KR20220004474A - Graft copolymer, method for preparing the copoymer and resin composition comprising the copolymer - Google Patents

Abstract

The present invention relates to a graft copolymer, and more specifically, to: a graft copolymer comprising a rubbery polymer, wherein the graft copolymer comprises 5 to 20 wt% of a silicone-based rubber, 2 to 10 wt% of an aromatic vinyl-based monomer unit, 35 to 78 wt% of a conjugated diene-based monomer unit, and 15 to 35 wt% of an alkyl (meth)acrylate-based monomer unit; a manufacturing method thereof; and a resin composition comprising the same.

Description

Graft copolymer, manufacturing method thereof, and resin composition comprising the same

The present invention relates to a graft copolymer, and to a graft copolymer excellent in impact strength and processability as an impact modifier for vinyl chloride resin, a method for preparing the same, and a resin composition comprising the same.

Vinyl chloride-based resins are widely used in various fields due to their low price, easy hardness control, various application fields, and excellent physical and chemical properties. However, since vinyl chloride resin itself is structurally weak in impact resistance, processing fluidity, heat resistance, etc., it is essential to use additives to compensate for the disadvantages of vinyl chloride resin for commercialization. are using

Examples of impact modifiers that can be used for vinyl chloride-based resins include MBS (methylmethacrylate-butadiene-styrene)-based impact modifiers, acrylic-based impact modifiers, CPE (chlorinated polyethylene), and EVA (ethylene vinyl acetate), such as thermoplastic polymer-based impact modifiers; and inorganic impact modifiers such as calcium carbonate coated with stearic acid. Among them, MBS-based impact modifiers and acrylic impact modifiers are most commonly used.

In general, impact modifiers containing butadiene rubber, such as MBS-based shock modifiers, use rubber in a high content to realize excellent impact strength. There is a problem in that the acidity is lowered and the fish-eye occurs after processing.

KR10-2012-0024231A

The present invention has been devised to solve the problems of the prior art, and it is an object of the present invention to improve impact strength while preventing deterioration of workability when a graft copolymer is applied as an impact modifier to a vinyl chloride-based resin.

In addition, in the present invention, when the graft copolymer is applied as an impact modifier to the vinyl chloride-based resin, the compatibility of the graft copolymer with the vinyl chloride-based resin is excellent, and the dispersibility of the graft copolymer is improved to improve processability. This is improved, and at the same time, it aims to improve the impact strength of the resin composition.

In order to solve the above problems, the present invention provides a graft copolymer comprising a rubbery polymer, 5 wt% to 20 wt% of silicone rubber, 2 wt% to 10 wt% of aromatic vinyl-based monomer units, and conjugated diene-based monomer units It provides a graft copolymer comprising 35 wt% to 78 wt% and 15 wt% to 35 wt% of an alkyl (meth)acrylate-based monomer unit.

In addition, the present invention comprises the steps of preparing a seed comprising a silicone-based rubber (S10); In the presence of 5 wt% to 20 wt% of the seed prepared in step (S10), 2 wt% to 10 wt% of an aromatic vinylic monomer is added and polymerized to form a cross-linked layer on the seed (S20); 35 wt% to 78 wt% of a conjugated diene-based monomer is added in the presence of the cross-linked layer-formed seed prepared in step (S20) and polymerized to prepare a rubbery polymer having a core layer formed on the cross-linked layer (S30); and 15 wt% to 35 wt% of an alkyl (meth)acrylate-based monomer in the presence of the rubbery polymer prepared in step (S30) and graft polymerization to prepare a graft copolymer in which a graft layer is formed on the rubbery polymer It provides a graft copolymer manufacturing method comprising the step (S40).

In addition, the present invention provides a resin composition comprising the graft copolymer and a vinyl chloride-based resin.

When the graft copolymer of the present invention is applied as an impact modifier to a vinyl chloride-based resin, the compatibility of the graft copolymer with the vinyl chloride-based resin is excellent, and the dispersibility of the graft copolymer is improved to improve processability and at the same time, there is an effect of improving the impact strength of the resin composition.

Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.

The terms or words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor must properly understand the concept of the term in order to best describe his invention. Based on the principle that can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

In the present invention, the term 'monomer unit' may refer to a component, structure, or material itself derived from a monomer. it could mean

As used herein, the term 'composition' includes reaction products and decomposition products formed from materials of the composition, as well as mixtures of materials comprising the composition.

The present invention provides a graft copolymer that can be used as an impact modifier.

According to an embodiment of the present invention, in the graft copolymer comprising a rubbery polymer, the graft copolymer comprises 5 wt% to 20 wt% of a silicone rubber, 2 wt% to 10 wt% of an aromatic vinyl-based monomer unit, It may include 35 wt% to 78 wt% of a conjugated diene-based monomer unit and 15 wt% to 35 wt% of an alkyl (meth)acrylate-based monomer unit.

According to an embodiment of the present invention, the rubbery polymer may include a silicone-based rubber, an aromatic vinyl-based monomer unit, and a conjugated diene-based monomer unit, and the graft copolymer may include an alkyl (meth)acrylate monomer unit. have.

According to an embodiment of the present invention, the rubbery polymer is a seed comprising a silicone-based rubber; a cross-linking layer formed on the seed and including an aromatic vinyl-based monomer unit; and a core layer formed on the cross-linking layer and including a conjugated diene-based monomer unit. As a specific example, the rubbery polymer may be one in which a conjugated diene-based monomer unit is grafted to a seed including a silicone-based rubber. As a more specific example, the rubbery polymer is one in which a core layer including a conjugated diene-based monomer unit is grafted by a cross-linking layer including a seed including a silicone-based rubber and an aromatic vinyl-based monomer unit formed on the seed. can

The graft copolymer of the present invention includes a silicone rubber in addition to the conjugated diene-based monomer unit in the rubbery polymer, thereby further improving the impact resistance efficiency of the rubbery polymer, and aromatic between the silicone-based rubber and the conjugated diene-based monomer unit. By including the vinyl-based monomer unit in the form of a crosslinking layer, there is an effect of securing a sufficient graft rate from the alkyl (meth)acrylate monomer unit, thereby improving dispersibility in the vinyl chloride-based resin.

According to an embodiment of the present invention, the silicone-based rubber may include an acrylic rubber including an aromatic vinyl-based monomer unit, a hydrophilic monomer unit, and an alkyl acrylate-based monomer unit; and a siloxane-based polymer. As a specific example, the silicone-based rubber may include an acrylic rubber including an aromatic vinyl-based monomer unit, a hydrophilic monomer unit, and an alkyl acrylate-based monomer unit; and a siloxane-based polymer.

According to an embodiment of the present invention, the silicone-based rubber is an acrylic rubber; and a siloxane-based polymer, and the acrylic rubber and the siloxane-based polymer may form an interpenetrating polymer network (IPN). As such, when an acrylic rubber and a siloxane-based polymer are simultaneously included as a silicone-based rubber together with a conjugated diene-based monomer unit in the rubbery polymer, they are crosslinked and dispersed in the acrylic rubber, and are grafted from a siloxane-based polymer having a low glass transition temperature. It is possible to lower the glass transition temperature of the entire coalescence, which has the effect of securing impact resistance.

According to an embodiment of the present invention, the acrylic rubber may be one in which an alkyl acrylate-based monomer unit is continuously formed on a vinyl-based seed polymer including an aromatic vinyl-based monomer unit and a hydrophilic monomer unit, and the siloxane-based polymer may be included as a discontinuous phase forming a mutual interpenetrating polymer network structure with the acrylic rubber.

According to an embodiment of the present invention, the aromatic vinyl-based monomer forming the aromatic vinyl-based monomer unit of the acrylic rubber is one selected from the group consisting of styrene, α-methyl styrene, vinyl toluene, and 3,4-dichloro styrene. or more, and a specific example may be styrene. In addition, the aromatic vinyl-based monomer unit of the acrylic rubber may be included in an amount of 1 wt% to 20 wt%, 3 wt% to 15 wt%, or 5 wt% to 10 wt%, based on the silicone rubber, within this range There is an effect excellent in the impact resistance by the silicone rubber.

According to an embodiment of the present invention, the hydrophilic monomer forming the hydrophilic monomer unit of the acrylic rubber is an alkyl acrylate such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, benzyl methacrylic It may be at least one selected from the group consisting of alkyl methacrylate, acrylonitrile, hydroxyl methyl methacrylate, and glycidyl methacrylate, such as lactate, and a specific example may be acrylonitrile. In addition, the hydrophilic monomer unit of the acrylic rubber may be included in an amount of 0.1 wt% to 10 wt%, 0.1 wt% to 5 wt%, or 0.5 wt% to 3 wt%, based on the silicone rubber, within this range the silicone rubber It has an excellent impact resistance effect.

According to an embodiment of the present invention, the vinyl-based seed polymer may include a cross-linkable monomer unit. The crosslinkable monomer forming the crosslinkable monomer unit is divinylbenzene, 3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylic rate, allyl acrylate, allyl methacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, and tetraethylene glycol dimethacrylate may be at least one selected from the group consisting of, a specific example may be divinylbenzene have. In addition, when the vinyl-based seed polymer includes a cross-linkable monomer unit, the cross-linkable monomer unit is 0.01 wt% to 1.00 wt%, 0.01 wt% to 0.50 wt%, or 0.01 wt% to 0.15 wt% based on the silicone rubber. It may be included in weight %.

According to an embodiment of the present invention, the alkyl acrylate-based monomer forming the alkyl acrylate-based monomer unit of the acrylic rubber may be at least one selected from the group consisting of alkyl acrylate-based monomers having 1 to 8 carbon atoms, and specific For example, it may be at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate, and more Specific examples may be at least one selected from the group consisting of ethyl acrylate, 2-ethylhexyl acrylate and butyl acrylate. In addition, the alkyl acrylate-based monomer unit of the acrylic rubber may be included in an amount of 60 wt% to 95 wt%, 70 wt% to 90 wt%, or 80 wt% to 90 wt%, based on the silicone rubber, within this range There is an excellent effect on the impact resistance by the silicone rubber.

According to an embodiment of the present invention, the acrylic rubber may include a crosslinkable monomer unit. The crosslinkable monomer forming the crosslinkable monomer unit is 3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acryl rate, allyl methacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and at least one selected from the group consisting of divinylbenzene, and a specific example of 1,3-butanediol It may be at least one selected from the group consisting of diacrylate, 1,3-butanediol dimethacrylate, allyl acrylate and allyl methacrylate. In addition, when the acrylic rubber includes a crosslinkable monomer unit, the crosslinkable monomer unit is 0.01 wt% to 3.00 wt%, 0.1 wt% to 1.0 wt%, or 0.5 wt% to 1.0 wt% based on the silicone rubber can be included as

According to an embodiment of the present invention, the siloxane-based polymer may be formed by a hydrosilylation reaction that proceeds simultaneously during polymerization of the acrylic rubber. As a specific example, the siloxane-based polymer may be formed by a hydrosilylation reaction of a vinyl-terminated polydialkylsiloxane including a vinyl group at the terminal.

According to an embodiment of the present invention, the vinyl-terminated polydialkylsiloxane may be vinyl-terminated polydimethylsiloxane (VPDMS), and a weight average molecular weight of 4,000 g/mol to 50,000 g/mol, 4,000 g/mol to 30,000 g /mol, or may be 5,000 g/mol to 10,000 g/mol, and while improving the impact resistance by the silicone rubber within this range, it prevents the viscosity increase during polymerization and has excellent latex stability. In addition, the vinyl-terminated polydialkylsiloxane of the siloxane-based polymer may be included in an amount of 1 wt% to 20 wt%, 1 wt% to 10 wt%, or 3 wt% to 8 wt%, based on the silicone rubber, in this range While preventing the appearance of brittleness due to the decrease in elasticity in the interior, there is an effect excellent in the impact resistance due to the silicone-based rubber.

According to an embodiment of the present invention, the siloxane-based polymer may be formed by a hydrosilylation reaction of a vinyl-terminated polydialkylsiloxane having a vinyl group at the terminal and a polyalkylhydrosiloxane that is a crosslinkable polymer.

According to an embodiment of the present invention, the polyalkylhydrosiloxane may be polymethylhydrosiloxane (PMHS), and has a weight average molecular weight of 1,000 g/mol to 15,000 g/mol, 3,000 g/mol to 10,000 g/mol, Alternatively, it may be 4,000 g/mol to 7,000 g/mol, and while improving the impact resistance by the silicone-based rubber within this range, the viscosity increase during polymerization is prevented and latex stability is excellent. In addition, the polyalkylhydrosiloxane of the siloxane-based polymer may be included in an amount of 0.01 wt% to 1.00 wt%, 0.01 wt% to 0.50 wt%, or 0.01 wt% to 0.10 wt%, based on the silicone rubber, within this range. While preventing the appearance of brittleness due to a decrease in elasticity, there is an effect of excellent impact resistance due to silicone-based rubber.

According to an embodiment of the present invention, the silicone rubber may be included in an amount of 5 wt% to 20 wt%, 10 wt% to 20 wt%, or 10 wt% to 15 wt%, based on the graft copolymer, There is an effect of improving the impact resistance efficiency by the rubbery polymer within the range. In particular, when the content of the silicone-based rubber is less than 5% by weight or 10% by weight, the effect of improving the impact resistance is insignificant, and when the content of the silicone-based rubber is more than 15% by weight or 20% by weight, the graft rate is lowered, so that the impact resistance and minutes There is a problem that the acidity is lowered.

According to an embodiment of the present invention, the graft copolymer, specifically, the aromatic vinyl-based monomer forming the aromatic vinyl-based monomer unit of the rubbery polymer is styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, It may be at least one selected from the group consisting of 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene, and a specific example may be styrene. .

According to an embodiment of the present invention, the aromatic vinyl-based monomer unit may be included in an amount of 2 wt% to 10 wt%, 3 wt% to 8 wt%, or 4 wt% to 5 wt%, based on the graft copolymer. And, within this range, when the conjugated diene-based monomer unit is grafted to the silicone-based rubber and formed, there is an effect of improving the crosslinking ability to improve the impact resistance efficiency of the rubbery polymer. In particular, when the content of the aromatic vinyl-based monomer unit is less than 2% by weight, 3% by weight, or 4% by weight, the graft rate is lowered to lower the impact resistance and dispersibility, and the content of the aromatic vinyl-based monomer unit is 5% by weight, When it is more than 8% by weight, or 10% by weight, the content of the rubber component in the graft copolymer is reduced, so that there is a problem in that the impact resistance is lowered.

According to an embodiment of the present invention, the conjugated diene-based monomer unit is for imparting impact resistance to the graft copolymer, and the conjugated diene-based monomer forming the conjugated diene-based monomer unit is 1,3-butadiene, 2 ,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, and at least one selected from the group consisting of 2-phenyl-1,3-butadiene, a specific example of which is 1 ,3-butadiene.

According to an embodiment of the present invention, the conjugated diene-based monomer unit may be 35 wt% to 78 wt%, 45 wt% to 70 wt%, or 55 wt% to 60 wt% based on the graft copolymer, , when using the graft copolymer as an impact modifier within this range, there is an excellent impact resistance effect. In particular, when the content of the conjugated diene-based monomer unit is less than 55 wt%, 45 wt%, or 35 wt%, impact resistance is reduced, and the content of the conjugated diene-based monomer unit is 60 wt%, 70 wt%, or 78 wt% In the case of more than weight %, sufficient dispersibility cannot be ensured, but there is a problem in that impact strength is lowered and workability is lowered.

According to an embodiment of the present invention, the rubbery polymer may include a crosslinkable monomer unit. The cross-linkable monomer unit is to improve cross-linking ability together with the aromatic vinyl-based monomer unit when the conjugated diene-based monomer unit is grafted to the silicone-based rubber, and may be included in the cross-linking layer. The crosslinkable monomer forming the crosslinkable monomer unit is divinylbenzene, 3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylic rate, allyl acrylate, allyl methacrylate, trimethylol propane triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate and polyalkylene glycol diacrylate may be at least one selected from the group consisting of .

According to an embodiment of the present invention, when the rubbery polymer includes the cross-linkable monomer unit, the cross-linkable monomer unit is 0.1 wt% to 1.0 wt%, 0.3 wt% to 0.8 wt%, based on the graft copolymer , or may be included in an amount of 0.4 wt% to 0.6 wt%, and when using the graft copolymer as an impact modifier within this range, there is an excellent impact resistance effect.

According to an embodiment of the present invention, the alkyl (meth) acrylate monomer unit is to improve compatibility between the rubber polymer and the target resin for impact reinforcement, for example, a vinyl chloride-based resin, and the rubber polymer may be grafted to As a specific example, the graft copolymer may include the rubbery polymer; and a graft layer formed on the rubbery polymer and including an alkyl (meth)acrylate monomer unit.

According to an embodiment of the present invention, the alkyl (meth) acrylate-based monomer forming the alkyl (meth) acrylate-based monomer unit may be an alkyl (meth) acrylate-based monomer having 1 to 12 carbon atoms. It may be a methyl (meth)acrylate-based monomer, and more specifically, may be methyl methacrylate.

According to an embodiment of the present invention, the alkyl (meth) acrylate-based monomer unit is 15 wt% to 35 wt%, 20 wt% to 30 wt%, or 23 wt% to 28 wt% based on the graft copolymer It can be included, and within this range, there is an excellent effect of compatibility with the target resin for impact reinforcement, for example, a vinyl chloride-based resin.

According to an embodiment of the present invention, the graft copolymer may further include an aromatic vinyl-based monomer unit in addition to the aromatic vinyl-based monomer unit included in the rubbery polymer. Here, the aromatic vinyl-based monomer unit is to improve compatibility with a rubber polymer and a target resin for impact reinforcement, for example, a vinyl chloride-based resin together with the alkyl (meth)acrylate-based monomer unit, It may be grafted together with an alkyl (meth)acrylate-based monomer unit to the polymer. That is, the aromatic vinyl-based monomer unit may be included in the graft layer.

According to an embodiment of the present invention, the aromatic vinyl-based monomer forming the aromatic vinyl-based monomer unit may be the same as or different from the aromatic vinyl-based monomer forming the cross-linking layer of the rubbery polymer described above, styrene, α -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene and 1-vinyl-5-hexylnaphthalene group consisting of It may be at least one selected from the group consisting of, and a specific example may be styrene.

According to an embodiment of the present invention, when the graft copolymer includes an aromatic vinyl-based monomer, the aromatic vinyl-based monomer unit is present in an amount of 0.1 wt% to 15 wt%, 1 wt% to 1 wt%, based on the graft copolymer. It may be included in 15% by weight, or 5% to 15% by weight, and within this range, there is an excellent effect of compatibility with the target resin for impact reinforcement, for example, a vinyl chloride-based resin.

The present invention provides a manufacturing method for preparing the graft copolymer.

The method for preparing a graft copolymer according to an embodiment of the present invention includes the steps of preparing a seed including a silicone rubber (S10); In the presence of 5 wt% to 20 wt% of the seed prepared in step (S10), 2 wt% to 10 wt% of an aromatic vinylic monomer is added and polymerized to form a cross-linked layer on the seed (S20); 35 wt% to 78 wt% of a conjugated diene-based monomer is added in the presence of the cross-linked layer-formed seed prepared in step (S20) and polymerized to prepare a rubbery polymer having a core layer formed on the cross-linked layer (S30); and 15 wt% to 35 wt% of an alkyl (meth)acrylate-based monomer in the presence of the rubbery polymer prepared in step (S30) and graft polymerization to prepare a graft copolymer in which a graft layer is formed on the rubbery polymer It may include a step (S40) of doing.

According to an embodiment of the present invention, the step (S10) is a step for preparing a silicone-based rubber used as a seed, and adding an aromatic vinyl-based monomer and a hydrophilic monomer and polymerizing to prepare a vinyl-based seed polymer (S1) ); And in the presence of the vinyl-based seed polymer prepared in step (S1), an alkyl acrylate-based monomer and a siloxane-based polymer are added and polymerized to prepare a silicone-based rubber (S2).

According to an embodiment of the present invention, the step (S1) is an acrylic rubber; And as a step for preparing a vinyl-based seed polymer for producing a silicone-based rubber comprising a siloxane-based polymer, it may be carried out by emulsion polymerization. Here, the aromatic vinyl-based monomer and the hydrophilic monomer in step (S1) may be the same as the monomer for forming the above-described vinyl-based seed polymer. In addition, the aromatic vinyl-based monomer and the hydrophilic monomer in step (S1) may be added in the same content as the content of the aromatic vinyl-based monomer unit and the content of the hydrophilic monomer unit of the vinyl-based seed polymer described above. In addition, the step (S1) may be carried out by including a cross-linkable monomer for forming the cross-linkable monomer unit of the above-described vinyl-based seed polymer.

According to an embodiment of the present invention, the step (S2) is an acrylic rubber; And when manufacturing the silicone-based rubber containing the siloxane-based polymer, the acrylic rubber and the siloxane-based polymer may be carried out to form an interpenetrating polymer network (IPN). In the case of step (S2), as compared to blending after polymerization of the acrylic rubber and the siloxane-based polymer, it is possible to form a network of interpenetrating polymers, thereby producing a structurally stable silicone rubber. . As a specific example, in the step (S2), an alkyl acrylate-based monomer for forming a continuous acrylic rubber in the vinyl-based seed polymer latex and a vinyl-terminated polydialkylsiloxane for forming a non-continuous siloxane-based polymer. It can be carried out by introducing the emulsion, and simultaneously adding the transition metal compound (VIII), which is a polymerization catalyst of the siloxane-based polymer, at the same time as the acrylic rubber radical polymerization at 50° C. to 100° C. and proceeding with the hydrosilylation reaction. Here, the alkyl acrylate-based monomer in step (S2) may be the same as the monomer for forming the acrylic rubber described above, and the vinyl-terminated polydialkylsiloxane may be the same as the polymer for forming the siloxane-based polymer described above. can In addition, the alkyl acrylate-based monomer and vinyl-terminated polydialkylsiloxane in step (S2) may be added in the same amount as the content of the alkyl acrylate-based monomer unit and the siloxane-based polymer of the silicone rubber described above. In addition, the step (S2) may be carried out including the crosslinkable monomer for forming the crosslinkable monomer unit of the acrylic rubber described above and polyalkylhydrosiloxane which is a crosslinkable polymer.

According to an embodiment of the present invention, the step (S2) may be carried out by emulsion polymerization, and the pre-emulsion is polymerized at a temperature of 50 ° C. to 100 ° C., preferably 60 ° C. to 90 ° C. under a catalyst. It is possible to form a silicone-based rubber having an interstitial polymer network (IPN) formed therein, in this case, the catalyst is a siloxane-based polymer polymerization catalyst, a transition metal compound (VIII), platinum (Pt), rhodium (Rd), cobalt (Co) , palladium (Pd), nickel (Ni), and the like, and may be platinum as a specific example.

According to an embodiment of the present invention, the step (S10) including the step (S1) and the step (S2) may be carried out by emulsion polymerization, and accordingly, the silicone rubber is a silicone rubber latex containing a silicone rubber. can be obtained in the form of

According to an embodiment of the present invention, the emulsion polymerization of step (S10) including step (S1) and step (S2) may be carried out in an aqueous solvent, and the aqueous solvent may be ion-exchanged water.

According to an embodiment of the present invention, in the step (S20), before graft polymerization of the conjugated diene-based monomer to the silicone-based rubber, the crosslinking layer is formed so that the conjugated diene-based monomer can be smoothly grafted to the silicone-based rubber. may be a step. Here, the aromatic vinyl-based monomer may be the same as the monomer for forming the aromatic vinyl-based monomer unit of the rubbery polymer described above. In addition, the aromatic vinyl-based monomer may be added in the same amount as the content of the aromatic vinyl-based monomer unit of the rubbery polymer described above.

According to an embodiment of the present invention, the step (S20) may be carried out by including the same cross-linkable monomer as the monomer for forming the cross-linkable monomer unit of the rubber polymer described above, and the content thereof is also cross-linking of the rubber polymer. It may be added in the same content as the content of the sex monomer unit.

According to an embodiment of the present invention, the step (S20) may be carried out by emulsion polymerization, the emulsion polymerization may be carried out in an aqueous solvent, and the aqueous solvent may be ion-exchanged water.

According to an embodiment of the present invention, the step (S30) is a step for preparing a rubber polymer in which a conjugated diene-based monomer is graft-polymerized through a cross-linking layer on a silicone-based seed. may be a step. Here, the conjugated diene-based monomer may be the same as the monomer for forming the above-described conjugated diene-based monomer unit of the rubbery polymer. In addition, the conjugated diene-based monomer may be added in the same amount as the content of the conjugated diene-based monomer unit of the rubbery polymer described above.

According to an embodiment of the present invention, the step (S30) may be carried out by emulsion polymerization, and thus the rubbery polymer may be obtained in the form of a rubbery polymer latex including the rubbery polymer.

According to an embodiment of the present invention, the step (S30) may be carried out by radical polymerization using a peroxide-based, redox, or azo-based initiator, and the redox initiator is, for example, t- It may be at least one selected from the group consisting of butyl hydroperoxide, diisopropylbenzene hydroperoxide and cumene hydroperoxide, and in this case, there is an effect of providing a stable polymerization environment.

In addition, according to an embodiment of the present invention, when the redox initiator is used, ferrous sulfate, sodium ethylenediaminetetraacetate and sodium formaldehyde sulfoxylate may be further included as redox catalysts.

In addition, according to an embodiment of the present invention, the emulsifier used in the emulsion polymerization of step (S30) may be at least one selected from the group consisting of anionic emulsifiers, cationic emulsifiers and nonionic emulsifiers, and specifically, alkylaryl sulfonate , alkali methyl alkyl sulfate, fatty acid soap, alkali oleic acid salt, alkali rosin acid salt, alkali lauric acid salt, sodium diethylhexyl phosphate, phosphonate polyoxyethylene alcohol, phosphonate polyoxyethylene phenol, etc. It may be one or more selected from the group consisting of, in this case, there is an effect of providing a stable polymerization environment.

According to an embodiment of the present invention, the emulsion polymerization of step (S30) may be carried out in an aqueous solvent, and the aqueous solvent may be ion-exchanged water.

According to an embodiment of the present invention, step (S40) is a step for preparing a graft copolymer, and may be a step of graft polymerization of an alkyl (meth)acrylate-based monomer to a rubbery polymer. Here, the alkyl (meth) acrylate-based monomer may be the same as the monomer for forming the above-described alkyl (meth) acrylate-based monomer unit of the graft copolymer. In addition, the alkyl (meth) acrylate-based monomer may be added in the same amount as the content of the alkyl (meth) acrylate-based monomer unit of the aforementioned graft copolymer.

According to an embodiment of the present invention, the step (S40) may be carried out including an aromatic vinyl-based monomer. Here, the aromatic vinyl-based monomer may be the same as the monomer for forming the aromatic vinyl-based monomer unit of the graft copolymer described above. In addition, the aromatic vinyl-based monomer may be introduced in the same amount as the content of the aromatic vinyl-based monomer unit of the graft copolymer described above.

According to an embodiment of the present invention, the graft polymerization in step (S40) may be carried out by emulsion polymerization, and thus the graft copolymer is in the form of a graft copolymer latex including the graft copolymer. can be obtained.

According to an embodiment of the present invention, the graft polymerization in step (S40) may be carried out by radical polymerization using a peroxide-based, redox, or azo-based initiator, and the redox initiator is For example, it may be at least one selected from the group consisting of t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, and cumene hydroperoxide, and in this case, there is an effect of providing a stable polymerization environment.

According to an embodiment of the present invention, when the redox initiator is used, ferrous sulfate, sodium ethylenediaminetetraacetate and sodium formaldehyde sulfoxylate may be further included as the redox catalyst.

In addition, according to an embodiment of the present invention, the emulsifier used in the emulsion polymerization of step (S40) may be at least one selected from the group consisting of anionic emulsifiers, cationic emulsifiers and nonionic emulsifiers, and specifically, alkylaryl sulfonate , alkali methyl alkyl sulfate, fatty acid soap, alkali oleic acid salt, alkali rosin acid salt, alkali lauric acid salt, sodium diethylhexyl phosphate, phosphonate polyoxyethylene alcohol, phosphonate polyoxyethylene phenol, etc. It may be one or more selected from the group consisting of, in this case, there is an effect of providing a stable polymerization environment.

According to an embodiment of the present invention, the emulsion polymerization of step (S40) may be carried out in an aqueous solvent, and the aqueous solvent may be ion-exchanged water.

In addition, the present invention provides a resin composition comprising the graft copolymer and a vinyl chloride-based resin.

According to an embodiment of the present invention, the resin composition may be a vinyl chloride-based resin composition including the graft copolymer as an impact modifier.

According to an embodiment of the present invention, the resin composition comprises 1 to 15 parts by weight, 3 to 12 parts by weight, or 5 to 5 parts by weight of the graft copolymer based on 100 parts by weight of the vinyl chloride-based resin. It may be included in an amount of 10 parts by weight.

According to an embodiment of the present invention, the resin composition may contain additives, such as antioxidants, heat stabilizers, plasticizers, processing aids, colorants and lubricants, known in the field of the present invention, as necessary, in conventional amounts.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

Example

Example 1

<Manufacture of silicone seed rubber latex>

In a four-neck flask reactor equipped with a stirrer, a thermometer, a nitrogen inlet and a circulation condenser, 47.06 parts by weight of ion-exchanged water, 0.33 parts by weight of potassium oleate, and 0.14 parts by weight of potassium persulfate were added, and the internal temperature of the reactor was adjusted to 70° C. under a nitrogen atmosphere. heated up to When the internal temperature of the reactor reached 70 °C, 8.40 parts by weight of styrene, 0.93 parts by weight of acrylonitrile, and 0.07 parts by weight of divinylbenzene were put in a batch and polymerized to prepare a vinyl-based seed polymer latex. The average particle diameter of the vinyl-based seed polymer particles in the prepared vinyl-based seed polymer latex was 56 nm.

Then, to the prepared vinyl seed polymer latex, 35.29 parts by weight of ion-exchanged water, 85.42 parts by weight of butyl acrylate, 0.65 parts by weight of allyl methacrylate, 4.48 vinyl-terminated polydimethylsiloxane (VPDMS, Mw=5,000 g/mol) A monomer pre-emulsion in which 0.05 parts by weight of polymethylhydrosiloxane (PMHS, Mw=6,000 g/mol), 0.02 parts by weight of platinum catalyst (SYL-PFF® 4000 Catalyst) and 1.36 parts by weight of potassium oleate were mixed beforehand, and potassium per 1.36 parts by weight of sulfate was continuously added at a temperature of 65° C. for 5 hours, followed by polymerization. After the polymerization was completed, it was aged for 1 hour to prepare a silicone-based seed rubber latex. The average particle diameter of the silicone-based seed rubber particles in the prepared silicone-based seed rubber latex was 115 nm.

<Production of rubbery polymer latex>

In a sealed polymerization reactor substituted with nitrogen, 10 parts by weight (based on solid content) of the silicone-based seed rubber latex prepared above was added, and 150 parts by weight of ion-exchanged water, 4.5 parts by weight of styrene, 0.5 parts by weight of divinylbenzene, 0.5 parts by weight of sodium sulfate parts, 2.0 parts by weight of potassium oleate, 0.0047 parts by weight of sodium ethylenediaminetetraacetate, 0.003 parts by weight of ferrous sulfate, 0.02 parts by weight of sodium formaldehyde sulfoxylate, and 0.1 parts by weight of diisopropylbenzene hydroperoxide were added at 50° C. A cross-linked layer was formed on the silicone-based seed rubber particles by polymerization at a temperature of 18 hours.

Subsequently, 150 parts by weight of ion-exchanged water, 60 parts by weight of 1,3-butadiene, 0.5 parts by weight of sodium sulfate, 2.0 parts by weight of potassium oleate, 0.0047 parts by weight of sodium ethylenediaminetetraacetate, 0.003 parts by weight of ferrous sulfate, sodium formaldehyde alcohol 0.02 parts by weight of foxylate and 0.1 parts by weight of diisopropylbenzene hydroperoxide were added, and polymerization was performed at a temperature of 50° C. for 18 hours to obtain a rubbery polymer latex.

<Production of graft copolymer latex>

In a closed polymerization reactor substituted with nitrogen, the entire amount of the prepared rubbery polymer latex was introduced, 0.0094 parts by weight of sodium ethylenediaminetetraacetate, 0.006 parts by weight of ferrous sulfate, and 0.04 parts by weight of sodium formaldehyde sulfoxylate were added, 25 parts by weight of methyl methacrylate, 0.15 parts by weight of potassium oleate, 15 parts by weight of ion-exchanged water and 0.64 parts by weight of sodium sulfate were added for 10 minutes, and polymerization was carried out at 50° C. for 1 hour. Thereafter, the polymerization was terminated when the final polymerization conversion rate was 98% to obtain a graft copolymer latex. At this time, the average particle diameter of the graft copolymer particles in the graft copolymer latex was 210 nm.

<Preparation of graft copolymer powder>

0.5 parts by weight of an antioxidant (IR-245) was added to 100 parts by weight of the obtained graft copolymer latex (based on solid content), agglomerated by adding aqueous sulfuric acid solution, and then the graft copolymer and water were phase separated at 80 ° C. , to obtain a graft copolymer powder by dehydration and drying.

Example 2

In Example 1, when preparing the rubbery polymer latex, 15 parts by weight (based on solids) of the silicone seed rubber latex was added instead of 10 parts by weight (based on solids), and 55 parts by weight of 1,3-butadiene was added instead of 60 parts by weight. Except for the above, it was carried out in the same manner as in Example 1. The average particle diameter of the graft copolymer particles in the prepared graft copolymer latex was 192 nm.

Comparative Example 1

<Production of rubbery polymer latex>

In a 120 L high pressure polymerization reactor equipped with a stirrer, based on a total of 100 parts by weight of 1,3-butadiene and methyl methacrylate, 150 parts by weight of ion-exchanged water, 0.5 parts by weight of sodium sulfate as an additive, 2.0 parts by weight of potassium oleate, sodium 0.0047 parts by weight of ethylenediaminetetraacetate, 0.003 parts by weight of ferrous sulfate, 0.02 parts by weight of sodium formaldehyde sulfoxylate and 0.1 parts by weight of diisopropylbenzene hydroperoxide were initially charged. 75 parts by weight of 1,3-butadiene was added thereto, followed by polymerization at 50° C. for 18 hours. Thereafter, the polymerization was terminated when the final polymerization conversion rate was 98% to obtain a rubbery polymer latex.

<Production of graft copolymer latex>

In a closed polymerization reactor substituted with nitrogen, the entire amount of the prepared rubbery polymer latex was introduced, 0.0094 parts by weight of sodium ethylenediaminetetraacetate, 0.006 parts by weight of ferrous sulfate, and 0.04 parts by weight of sodium formaldehyde sulfoxylate were added, 25 parts by weight of methyl methacrylate, 0.15 parts by weight of potassium oleate, 15 parts by weight of ion-exchanged water and 0.64 parts by weight of sodium sulfate were added for 10 minutes, and polymerization was carried out at 50° C. for 1 hour. Thereafter, the polymerization was terminated when the final polymerization conversion rate was 98% to obtain a graft copolymer latex. At this time, the average particle diameter of the graft copolymer particles in the graft copolymer latex was 215 nm.

<Preparation of graft copolymer powder>

0.5 parts by weight of an antioxidant (IR-245) was added to 100 parts by weight of the obtained graft copolymer latex (based on solid content), agglomerated by adding aqueous sulfuric acid solution, and then the graft copolymer and water were phase separated at 80 ° C. , to obtain a graft copolymer powder by dehydration and drying.

Comparative Example 2

In Example 1, when preparing the rubbery polymer latex, 25 parts by weight (based on solids) of silicone-based seed rubber latex was added instead of 10 parts by weight (based on solids), and 45 parts by weight of 1,3-butadiene was added instead of 60 parts by weight. Except for the above, it was carried out in the same manner as in Example 1. The average particle diameter of the graft copolymer particles in the prepared graft copolymer latex was 164 nm.

Comparative Example 3

In Example 1, the preparation of the rubbery polymer latex was carried out in the same manner as in Example 1, except that it was carried out as follows. The average particle diameter of the graft copolymer particles in the prepared graft copolymer latex was 210 nm.

<Production of rubbery polymer latex>

In a sealed polymerization reactor substituted with nitrogen, 10 parts by weight (based on solid content) of the prepared silicone-based seed rubber latex was added, and 150 parts by weight of ion-exchanged water, 65 parts by weight of 1,3-butadiene, 0.5 parts by weight of sodium sulfate, and oleic acid 2.0 parts by weight of potassium, 0.0047 parts by weight of sodium ethylenediaminetetraacetate, 0.003 parts by weight of ferrous sulfate, 0.02 parts by weight of sodium formaldehyde sulfoxylate and 0.1 parts by weight of diisopropylbenzene hydroperoxide were added, and at a temperature of 50° C. Polymerization for 18 hours gave a rubbery polymer latex.

Comparative Example 4

In Example 1, when preparing the rubbery polymer latex, 13.5 parts by weight instead of 4.5 parts by weight of styrene, 1.5 parts by weight of divinylbenzene instead of 0.5 parts by weight, and 50 parts by weight of 1,3-butadiene instead of 60 parts by weight Except for the above, it was carried out in the same manner as in Example 1. The average particle diameter of the graft copolymer particles in the prepared graft copolymer latex was 212 nm.

Comparative Example 5

In Example 1, when preparing the rubbery polymer latex, 15 parts by weight (based on solids) of silicone seed rubber latex was added instead of 10 parts by weight (based on solids), and 30 parts by weight of 1,3-butadiene was added instead of 60 parts by weight. and, when preparing the graft copolymer latex, it was carried out in the same manner as in Example 1, except that 50 parts by weight of methyl methacrylate was added instead of 25 parts by weight. The average particle diameter of the graft copolymer particles in the prepared graft copolymer latex was 198 nm.

Comparative Example 6

In Example 1, when preparing the rubbery polymer latex, 15 parts by weight (based on solids) instead of 7 parts by weight (based on solids) of silicone-based seed rubber latex, 2.7 parts by weight instead of 4.5 parts by weight of styrene, and 0.5 parts by weight of divinylbenzene Instead, 0.3 parts by weight is added, 1,3-butadiene is added in 80 parts by weight instead of 60 parts by weight, and when preparing the graft copolymer latex, 10 parts by weight of methyl methacrylate is added instead of 25 parts by weight. It was carried out in the same manner as in Example 1. The average particle diameter of the graft copolymer particles in the prepared graft copolymer latex was 231 nm.

Experimental example

In order to evaluate the physical properties of the resin composition comprising the graft copolymer prepared in Examples 1 to 2 and Comparative Examples 1 to 6 as an impact modifier, 100 parts by weight of a vinyl chloride polymer (manufactured by LG Chem, product name LS080), Heat stabilizer (tin stearate) 1.5 parts by weight, internal lubricant (potassium stearate) 1.0 part by weight, external lubricant (paraffin wax) 0.3 parts by weight, processing aid (manufactured by LG Chem, product name PA-910) 0.5 parts by weight and pigment 0.5 After sufficiently mixing parts by weight at a temperature of 130° C. using a high-speed stirrer, it was cooled to prepare a vinyl chloride polymer master batch. 7 parts by weight of the graft copolymer powder prepared in Examples 1 to 2 and Comparative Examples 1 to 6 were respectively added to the prepared vinyl chloride polymer master batch, and sheets were prepared using a roll mill at 195°C. The physical properties of each specimen were measured by the following method and are shown in Table 1 below along with the composition of each graft copolymer.

* Impact strength (Izod notched, kg·cm/cm): The prepared 1/8” specimen was measured at 23° C. according to ASTM D256.

* Processability (non-dispersion melting characteristics, Fish-eye, 5-point method): The graft copolymer powder 8 prepared in Examples 1 to 2 and Comparative Examples 1 to 6 in 100 g of a vinyl chloride resin containing a plasticizer (DOP50) g, and then processed for 90 seconds using a roll at 175 ° C. to prepare a specimen of 15 cm (width) X 15 cm (length) X 0.4 mm (thickness), and protrusions ( The number of fish-eye) was checked, and the score was expressed in a 5-point method according to the following criteria.

- 5 points: 0 to 5 projections

- 4.5 points: 6 to 10 bumps

- 4 points: 11 to 20 projections

- 3 points: 21 to 30 projections

- 2 points: 31 to 40 projections

- 1 point: 41 to 50 projections

division Example comparative example One 2 One 2 3 4 5 6 graft copolymer Si-Rubber (parts by weight) 10 15 - 25 10 10 15 7 SM (parts by weight) 4.5 4.5 - 4.5 - 13.5 4.5 2.7 DVB (parts by weight) 0.5 0.5 - 0.5 - 1.5 0.5 0.3 BD (parts by weight) 60 55 75 45 65 50 30 80 MMA (parts by weight) 25 25 25 25 25 25 50 10 impact strength (kg cm/cm) 102 115 26 15 21 12 8 6 machinability (5 points method) 5 5 5 One 2 5 5 One

As shown in Table 1, it was confirmed that the resin composition comprising the graft copolymer prepared according to the present invention as an impact modifier has excellent impact strength and excellent processability.

On the other hand, in the case of Comparative Example 1 containing only a conjugated diene-based rubber polymer without forming a silicone-based rubber and a cross-linking layer during the preparation of the graft copolymer, it was confirmed that the impact strength was poor.

In addition, in the case of Comparative Example 2 containing an excessive amount of silicone rubber even though the silicone rubber and the crosslinking layer were included, and Comparative Example 3 in which the crosslinking layer was not formed even if the silicone rubber was included, the graft polymerization was not performed smoothly, so the dispersibility It was confirmed that the impact strength and workability were significantly reduced due to this decrease.

In addition, in the case of Comparative Example 4 including the cross-linking layer in excess and Comparative Example 5 including the methyl methacrylate unit, that is, the graft layer in excess, it was confirmed that the content of the rubber component of the rubbery polymer was relatively reduced and the impact strength was poor. could

In addition, in the case of Comparative Example 6 in which the content of the rubber component of the rubbery polymer was excessive, dispersibility was lowered, and it was confirmed that the impact strength and workability were remarkably reduced.

From these results, when the graft copolymer of the present invention is applied as an impact modifier to a vinyl chloride-based resin, the compatibility of the graft copolymer with the vinyl chloride-based resin is excellent, and the dispersibility of the graft copolymer is It was confirmed that the processability was improved and, at the same time, the impact strength of the resin composition was improved.

Claims (10)

In the graft copolymer comprising a rubbery polymer,
5 wt% to 20 wt% of silicone-based rubber,
2 wt% to 10 wt% of aromatic vinyl-based monomer units;
35 wt% to 78 wt% of a conjugated diene-based monomer unit, and
A graft copolymer comprising 15 wt% to 35 wt% of an alkyl (meth)acrylate-based monomer unit. According to claim 1,
The rubbery polymer includes a silicone-based rubber, an aromatic vinyl-based monomer unit, and a conjugated diene-based monomer unit,
The graft copolymer is a graft copolymer comprising an alkyl (meth) acrylate monomer unit. According to claim 1,
The rubbery polymer is a seed comprising a silicone-based rubber;
a crosslinking layer formed on the seed and including an aromatic vinyl-based monomer unit; and
The graft copolymer is formed on the cross-linking layer and includes a core layer including a conjugated diene-based monomer unit. According to claim 1,
The silicone-based rubber may include an acrylic rubber including an aromatic vinyl-based monomer unit, a hydrophilic monomer unit, and an alkyl acrylate-based monomer unit; And a graft copolymer comprising a siloxane-based polymer. 5. The method of claim 4,
The acrylic rubber and the siloxane-based polymer is a graft copolymer that forms a mutual interpenetrating polymer network structure. According to claim 1,
The rubbery polymer is a graft copolymer comprising a crosslinkable monomer unit. According to claim 1,
The graft copolymer is formed on the rubbery polymer, the graft copolymer comprising a graft layer comprising an alkyl (meth) acrylate monomer unit. Preparing a seed comprising a silicone-based rubber (S10);
Forming a cross-linked layer on the seed by adding 2 wt% to 10 wt% of an aromatic vinylic monomer in the presence of 5 wt% to 20 wt% of the seed prepared in step (S10) and polymerization (S20);
35 wt% to 78 wt% of a conjugated diene-based monomer is added in the presence of the cross-linked layer-formed seed prepared in step (S20) and polymerized to prepare a rubbery polymer having a core layer formed on the cross-linked layer (S30); and
15 wt% to 35 wt% of an alkyl (meth)acrylate-based monomer is added in the presence of the rubbery polymer prepared in step (S30), and graft polymerization is performed to prepare a graft copolymer in which a graft layer is formed on the rubbery polymer A method for preparing a graft copolymer comprising the step (S40). 9. The method of claim 8,
In the step (S10), an aromatic vinyl-based monomer and a hydrophilic monomer are added and polymerized to prepare a vinyl-based seed polymer (S1); and
In the presence of the vinyl-based seed polymer prepared in step (S1), an alkyl acrylate-based monomer and a siloxane-based polymer are added and polymerized to prepare a silicone-based rubber (S2). manufacturing method. A resin composition comprising the graft copolymer according to any one of claims 1 to 7 and a vinyl chloride-based resin.