WO2015047026A1

WO2015047026A1 - Rubber polymer, graft copolymer, preparation methods therefor, and impact resistant and heat resistant resin composition

Info

Publication number: WO2015047026A1
Application number: PCT/KR2014/009196
Authority: WO
Inventors: 채주병; 정유성; 박은선; 전태영; 김영민; 이진호
Original assignee: (주) 엘지화학
Priority date: 2013-09-30
Filing date: 2014-09-30
Publication date: 2015-04-02

Abstract

The present invention relates to a rubber polymer, a graft copolymer, preparation methods therefor, and an impact resistant and heat resistant resin composition. According to the present invention, provided are: a rubber latex and a graft copolymer which can be implemented in products so as to have excellent impact resistance, heat resistance and chemical resistance by including a particular crosslinking control agent in a rubber polymer; preparation methods therefor; and an impact resistant and heat resistant resin composition.

Description

Rubbery polymers, graft copolymers and preparation methods thereof, impact resistant resin compositions

The present invention relates to a rubbery polymer, a graft copolymer and a preparation method thereof, and an impact resistant resin composition, and more particularly, by including a specific crosslinking regulator in the rubbery polymer, a product having excellent impact resistance, heat resistance, and chemical resistance can be realized. Rubber latex, graft copolymers and preparation methods thereof, and impact-resistant heat-resistant resin compositions.

In general, rubber-reinforced graft copolymers, in particular, rubber-reinforced graft copolymers produced by the emulsion polymerization method is typical of ABS, MBS, ASA, ATM, etc. These are usually rubbery polymers produced by the emulsion polymerization method Manufactured by graft copolymerization of various monomers considering matrix dispersibility in core to outer shell. Especially in ABS, polybutadiene latex is used as a core and PSAN (styrene-acrylonitrile copolymer) is grafted to outer shell. It is prepared through the process of copolymerization. In particular, ABS products are excellent in impact resistance, heat resistance, chemical resistance and processing characteristics such as excellent appearance characteristics are widely used in materials such as automotive interior and exterior materials, housings and toys of home appliances.

In particular, in order to manufacture ABS having high thermal properties (heat deformation resistance, HDT), that is, heat resistance, such as automobiles, a resin having a high glass transition temperature (Tg) is produced through emulsion polymerization or solution polymerization (heat resistant SAN) and emulsification. By the polymerization method, the rubber-reinforced graft copolymer in which the SAN is graft copolymerized may be mixed melt blended to have a constant rubber content to prepare a final product.

Representative monomers used in the production of heat-resistant resins having a high glass transition temperature include styrene derivatives such as alpha methyl styrene (AMS) and imide monomers such as N-phenyl maleimide (PMI). As the ratio of AMS increases, heat resistance tends to be improved, but there are many problems in the polymerization step of preparing a resin.

Accordingly, various methods have been tried to solve the problems caused by the use of AMS. For example, US Pat. No. 2,908,666 attempts to improve the impact resistance, chemical crack stability (ESCR) and heat resistance by grafting AMS monomers and acrylonitrile monomers on polydiene rubber latexes, but it takes a long time to polymerize and improves the polymerization conversion rate. Although it is not specified, it is hard to say that it is excellent in impact strength in terms of impact resistance.

In US 5,266,642, the polymerization of AMS polymer was carried out in the presence or absence of rubbery polymer to increase the polymerization rate during emulsion polymerization. However, the content of rubbery polymer is very low and polymerization conversion is not high. And thermal properties are not mentioned.

In addition, US 4,774,287 mentions a method of preventing thermal decomposition of AMS at high processing temperatures and excellent thermal properties at high temperatures, but it cannot be said to show a high level in polymerization conversion rate, reaction time and impact resistance.

There is still a need for a rubber polymer and a graft copolymer related technology that efficiently provide impact resistance, thermal properties and the like, and further shorten the polymerization time.

Accordingly, an object of the present invention is to solve the problems of the prior art by including a specific crosslinking regulator in the rubbery polymer to implement a product excellent in impact resistance, heat resistance and chemical resistance.

The present invention to achieve the above object

An emulsion polymer of a diene monomer provides a rubbery polymer, characterized in that the crosslinking regulator is included in the range of 5 to 20% by weight of the total 100% by weight of the total monomers constituting the polymer.

In addition, the present invention is to prepare a rubbery polymer by emulsion polymerization, comprising a crosslinking regulator in the range of 5 to 20% by weight of the total 100% by weight of the total monomer constituting the rubbery polymer of the rubbery polymer, characterized in that Characterized in the manufacturing method.

In addition, the present invention provides a method for producing a graft copolymer, characterized in that in preparing the graft copolymer from the rubbery polymer, a crosslinking regulator-containing rubbery polymer obtained by the above-described method is used as the rubbery polymer. .

Further comprising graft copolymers and heat-resistant thermoplastics,

The graft copolymer provides a shock-resistant heat-resistant resin composition comprising a crosslinking agent-containing rubber polymer-containing graft copolymer obtained by the above-mentioned method within the range of 50 to 80% by weight in 100% by weight of the total composition. .

According to the present invention, by including a specific cross-linking regulator in the rubber polymer, rubber latex, graft copolymers and a method for producing them, and impact resistance to provide a heat-resistant resin composition capable of realizing a product excellent in impact resistance, heat resistance and chemical resistance There is.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The rubbery polymer of the present invention is an emulsion polymer of a diene-based monomer, characterized in that the crosslinking regulator is included in the polymer within a range of 5 to 20% by weight of 100% by weight of the total monomers constituting the polymer.

For example, the crosslinking regulator may be located at 50% or less based on a total of 100% of the target particle size of the polymer.

The crosslinking control agent may be a polymer of a crosslinking control monomer, and for example, the crosslinking control monomer may be at least one selected from vinyl aromatic monomers, vinyl cyanic monomers, acrylate monomers and unsaturated carboxylic acid monomers.

In the rubber polymer manufacturing method of the present invention, for example, in preparing the rubber polymer by emulsion polymerization, it is prepared to include a crosslinking regulator within the range of 5 to 20% by weight of the total 100% by weight of the total monomers constituting the rubbery polymer. It features.

For example, the emulsion polymerization may include adding 45 to 60 wt% of a diene monomer and 5 to 20 wt% of a crosslinking control monomer with respect to 100 wt% of the total monomers constituting the rubbery polymer and initiating an emulsion polymerization; And emulsion polymerization to a polymerization conversion rate of 90 to 98% while continuously feeding 20 to 50% by weight of a diene monomer at a conversion rate of 40 to 60% of the polymerization to a conversion rate of 70 to 80%. It may include.

According to the method of the present invention, a rubbery polymer having a gel content of less than 70 to 95% and a swelling index of less than 15 to 25 can be prepared under a polymerization conversion rate of 90 to 95%.

The method for producing a graft copolymer according to the present invention is characterized by using the above-described crosslinking regulator-containing rubbery polymer as the rubbery polymer in producing the graft copolymer from the rubbery polymer.

The manufacturing method, for example, to 50 to 80% by weight of the crosslinking agent-containing rubber polymer, 20 to 50% by weight of one or more monomers selected from styrene monomer, vinyl cyanated monomer and acrylic acid ester monomer and graft copolymerization on the rubber particles It may be made.

The impact-resistant heat-resistant resin composition of the present invention includes a graft copolymer and a heat-resistant thermoplastic resin, wherein the graft copolymer comprises a graft copolymer containing a crosslinking regulator-containing rubbery polymer-containing graft copolymer obtained by the method of claim 13. It may be included in the range of 50 to 80% by weight in weight percent.

Hereinafter, a detailed configuration of the rubbery latex and its preparation method is as follows. The steps presented in the present invention correspond to the nominally presented steps, and there is no need to clearly perform the polymerization by dividing the steps clearly, and it is possible to proceed with the polymerization through a continuous polymerization step.

A) rubbery polymers and their preparation

Referring to the configuration and manufacturing method of the rubbery polymer proposed by the present invention.

Specifically, the rubbery polymer of the present invention is an emulsified polymer of a diene monomer, and is characterized in that the polymer contains a crosslinking regulator.

For reference, as used herein, the term "crosslinking regulator" refers to an agent, (co) polymer, etc., which can control and reduce the high crosslinking density of the rubbery polymer, unless otherwise specified.

The term "comprising a crosslinking agent" also refers to the inclusion of a crosslinking regulator at a specific position within the rubbery polymer, unless otherwise specified.

The crosslinking regulator may be in the range of 5 to 20% by weight, 5 to 15% by weight, or 10 to 15% of the total 100% by weight of the total monomers constituting the polymer.

For example, the crosslinking modifier may be positioned at 50% or less, 10 to 50%, 20 to 45%, or 25 to 40% of the total particle size of the polymer based on 100%. Within this range, it is possible to increase the swelling index and to increase the impact strength.

The crosslinking regulator may be, for example, a polymer or a copolymer of a crosslinking monomer.

As a specific example, the crosslinking control monomer may be at least one selected from vinyl aromatic monomers, vinyl cyan monomers, acrylate monomers and unsaturated carboxylic acid monomers.

Optionally selected from divinyl benzene, aryl methacrylate, diallyl phthalate, ethylene glycol diacrylate, triethylene diacrylate, tetraethylene diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate. The above can be used together in 0.5-2 weight part of all the monomers used for this invention.

In addition, the term "target particle diameter of the polymer" may refer to an average particle diameter of the rubbery polymer is 1000 to 3500 mm 3, 2000 to 3500 mm 3, 3000 to 3500 mm 3 or 3000 to 3300 mm 3 unless otherwise specified.

As a specific example, the rubbery polymer may be prepared with a particle diameter of 3000 to 3500 mm 3, and if necessary, after preparing a particle diameter of 500 to 1500 mm 3, the rubber latex may be directly used or 3000 to 3500 mm 3 through a flocculation method. Can also be large diameter.

The rubbery polymer may be prepared by various methods, for example, may be prepared in the following manner:

First, 45 to 60 wt% of the diene monomer and 5 to 20 wt% of the crosslinking control monomer are added to 100 wt% of the total monomers constituting the rubbery polymer, and the emulsion polymerization is started.

20 to 50% by weight of the diene monomer at a conversion rate of 40 to 60% of the polymerization is emulsion polymerization to a polymerization conversion rate of 90 to 95% while continuously adding up to 70 to 80% of the conversion.

The continuous input may be, for example, a diene monomer at an input amount of 1 to 10 parts / hr, or 1 to 3 parts / hr.

In the start of the emulsion polymerization, for example, a diene monomer is added in a batch, and the crosslinking control monomer is mixed with an emulsifier-containing additive, and then nitrogen is maintained for 30 minutes to 1 hour, and the pH is maintained at 9 to 11. It may be more desirable.

The diene monomer is, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene And at least one selected from 2-phenyl-1,3-butadiene.

In one example, the crosslinking control monomers are styrene, alpha-methylstyrene, alpha-methyl-4-butylstyrene, 4-phenyl styrene, 2,5-dimethylstyrene, 2-methylstyrene, alpha-methyl-3,5-di It may include one or more styrenic monomers selected from -t- butyl styrene, alpha-methyl-3,4,5-trimethyl styrene, alpha-methyl-4-benzyl styrene, alpha-methyl-4-cyclohexyl styrene. .

As another example, the crosslinking control monomer may include one or more acrylic ester monomers selected from methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate.

As another example, the crosslinking control monomer may include one or more vinyl cyanide monomers selected from acrylonitrile, methacrylonitrile, and ethacrylonitrile.

As another example, the crosslinking control monomer may include one or more unsaturated carboxylic acids selected from acrylic acid, maleic acid, methacrylic acid, itaconic acid, and fumaric acid.

In the emulsion polymerization initiation step, for example, a hydrophilic persulfate-based initiator or a hydrophobic hydroperoxide-based initiator, an anionic emulsifier or nonionic emulsifier, mercaptans molecular weight regulator and electrolyte (emulsifier-initiator-molecular weight regulator-electrolyte solution) It may be.

As a specific example, after the emulsifier-initiator-molecular weight regulator-electrolyte solution is added or stirred in a batch, for 0.1 to 2 hours, or 0.5 to 1 hour, the reaction temperature is raised to 55 to 65 ° C, or 58 to 65 ° C. The reaction can be carried out. The reaction time may be, for example, 4.5 to 5.5 hours, or 4.8 to 5.2 hours.

The emulsifier may be an emulsifier having a common sulfonate end group, an emulsifier having a carboxylic acid terminal, or the like, and a nonionic emulsifier or a reactive emulsifier may be used alone or in combination.

The initiator can be applied to a pyrolysis initiator such as potassium persulfate, ammonium persulfate, sodium persulfate, for example, strong hydrophilic property, and isohydrogen diisopropylbenzene hydroperoxide, cumene hydroper Hydroperoxide-based initiators such as oxides, tertiary butyl hydroperoxides and the like may be used with commonly applicable redox catalysts such as ferrous sulfate, dextrose, sodium pyrrole phosphate, sodium sulfite and the like, but preferably In the case of the seed polymerization step and the diene monomer, it is preferable to apply an initiator having strong hydrophilic properties, and in the step of applying an aromatic or non-aromatic monomer having an unsaturated double bond, a hydrophobic initiator is used alone or as an oxidation-reduction catalyst. It is desirable to be.

When the diene monomer and the crosslinking control monomer are added, and the diene monomer is continuously added, for example, a hydrophilic initiator selected from the group consisting of potassium persulfate, ammonium persulfate and sodium persulfate may be used.

When the hydrophilic initiator is applied, one or more redox catalysts selected from the group consisting of ferrous sulfate, dextrose, sodium pyrrole phosphate and sodium sulfite may be used in combination.

As the electrolyte, for example, KCl, CHCO ₃ , Na ₂ CO ₃ , CaCO ₃ , NaHSO _4, and the like may be used in combination of two or more kinds.

For example, the molecular weight regulator may be a molecular weight regulator used in conventional emulsion polymerization such as mercaptans such as n-dodecyl mercaptan, n-decyl mercaptan, t-dodecyl mercaptan, and alpha methyl styrene dimer.

When the conversion rate of the polymerization is 40 to 60%, 50 to 60%, or 55 to 60%, for example, the diene monomer may be continuously added to the polymerization.

The continuous dosing may be, for example, 5 to 12 hours, or 6 to 10 hours.

Anionic emulsifier or nonionic emulsifier and a hydrophilic persulfate initiator or a hydrophobic hydroperoxide initiator (emulsifier-initiator solution) may be added during the continuous dosing.

The emulsifier-initiator solution may be added or collectively added after 1.5 to 2.5 hours, or 1.8 to 2.2 hours after the continuous input time.

After completion of the continuous dosing may be further added an anionic emulsifier or a nonionic emulsifier.

For reference, the emulsifier may be 0.1 to 1 parts by weight, or 0.2 to 0.5 parts by weight based on a total of 100 parts by weight of the total monomers constituting the rubbery polymer per dose.

The initiator may be 0.1 to 5 parts by weight, or 0.1 to 1 part by weight based on a total of 100 parts by weight of the total monomers constituting the rubbery polymer per dose.

The molecular weight modifier may be 0.1 to 1 parts by weight, or 0.2 to 0.5 parts by weight based on 100 parts by weight of the total monomers constituting the rubbery polymer.

The electrolyte may be 0.1 to 5 parts by weight, or 0.1 to 1 part by weight of potassium carbonate and the like.

After the addition of the emulsifier-initiator solution, the reaction temperature may be increased to 70 to 85 ° C., or 75 to 80 ° C., and the reaction may be performed for 4 to 6 hours or 4.5 to 5.5 hours.

After the reaction, for example, one or more redox catalysts (redox catalyst solution) selected from ferrous sulfate, dextrose, sodium pyrophosphate, and sodium sulfite are added and collectively added to terminate the reaction.

Another example, 0.1 to 1.5 parts by weight of an emulsifier, 0.01 to 2.0 parts by weight of a polymerization initiator, 0.01 to 0.4 parts by weight of a molecular weight modifier, and 0.1 to electrolyte based on 50 to 60 parts by weight of a diene monomer and 10 to 15 parts by weight of a crosslinking control monomer. 2.0 parts by weight may be polymerized by a batch addition method, and 35 to 40 parts by weight of diene monomer may be continuously added at a particle diameter of 1500 to 2500 Pa polymerization conversion rate of 40 to 60% to obtain a rubbery polymer including a crosslinking regulator.

The rubbery polymer of the present invention can be obtained, for example, in latex form.

The latex, for example, may have a solid content of 35 to 60% by weight.

The process can produce a rubbery polymer having a gel content of less than 70 to 95%, or 70 to 75%, a swelling index of less than 15 to 25, or 15 to 20 under a conversion of 90 to 98%, or 93 to 96% of polymerization. .

For reference, the swelling index corresponds to an indirect indicator of the crosslinking density of the present invention. Since the product having a low swelling index has a high crosslinking density, the impact strength of the impact resistant resin composition deteriorates, and the product having a high swelling index The impact strength is improved (see Table 1 and Table 3 below).

B) Graft Copolymer Preparation

When preparing the graft copolymer through the emulsion polymerization method for the rubbery polymer prepared by the same method as described above A as described in detail as follows.

The method for preparing a graft copolymer including the rubbery polymer may be performed as follows, for example.

That is, to 50 to 80% by weight of the obtained crosslinking agent-containing rubbery polymer, 20 to 50% by weight of at least one monomer selected from a styrene monomer, a vinyl cyanide monomer and a (methyl) acrylic acid ester monomer are added to the rubber through a method of emulsion polymerization. It may be graft copolymerized on the particles.

For example, 10 to 40% by weight of one or more monomers selected from styrene-based monomers, vinyl cyanide monomers, and acrylic ester monomers may be used based on 100% by weight of the monomers (excluding the content of the rubber polymer).

The styrene monomer, the vinyl cyanide monomer, and the acrylic acid ester monomer may be those using the above-described types.

In the preparation of the graft copolymer of the present invention through an emulsion polymerization method, the method is not particularly limited. For example, 20 to 50 monomers to form the graft copolymer with respect to 50 to 80% by weight of the rubbery polymer The weight percent is administered together with the emulsifier and the molecular weight modifier, the graft aid, the initiator and the reaction is continued until the reaction conversion level is 95 to 99%, or 97 to 99% and then terminated.

The emulsifiers that can be used herein include, for example, carboxyl salt type adsorption type emulsifiers such as potassium rosin and potassium fatty acids, and sulfonate type adsorption type emulsifiers such as sodium lauryl sulfate, alkyl benzene sulfonates, or reactive emulsifiers. It is possible to be used alone or in combination.

In preparing the graft copolymer, for example, a molecular weight regulator such as n-dodecyl mercaptan, n-decyl mercaptan, t-dodecyl mercaptan and alpha methyl styrene dimer may be used. It is preferable to apply 0.2 to 1.0 parts by weight of tertiary dodecyl mercaptan. The weight part at this time is based on 100 weight part of the sum total of a rubbery polymer and a monomer.

The initiator may be used in an amount of 0.01 to 1 parts by weight, and the initiator which can be used is not particularly limited but may be, for example, oxidized with a peroxide initiator such as tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzenehydro peroxide, or the like. The use of a reduction catalyst together may be advantageous in terms of securing impact resistance and latex stability during graft copolymerization.

In addition, in the preparation of the graft copolymer, the addition of monomers may be performed by directly adding each monomer to a reactor, adding a monomer mixture, and adding a monomer emulsion prepared by mixing an emulsifier, water, and an initiator. Optionally, when the monomer is added, the initial reaction of 0 to 20% by weight, or 1 to 20% by weight of the monomer based on the total 100% by weight of the monomer is added in a batch input method, the remaining monomers in a continuous input method It is possible to be committed. In addition, it is also possible to inject the entire quantity continuously or batchwise batching method 3 to 4 times at regular intervals.

After completion of the reaction, the graft copolymer is added with an antioxidant and a heat stabilizer, and then aggregated through an acid such as sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, or a metal salt such as calcium chloride, magnesium sulfate, aluminum sulfate, etc., to separate solids. It may be made into a powder form by washing, dehydrating and drying it, and this powder form graft copolymer may be used in combination with a thermoplastic resin copolymer generally made by solution polymerization.

According to the method, it is possible to provide a graft copolymer having a coagulation content of 0.1% or less and a graft ratio of 35 to 50% under a polymerization conversion rate of 96 to 99%.

The graft copolymer may be, for example, an acrylonitrile-butadiene-styrene (ABS) -based resin.

The final polymer obtained had a particle size of 3000 to 3,500 Pa, and the polymerization coagulated product to the polymer was 0.01% or less based on the total charged solid content.

C) providing impact resistant heat resistant resin composition

The graft copolymer prepared by the above method is usually melted and mixed with a heat-resistant thermoplastic resin through an extrusion process to be processed into pellets to produce a final impact-resistant heat-resistant resin. Alpha methylstyrene-acrylonitrile-styrene copolymer (AMS-SAN), acrylonitrile-styrene copolymer (SAN), acrylonitrile-styrene-methyl methacrylate (MS), polycarbonate (PC), polybutyl There may be resins such as lenterephthalate (PBT), polyvinyl chloride (PVC).

As a specific example, the heat resistant thermoplastic resin may be included in the range of 20 to 50% by weight of the composition.

In another example, the heat-resistant thermoplastic resin is styrene, alpha-methylstyrene, alpha-methyl-4-butylstyrene, 4-phenyl styrene, 2,5-dimethylstyrene, 2-methylstyrene, alpha-methyl-3,5- 65 to 80% by weight of at least one styrenic monomer selected from di-t-butylstyrene, alpha-methyl-3,4,5-trimethylstyrene, alpha-methyl-4-benzylstyrene and alpha-methyl-4-cyclohexylstyrene And it may be a bulk polymer of 20 to 35% by weight of at least one vinyl cyanide monomer selected from acrylonitrile, methacrylonitrile, ethacrylonitrile.

In another example, the heat-resistant thermoplastic resin is alpha-methylstyrene, alpha-methyl-4-butylstyrene, 4-phenyl styrene, 2,5-dimethylstyrene, 2-methylstyrene, alpha-methyl-3,5-di- 64 to 75% by weight of one or more styrenic derivatives selected from t-butylstyrene, alpha-methyl-3,4,5-trimethylstyrene, alpha-methyl-4-benzylstyrene and alpha-methyl-4-cyclohexylstyrene, acryl 20 to 35% by weight of at least one vinyl cyanide monomer selected from ronitrile, methacrylonitrile, ethacrylonitrile and 1 to 5% by weight of styrene.

In addition, these graft copolymers can be used with additives for lubricants, heat stabilizers and other processing in the process of melt molding through heat-resistant thermoplastic resin and extrusion, injection process, and greatly limited to these types Do not put

Impact-resistant resin prepared by the above method has a characteristic that the impact resistance is improved and the colorability is excellent, unlike the conventional manufacturing method.

Hereinafter, preferred examples are provided to help the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and various changes and modifications within the scope and spirit of the present invention are apparent to those skilled in the art. It goes without saying that changes and modifications belong to the appended claims.

EXAMPLE

[고무질 중합체의 제조][Production of Rubber Polymer]

실시예 1: 라텍스 제조 A1 제조Example 1 Latex Preparation A1 Preparation

100 parts by weight of ion-exchanged water was added to a nitrogen-substituted pressurized reactor, and then the monomer A shown in Table 1 was added, 0.5 parts by weight of potassium rosinate, 0.3 parts by weight of tertiary dodecyl mercaptan, 1.0 part by weight of potassium carbonate, and potassium per 0.1 parts by weight of sulfate was added to room temperature, followed by stirring for 1 hour.

Then, the reaction temperature was raised to 65 ° C. for 5 hours, and the monomer B shown in Table 1 was continuously added for 7 hours at the point where the polymerization conversion was 60%. 0.5 parts by weight of potassium rosin and 0.1 parts by weight of potassium persulfate were added at 2 hours after the continuous addition, and 0.2 parts by weight of potassium rosin was further added after completion of the continuous addition. At this time, the reaction temperature was 70 ° C.

The reaction temperature was then raised to 80 ° C. to maintain the reaction for 5 hours. At this time, a solution consisting of 0.0005 parts by weight of ferrous sulfide, 0.05 dextrose, 0.04 parts by weight of sodium pyrophosphate, and 2 parts by weight of ion-exchanged water was added. And the reaction was terminated. The polymerization conversion and physical properties were summarized in Table 1 below.

실시예 2: 라텍스 A2 제조Example 2: Latex A2 Preparation

The same process as in Example 1 was repeated except that the monomers A and B were replaced with the amounts and types shown in Table 1 in Example 1. The polymerization conversion and physical properties were summarized in Table 1 below.

실시예 3: 라텍스 A3 제조Example 3: Latex A3 Preparation

비교예 1: 라텍스 B1 제조Comparative Example 1: Manufacture of Latex B1

In Example 1, the same process as in Example 1 was repeated except that monomers A and B were replaced with the amounts and types shown in Table 1, and alpha methylstyrene (AMS) was not used in both the core and the shell. . The polymerization conversion and physical properties were summarized in Table 1 below.

비교예 2: 라텍스 B2 제조Comparative Example 2: Latex B2 Preparation

In Example 1, the monomers A and B were replaced with the amounts and types shown in Table 1 below, and the entirety of alpha methylstyrene (AMS) was added immediately before the 1,3-diene (BD) was added and the temperature was increased. The same process as in Example 1 was repeated except for the above. The polymerization conversion and physical properties were summarized in Table 1 below.

비교예 3: 라텍스 B3 제조Comparative Example 3: Latex B3 Preparation

<물성 측정 방식><Measurement Method>

* Polymerization conversion: After drying for 15 minutes in a 150 ℃ hot air dryer for each step of the prepared latex, the total solid content (TSC) was calculated, and then the polymerization conversion was calculated according to the following equation.

* Latex particle size measurement : The weight average particle size was measured using a Nicomp instrument.

* Gel content measurement: Methanol was added to the prepared rubber latex, sulfuric acid was precipitated, washed and dried to extract the solid component (A), which was then placed in toluene, and left for 18 hours. B) is measured and gel content is calculated | required by the following formula.

Gel content = weight of rubbery polymer remaining after dissolution (B) / initial rubbery polymer (A)

* Swelling index: Corresponding to the indirect index of the crosslinking density of the present invention, specifically, the rubber component solids prepared for gel content measurement was left in toluene for 18 hours and dried in 80 mesh nets (A). After standing for 24 hours in a toluene solvent, the weight (B) of the swollen rubbery resin was measured, and the swelling index was obtained based on the following equation.

Swelling index = (weight of swelled rubbery resin (B)-dried initial rubbery resin (A)) / dried initial rubbery resin (A)

For reference, a product having a low swelling index has a high crosslinking density, and as a result, the impact strength (see Table 3 below) of the impact resistant resin composition is deteriorated, and a product having a high swelling index has a result of improving the impact strength. .

Table 1

division		Example			Comparative example
division		1 (A1)	2 (A2)	3 (A3)	1 (B1)	2 (B2)	3 (B3)
Monomer A (Batch)	BD *	50	50	50	65	50	50
	AMS	10	15	10
	AN			5
	ST
	DVB						5
Monomer B (continuous injection)	BD	40	35	35	35	35	45
Monomer B (continuous injection)	AMS					15
Monomer sum		100	100	100	100	100	100
Conversion rate	%	95	93	96	90	82	94
Particle diameter	Å	3200	3300	3100	3200	2900	3200
Gel content	%	73	70	75	85	82	95
Swelling index		18	20	15	10	10	7

* ST: styrene, BD: 1,3-butadiene, AMS: alpha methyl styrene.

As shown in Table 1, in Examples 1 to 3 using latex A1 to A3 prepared rubber latex containing a styrene derivative, unlike Comparative Examples 1 to 3 using latex B1 to B3, the same polymerization reaction time It was confirmed that a rubbery polymer having a low gel content and a high swelling index (and thus a low crosslinking density) can be obtained without lowering the polymerization conversion rate.

In particular, as shown in Comparative Example 3 in which the usual crosslinking agent alone was added, it was confirmed that the swelling index was sharply reduced (and thus the crosslinking density was high).

[그라프트 공중합체의 제조][Production of Graft Copolymer]

추가 실시예 1 :그라프트 공중합체 C1 제조Additional Example 1 Preparation of Graft Copolymer C1

In a nitrogen-substituted reactor, 60 parts by weight of ion-exchanged water and rubber prepared in the latex (A1 to A3) of the Examples 1 to 3 and the latex (B1 to B3) of Comparative Examples 1 to 3 and the monomer C component of Table 2 , 0.2 parts by weight of alkenyl potassium succinate (trade name latemul ASK), stirred sufficiently at 25 ° C., then heated to 50 ° C., 0.08 part by weight of tertiary butyl hydroperoxide, 0.003 part by weight of ferric sulfide, and dextrose 0.005 The reaction was carried out while adding parts by weight, 0.025 part by weight of sodium pyrrole phosphate, and 2.5 parts by weight of ion-exchanged water, and the temperature was raised to 65 ° C for 30 minutes.

At this time, the monomer corresponding to the monomer D in Table 2 was made into an emulsion comprising 0.3 parts by weight of potassium alkenyl potassium succinate, 0.4 parts by weight of tertiary dodecyl mercaptan, 0.1 parts by weight of cumene hydroperoxide, and 20 parts by weight of ion-exchanged water. The reactor was administered for 1 hour 30 minutes. At this time, the final polymerization temperature was 70 ℃.

Then, 0.05 parts by weight of cumene hydroperoxide, 0.003 parts by weight of ferrous sulfide, 0.005 parts by weight of dextrose, 0.025 parts by weight of sodium pyrophosphate, and 2.5 parts by weight of ion-exchanged water were added, and the polymerization temperature was raised to 75 ° C. The reaction was terminated after continuing the time reaction. The composition and physical properties of the prepared graft copolymer latex are shown in Table 2.

추가 실시예 2 내지 4 :그라프트 공중합체 C2 내지 C4 제조Additional Examples 2-4: Preparation of Graft Copolymers C2 to C4

The same process as in Example 1 was repeated except that monomers C and D were replaced with the amounts and types shown in Table 2 below. The polymerization conversion and physical properties were summarized in Table 2 below.

추가 비교실시예 1 내지 3:그라프트 공중합체 D1 내지 D4 제조Additional Comparative Examples 1 to 3: Preparation of Graft Copolymers D1 to D4

The same process as in Example 1 was repeated except that the rubber type and the monomers C and D were replaced with the amounts and kinds shown in Table 2 below. The polymerization conversion and physical properties were summarized in Table 2 below.

<물성 측정 방식><Measurement Method>

* Polymerized coagulated product: The latex produced by emulsion polymerization method is filtered through a 100 mesh wire mesh filter, and the polymerized material filtered on the wire mesh is dried in a 100 ° C. hot air dryer for 1 hour, and then the total amount of monomers and additives (emulsifiers, etc.) added is added to the theoretical total amount. Expressed as a ratio.

* Graft rate: 10 g of the graft copolymer powder was dried in a 60 degree oven to measure the weight (A) from which moisture was removed, stirred in acetone solvent 100 for 24 hours, and then separated from the sol and gel components in a centrifuge at 10000 rpm. The weight (B) which dried the remainder which was not dissolved on the oven was measured, and the graft ratio was calculated | required by the following formula.

Graft rate = (% rubber content in B-A * graft polymerization) / (% rubber content in A * graft polymerization)

TABLE 2

division		Additional Example				Additional Comparative Examples
division		1 (C1)	2 (C2)	3 (C3)	4 (C4)	1 (D1)	2 (D2)	3 (D3)	4 (D4)
Rubber	Kinds	A1	A1	A2	A3	B1	B1	B2	B3
Rubber	content	60	66.7	60	60	60	60	60	60
Monomer (C)	AMS	7	3.5	7	7	7	3.5	7	7
	AN	3	3	3	3	3	3	3	3
	ST		3.5				3.5
Monomer (D)	AMS	21	7	21	21	21	14	21	21
	AN	9	9	9	9	9	9	9	9
	ST		7				7
Copolymer Composition	BD	54	60	51	51	60	60	51	60
	AMS	34	17	37	34	28	17	37	28
	AN	12	12	12	15	12	12	12	12
	ST		11				11
	synthesis	100	100	100	100	100	100	100	100
Conversion rate	%	98.2	99.1	97.5	98.3	94.0	90.0	88.0	92.5
Coagulum	%	0.02	0.01	0.03	0.03	2.5	5.0	3.5	4.5
G / R	%	40	48	42	43	25	30	22	30

* G / R (Graft ratio)

As shown in Table 2, the graft copolymer of the additional examples C1 to C4 based on Examples 1 to 3 of the latex A1 to A3 described above, based on Comparative Examples 1 to 3 of the latex B1 to B3 described above. The gel content of the rubber particles compared to the graft copolymers of the comparative examples D1 to D4 was lowered, and in particular, when the alphamethyl styrene monomer was used for the graft copolymerization, polymerization inside the rubber particles was more easily performed. Due to the high polymerization conversion can be achieved within the same polymerization time as well as ensuring the polymerization stability by increasing the graft reaction efficiency.

[내충격 내열수지 조성물][Impact resistant heat resistant resin composition]

Powders were prepared by adding 2 parts by weight of sulfuric acid to each of the graft copolymer latexes of Examples 1 to 4 and Comparative Examples 1 to 4, coagulating and washing with water, followed by hot air drying in a fluidized bed dryer. The powder was kneaded with a heat-resistant SAN (70 parts by weight of AMS monomer, 28 parts by weight of AN, 2 parts by weight of SM) prepared by solution polymerization to prepare pellets and then injected to prepare a specimen for measuring physical properties.

At this time, the rubber content of the prepared specimen was prepared in the same manner as 16% and measured physical properties, the physical properties measured in Table 3 below.

<물성 측정 방식><Measurement Method>

* Izod impact strength: measured in accordance with ASTM D256 method with a 1/4 "thickness of the specimen, the unit is Kg.cm / cm.

* Chemical Crack Stability (ESCR): Tensile strength specimens prepared by injection molding were placed on a 1.0% jig, and 1 mg of thinner was dropped in the center of the specimen, and the time until fracture occurred was recorded. The failure that did not occur for more than 10 minutes was marked as NC (No crack).

* Heat resistance (HDT, ℃): The heat distortion temperature was measured by the ASTM D-648 method.

TABLE 3

division		Additional Example				Additional Comparative Examples
division		1 (C1)	2 (C2)	3 (C3)	4 (C4)	1 (D1)	2 (D2)	3 (D3)	4 (D4)
IMP (1/4 ")	Kgcm / cm	27	25	24	24	15	12	10	10
ESCR	second	NB	500	450	NB	45	30	25	20
HDT	℃	110	105	112	114	102	99	104	101

As shown in Table 3, when the impact-resistant heat-resistant resin composition comprising the graft copolymer of the additional Examples 1 to 4 is used, the thermoplastic resin composition comprising the graft copolymer of the additional Comparative Examples 1 to 4 It was confirmed that the impact strength, chemical crack stability (ESCR), and heat resistance (HDT) characteristics were improved in comparison with the case of use. As shown in Table 1, it was possible to determine that due to the cross-linking density reduction effect of the rubbery polymer.

In particular, when the thermoplastic resin composition comprising the graft copolymer of Comparative Example 4 is used, the impact resistance is lowered as the impact reinforcing effect of the rubber particles is lower than that of the additional Examples 1 to 4, and the heat resistance is expected to improve. The results showed that the chemical crack stability (ESCR) was also difficult to do.

Claims

An emulsified polymer of a diene monomer, wherein the polymer comprises a crosslinking regulator in a range of 5 to 20% by weight of the total 100% by weight of the total monomers constituting the polymer.
The method of claim 1,

The crosslinking regulator is a rubbery polymer, characterized in that located in 50% or less, based on a total of 100% of the target particle size of the polymer.
The method of claim 1,

The crosslinking regulator is a rubbery polymer, characterized in that located in 50% or less, based on a total of 100% of the target particle size of the polymer.
The method of claim 1,

The crosslinking regulator is a rubbery polymer, characterized in that the polymer of the crosslinking control monomer.
In preparing a rubbery polymer by emulsion polymerization, a method of producing a rubbery polymer comprising a crosslinking regulator in a range of 5 to 20% by weight of the total 100% by weight of the total monomers constituting the rubbery polymer.
The method of claim 5,

The emulsion polymerization may include adding 45 to 60 wt% of a diene monomer and 5 to 20 wt% of a crosslinking monomer with respect to 100 wt% of the total monomers constituting the rubbery polymer and initiating an emulsion polymerization; And

Emulsion polymerization to a polymerization conversion rate of 90 to 98% while continuously adding 20 to 50% by weight of a diene monomer at a conversion rate of 40 to 60% of the polymerization to a conversion rate of 70 to 80% of the polymerization; Method for producing a rubbery polymer comprising a.
The method of claim 6,

The diene monomers include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, and Method for producing a rubbery polymer, characterized in that at least one selected from 2-phenyl-1,3-butadiene.
The method of claim 6,

The crosslinking control monomers are styrene, alpha-methylstyrene, alpha-methyl-4-butylstyrene, 4-phenyl styrene, 2,5-dimethylstyrene, 2-methylstyrene, alpha-methyl-3,5-di-t- Rubber polymer comprising at least one styrene monomer selected from butyl styrene, alpha-methyl-3,4,5-trimethyl styrene, alpha-methyl-4-benzyl styrene, alpha-methyl-4-cyclohexyl styrene Manufacturing method.
The method of claim 6,

The crosslinking control monomer is a method for producing a rubbery polymer, characterized in that it comprises at least one acrylic ester monomer selected from methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate.
The method of claim 6,

The crosslinking control monomer is a method for producing a rubbery polymer, characterized in that it comprises at least one vinyl cyanide monomer selected from acrylonitrile, methacrylonitrile, ethacrylonitrile.
The method of claim 6,

The crosslinking control monomer is a method for producing a rubbery polymer, characterized in that it comprises at least one unsaturated carboxylic acid selected from acrylic acid, maleic acid, methacrylic acid, itaconic acid, fumaric acid.
The method of claim 6,

The method for producing a rubbery polymer, characterized in that to produce a rubbery polymer having a gel content of less than 70 to 95%, a swelling index of less than 15 to 25 under a polymerization conversion rate of 90 to 95%.
In preparing the graft copolymer from the rubbery polymer,

A method for producing a graft copolymer, characterized in that the crosslinking regulator-containing rubbery polymer obtained by the method of claim 5 is used as the rubbery polymer.
The method of claim 13,

The production method is a 50 to 80% by weight of the cross-linking agent-containing rubbery polymer, 20 to 50% by weight of one or more monomers selected from styrene monomer, vinyl cyanated monomer and acrylic acid ester monomer and graft copolymerized on rubber particles Of graft copolymers
Graft copolymers and heat-resistant thermoplastics,

The graft copolymer is a shock-resistant resin composition comprising a cross-linking agent-containing rubber polymer-containing graft copolymer obtained by the method of claim 13 in the range of 50 to 80% by weight of 100% by weight of the total composition.
The method of claim 15,

The heat-resistant thermoplastic resin is alpha methyl styrene-acrylonitrile-styrene copolymer (AMS-SAN), acrylonitrile-styrene copolymer (SAN), acrylonitrile-styrene-methyl methacrylate (MS), polycarbonate ( PC), polybutylene terephthalate (PBT), and polyvinyl chloride (PVC) is at least one member selected from the impact-resistant heat-resistant resin composition.