 parts of VA. Then added 0.01 to frequent the of potassium persulfate and stirring was continued for 1 hour, to the polymerization essentially be over. At this stage of the latex was obtained a white powder resin and perform the measurement of the characteristic viscosity of the resin. Table 1 shows the result. After the above-described polymerization of the first stage continuously for 40 minutes was added dropwise a monomer mixture of the second stage, consisting of 6 parts of MMA and 14 parts of VA. When you are finished adding the content was kept at 70°C for 90 minutes in order in the polymerization to be over. The degree of conversion to polymer was 99.4%. Thus obtained latex obtained in two stages polymer based on methyl methacrylate was vysalivanie of an aqueous solution of calcium chloride, was heated and then held dehydration/drying obtaining thus a white powdery resin.

0.1 g of thus obtained obtained in two stages polymer based on methyl methacrylate was dissolved in 100 ml of chloroform and 30°conducted the measurement of the characteristic viscosity (ηsp). Table 1 shows the result.

(3) Evaluation

(3-1) evaluation of the impact

100 parts of vinyl chloride resin (Kanevinyl S-1001, produced by Kanegafuchi Chemical Industry Co., Ltd.; the average degree of polymerization: 1000), and 4.5 parts odnoupakovochnye lead stabilizer (LGC3203, made the necessary company ACROS), 4.5 parts of titanium oxide, 8 parts of calcium carbonate, 7 parts of grafted copolymer and 0.5 parts obtained in two stages polymer based on methyl methacrylate were mixed in the mixer hensely to obtain a powdery compound. After that, the molding method of the processed workpieces of it made the window frame, using the following molding conditions.

Machine for molding: extruder with two parallel screws 65 mm, manufactured by the company Batenfeld.

The molding temperature: C1/C2/C3/C4/AD/D1/D2/D3/D4/D5:

175/180/180/175/185/202/202/206/202/200°).

Screw rotation speed: 24 rpm. Capacity: 110 kg/hour.

The sample for testing the impact resistance was obtained from the window frame, made so in the molding of the processed workpieces, and in accordance with JIS K 7111 conducted measurement of impact strength Charpy.

(3-2) Assessment Shine

Measurement of gloss (gloss on gloss with the reflection of light at an angle of 60°) for window frames, made so in the molding of the shaped extrudable blanks, conducted in accordance with JIS K 7105.

Table 1 shows the results.

Example 2

(1) preparation of graft copolymer

The grafted copolymer was obtained in the same way as in example 1.

(2) the Receipt obtained in two stages is alimera on the basis of methyl methacrylate

In a glass reactor equipped with a thermometer, a stirrer, a partial condenser hot irrigation, a device for supplying nitrogen and boot device for the monomer, gave 200 parts of distilled water and 0.7 part of dioctylmaleate sodium. After removal of the volume of oxygen and water from the reactor by passing through the liquid phase of nitrogen content with stirring, they were heated to 70°C. After that, the reactor was immediately added to the Monomeric mixture consisting of 70 parts of MMA and 10 parts of VA. Then added 0.01 part of potassium persulfate and stirring was continued for 1 hour to ensure that, as a result of polymerization essentially be over. At this stage of the latex was obtained a white powder resin and perform the measurement of the characteristic viscosity of the resin. Table 1 shows the result. After the above-described polymerization of the first stage continuously for 40 minutes was added dropwise a monomer mixture of the second stage, consisting of 6 parts of MMA and 14 parts of VA. When you are finished adding the content was kept at 70°C for 90 minutes in order in the polymerization to be over. The degree of conversion to polymer was 99.4%. Thus obtained latex obtained in two stages polymer based on methyl methacrylate was vysalivanie of aqueous solution of chlorite is and calcium, was heated and then held dehydration/drying obtaining thus a white powdery resin.

0.1 g of thus obtained obtained in two stages polymer based on methyl methacrylate was dissolved in 100 ml of chloroform and 30°conducted the measurement of the characteristic viscosity (ηsp). Table 1 shows the result. When using the thus obtained graft copolymer obtained in two stages polymer based on methyl methacrylate measured impact strength according to Charpy and Shine the same way as in example 1. Table 1 shows the results.

Example 3

Grafted copolymer obtained in two stages polymer based on methyl methacrylate was obtained in the same way as in example 1, but upon receipt obtained in two stages polymer based on methyl methacrylate was added 0.05 part of potassium persulfate. After this evaluation was performed in the same way. Table 1 shows the results.

Example 4

Grafted copolymer obtained in two stages polymer based on methyl methacrylate was obtained in the same way as in example 1, but upon receipt obtained in two stages polymer based on methyl methacrylate was added to 0.001 part of potassium persulfate. After this evaluation was performed in the same way. Table 1 shows the results.

Example 5

The grafted copolymer and get in on the e-stage polymer based on methyl methacrylate was obtained in the same way, as in example 1, but upon receipt obtained in two stages polymer based on methyl methacrylate was first added to 0.001 part of potassium persulfate and then before polymerization of the second stage was added to 0.001 part of potassium persulfate. After this evaluation was performed in the same way. Table 1 shows the results.

Example 6

(1) preparation of graft copolymer

In a glass reactor equipped with a thermometer, a stirrer, a partial condenser hot irrigation, a device for supplying nitrogen and boot device for the monomer and emulsifier, gave 200 parts of distilled water and 0.05 part of sodium dodecyl sulfate and the resulting mixture was heated to 50°under stirring in a stream of nitrogen gas. After that, there was introduced a mixture consisting of 7,15 part VA, the 1.3 part 2-ENE, 0.05 part of AMA and 0.01 part of cumene hydroperoxide. 10 minutes after this there was introduced a mixture obtained by dissolving 0.2 part of formaldehydeinduced sodium in 5 parts of distilled water and a mixture obtained by dissolving 5 parts of distilled water, 0.01 part of disodium salt of ethylenediaminetetraacetic acid and 0.005 part of sulfate heptahydrate iron(II). After stirring for 1 hour here for 4 hours was added dropwise a monomer mixture consisting of 4,35 part VA, 11,7 part 2-ENE, 0.45 part of AMA and 0.1 part of cumene hydroperoxide. Simultaneously with the addition of the monomer mixture for 4 hours continuously added 5% of the mass. an aqueous solution of 1 part of sodium dodecyl sulfate. After adding the monomer mixture, the resulting mixture was stirred for 1.5 hours. Thus obtained latex kauchukopodobnoe polymer (degree of conversion of 99.7%, average particle diameter of 0.17 μm). A small portion of the latex of this kauchukopodobnoe polymer was collected, vysalivanie of an aqueous solution of calcium chloride and then dried. The thus obtained solid product was extracted with toluene at 23°C for 40 hours and perform the measurement of the gel content (97,7%). To this latex kauchukopodobnoe polymer at 50°C for 1 hour continuously added as monomer components for inoculation of 13 parts of MMA and 2 of part VA and 0.01 part of cumene hydroperoxide. After addition was added 0.01 part of cumene hydroperoxide, and the resulting mixture was stirred for a further 2 hours to complete thus polymerization. The degree of conversion of monomer components for vaccination was 98,0%. Thus obtained latex grafted copolymer was vysalivanie of an aqueous solution of calcium chloride, was heated and then obezvozhivani/drying is whether, thus obtaining a white powdery resin.

(2) the Receipt obtained in two stages polymer based on methyl methacrylate

Obtained in two stages polymer based on methyl methacrylate was obtained as in example 4.

When using the thus obtained graft copolymer obtained in two stages polymer based on methyl methacrylate measured impact strength according to Charpy and Shine the same way as in example 1. Table 1 shows the results.

Example 7

(1) preparation of graft copolymer

In a glass reactor equipped with a thermometer, a stirrer, a partial condenser hot irrigation, a device for supplying nitrogen and boot device for the monomer and emulsifier, gave 200 parts of distilled water and 0.1 part of sodium dodecyl sulfate and the resulting mixture was heated to 50°under stirring in a stream of nitrogen gas. After that, there was introduced a mixture of 13 parts of 2-ENE, 0.1 part of AMA and 0.02 parts of cumene hydroperoxide. 10 minutes after this there was introduced a mixture obtained by dissolving 0.2 part of formaldehydeinduced sodium in 5 parts of distilled water and a mixture obtained by dissolving 5 parts of distilled water, 0.01 part of disodium salt of ethylenediaminetetraacetic sour the s and 0.005 part of sulfate heptahydrate iron (II). After stirring for 1 hour here for 4 hours was added dropwise a monomer mixture consisting of 71,4 part VA, 0.5 parts of AMA and 0.09 parts of cumene hydroperoxide. Simultaneously with the addition of the monomer mixture for 4 hours continuously added 5% of the mass. an aqueous solution of 1 part of sodium dodecyl sulfate. After adding the monomer mixture, the resulting mixture was stirred for 1.5 hours. Thus obtained latex kauchukopodobnoe polymer (degree of conversion of 99.5%, average particle diameter of 0.17 μm). A small portion of the latex of this kauchukopodobnoe polymer was collected, vysalivanie of an aqueous solution of calcium chloride and then dried. The thus obtained solid product was extracted with toluene at 23°C for 40 hours and perform the measurement of the gel content (97,3%). To this latex kauchukopodobnoe polymer at 50°C for 1 hour continuously added as monomer components for inoculation of 13 parts of MMA and 2 of part VA and 0.01 part of cumene hydroperoxide. After addition was added 0.01 part of cumene hydroperoxide, and the resulting mixture was stirred for a further 2 hours to complete thus polymerization. The degree of conversion of monomer components for vaccination was 98.2%. Thus obtained latex privatov the copolymer was vysalivanie of an aqueous solution of calcium chloride, was heated and then obezvozhivani/dried, thus obtaining a white powdery resin.

(2) the Receipt obtained in two stages polymer based on methyl methacrylate

Obtained in two stages polymer based on methyl methacrylate was obtained as in example 4.

When using the thus obtained graft copolymer obtained in two stages polymer based on methyl methacrylate measured impact strength according to Charpy and Shine the same way as in example 1. Table 2 shows the results.

Example 8

(1) preparation of graft copolymer

In a glass reactor equipped with a thermometer, a stirrer, a partial condenser hot irrigation, a device for supplying nitrogen and boot device for the monomer and emulsifier, gave 200 parts of distilled water and 0.2 part of sodium dodecyl sulfate and the resulting mixture was heated to 50°under stirring in a stream of nitrogen gas. After that, there was introduced a mixture consisting of 25 parts 2-ENE, 0.2 parts of AMA and 0.04 parts of cumene hydroperoxide. 10 minutes after this there was introduced a mixture obtained by dissolving 0.2 part of formaldehydeinduced sodium in 5 parts of distilled water and a mixture obtained by dissolving 5 parts of distilled water and 0.01 part of the active ingredient is sodium salt of ethylenediaminetetraacetic acid and 0.005 part of sulfate heptahydrate iron(II). After stirring for 1 hour here for 4 hours was added dropwise a monomer mixture consisting of 59,5 part VA, 0.3 part of AMA and 0.08 parts of cumene hydroperoxide. Simultaneously with the addition of the monomer mixture for 4 hours continuously added 5% of the mass. an aqueous solution of 1 part of sodium dodecyl sulfate. After adding the monomer mixture, the resulting mixture was stirred for 1.5 hours. Thus obtained latex kauchukopodobnoe polymer (degree of conversion and 99.8%, average particle diameter of 0.17 μm). A small portion of the latex of this kauchukopodobnoe polymer was collected, vysalivanie of an aqueous solution of calcium chloride and then dried. The thus obtained solid product was extracted with toluene at 23°C for 40 hours and perform the measurement of the gel content (97,4%). To this latex kauchukopodobnoe polymer at 50°C for 1 hour continuously added as monomer components for inoculation of 13 parts of MMA and 2 of part VA and 0.01 part of cumene hydroperoxide. After addition was added 0.01 part of cumene hydroperoxide, and the resulting mixture was stirred for a further 2 hours to complete thus polymerization. The degree of conversion of monomer components for vaccination was 98,0%. Thus obtained latex privatov the copolymer was vysalivanie of an aqueous solution of calcium chloride, was heated and then obezvozhivani/dried, thus obtaining a white powdery resin.

(2) the Receipt obtained in two stages polymer based on methyl methacrylate

Obtained in two stages polymer based on methyl methacrylate was obtained as in example 4.

When using the thus obtained graft copolymer obtained in two stages polymer based on methyl methacrylate measured impact strength according to Charpy and Shine the same way as in example 1. Table 2 shows the results.

Comparative example 1

Grafted copolymer obtained in two stages polymer based on methyl methacrylate was obtained in the same way as in example 1, but upon receipt obtained in two stages polymer based on methyl methacrylate was added to 0.12 part of potassium persulfate. After this evaluation was performed in the same way. Table 2 shows the results.

Comparative example 2

Grafted copolymer obtained in two stages polymer based on methyl methacrylate was obtained in the same way as in example 1, but upon receipt obtained in two stages polymer based on methyl methacrylate was added to 0.08 part of potassium persulfate. After this evaluation was performed in the same way. Table 2 shows the results.

Comparative example 3

Grafted copolymer obtained in two-stage polymer, based on the E. of methyl methacrylate was obtained in the same way, as in example 1, but upon receipt obtained in two stages polymer based on methyl methacrylate was added to 0.03 part of potassium persulfate. After this evaluation was performed in the same way. Table 2 shows the results.

Comparative example 4

Grafted copolymer obtained in two stages polymer based on methyl methacrylate was obtained in the same way as in example 1, except that upon receipt obtained in two stages polymer based on methyl methacrylate monomer mixture consisting of 35 parts of MMA and 5 parts of VA, was added immediately to complete thereby the polymerization, and then dropwise continuously added another Monomeric mixture consisting of 18 parts of MMA and 42 parts of VA. After this evaluation was performed in the same way. Table 2 shows the results.

Example 9

(1) preparation of graft copolymer

In a glass reactor equipped with a thermometer, a stirrer, a partial condenser hot irrigation, a device for supplying nitrogen and boot device for the monomer and emulsifier, gave 200 parts (mass parts mass parts of the measurement will be carried out later in this document) of distilled water, 0.5 parts of potassium stearate, 0.2 part of formaldehydeinduced sodium, 0.01 part of disodium salt of this is indianinternet acid and 0.005 part of sulfate heptahydrate iron(II) and the resulting mixture was heated to 50° With under stirring in a stream of nitrogen gas. After that here for 5 hours dropwise introduced a Monomeric mixture consisting of 89 parts of VA, 1 part of AMA and 0.1 part of cumene hydroperoxide. Simultaneously with the addition of the monomer mixture for 5 hours continuously added 5% of the mass. an aqueous solution of 2 parts of potassium stearate. After adding the monomer mixture, the resulting mixture was stirred for 1.5 hours. After that here for 1 hour continuously added 10 parts of MMA, which was used as a monomer component for vaccinations, and 0.01 part of cumene hydroperoxide. After addition was added 0.01 part of cumene hydroperoxide, and the resulting mixture was stirred for a further 2 hours to complete thus polymerization. The degree of conversion was 99.9 percent.

(2) the Receipt obtained in two stages polymer based on methyl methacrylate

In a glass reactor equipped with a thermometer, a stirrer, a partial condenser hot irrigation, a device for supplying nitrogen and boot device for the monomer, gave 200 parts of distilled water and 0.7 part of dioctylmaleate sodium. After removal of the volume of oxygen and water from the reactor by passing through the liquid phase of nitrogen content with stirring, they were heated to 70°C. After that in R the actor was immediately added to the monomer mixture, consisting of 70 parts of MMA and 10 parts of VA. Then added 0,001 part of potassium persulfate and stirring was continued for 1 hour to ensure that, as a result of polymerization essentially be over. At this stage of the latex was obtained a white powder resin and perform the measurement of the characteristic viscosity of the resin. Table 2 shows the result. After the above-described polymerization of the first stage continuously for 40 minutes was added dropwise a monomer mixture of the second stage, consisting of 6 parts of MMA and 14 parts of VA. When you are finished adding the content was kept at 70°C for 90 minutes in order in the polymerization to be over. The degree of conversion to polymer was 99.4%. To obtain a white powdery resin was collected portion of this latex obtained in two stages polymer based on methyl methacrylate. After that conducted the measurement of the characteristic viscosity of this resin. Table 3 shows the results.

Thus obtained latex grafted copolymer latex obtained in two stages polymer based on methyl methacrylate were mixed with a mass ratio (based on solids)of 14:1, was then vysalivanie of an aqueous solution of calcium chloride, was heated and then obezvozhivani/dried, thus obtaining a white powder is the crustacean leaves the resin. Assessment of impact strength according to Charpy and Shine for this polymer was performed as in example 1. Table 3 shows the results.

Example 10

Grafted copolymer obtained in two stages polymer based on methyl methacrylate was obtained in the same way as in example 9, except that upon receipt obtained in two stages polymer based on methyl methacrylate monomer mixture consisting of 60 parts of MMA and 20 parts of MMA was added at once to complete thereby the polymerization, and then dropwise continuously added another Monomeric mixture consisting of 6 parts of MMA and 14 parts of VA. After this evaluation was performed in the same way. Table 3 shows the results.

Example 11

(1) preparation of graft copolymer

In a glass reactor equipped with a thermometer, a stirrer, a partial condenser hot irrigation, a device for supplying nitrogen and boot device for the monomer and emulsifier, gave 200 parts of distilled water and 0.05 part of sodium dodecyl sulfate and the resulting mixture was heated to 50°under stirring in a stream of nitrogen gas. After that, there was introduced a mixture consisting of 7,65 part VA, the 1.3 part 2-ENE, 0.05 part of AMA and 0.01 part of cumene hydroperoxide. 10 minutes after this there was introduced a mixture obtained by dissolving 0.2 part of the formal is of aidslifecycle sodium in 5 parts of distilled water, and another mixture obtained by dissolving 5 parts of distilled water, 0.01 part of disodium salt of ethylenediaminetetraacetic acid and 0.005 part of sulfate heptahydrate iron(II). After stirring for 1 hour here for 4 hours was added dropwise a monomer mixture consisting of 68,85 part VA, 11,7 part 2-ENE, 0.45 part of AMA and 0.1 part of cumene hydroperoxide. Simultaneously with the addition of the monomer mixture for 4 hours continuously added 5% of the mass. an aqueous solution of 1 part of sodium dodecyl sulfate. After adding the monomer mixture, the resulting mixture was stirred for 1.5 hours. Thus obtained latex kauchukopodobnoe polymer (degree of conversion of 99.7%, average particle diameter of 0.17 μm). A small portion of the latex of this kauchukopodobnoe polymer was collected, vysalivanie of an aqueous solution of calcium chloride and then dried. The thus obtained solid product was extracted with toluene at 23°C for 40 hours and perform the measurement of the gel content (97,4%). To this latex kauchukopodobnoe polymer at 50°C for 1 hour continuously added as a monomer component for inoculation of 10 parts of MMA and 0.01 part of cumene hydroperoxide. After addition was added 0.01 part of cumene hydroperoxide, and the resulting mixture is stirred for a further 2 hours to complete thus polymerization. The degree of conversion of monomer components for vaccination was 97,0%.

To obtain white powder of graft copolymer was mixed with the latex obtained in two stages polymer based on methyl methacrylate as in example 9. The evaluation was performed in the same way. Table 3 shows the results.

Example 12

(1) preparation of graft copolymer

In a glass reactor equipped with a thermometer, a stirrer, a partial condenser hot irrigation, a device for supplying nitrogen and boot device for the monomer and emulsifier, gave 200 parts of distilled water and 0.1 part of sodium dodecyl sulfate and the resulting mixture was heated to 50°under stirring in a stream of nitrogen gas. After that, there was introduced a mixture of 13 parts of 2-ENE, 0.1 part of AMA and 0.02 parts of cumene hydroperoxide. 10 minutes after this there was introduced a mixture obtained by dissolving 0.2 part of formaldehydeinduced sodium in 5 parts of distilled water and a mixture obtained by dissolving 5 parts of distilled water, 0.01 part of disodium salt of ethylenediaminetetraacetic acid and 0.005 part of sulfate heptahydrate iron(II). After stirring for 1 hour here for 4 hours was added dropwise a monomer mixture consisting of 76,4 part VA, 0.5 to frequent the AMA and 0.09 parts of cumene hydroperoxide. Simultaneously with the addition of the monomer mixture for 4 hours continuously added 5% of the mass. an aqueous solution of 1 part of sodium dodecyl sulfate. After adding the monomer mixture, the resulting mixture was stirred for 1.5 hours. Thus obtained latex kauchukopodobnoe polymer (degree of conversion of 99.7%, average particle diameter of 0.17 μm). A small portion of the latex of this kauchukopodobnoe polymer was collected, vysalivanie of an aqueous solution of calcium chloride and then dried. The thus obtained solid product was extracted with toluene at 23°C for 40 hours and perform the measurement of the gel content (97,5%). To this latex kauchukopodobnoe polymer at 50°C for 1 hour continuously added as a monomer component for inoculation of 10 parts of MMA and 0.01 part of cumene hydroperoxide. After addition was added 0.01 part of cumene hydroperoxide, and the resulting mixture was stirred for a further 2 hours to complete thus polymerization. The degree of conversion of monomer components for vaccination was 97.1 per cent.

To obtain white powder of graft copolymer was mixed with the latex obtained in two stages polymer based on methyl methacrylate as in example 9. The evaluation was performed in the same way. Table 3 shows p the results.

Example 13

(1) preparation of graft copolymer

In a glass reactor equipped with a thermometer, a stirrer, a partial condenser hot irrigation, a device for supplying nitrogen and boot device for the monomer and emulsifier, gave 200 parts of distilled water and 0.2 part of sodium dodecyl sulfate and the resulting mixture was heated to 50°under stirring in a stream of nitrogen gas. After that, there was introduced a mixture consisting of 25 parts 2-ENE, 0.2 parts of AMA and 0.04 parts of cumene hydroperoxide. 10 minutes after this there was introduced a mixture obtained by dissolving 0.2 part of formaldehydeinduced sodium in 5 parts of distilled water and a mixture obtained by dissolving 5 parts of distilled water, 0.01 part of disodium salt of ethylenediaminetetraacetic acid and 0.005 part of sulfate heptahydrate iron(II). After stirring for 1 hour here for 4 hours was added dropwise a monomer mixture consisting of 64,4 part VA, 0.4 parts of AMA and 0.08 parts of cumene hydroperoxide. Simultaneously with the addition of the monomer mixture for 4 hours continuously added 5% of the mass. an aqueous solution of 1 part of sodium dodecyl sulfate. After adding the monomer mixture, the resulting mixture was stirred for 1.5 hours. Thus recip is whether latex kauchukopodobnoe polymer (degree of conversion of 99.6%and the average particle diameter of 0.17 μm). A small portion of the latex of this kauchukopodobnoe polymer was collected, vysalivanie of an aqueous solution of calcium chloride and then dried. The thus obtained solid product was extracted with toluene at 23°C for 40 hours and perform the measurement of the gel content (97,2%). To this latex kauchukopodobnoe polymer at 50°C for 1 hour continuously added as a monomer component for inoculation of 10 parts of MMA and 0.01 part of cumene hydroperoxide. After addition was added 0.01 part of cumene hydroperoxide, and the resulting mixture was stirred for a further 2 hours to complete thus polymerization. The degree of conversion of monomer components for vaccination was 97,5%.

To obtain white powder of graft copolymer was mixed with the latex obtained in two stages polymer based on methyl methacrylate as in example 9. The evaluation was performed in the same way. Table 3 shows the results.

Comparative example 5

Grafted copolymer obtained in two stages polymer based on methyl methacrylate was obtained in the same way as in example 9, but when the obtained two-stage polymer based on methyl methacrylate was added to 0.12 part of potassium persulfate.

After this evaluation was performed in the same way. Tablica shows the results.

Comparative example 6

Grafted copolymer obtained in two stages polymer based on methyl methacrylate was obtained in the same way as in example 10, but when the obtained two-stage polymer based on methyl methacrylate was added to 0.12 part of potassium persulfate. After this evaluation was performed in the same way. Table 3 shows the results.

Table 3.
No. of orderComposition (parts)The result of evaluating
Graft copolymer (B)Hard copolymer (C)The characteristic viscosity of the polymer obtained in stage 1 (p-1)Characteristic viscosity obtained in two stages polymer-based MMA (C)Impact strength according to Charpy (Kj/m2)Gloss (%)
Koutsokoumnis polymer (b-1)The vinyl monomer (b-2)The composition obtained in stage 1The composition obtained in stage 2Full track
Example 9VA (89)

The AMA (1)
MMA (10)MMA (70)

VA (10)
MMA (6)

VA (14)
MMA (7)

VA (24)
1,121,0910863
Example 10VA (89)

The AMA (1)
MMA (10)MMA (60) MMA (20)MMA (6)

VA (14)
MMA (66) MMA (20)

VA (14)
0,800,7711066
Example 11VA (76,5)

2-ENE (13)

AMA (0,5)
MMA (10)MMA (70)

VA (10)
MMA (6)

VA (14)
MMA (76)

VA (24)
1,121,0912063
Example 12Stage 1.

2-ENE (13)

AMA (0,1) stage 2.

VA (76,4)

AMA (0,5)
MMA (10)MMA (70)

VA (10)
MMA (6)

VA (14)
MMA (76)

VA (24)
1,121,0912962
Example 13Stage 1.

2-ENE (25) AMA (0,2) stage 2.

VA (64,4)

AMA (0,4)
MMA (10)MMA (70) VA (10)MMA (6) VA (14)MMA (76) VA (24)1,121,0912860
Compare-local example 5VA (89)

The AMA(1)
MMA (10)MMA (70)

VA (10)
MMA (6)

VA (14)
MMA (76)

VA (24)
0,350,339538
Compare-local example 6VA (89)

The AMA(1)
MMA (10)MMA (60)

VA (20)
MMA (6)

VA (14)
MMA (66)

MMA (20)

VA (14)
0,470,327835

When using the resin composition based on vinyl chloride of the present invention, where the grafted copolymer based on acrylic rubber is mixed with the resulting two-stage polymer based on methyl methacrylate containing methyl methacrylate as a main component, and with calcium carbonate, it is possible to obtain a molded product with excellent pererabatyvaemogo, weather resistance, impact resistance and gloss.

Although this invention has been described in detail, including links to specific solutions, a specialist in the relevant field should be obvious that without deviating from the essence and scope of the invention in the invention can be made various changes and modifications.

This application is based on Japanese patent application No. 2000-098519, filed on March 31, 2000, the contents of which in full is incorporated herein by reference.

1. The composition for molding articles, which contains

(A) 100 mA is C resins based on vinyl chloride;

(B) from 1 to 30 parts by weight of the grafted copolymer, which is obtained in the graft-polymerization, in the presence of from 70 to 95 parts by weight of crosslinked polymer type acrylic rubber (b-1), from 5 to 30 parts by weight of a vinyl monomer (b-2) despite the fact that the total number of (b-1) and (b-2) withstand 100 parts by weight of;

(C) from 0.1 to 5 parts by weight obtained in two stages polymer based on methyl methacrylate, which is produced in the presence of a polymer obtained by emulsion polymerization of from 50 to 100 parts by weight of monomer or monomer mixture (C-1)containing 50 to 100 wt.% of methyl methacrylate, 0 to 50 wt.% monomer selected from the group consisting of alkyl methacrylates other than methyl methacrylate, and alkylacrylate, and from 0 to 20 wt.% vinyl monomer, copolymerizable with other components of the mixture, given that the total number of monomers withstand equal 100 wt.%, a solution of 0.1 g of the above polymer in 100 ml of chloroform detects the characteristic viscosity of 0.7 or more at 30°With, by adding from 0 to 50 parts by weight of monomer or monomer mixture (C-2)containing from 0 to 50 wt.% of methyl methacrylate, from 50 to 100 wt.% at least one monomer selected from the group consisting of alkyl methacrylates other than methyl methacrylate, and alkylacrylate, and from 0 to 20 wt.% vinyl MES is a measure copolymerizing with other components of the mixture, given that the total number of monomers withstand equal 100 wt.%, and the total number of (s-1) and (2) maintain 100 parts by weight, and a solution of 0.1 g referred obtained in two stages polymer in 100 ml of chloroform detects the characteristic viscosity of 0.5 or more at 30°and

(D) from 1 to 20 parts by weight of calcium carbonate.

2. The composition according to claim 1 where the above-mentioned obtained in two stages polymer (C) on the basis of methyl methacrylate is obtained in two stages polymer based on methyl methacrylate, a solution of 0.1 g to 100 ml of chloroform detects the characteristic viscosity of 0.7 or more at 30°C.

3. The composition according to claim 1 or 2 where the above-mentioned graft copolymer (B) is a graft copolymer that is obtained in the polymerization in the presence of from 70 to 95 parts by weight of crosslinked polymer type acrylic rubber obtained from alkylacrylate from 70 to 99.99 wt.%, the alkyl group of which contains from 2 to 8 carbon atoms, and from 0.01 to 5 wt.% polyfunctional monomer and from 0 to 30 wt.% monomer, copolymerizable with other components of the mixture, given that the total number of monomers withstand equal 100 wt.%, from 5 to 30 parts by weight of a vinyl monomer containing from 60 to 100 wt.% of methyl methacrylate and from 0 to 40 wt.% at least one is anomura, selected from the group consisting of alkyl methacrylates other than methyl methacrylate, alkylacrylate, unsaturated NITRILES and aromatic vinyl compounds, despite the fact that the total number of sustain 100 parts by weight of

4. A molded product obtained by molding the composition according to any one of claims 1 to 3.

5. Window frame or door frame, obtained by molding the composition according to any one of claims 1 to 3.



 

Same patents:

FIELD: polymer materials.

SUBSTANCE: composition comprises polyolefin A, containing anhydride function and having viscosity at least 20 g/10 min measured at 190°C and loading 2,16 kg, and epoxy function-containing product B destined for cross-linking polyolefin A. Relative proportions of A and B are such that for each epoxy function there are from 0.1 to 1.5 anhydride functions. Composition can be used in slush molding process, in thermal molding of sheets, or in on-rod casting process.

EFFECT: increased flowability resistance and wear resistance.

6 cl, 1 tbl, 6 ex

The invention relates to polymeric compositions and method of slow depolymerization

Polymer composition // 2171821
The invention relates to compositions containing graft copolymers of polypropylene, polycarbonate, aliphatic polyester and, optionally, a rubber component and/or polypropylene

The invention relates to compositions comprising graft copolymers, which include polystyrene grafted to the main chain or the basis of polypropylene, and in particular, this invention relates to compositions based on graft copolymers having a heterogeneous morphology, characterized in that the polypropylene is a continuous phase, and the polystyrene dispersed phase

Polymer composition // 2088614
The invention relates to polymeric compositions based on thermoplastic elastomer grafted copolymer of vinyl chloride (I) a copolymer of ethylene-vinyl acetate (EVA) for medical products that do not contain low molecular weight plasticizer, characterized by increased flexibility, transparency, resistance to various types of sterilization

Polymer composition // 2087496
The invention relates to the composition of the polymer composition on the basis of modified polymer of vinyl chloride (I) used, for example, for the manufacture of core-molded products, sheets, films, etc

Polymer composition // 2086584
The invention relates to polymeric compositions based on unplasticized polyvinyl chloride /PVC/ processed, for example, in molding articles /window and door frames/ s high white

The invention relates to the chemistry of macromolecular compounds, or more precisely to the grafted polymers of vinyl acetate on butyl rubber, the General formula:

< / BR>
where a 98,0-to 98.4 mol

FIELD: chemical technology, in particular plasticized composition based on polyvinylchloride for cable plasticate.

SUBSTANCE: claimed composition contains polyvinylchloride, dioctylphtalate, chloroparaffin, tribasic lead sulfate, calcium stearate, antimony trioxide, chalk, diphenylolpropane, carbon black and additionally contains metal-containing lubricant with acidic number at most 30 mg KOH/g. Lubricant is obtained by interaction of alpha-branched saturated monocarboxylic C10-C28-acids with polyhydric alcohol at 180-220°C in molar ratio of 1:(1-2) in presence of bivalent metal oxides: CaO, PbO, ZnO, MgO, BaO or two-component mixture thereof in ratio of 0.25-1:0.5-1, in amount of 0.5-2.0 mass % calculated as total reaction mass. As polyhydric alcohol ethylene glycol, glycerol, polyglycerol, which represents slop from glycerol distillation, are used.

EFFECT: articles with increased extension strength, elongation, heat resistance, improved appearance, decreased brittle point; resin composition assortment expansion.

2 cl, 16 ex, 1 tbl

Resin composition // 2251558

FIELD: organic chemistry, in particular polymers.

SUBSTANCE: invention relates to plasticized composition based on emulsion polyvinylchloride, i.e. plastisols useful in production of polymeric articles. Plastisol contains emulsion polyvinylchloride, ester plasticizer such as dioctylphtalate, chalk, titanium dioxide, epoxy resin, barium stearate, and additionally contains metal-containing lubricant with acidic number at most 3 mg KOH/g. Lubricant is obtained by interaction of alpha-branched saturated monocarboxylic C10-C28-acids with polyhydric alcohol at 180-220°C in molar ratio of 1:(1-2) in presence of bivalent metal oxides: CaO, PbO, ZnO, MgO or two-component mixture thereof in ratio of 0.25-1:0.5-1, in amount of 0.5-2.0 mass % calculated as total reaction mass. As polyhydric alcohol ethylene glycol, glycerol, polyglycerol, which represents slop from glycerol distillation, are used. Composition of present invention is useful in production of thin-layer polymeric articles.

EFFECT: decreased viscosity rising during storage; drier surface of finished articles; resin composition assortment expansion.

2 cl, 14 ex, 1 tbl

Resin composition // 2251557

FIELD: treatment of thermoplastic resin composition based on polyvinylchloride by extrusion for pipelines manufacturing.

SUBSTANCE: claimed composition contains polyvinylchloride with Kf = 55-60, tribasic lead sulfate, dibasic lead stearate, titanium dioxide, paraffin, metal-containing lubricant with acidic number at most 3 mg KOH/g. Lubricant is obtained by interaction of alpha-branched saturated monocarboxylic C10-C28-acids with polyhydric alcohol at 180-220°C in molar ratio of 1:(1-2) in presence of bivalent metal oxides: CaO, PbO, ZnO, MgO or two-component mixture thereof in ratio of 1:1, in amount of 0.5-2.0 mass % calculated as total reaction mass. As polyhydric alcohol ethylene glycol, glycerol, polyglycerol, which represents slop from glycerol distillation, are used.

EFFECT: resin composition of improved workability, heat resistance and melt index; articles with more glazed surface.

2 cl, 15 ex, 1 tbl

FIELD: polymer materials.

SUBSTANCE: invention relates to composition based on powderlike emulsion polyvinylchloride efficiently processed into microporous plastic separator to separate opposite-charge electrodes of lead accumulators. Composition containing 85-95% emulsion polyvinylchloride, preferably the one with Fikentcher constant equal to 62-69, and 5-15% suspension polyvinylchloride with Fikentcher constant equal to 80-110. Composition is characterized by thermostability 342-365 sec. Caking of composition leads to separators with following properties: volume porosity 40.0-50.3%, resistivity of equivalent layer 0.25-0.30 cm, rupture strength 5.2-6.7 MPa, and maximum pore size 28.0-31.0 μm. Hourly productivity of caking draw frame is 242-250 m2 separators.

EFFECT: increased volume porosity and lowered resistivity of equivalent layer of microporous plastic separator.

2 cl, 1 tbl

Polymer composition // 2249019

FIELD: polymer materials.

SUBSTANCE: invention relates to creation plasticized compositions based on suspension polyvinylchloride, which are used in manufacturing film materials, in particular polyvinylchloride insulation tape. Composition contains suspension polyvinylchloride, dioctyl phthalate plasticizer, lead(III) sulfate, calcium stearate lubricant, carbon black, mixture of chlorinated C10-C30-hydrocarbons with 40-50% Cl content as secondary plasticizer, and residue of vacuum distillation of cobalt-freed still residue obtained in rectification of propylene hydroformylation product with boiling range 300-310°C.

EFFECT: improved quality of insulation tape, reduced production expenses, and enabled partial utilization of waste.

1 tbl

FIELD: polymer materials.

SUBSTANCE: cable plastic composition contains polyvinylchloride, dioctyl phthalate, lead(III) sulfate, calcium stearate, antimony trioxide, chalk, diphenylolpropane, and secondary plasticizer, in particular chloro-C14-C32-hydrocarbons with chlorination degree 24-55%, obtained through chlorination of ethylene oligomerization production waste.

EFFECT: improved workability of plasticized material due to diminished sticking of grain, improved physico-mechanical characteristics, and reduced cost price of product.

1 tbl

FIELD: composite materials.

SUBSTANCE: invention discloses a method for manufacturing composite material for shielding-mediated protection against electromagnetic emission and can be used in electronics, in radio engineering, and also in a series of special-destination articles. In addition, material may be used for anechoic boxes and in various assemblies of technical devices and radio apparatuses. Method comprises mixing modified graphite-containing conducting filler and polymeric binder at weight ratio (50-80):(20-50). Once ingredients combined, mixture is additionally subjected to thermal expansion in thermal shock mode at 250-310оС and then molded. Polymeric binder is selected from polyolefins, polystyrene, fluoroplastic, polyvinylchloride paste and modified graphite is product obtained by modifying graphite with concentrated sulfuric and nitric acids. Material is characterized by that, in wavelength band from 2 to 5 cm at thickness of material up to 0.1 mm, transmission coefficient is decreased from -40 to -85 dB.

EFFECT: improved performance characteristics.

6 cl, 1 tbl, 2 ex

The invention relates to petrochemical synthesis, namely the method of producing stearates of calcium, zinc, barium and cadmium are used as stabilizers in the processing of polyvinyl chloride, as well as in the manufacture of varnishes, surface-active compounds that are used as flotation agents

The invention relates to the production of a composite material for protection against electromagnetic radiation absorption and can be used in electronics, electrical engineering, and also in a number of products for special applications
The invention relates to polymer industry and can be used in the manufacture of plastic consumer goods, medical and agricultural purposes

FIELD: rubber materials, polymers.

SUBSTANCE: invention relates to composition based on ethylene-propylene or ethylene-propylenediene rubber and copolymer of ethylene and octyne that is used as an inter-strand filling agent in cables. Method involves preparing the composition containing the following components, mas. p. p.: rubber, 100; copolymer of ethylene and octyne, 25-55; paraffin, 50-170; stearic acid, 4-30; dibutyl phthalate, 4-25; chalk, 500-1600. The composition can comprise aluminum trihydrate additionally, 180-270 mas. p. p. per 100 mas. p. p. of rubber. Invention provides enhancing electric, physical and technological indices of materials used for filling cable articles.

EFFECT: improved and valuable properties of composition.

1 ex

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