KR20170087152A - Surface modified expandable polystyrene beads having excellent bonding and a method of manufacturing the same - Google Patents
Surface modified expandable polystyrene beads having excellent bonding and a method of manufacturing the same Download PDFInfo
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- KR20170087152A KR20170087152A KR1020160006791A KR20160006791A KR20170087152A KR 20170087152 A KR20170087152 A KR 20170087152A KR 1020160006791 A KR1020160006791 A KR 1020160006791A KR 20160006791 A KR20160006791 A KR 20160006791A KR 20170087152 A KR20170087152 A KR 20170087152A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- C08F2/18—Suspension polymerisation
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- C08F12/00—Homopolymers and 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
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
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- 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
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- C08L25/06—Polystyrene
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Abstract
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-modified expandable polystyrene particle having excellent melt adhesion and a method for producing the same. More specifically, when the proportion of the styrene-based monomer to the water in the reactor is less than a predetermined ratio and the content of the styrene-based monomer added is higher than the content of the seed, (1) a part of the styrene- (2) a step of adsorbing the polystyrene particles undergoing self-polymerization on the surface of the seed under polymerization, thereby producing a foamed polystyrene particle modified on the surface thereof. The surface-modified foamed polystyrene particles of the present invention are characterized in that the portion adsorbed on the surface serves as a compatibilizer and an adhesive agent between the foamed lips, so that when the foamed body is molded, the foamability is excellent and the mechanical strength is improved.
Description
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-modified expandable polystyrene particle having excellent melt adhesion and a method for producing the same. More specifically, the present invention relates to a process for producing a surface-modified expanded polystyrene particle under two conditions in which the ratio of the styrene monomer to the water in the reactor is not more than a predetermined ratio and the content of the styrene monomer is higher than the content of the seed. The surface-modified expandable polystyrene particles of the present invention are characterized by being excellent in fusion-bondability and improving mechanical strength.
As a method for producing expandable polystyrene particles, a suspension polymerization method, an extrusion method and a seed polymerization method are widely known.
The foamable polystyrene produced by the above three production methods has been known for a long time after the invention and proved to be useful in various fields. Foams made from expandable polystyrene particles have excellent heat insulating performance and are widely used as building materials because of their easy construction properties. Foam boards using expandable polystyrene typically exhibit a minimum thermal conductivity at a high density of about 30 g / l, but in order to conserve material, it is preferred to use a foam board for insulation which has a low density, in particular a density of less than 20 g / l . However, such low density foam boards have the disadvantage that they have increased thermal conductivity and do not have the insulating properties to meet the requirements of the insulation grade 'KSM 3808'. Further, the foam made from expandable polystyrene particles has a lower flame retardancy than an inorganic heat insulator such as glass fiber and gypsum board, and is required to have a flame retardancy of a level of flame retardant (flame retardant grade 3) in order to be used as a sandwich panel of a building.
Accordingly, in Korean Patent Publication No. 2005-0111820, Korean Patent Publication No. 2006-0101593, Korean Patent Publication No. 2007-0118208, and Korean Patent Publication No. 2012-0093047, insoluble materials such as graphite, carbon black, charcoal , Aluminum and the like have been added in various ways in order to further reduce the thermal conductivity of the foamable polystyrene insulating board. In Korean Patent Laid-Open Publication No. 2008-0130056, aluminum hydroxide and magnesium hydroxide, which are inorganic flame retardants, are added to improve the flame retardancy of the expandable polystyrene foam, Korean Patent Publication No. 2010-0051500 discloses an expandable polystyrene foam And excellent flame retardancy.
However, when a functional additive such as an impermeable material and an inorganic flame retardant is added to existing expandable polystyrene particles as described above, the cells in the pre-expanded lips are dispersed to inhibit secondary foaming by steam, and the additives are present on the surface of the pre- Therefore, there is a problem that the fusion strength between the foamed lip particles is inhibited during the process of making the foam board, and the mechanical strength is lowered. Therefore, various studies have been made on various methods for improving the mechanical strength and excellent fusion-bondability even when the insufficiently heat-resistant material and the inorganic flame retardant are added to expandable polystyrene particles.
It is an object of the present invention to provide an efficient method for producing surface-modified expandable polystyrene particles having excellent surface properties that are excellent in fusion strength and mechanical strength even when a functional additive is added.
It is still another object of the present invention to provide a novel production method in which a part of the styrene-based monomer does not penetrate into the seed during polymerization of the seed, but is self-polymerized and adsorbed on the surface of the seed under polymerization.
In the present invention, unlike the conventional seed polymerization method in which the added styrenic monomer is infiltrated into the whole particle to swell the seed, the ratio of the styrenic monomer and the seed to the water in the reactor is less than a certain ratio, When the content of the monomer is high, a part of the styrene-based monomer is not self-permeated into the seed but is polymerized to form polystyrene particles, and the surface is modified through the step of adsorbing the polystyrene particles in- Expandable polystyrene particles can be produced.
Since the portion adsorbed on the surface of the surface-modified expandable polystyrene particles serves as a compatibilizing agent and an adhesive agent between the foamed lips, when the foamed product is produced, it has excellent melt adhesion and mechanical strength, .
Figure 1 shows a foamed lip surface (Example 1) made from surface modified foamed polystyrene particles,
Fig. 2 shows the surface of the foamed lip made from expandable polystyrene particles whose surface was not modified (Comparative Example 1, Comparative Example 2)
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-modified expandable polystyrene particle having excellent melt adhesion and a method for producing the same. More specifically, when the proportion of the styrene-based monomer to the water in the reactor is less than a predetermined ratio and the content of the styrene-based monomer added is higher than the content of the seed, a part of the styrene-based monomer does not penetrate into the seed, Thereby forming polystyrene particles, and a step of adsorbing the polystyrene particles undergoing self-polymerization on the surface of the seed under polymerization, thereby producing a foamed polystyrene particle modified on the surface.
(2) a step (3) of forming an aqueous dispersion containing a seed, a dispersant and / or a surfactant; and (3) a step ) Swelling the seed by adding a styrenic monomer in which the initiator is dissolved, (4) polymerizing while adding the remaining styrene monomer, and (5) impregnating the polymer with the blowing agent.
In the practice of the present invention, (1) In the step of obtaining a uniform particle seed by melting and extruding the styrene type resin and the functional additive, the seed of the uniform particle is carried out by using the conventional cylindrical pellets, spherical beads, .
In the practice of the present invention, the styrene series resin may be styrene; Alkylstyrenes, such as ethylstyrene, dimethylstyrene and para-methylstyrene; Alpha-alkylstyrenes, such as alpha-methylstyrene, alpha-ethylstyrene, alpha-propylstyrene and alpha-butylstyrene; Halogenated styrenes, such as chlorostyrene, and bromostyrene; And vinyl toluene. Examples of the monomer copolymerizable with the styrenic monomer include acrylonitrile, butadiene, alkyl acrylates such as methyl acrylate, alkyl methacrylate, and the like. Methyl methacrylate, isobutylene, vinyl chloride, isoprene, and mixtures thereof. In a preferred embodiment of the present invention, the styrene resin is a polystyrene resin having a weight average molecular weight of 180,000 to 400,000 g / mol.
In the practice of the present invention, (1) at the stage of obtaining a uniform particle seed by melting and extruding a styrene resin and a functional additive, graphite, carbon black, carbon nanotubes, metal powder, metal Various additives such as oxides, metal hydroxides, expanded graphite and inorganic flame retardants are selectively introduced to impart heat insulating performance, antistatic ability, and non-flammability.
In the practice of the present invention, the ratio of the styrenic monomer to the water relative to water as the solvent of the aqueous dispersion comprising the seed, dispersant and / or surfactant containing the additive material is preferably from 0.1 to 0.8, The ratio of 0.1 to 0.5 is used.
In the practice of the present invention, the styrenic monomer may be styrene, styrene; Alkylstyrenes, for example, ethylstyrene, dimethylstyrene and para-methylstyrene; Alpha-alkyl styrenes, such as alpha-methyl styrene, alpha-ethyl styrene, alpha-propyl styrene and alpha-butyl styrene. In the present invention, the weight ratio of the seed to the styrene-based monomer is 10 to 45: 90 to 55 based on 100 parts by weight of the expandable polystyrene particles.
The dispersing agent in the suspension can be prepared by using any dispersing agent commonly used in conventional expandable polystyrene polymerization, and examples thereof include inorganic dispersing agents; Tricalcium phosphate, magnesium pyrophosphate, organic dispersant; In the present invention, 0.01-1.0 parts by weight of sodium pyrophosphate and 0.01-1.0 parts by weight of magnesium chloride are mixed with 100 parts by weight of water, with stirring.
In the practice of the present invention, the surfactant in the suspension is sodium laurylsulfonate, sodium alkylbenzenesulfonate, sodium oleinsulfonate, and the like. In the present invention, 0.01 to 0.15 parts by weight of sodium alkylbenzenesulfonate is used relative to 100 parts by weight of water.
In the practice of the present invention, in the step of swelling a seed by adding a styrenic monomer in which an initiator and an additive are dissolved, the initiator uses two kinds of initiators having different initiation temperatures, and usually all of the initiators used in the expandable polystyrene polymerization In the practice of the present invention, two kinds of initiators such as benzoyl peroxide (BPO) and t-butyl peroxybenzoate (TBPB) may be added in an amount of 0.1 to 0.5 parts by weight per 100 parts by weight of the styrene- To use.
In the practice of the present invention, the blowing agent may be blowing agents C4 to C6 used in the production of general expandable polystyrene, and examples thereof include butane, i-butane, n-pentane, i-pentane, neo-pentane, cyclopentane, Hydrocarbons can be used, and 4 to 15 parts by weight are used per 100 parts by weight of expandable polystyrene particles.
EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.
Example 1 Production test of expandable polystyrene particles (100 parts by weight of expandable polystyrene beads were prepared with 40 parts by weight of allergic seed, 60 parts by weight of styrene monomer, and 0.5 parts of styrene monomer and seed to water)
10 kg of graphite (WF99-5) was added to 100 kg of polystyrene (Kumho Petrochemical GP150), and the resulting mixture was melted at 230 DEG C in a twin-screw extruder and then melt-kneaded using underwater cutting The average diameter is 1.2 mm Uniform graphite-containing resin particles were obtained.
(KKPC: MP20G) 1.6 (product of KKPC) containing graphite was charged with 8.0 kg of water, 21 g of sodium pyrophosphate (Youngjin Industry) and 60 g of magnesium chloride kg.
Thereafter, the reactor temperature was raised to 70 DEG C, 32 g of a flame retardant (hexabromocyclododecane; GLC; CD75P ( TM )), 6.4 g of a low temperature initiator (benzoyl peroxide; Hansol Chemical) 3.6 g of a high-temperature initiator (t-butylperoxy benzoate; HOPE CEMEX) was dissolved and added for 2 hours. At the same time, 0.4 kg of styrene monomer (SK) was slowly introduced into the reactor to proceed the swelling step. Thereafter, the inlet of the reactor was closed, and 1.5 kg of the styrene monomer was slowly added thereto while being heated from 70 ° C to 110 ° C for 3.5 hours to carry out the polymerization. After this was completed, 0.3 kg of a blowing agent (pentane; SK) was introduced into the reactor at a pressure of nitrogen at 110 ° C., and the impregnation was carried out for 5 hours while maintaining the final reactor pressure at 13 kgf / cm 2 . Thereafter, the mixture was cooled to 30 DEG C or lower and the product was discharged to the reactor. The product was washed with water, dried, and then subjected to foaming evaluation by applying a blending agent used in ordinary foam polystyrene particle production.
Comparative Example 1 Production test of expandable polystyrene particles (100 parts by weight of expandable polystyrene particles were prepared with 50 parts by weight of an allergic seed, 50 parts by weight of a styrene monomer, and a ratio of a styrene monomer and a seed to water: 0.5)
(KKPC; MP20G) 2.0 (graphite-containing) containing graphite was charged to a 15 L reactor equipped with a stirrer, a stirrer, kg.
Thereafter, the reactor temperature was raised to 70 DEG C, 32 g of a flame retardant (hexabromocyclododecane; GLC; CD75P TM ), 6.0 g of a low temperature initiator (benzoyl peroxide; Hansol Chemical Co., Ltd.) 3.0 g of a high-temperature initiator (t-butyl peroxybenzoate; HosungChemex) was dissolved and added for 2 hours. Thereafter, the inlet of the reactor was closed, and 1.5 kg of the styrene monomer was slowly added thereto while being heated from 70 ° C to 110 ° C for 3.5 hours to carry out the polymerization. The blowing agent at 110 ℃ after this is completed (Pentane; SK) to 0.3kg added to the reactor with nitrogen pressure and the final reactor pressure 13kgf / cm 2 And the impregnation was carried out for 5 hours. Thereafter, the mixture was cooled to 30 DEG C or lower and the product was discharged to the reactor. The product was washed with water, dried, and then subjected to foaming evaluation by applying a blending agent used in ordinary foam polystyrene particle production.
(Comparative Example 2) Production test of expanded polystyrene particles (100 parts by weight of expandable polystyrene fine particles were prepared with 40 parts by weight of an allergic seed, 60 parts by weight of a styrene monomer, and a ratio of a styrene monomer and a seed to water: 0.9)
(KKPC: MP20G) containing graphite was charged with 2.3 kg of water, 30 g of sodium pyrophosphate (Youngjin Industrial Co., Ltd.) and 85 g of magnesium chloride (SiMei, 30% aqueous solution) kg.
Thereafter, the reactor temperature was raised to 70 DEG C, 45 g of a flame retardant (hexabromocyclododecane; GLC; CD75P TM ), 9.0 g of a low temperature initiator (benzoyl peroxide; Hansol Chemical Co., Ltd.) 5.0 g of a high temperature initiator (t-butylperoxy benzoate; HOPE CEMEX) was dissolved and added for 2 hours while 0.45 kg of styrene monomer (SK) was slowly introduced into the reactor to proceed the swelling step. Thereafter, the inlet of the reactor was closed, and 2.2 kg of the styrene monomer was slowly added thereto while heating the temperature from 70 ° C to 110 ° C for 3.5 hours to proceed the polymerization. After this was completed, 0.4 kg of a foaming agent (pentane; SK) was introduced into the reactor at a pressure of nitrogen at 110 ° C. and impregnation was carried out for 5 hours while maintaining the final reactor pressure at 13 kgf / cm 2 . Thereafter, the mixture was cooled to 30 DEG C or lower and the product was discharged to the reactor. The product was washed with water, dried, and then subjected to foaming evaluation by applying a blending agent used in ordinary foam polystyrene particle production.
Table 1 below shows the properties of the test pieces produced by the above examples.
(
Weight portion
)
(
Weight portion
)
In Table 1, graphite content, surface modification, fusibility, and flexural strength were specifically performed as follows.
One) Graphite content: dissolved in THF (tetrahydrofuran) solvent and filtered (wet process)
2) Whether the surface is modified: When the foam is observed, the outer surface of the foam lip is visually observed
3) (%) In which the inside of the foamed particles in the cross section of the molded product is broken,
4) Flexural strength: According to the method of measuring the combustibility of expanded polystyrene insulation materials specified in Korean Industrial Standard KS M 3808 (Kgf / cm 2 )
From the results shown in the above Table 1, it can be seen that, in the case of the expandable polystyrene particles produced by the seed polymerization method of Comparative Example 1, the ratio of the styrene monomer to the seed is low at a ratio of 0.5 to the water, but the seed content and the styrene monomer content are 1 : 1, the surface of expandable polystyrene particles is not modified. In the case of <Comparative Example 2>, even if the styrene monomer content is higher than the seed content (1: 1.5), the surface of the expandable polystyrene particles is not modified when the ratio of the styrene monomer to the seed is high.
In the case of expandable polystyrene particles prepared by the seed polymerization method of Example 1, the ratio of monomer to seed to water was low at 0.5, and the content of seed was lower than that of styrene monomer (1: 1.5) And the surface of the expandable polystyrene particles is modified. The shape of the foamed lip particles whose surface was modified can be seen in FIG. 1, and the <Example 1> improves the melt adhesion and the <Comparative Example 1> and <Comparative Example 2> have higher mechanical strength, that is, the flexural strength.
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