KR20170056127A - Thermoplastic resin, method for prepating the resin and thermoplastic resin composition comprising the resin - Google Patents
Thermoplastic resin, method for prepating the resin and thermoplastic resin composition comprising the resin Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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Abstract
Description
The present invention relates to a thermoplastic resin, a method for producing the same, and a thermoplastic resin composition containing the thermoplastic resin. More particularly, the present invention relates to a thermoplastic resin composition comprising a thermoplastic resin, A thermoplastic resin having a high transition temperature, a method for producing the same, and a thermoplastic resin composition having excellent mechanical properties, processability and heat resistance by including the thermoplastic resin.
Acrylonitrile-butadiene-styrene (ABS) resins are widely used in automotive products, electrical and electronic equipment due to stiffness and chemical resistance of acrylonitrile, butadiene and styrene processability, mechanical strength and beautiful appearance characteristics. Electronic products and office equipment.
However, since the ABS resin is low in heat resistance of the resin itself, it is limited in use for parts requiring heat resistance such as automobile interior materials and exterior materials.
In order to increase the heat resistance of the ABS resin, an ABS resin is prepared by incorporating a heat-resistant monomer (e.g.,? -Methylstyrene) having a high glass transition temperature upon grafting, or the ABS resin is mixed with a heat- (α-methylstyrene-acrylonitrile copolymer or the like). However, since the heat-resistant copolymer has low reactivity of alpha-methylstyrene and poor polymerization stability in the emulsion polymerization step, There is a problem that the polymerization rate is greatly lowered and the amount of the coagulated product is increased, thereby lowering the productivity and the heat resistance.
DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a thermoplastic resin having a high glass transition temperature without lowering the reaction rate by introducing a crosslinking agent in a certain amount in the production of a copolymer containing a thermostable monomer having low reactivity .
Another object of the present invention is to provide a method for producing the thermoplastic resin.
It is another object of the present invention to provide a thermoplastic resin composition having excellent mechanical properties, processability and heat resistance by including the thermoplastic resin.
These and other objects of the present invention can be achieved by the present invention described below.
In order to accomplish the above object, the present invention provides a thermoplastic resin composition comprising 100 parts by weight of a monomer mixture comprising a heat-resistant monomer and a vinyl cyan compound; And from 2 to less than 20 parts by weight of a crosslinking agent.
The present invention also provides a thermosetting resin composition comprising 100 parts by weight of a monomer mixture comprising a heat-resistant monomer and a vinyl cyan compound; And a crosslinking agent in an amount of more than 2 parts by weight and less than 20 parts by weight, based on the total weight of the thermoplastic resin.
The present invention also provides a thermoplastic resin composition comprising the thermoplastic resin and the aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer.
According to the present invention, there is provided a thermoplastic resin having a high glass transition temperature without lowering the reaction rate by introducing a crosslinking agent in a certain amount in the production of a copolymer containing a thermostable monomer having low reactivity, and a method for producing the same. Thereby providing a thermoplastic resin composition excellent in mechanical properties, workability, and heat resistance.
Hereinafter, the present invention will be described in detail.
The inventors of the present invention have made it possible to produce a copolymer having a high glass transition temperature without lowering the reaction rate when a crosslinking agent is introduced in a certain amount in the production of a heat resistant copolymer.
The thermoplastic resin according to the present invention will now be described in detail.
Said thermoplastic resin comprising 100 parts by weight of a monomer mixture comprising a heat-resistant monomer and a vinyl cyan compound; And from 2 to less than 20 parts by weight of a crosslinking agent.
The heat-resistant monomer means a monomer which contains the heat-resistant monomer and increases the glass transition temperature of the polymerized polymer to increase the heat resistance. Usually, the monomer is not limited as long as it is a monomer used as a heat-resistant monomer. methylstyrene.
The heat-resistant monomer may be contained in an amount of 50 to 90% by weight, 55 to 85% by weight, or 60 to 80% by weight based on the monomer mixture. Within this range, the heat-resistant monomer is excellent in mechanical properties and heat resistance.
The vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. The vinyl cyan compound may be used in an amount of 10 to 50 wt%, 15 to 45 wt%, or 20 By weight to 40% by weight, and within this range, reactivity with the heat-resistant monomer is high and mechanical properties are excellent.
The crosslinking agent acts to increase the glass transition temperature of the thermoplastic resin and to increase the molecular weight by strengthening the bonds in the copolymer chain by crosslinking each monomer when copolymerizing the heat resistant monomer and the vinyl cyan compound, For example, it may have an activated vinyl group. Specific examples thereof include divinyl benzene, trivinyl benzene, divinyl toluene, divinyl xylene, divinyl naphthalene divinyl naphthalene, divinyl alkyl benzene, divinyl phenanthrene, divinyl biphenyl, divinyldiphenyl methane, divinyl benzyl, divinyl benzene, But are not limited to, divinyl phenyl ether, divinyl diphenyl sulfide, divinyl furan, divinyl sulfide and divinyl sulfone (divinyl sulfone).
The crosslinking agent may be contained in an amount of more than 2 parts by weight, less than 20 parts by weight, 3 to 18 parts by weight, or 5 to 15 parts by weight based on 100 parts by weight of the monomer mixture. Within this range, mechanical properties, workability, heat resistance, Has an excellent effect.
The polymerization method is not particularly limited as long as it is a method capable of copolymerizing the heat-resistant monomer and the vinyl cyan compound together with the cross-linking agent, and may be, for example, emulsion polymerization.
For example, the thermoplastic resin may have a glass transition temperature of 136 ° C or higher, 136-145 ° C or 137-143 ° C, and an excellent balance of heat resistance and physical properties within this range.
For example, the thermoplastic resin may have a weight average molecular weight of 100,000 to 180,000 g / mol, 100,000 to 160,000 g / mol, or 110,000 to 155,000 g / mol, excellent balance of workability and physical properties within this range, So that the processability is excellent.
The method for producing a thermoplastic resin according to the present invention comprises: 100 parts by weight of a monomer mixture comprising a heat-resistant monomer and a vinyl cyan compound; And a crosslinking agent in an amount of more than 2 parts by weight and less than 20 parts by weight.
The thermoplastic resin can be polymerized by, for example, an emulsion polymerization method. In this case, the thermoplastic resin is excellent in mechanical properties and is not particularly limited as long as it is an ordinary emulsion polymerization method.
The heat-resistant monomer, the vinyl cyan compound and the cross-linking agent can be injected in one batch, continuously, or in a mixture of batch and continuous.
The thermoplastic resin may be polymerized by, for example, including an emulsifier, an electrolyte, a polymerization initiator, and a molecular weight regulator.
The emulsifier is not particularly limited as long as it is an emulsifier used in emulsion polymerization. For example, a fatty acid metal salt can be used. Examples of the fatty acid include palmitic acid, oleic acid, lauric acid, stearic acid, Metal.
The emulsion polymerization may be, for example, a polymerization conversion rate of 95% or more, 97% or 97% or 99.9%.
The thermoplastic resin may have a solid solid content of 1% by weight or less, 0.01 to 0.8% by weight, or 0.05 to 0.5% by weight, for example.
The thermoplastic resin manufacturing method may include, for example, agglomerating and aging a latex-type copolymer emulsion-polymerized.
The coagulation can be carried out by introducing a metal salt coagulant. The coagulation can be carried out at 80 to 120 ° C, 90 to 110 ° C, or 95 to 105 ° C to prevent thermal decomposition of the copolymer latex within the temperature range , And the heat resistance of the produced resin is excellent.
The aging may be carried out at 100-140 ° C, 110-130 ° C, or 115-125 ° C. Specific examples of the aging may be press aging under aging at a pressure of 0.1-0.23 MPa or 0.17-0.23 MPa, There is an effect of reducing the water content of the thermoplastic resin produced within the temperature and pressure range.
The thermoplastic resin composition according to the present invention is characterized by containing the thermoplastic resin and the aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer.
The aromatic vinyl compound-conjugated diene-based compound-vinyl cyanide copolymer may be obtained, for example, by graft-polymerizing a conjugated diene-based rubber polymer containing the conjugated diene-based compound by graft-polymerizing the aromatic vinyl compound and the vinyl cyan compound Lt; / RTI > copolymer.
The thermoplastic resin composition may be, for example, a graft copolymer in which the graft copolymer is dispersed in a matrix resin made of the thermoplastic resin. In this case, the impact strength and balance of physical properties are excellent.
Examples of the aromatic vinyl compound of the aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer include aromatic vinyl compounds such as styrene,? -Methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene and vinyltoluene And may be contained in an amount of 20 to 45% by weight, 20 to 40% by weight, or 20 to 35% by weight based on the aromatic vinyl compound-conjugated diene-based compound-vinyl cyanide copolymer, The balance of mechanical properties and physical properties is excellent.
Examples of the conjugated diene compound of the aromatic vinyl compound-conjugated diene compound-vinyl cyan compound copolymer include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl- , 2-ethyl-1,3-butadiene, 1,3-pentadiene, and chloroprene, and may be copolymerized in the form of a rubbery polymer polymerized with the conjugated diene compound, 50 to 90% by weight, 50 to 80% by weight, or 50 to 70% by weight, based on the aromatic vinyl compound-conjugated diene-based compound-vinyl cyanide copolymer, and a balance of mechanical properties and physical properties It has excellent effect.
The vinyl cyan compound of the aromatic vinyl compound-conjugated diene compound-vinyl cyan compound copolymer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, and the aromatic vinyl compound 1 to 20% by weight, 1 to 15% by weight, or 5 to 15% by weight based on the total amount of the conjugated diene compound-vinyl cyanide copolymer, and excellent balance of mechanical properties and physical properties within this range .
The thermoplastic resin may include, for example, 50 to 90% by weight, 60 to 90% by weight, or 60 to 85% by weight of the thermoplastic resin composition, and the aromatic vinyl compound-conjugated dienic compound-vinyl cyanide copolymer For example, 10 to 50% by weight, 10 to 40% by weight, or 15 to 40% by weight based on the thermoplastic resin composition, and excellent balance of heat resistance, mechanical properties and physical properties within this range.
The thermoplastic resin composition may further contain additives such as a heat stabilizer, a light stabilizer, an antioxidant, an antistatic agent, an antimicrobial agent or a lubricant within a range not affecting the physical properties of the thermoplastic resin composition.
For example, the thermoplastic resin composition may have a melt index (220 ° C, 10 kg) of 2.5 g / 10 min or more, 2.5 to 4 g / 10 min, or 2.7 to 3.6 g / 10 min, , And excellent balance of workability and physical properties.
The thermoplastic resin composition may have a heat distortion temperature (HDT) of 105 ° C or higher, 105 ° C to 115 ° C, or 107 ° C to 112 ° C, for example.
It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory only and are not to be taken by way of illustration in the practice of the practice of this invention. And it is natural that such variations and modifications are included in the appended claims.
[Example]
Example 1
Thermoplastic resin manufacturing
To 150 parts by weight of ion-exchanged water and 150 parts by weight of ion-exchanged water, 150 parts by weight of ion-exchanged water, 71 parts by weight of? -Methyl styrene, 10 parts by weight of acrylonitrile, 2.5 parts by weight of potassium fatty acid as an emulsifier , 0.05 part by weight of potassium carbonate as an electrolyte, 0.45 part by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight modifier and 5 parts by weight of divinylbenzene as a crosslinking agent were mixed and stirred at 50 DEG C for 30 minutes, 0.02 part by weight of ropferoxide, 0.035 part by weight of dextrose, 0.06 part by weight of sodium pyrophosphate, and 0.0015 part by weight of ferrous sulfate was added in one portion, and the mixture was heated at 70 DEG C for 1 hour. Subsequently, an emulsion composed of 30 parts by weight of ion-exchanged water, 17 parts by weight of acrylonitrile and 1 part by weight of potassium fatty acid was continuously introduced at 75 DEG C for 2 hours while being heated. Subsequently, 2 parts by weight of acrylonitrile was added together with an oxidation-reduction catalyst composed of 0.03 part by weight of t-butyl hydroperoxide, 0.035 part by weight of dextrose, 0.06 parts by weight of sodium pyrophosphate and 0.0015 part by weight of ferrous sulfate, Lt; 0 > C, and the polymerization reaction was terminated to obtain a copolymer latex. The polymerization conversion ratio and the solidified solid content of the copolymer are shown in Table 1 below. Thereafter, the copolymer latex was agitated at 100 캜 by adding 3 parts by weight of a 23 wt% aqueous solution of calcium chloride, aged under pressure at 120 캜 under pressure of 0.2 MPa, dehydrated using a dehydrator, and dried to obtain a thermoplastic resin powder. The glass transition temperature and the weight average molecular weight of the thermoplastic resin produced at this time are shown in Table 1 below.
Preparation of aromatic vinyl compound-conjugated diene compound-vinyl cyanide copolymer
To the polymerization reactor filled with nitrogen, 60 parts by weight of the polybutadiene rubber polymer latex (based on solid content), 7.5 parts by weight of styrene, 2.5 parts by weight of acrylonitrile, 140 parts by weight of ion-exchanged water, 0.3 parts by weight of potassium rosinate, 0.1 part by weight of tetraacetate, 0.005 part by weight of ferrous sulfate, and 9.23 parts by weight of formaldehyde sodium sulfoxylate were added all at once and the temperature was raised to 70 占 폚. Subsequently, 30 parts by weight of ion-exchanged water, 0.3 part by weight of potassium rosinate, 22.5 parts by weight of styrene, 7.5 parts by weight of acrylonitrile, 0.4 part by weight of tertiary dodecyl mercaptan (TDDM) and 0.4 part by weight of diisopropylene benzene hydroperoxide The mixed emulsion solution was added continuously for 3 hours, and then the temperature of the polymerization was raised to 80 ° C., and the reaction was terminated by aging for 1 hour. Thereafter, 2.5 parts by weight of a 23 wt% aqueous solution of magnesium sulfate was added to coagulate, washed, and dried to obtain an aromatic vinyl compound-conjugated diene compound-vinyl cyanide compound graft copolymer powder.
Production of thermoplastic resin composition
75 parts by weight of the obtained thermoplastic resin and 25 parts by weight of the obtained aromatic vinyl compound-conjugated dienic compound-vinyl cyanide copolymer powder were mixed in a conventional mixer and mixed and melted at 240 to 250 ° C using an extruder, Kneaded and pelletized, and then specimens for physical property measurement were prepared using an injection machine.
Example 2
The procedure of Example 1 was repeated except that 10 parts by weight of divinylbenzene as a crosslinking agent was added instead of 5 parts by weight of the thermoplastic resin of Example 1.
Example 3
The procedure of Example 1 was repeated except that 15 parts by weight of divinylbenzene as a crosslinking agent was added instead of 5 parts by weight of the thermoplastic resin of Example 1.
Comparative Example 1
The same procedure as in Example 1 was carried out except that divinylbenzene as a crosslinking agent was not added during the production of the thermoplastic resin of Example 1.
Comparative Example 2
The procedure of Example 1 was repeated except that 2 parts by weight of divinylbenzene as a crosslinking agent was added instead of 5 parts by weight of the thermoplastic resin of Example 1.
Comparative Example 3
The procedure of Example 1 was repeated except that 20 parts by weight of divinylbenzene as a crosslinking agent was added instead of 5 parts by weight of the thermoplastic resin of Example 1.
[Test Example]
The physical properties of the respective thermoplastic resins and thermoplastic resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 1 below.
How to measure
Polymerization Conversion Rate (%): 1.5 g of the graft copolymer latex was dried in a hot air drier at 150 캜 for 15 minutes, and the weight was measured to determine the total solid content (TSC).
TSC: total solid content (parts by weight)
M: total monomer content (parts by weight)
W: Water content (parts by weight)
S: Amount of emulsifier and other additives added (parts by weight)
* Solidified solid content (% by weight): The weight of the solidified product, the total rubber weight and the weight of the monomer produced in the reaction tank were measured and the solidified content was calculated by the following formula (2).
Glass transition temperature (Tg, 占 폚): The temperature was raised to 180 占 폚 using a DSC1 Star System manufactured by METTLER TOLEDO, cooled to 30 占 폚 at a cooling rate of 20 占 폚 / min to remove the thermal history, And the glass transition temperature was measured.
* Weight average molecular weight (Mw, g / mol): The relative value to a standard PS (standard polystyrene) sample was measured by gel chromatography (GPC).
Melt Index (g / 10 min): Measured according to standard measurement ASTM D1238 (220 ° C, 10 kg condition) using specimen.
* Heat distortion temperature (HDT, ° C): Measured according to standard measurement ASTM D648 using 1/4 "specimen.
As shown in Table 1, the thermoplastic resins of Examples 1 and 3 prepared according to the present invention had a higher polymerization conversion and a higher glass transition temperature and weight average molecular weight than Comparative Example 1 in which no crosslinking agent was added I could confirm. In addition, it was confirmed that the thermoplastic resin composition containing the thermoplastic resin had remarkably excellent heat resistance while maintaining the same level of the melt index.
On the other hand, it was confirmed that the effect of improving the glass transition temperature and heat resistance was extremely small in Comparative Example 2 containing a slight amount of the crosslinking agent, and in Comparative Example 3 containing the crosslinking agent in an excessive amount, the weight average molecular weight was extremely increased, As a result, it was confirmed that the processability was very poor.
From the above results, it was confirmed from the above results that a thermoplastic resin composition having a high glass transition temperature and excellent heat resistance can be obtained by introducing a crosslinking agent in a certain amount in the production of a heat-resistant copolymer without lowering the reaction rate .
Claims (14)
Wherein the heat-resistant monomer is? -Methylstyrene.
Wherein the heat-resistant monomer is contained in an amount of 50 to 90% by weight based on the monomer mixture.
Wherein the vinyl cyan compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.
The crosslinking agent may be selected from the group consisting of divinyl benzene, trivinyl benzene, divinyl toluene, divinyl xylene, divinyl naphthalene, divinyl alkyl benzene, divinyl phenanthrene, divinyl biphenyl, divinyldiphenyl methane, divinyl benzyl, divinyl phenyl ether, And at least one member selected from the group consisting of divinyl diphenyl sulfide, divinyl furan, divinyl sulfide, and divinyl sulfone. Or more of the thermoplastic resin.
Wherein the thermoplastic resin has a glass transition temperature of 136 占 폚 or higher.
Wherein the thermoplastic resin has a weight average molecular weight of 100,000 to 180,000 g / mol.
And agglomerating and aging the emulsion-polymerized copolymer latex.
The aromatic vinyl compound-conjugated diene-based compound-vinyl cyanide copolymer is obtained by graft-copolymerizing graft-copolymerized aromatic vinyl compound and vinyl cyan compound with a conjugated diene-based rubber- Wherein the thermoplastic resin composition is a thermoplastic resin composition.
Wherein the thermoplastic resin is contained in an amount of 50 to 90% by weight, and the aromatic vinyl compound-conjugated dienic compound-vinyl cyanide copolymer is contained in an amount of 10 to 50% by weight.
Wherein the thermoplastic resin composition has a melt index (220 DEG C, 10 kg) of 2.5 g / 10 min or more.
Wherein the thermoplastic resin composition has a heat distortion temperature (HDT) of 105 占 폚 or higher.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111454384A (en) * | 2020-03-24 | 2020-07-28 | 上海交通大学 | Crosslinked polyethylene and preparation method and application thereof |
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2015
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| KR0125872B1 (en) * | 1992-11-16 | 1997-12-26 | 채오병 | Preparation of thermoplastic polystyrene resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111454384A (en) * | 2020-03-24 | 2020-07-28 | 上海交通大学 | Crosslinked polyethylene and preparation method and application thereof |
| CN111454384B (en) * | 2020-03-24 | 2021-10-29 | 上海交通大学 | Crosslinked polyethylene and preparation method and application thereof |
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| KR102013709B1 (en) | 2019-08-23 |
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